U.S. patent application number 14/431345 was filed with the patent office on 2015-08-27 for process of controlled chemical reaction of a solid filler material surface and additives to produce a surface treated filler material product.
The applicant listed for this patent is OMYA INTERNATIONAL AG. Invention is credited to Rene Vinzenz Blum, Martin Brunner, Matthias Buri, Patrick A.C. Gane, Samuel Rentsch.
Application Number | 20150240056 14/431345 |
Document ID | / |
Family ID | 47022577 |
Filed Date | 2015-08-27 |
United States Patent
Application |
20150240056 |
Kind Code |
A1 |
Rentsch; Samuel ; et
al. |
August 27, 2015 |
PROCESS OF CONTROLLED CHEMICAL REACTION OF A SOLID FILLER MATERIAL
SURFACE AND ADDITIVES TO PRODUCE A SURFACE TREATED FILLER MATERIAL
PRODUCT
Abstract
The present invention relates to a process for preparing a
surface treated filler material product with succinic anhydride(s),
a surface treated filler material product, a polymer composition, a
fiber and/or filament and/or film and/or thread comprising the
surface treated filler material product and/or the polymer
composition, an article comprising the surface treated filler
material product and/or the polymer composition and/or the fiber
and/or filament and/or film and/or thread as well as the use of a
mono-substituted succinic anhydride for decreasing the
hydrophilicity of a calcium carbonate-containing filler material
surface and the use of a surface-treated filler material product
for initiating the crosslinking reaction in epoxide resins.
Inventors: |
Rentsch; Samuel; (Aaburg,
CH) ; Buri; Matthias; (Rothrist, CH) ; Blum;
Rene Vinzenz; (St. Urban, CH) ; Brunner; Martin;
(Wallbach, CH) ; Gane; Patrick A.C.; (Rothrist,
CH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
OMYA INTERNATIONAL AG |
Oftringen |
|
CH |
|
|
Family ID: |
47022577 |
Appl. No.: |
14/431345 |
Filed: |
October 10, 2013 |
PCT Filed: |
October 10, 2013 |
PCT NO: |
PCT/EP2013/071185 |
371 Date: |
March 26, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61717135 |
Oct 23, 2012 |
|
|
|
Current U.S.
Class: |
442/327 ;
106/465; 427/214; 427/221; 523/200; 524/425; 549/233 |
Current CPC
Class: |
D01F 1/02 20130101; C07D
307/60 20130101; D10B 2501/00 20130101; C01P 2004/61 20130101; D10B
2505/04 20130101; C01P 2004/62 20130101; Y10T 442/60 20150401; D04H
3/007 20130101; C08K 9/04 20130101; D10B 2321/022 20130101; C01P
2006/12 20130101; D10B 2509/00 20130101; C09C 1/021 20130101 |
International
Class: |
C08K 9/04 20060101
C08K009/04; D01F 1/02 20060101 D01F001/02; C07D 307/60 20060101
C07D307/60; D04H 3/007 20060101 D04H003/007 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 16, 2012 |
EP |
12188739.2 |
Claims
1. A process for preparing a surface treated filler material
product with succinic anhydride(s), the process comprising at least
the steps of: a) providing at least one calcium
carbonate-containing filler material having i) a weight median
particle size d.sub.50 value in the range from 0.1 .mu.m to 7
.mu.m, ii) a top cut (d.sub.98) of.ltoreq.15 .mu.m, iii) a specific
surface area (BET) of from 0.5 to 150 m.sup.2/g as measured by the
BET nitrogen method, and iv) a residual total moisture content of
from 0.01 wt.-% to 1 wt.-%, based on the total dry weight of the at
least one calcium carbonate-containing filler material, b)
providing at least one mono-substituted succinic anhydride and
optionally at least one mono-substituted succinic acid in an amount
of from 0.1 to 3 wt.-%, based on the total dry weight of the at
least one calcium carbonate-containing filler material of step a),
c) contacting the surface of the at least one calcium
carbonate-containing filler material of step a) under mixing, in
one or more steps, with the at least one mono-substituted succinic
anhydride and the optional at least one mono-substituted succinic
acid of step b) such that a treatment layer comprising the at least
one mono-substituted succinic anhydride and the optional at least
one mono-substituted succinic acid and/or salty reaction product(s)
thereof is formed on the surface of said at least one calcium
carbonate-containing filler material of step a), wherein the
temperature before and/or during contacting step c) is adjusted
such that the temperature is at least 2.degree. C. above the
melting point of the at least one mono-substituted succinic
anhydride and the optional at least one mono-substituted succinic
acid.
2. The process according to claim 1, wherein the at least one
calcium carbonate-containing filler material of step a) is selected
from among ground calcium carbonate (GCC), precipitated calcium
carbonate (PCC), modified calcium carbonate (MCC) and mixtures
thereof.
3. The process according to claim 1, wherein the at least one
calcium carbonate-containing filler material of step a) comprises
at least one ground calcium carbonate (GCC) selected from the group
comprising marble, chalk, dolomite, limestone and mixtures thereof
and/or at least one precipitated calcium carbonate (PCC) selected
from the group comprising one or more of the aragonitic, vateritic
and calcitic mineralogical crystal forms and/or at least one
modified calcium carbonate (MCC).
4. The process according to claim 1, wherein the at least one
calcium carbonate-containing filler material of step a) has a
weight median particle size d.sub.50 from 0.25 .mu.m to 5 .mu.m and
preferably from 0.7 .mu.m to 4 .mu.m.
5. The process according to claim 1, wherein the at least one
calcium carbonate-containing filler material of step a) has a top
cut (d.sub.98).ltoreq.12.5 .mu.m, preferably.ltoreq.10 .mu.m and
most preferably.ltoreq.7.5 .mu.m.
6. The process according to claim 1, wherein the at least one
calcium carbonate-containing filler material of step a) has a
specific surface area (BET) of from 0.5 to 50 m.sup.2/g, more
preferably of from 0.5 to 35 m.sup.2/g and most preferably of from
0.5 to 15 m.sup.2/g as measured by the BET nitrogen method.
7. The process according to claim 1, wherein the at least one
calcium carbonate-containing filler material of step a) has a
residual total moisture content of from 0.01 to 0.2 wt.-%,
preferably from 0.02 to 0.15 wt.-% and most preferably from 0.04 to
0.15 wt.-%, based on the total dry weight of the at least one
calcium carbonate-containing filler material.
8. The process according to claim 1, wherein the at least one
calcium carbonate-containing filler material of step a) is
preheated before contacting step c) is carried out, preferably the
at least one calcium carbonate-containing filler material of step
a) is preheated at a temperature of from 50 to 200.degree. C., more
preferably of from 80 to 200.degree. C., even more preferably of
from 90 to 150.degree. C. and most preferably of from 100 to
130.degree. C.
9. The process according to claim 1, wherein the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid of step b) are provided in a total
amount of from 0.1 to 2.5 wt.-%, preferably in an amount of from
0.1 to 2 wt.-%, more preferably in an amount of from 0.1 to 1.5
wt.-%, even more preferably in an amount of from 0.1 to 1 wt.-% and
most preferably in an amount of from 0.2 to 0.8 wt.-% based on the
total dry weight of the at least one calcium carbonate-containing
filler material.
10. The process according to claim 1, wherein the at least one
mono-substituted succinic anhydride of step b) consists of succinic
anhydride mono-substituted with a group selected from a linear,
branched, aliphatic and cyclic group having a total amount of
carbon atoms from C2 to C30, preferably from C3 to C25 and most
preferably from C4 to C20 in the substituent.
11. The process according to claim 1, wherein the at least one
mono-substituted succinic anhydride of step b) is at least one
alkyl mono-substituted succinic anhydride, preferably at least one
alkyl mono-substituted succinic anhydride selected from the group
comprising ethylsuccinic anhydride, propylsuccinic anhydride,
butylsuccinic anhydride, triisobutyl succinic anhydride,
pentylsuccinic anhydride, hexylsuccinic anhydride, heptylsuccinic
anhydride, octylsuccinic anhydride, nonylsuccinic anhydride, decyl
succinic anhydride, dodecyl succinic anhydride, hexadecanyl
succinic anhydride, octadecanyl succinic anhydride, and mixtures
thereof.
12. The process according to claim 1, wherein the at least one
mono-substituted succinic anhydride of step b) is at least one
alkenyl mono-substituted succinic anhydride, preferably at least
one alkenyl mono-substituted succinic anhydride selected from the
group comprising ethenylsuccinic anhydride, propenylsuccinic
anhydride, butenylsuccinic anhydride, triisobutenyl succinic
anhydride, pentenylsuccinic anhydride, hexenylsuccinic anhydride,
heptenylsuccinic anhydride, octenylsuccinic anhydride,
nonenylsuccinic anhydride, decenyl succinic anhydride, dodecenyl
succinic anhydride, hexadecenyl succinic anhydride, octadecenyl
succinic anhydride, and mixtures thereof.
13. The process according to claim 1, wherein the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid of step b) are added in contacting
step c) in a total amount of from 0.1 to 2 wt.-%, preferably of
from 0.2 to 1.5 wt.-% and most preferably of from 0.3 to 1 wt.-%,
based on the total dry weight of the at least one calcium
carbonate-containing filler material of step a).
14. The process according to claim 1, wherein the at least one
mono-substituted succinic acid of step b) is present in an amount
of.ltoreq.10 mol.-%, based on the molar sum of the at least one
mono-substituted succinic anhydride and the at least one
mono-substituted succinic acid.
15. The process according to claim 1, wherein contacting step c) is
carried out at a temperature of from 30 to 200.degree. C.,
preferably of from 80 to 150.degree. C. and most preferably of from
110 to 130.degree. C.
16. The process according to claim 1, wherein contacting step c) is
carried out in a batch or continuous process, preferably for a
period of time from 0.1 to 1000 seconds.
17. The process according to claim 16, wherein the contacting step
c) is a continuous process and comprises one or several contacting
steps and the total contacting time is from 0.1 to 20 s, preferably
from 0.5 to 15 s and most preferably from 1 to 10 s.
18. The process according to claim 1, wherein the salty reaction
product(s) of the mono-substituted succinic acid and/or the at
least one mono-substituted succinic anhydride formed on the surface
of said at least one calcium carbonate-containing filler material
in step c) are one or more calcium salts and/or one or more
magnesium salts thereof.
19. The process according to claim 1, wherein the process further
comprises step d) of contacting the at least one calcium
carbonate-containing filler material of step a), in one or more
steps, with at least one organic material such as
polysiloxanes.
20. The process according to claim 19, wherein contacting step d)
is carried out during and/or after contacting step c), preferably
after contacting step c).
21. The process according to claim 19, wherein contacting step d)
is carried out at a temperature of from 40 to 200.degree. C.,
preferably of from 50 to 150.degree. C. and most preferably of from
60 to 120.degree. C.
22. The process according to claim 19, wherein the at least one
organic material is added in contacting step d) in an amount of
from 100 to 1000 ppm, preferably from 200 to 800 ppm and most
preferably from 300 to 700 ppm, based on the total dry weight of
the at least one calcium carbonate-containing filler material of
step a).
23. The process according to claim 1, wherein the obtained surface
treated filler material product has a water pick-up of from 0.1 to
0.8 mg/g, preferably of from 0.2 to 0.7 mg/g and most preferably of
from 0.2 to 0.6 mg/g at a temperature of 23.degree. C.
(.+-.2.degree. C.).
24. The process according to claim 1, wherein the obtained surface
treated filler material product has a volatile onset temperature of
.gtoreq.250.degree. C., preferably of.gtoreq.260.degree. C. and
most preferably of.gtoreq.270.degree. C.
25. The process according to claim 1, wherein the obtained surface
treated filler material product has a hydrophilicity of below 8:2
volumetric ratio of water:ethanol measured at +23.degree. C.
(.+-.2.degree. C.) with the sedimentation method.
26. Surface treated filler material product comprising a) at least
one calcium carbonate-containing filler material, as defined in
claim 1, having i) a weight median particle size d.sub.50 value in
the range from 0.1 .mu.m to 7 .mu.m, ii) a top cut
(d.sub.98).ltoreq.15 .mu.m, iii) a specific surface area (BET) of
from 0.5 to 150 m.sup.2/g as measured by the BET nitrogen method,
and iv) a residual total moisture content of.ltoreq.1 wt.-%, based
on the total dry weight of the at least one calcium
carbonate-containing filler material, and b) a treatment layer on
the surface of the at least one calcium carbonate-containing filler
material comprising at least one mono-substituted succinic
anhydride and at least one mono-substituted succinic acid and/or
salty reaction product(s) thereof, wherein the surface treated
filler material product comprises the treatment layer in an amount
of from 0.1 to 3 wt.-%, based on the total dry weight of the at
least one calcium carbonate-containing filler material.
27. Surface treated filler material product according to claim 26,
wherein the molar ratio of the at least one mono-substituted
succinic anhydride and the optional at least one mono-substituted
succinic acid to the salty reaction product(s) thereof is from
99.9:0.1 to 0.1:99.9, preferably from 70:30 to 90:10.
28. Surface treated filler material product according to claim 26,
wherein the salty reaction product(s) of the mono-substituted
succinic acid and/or the at least one mono-substituted succinic
anhydride are one or more calcium and/or magnesium salts
thereof.
29. Surface treated filler material product according to claim 26,
wherein the treatment layer further comprises at least one organic
material such as polysiloxanes.
30. Surface treated filler material product according to claim 26,
wherein the surface treated filler material product comprises the
treatment layer in an amount of from 0.1 to 2.5 wt.-%, preferably
in an amount of from 0.1 to 2 wt.-%, more preferably in an amount
of from 0.1 to 1.5 wt.-%, even more preferably in an amount of from
0.1 to 1 wt.-% and most preferably in an amount of from 0.2 to 0.8
wt.-% based on the total dry weight of the at least one calcium
carbonate-containing filler material.
31. A polymer composition comprising at least one polymeric resin
and from 1 to 85 wt.-%, based on the total weight of the polymer
composition, of a surface treated filler material product as
defined in claim 26.
32. The polymer composition according to claim 31, wherein the at
least one polymeric resin is at least one thermoplastic polymer,
preferably a thermoplastic polymer selected from the group
comprising homopolymers and/or copolymers of polyolefins,
polyamides, halogen-containing polymers and/or polyesters.
33. The polymer composition according to claim 31, wherein the
polymer composition is a masterbatch, preferably the masterbatch
comprises the surface treated filler material product in an amount
of from 50 to 85 wt.-%, preferably from 60 to 85 wt.-% and more
preferably from 70 to 80 wt.-%, based on the total weight of the
masterbatch.
34. A fiber and/or filament and/or film and/or thread comprising a
surface treated filler material product according to claim 26
and/or a polymer composition comprising the surface treated filler
material product.
35. Article comprising a surface treated filler material product
according to claim 26 and/or a polymer composition comprising the
surface treated filler material product and/or a fiber and/or
filament and/or film and/or thread comprising the surface treated
filler material product, wherein the article is selected from the
group comprising hygiene products, medical and healthcare products,
filter products, geotextile products, agriculture and horticulture
products, clothing, footwear and baggage products, household and
industrial products, packaging products, construction products and
the like.
36. Use of a mono-substituted succinic anhydride, as defined in
claim 1, for decreasing the hydrophilicity of a calcium
carbonate-containing filler material surface.
37. Use of a surface-treated filler material product, as defined in
claim 26, for initiating the crosslinking reaction in epoxide
resins.
Description
[0001] The present invention relates to a process for preparing a
surface treated filler material product with succinic anhydride(s),
a surface treated filler material product, a polymer composition, a
fiber and/or filament and/or film and/or thread comprising the
surface treated filler material product and/or the polymer
composition, an article comprising the surface treated filler
material product and/or the polymer composition and/or the fiber
and/or filament and/or film and/or thread as well as the use of a
mono-substituted succinic anhydride for decreasing the
hydrophilicity of a calcium carbonate-containing filler material
surface and the use of a surface-treated filler material product
for initiating the crosslinking reaction in epoxide resins.
[0002] In practice, filler materials and especially calcium
carbonate-containing filler materials are often used as particulate
fillers in thermoplastic polymer products, like fibers, filaments,
films and/or threads, usually made of polyethylene (PE),
polypropylene (PP), polyurethane (PU), polyvinylchloride (PVC),
polyester (PES) and/or polyamide (PA). However, additives are
introduced to provide the filler material with a coating and to
improve the dispersability of said mineral filler material in the
polymer composition as well as possibly to improve the
processability of this polymer composition and/or properties of the
final application products such as fibers, filaments, films and/or
threads. An elimination of such additives would unacceptably reduce
the resulting fiber, filament, film and/or thread quality.
Furthermore, it is to be noted that such mineral filler materials
are generally associated with the presence of volatiles evolving at
temperatures reached during the application of such mineral fillers
and/or in the processing of said polymer products comprising such
mineral fillers. Such volatiles may, for example, be: [0003]
inherently associated with the mineral filler ("inherent
volatiles"), and is especially associated water, and/or [0004]
introduced during the treatment of the mineral filler ("added
volatiles"), for example, to render the mineral filler more
dispersible within a polymeric plastic medium, and/or [0005]
generated by the reaction of inherent organic materials and/or
added organic materials, with the mineral filler; such reactions
may especially be induced or enhanced by temperatures reached
during the introduction and/or processing of the polymeric material
comprising the mineral filler, such as during extrusion or
compounding processes; and/or [0006] generated by the degradation
of inherent organic materials and/or added organic materials,
forming CO.sub.2, water and possibly low molecular mass fractions
of these organic materials; such a degradation may especially be
induced or enhanced by temperatures reached during the introduction
and/or processing of the polymeric material comprising the mineral
filler, such as during extrusion or compounding processes.
[0007] As a result of the presence of such volatiles, it may be
difficult to prepare a fiber, filament, film and/or thread free of
voids leading to uneven surfaces and thus to a degradation of the
quality of the final polymer product comprising such filler
material. Moreover, volatiles may lead to a reduction in the
tensile and tear strength of such a fiber, filament, films and/or
threads, and may degrade its visible aspects, in particular of its
visible uniformity. Furthermore, volatiles can generate excessive
foaming of the mineral filled polymer melt during a step of
compounding, causing unwanted product build-up at the vacuum
extraction and hence, forcing a reduced output rate.
[0008] In the art, several attempts have been made to improve the
applicability of mineral filler materials and especially calcium
carbonate-containing mineral filler materials, e.g. by treating
such mineral filler materials with aliphatic carboxylic acids, and
aliphatic carboxylic acid salts, which in some cases may also be
referred to as fatty acids and fatty acid salts. For instance, WO
00/20336 relates to an ultrafine natural calcium carbonate, which
may optionally be treated with one or several fatty acids or one or
several salts or mixtures thereof, and which is used as a theology
regulator for polymer compositions.
[0009] Likewise, U.S. Pat. No. 4,407,986 relates a precipitated
calcium carbonate that is surface-treated with a dispersant that
may include higher aliphatic acids and their metal salts in order
to limit the addition of lubricant additives when kneading this
calcium carbonate with crystalline polypropylene and to avoid the
formation of calcium carbonate aggregates that limit the impact
strength of the polypropylene.
[0010] EP 0 998 522 relates to surface treated calcium carbonate
filler for breathable films using fatty acids of at least 10 carbon
atoms wherein the filler before and after the treatment process has
to be mostly free of moisture in the range of below 0.1 wt.-%.
[0011] However, to achieve and maintain such low moisture content,
a high consumption of energy and costs is required. Thus, such low
moisture content is not the ideal parameter for influencing and
controlling the reaction of a solid mineral surface with treatment
additives to achieve a good quality of surface treated filler
material product at low energy costs.
[0012] DeArmitt et al., Improved thermoplastic composites by
optimised surface treatment of the mineral fillers, Institute for
Surface Chemistry, August 2000, describes a wet treatment process
in which a batch suspension comprising a mineral filler material is
contacted with a dispersant at room temperature for one hour.
However, such wet treatment process has the disadvantage that the
wetting of a dry product for treatment and the subsequent drying is
energy- and cost-consuming.
[0013] In EP 0 325 114, relating to non-sagging underseal
compositions for motor vehicles based on polyvinyl chloride which
has improved rheological and adhesion properties, Example 7
discloses a mixture of an ammonium salt of 12-hydroxystearic acid
in combination with a fatty acid (in a weight ratio of 1:1) used to
treat a mineral filler.
[0014] WO 03/082966 relates to a cross-linkable and/or
cross-linkable and/or cross-linked nanofiller composition which, in
optional embodiments, may additionally include fillers that may or
may not be coated with stearic acid, stearate, silane, siloxane
and/or titanate. Such nanofiller compositions are used to increase
barrier properties, strength and heat distortion temperatures,
making them useful in medical, automotive, electrical, construction
and food application.
[0015] US 2002/0102404 describes dispersible calcium carbonate
particles coated on their surface with a combination of saturated
and unsaturated aliphatic carboxylic acids and salts thereof along
with an organic compound such as a phthalic ester, which are used
in adhesive compositions to improve viscosity stability and
adhesion properties.
[0016] Moreover, US 2002/0102404 requires the implementation of a
mixture of saturated and unsaturated aliphatic carboxylic
acids/salts. The presence of unsaturated aliphatic carboxylic
acids/salts increases the risk or unwanted in situ side reactions
with the double bond during processing of any unsaturated aliphatic
carboxylic acid/salt-comprising material. Additionally, the
presence of unsaturated aliphatic carboxylic acids/salts may result
in discoloration of, or unwanted odour development, and notably
rancid odours, in the material in which they are implemented.
[0017] Claim 11 of WO 92/02587 indicates that a saponified sodium
salt solution of at least one high molecular weight unsaturated
fatty acid or combination of at least one high molecular weight
unsaturated fatty acid and at least one high molecular weight
unsaturated fatty acid, may be added to a pre-heated slurry of
precipitated calcium carbonate, to ultimately produce a desired
level of fatty acid coating on the calcium carbonate before
proceeding with further process steps.
[0018] The abstract of JP54162746 discloses a composition
comprising given relative amounts of rigid vinyl chloride resin,
fatty acid treated-colloidal calcium carbonate, and barium stearate
used in order to improve the heat stability of the vinyl chloride
composition.
[0019] U.S. Pat. No. 4,520,073 describes mineral filler materials
with improved hydrophobic coatings prepared by pressure coating of
porous minerals using steam as a carrier for the coating material.
Said coating material may be selected, among other options, from
long chain aliphatic fatty acids and their salts.
[0020] WO 01/32787 describes a particulate alkaline earth metal
carbonate material product which has on its particles a coating of
hydrophobic material comprising a composition formed of (a) a first
component which comprises the reaction product of the alkaline
earth metal carbonate and at least one given aliphatic carboxylic
acid and (b) a second component having a carbonate release
temperature substantially higher than the first component comprises
a compound of formula CH.sub.3(CH.sub.2).sub.mCOOR.
[0021] WO 2008/077156 A2 relates to spunlaid fibers comprising at
least one polymeric resin and at least one filler having an average
particle size of less than or equal to about 5 microns and/or
having a top cut of less than about 15 microns, wherein the at
least one filler is present in an amount of less than about 40% by
weight, relative to the total weight of the spunlaid fibers. The
coating of the filler is described as being at least one organic
material chosen from fatty acids and salts and esters thereof, e.g.
stearic acid, stearate, ammonium stearate and calcium stearate.
[0022] GB 2 336 366 A relates to filled thermoplastic compositions,
and, in particular, filled low density polyethylene compositions
which are to be formed into products of articles by the process of
extrusion. It is further described that the hydrophobising agent is
preferably an organic carboxylic acid or partially or fully
neutralised salt thereof which has at least one saturated or
unsaturated hydrocarbon chain having from 8 to 28 carbon atoms, if
the particulate mineral filler has a neutral to alkaline surface
reaction, for example calcium carbonate.
[0023] However, the prior art does rarely disclose surface treated
mineral filler materials that are suitable for polymer compositions
and which would solve the following multifaceted technical problem:
[0024] to prepare a surface treated filler material such that it is
sufficiently hydrophobic for fibers, filaments and/or films and/or
thread applications; [0025] to prepare a surface treated filler
material having a low moisture pick up susceptibility such that the
moisture absorption is e.g. of.gtoreq.0.8 mg/g; [0026] to prepare a
surface treated filler material featuring an increased volatile
onset temperature; [0027] to prepare surface treated filler
material featuring a limited total quality of volatiles evolved
between 25.degree. C. and 350.degree. C.; [0028] to prepare a
surface treated filler material by using a surface treatment agent
featuring a workable viscosity, that is to say a viscosity of less
than 1.000 mPas at 20.degree. C.; [0029] to identify a surface
treatment agent featuring at least an equal flash point than an
aliphatic carboxylic acid comprising the same alkyl substituent
such that the safety requirements during surface treatment under
heat exposure and are not increased and/or the safety risks at
equal treatment temperature are about the same; [0030] to identify
a surface treatment agent that achieves the above regardless of
whether or not the eat least one surface treated filler material
undergoes a salt exchange on contact with the surface treatment
agent to create corresponding calcium salts on the surface of the
surface treated filler material; [0031] the fibers, filaments,
films and threads comprising such mineral filler material show good
mechanical properties such as tensile modulus, tensile test at
yield and at break, elongation at break and tear resistance.
[0032] Thus, there is still a need for providing processes for
preparing surface treated filler material products which address
the foregoing technical problems described and especially allows
for preparing surface treated calcium carbonate-containing mineral
filler materials for improving the mechanical properties of final
application products such as fibers, filaments, films and threads
comprising such surface treated filler material products.
[0033] Accordingly, it is an objective of the present invention to
provide a process for preparing a surface treated filler material
product having improved surface characteristics, and especially a
low hydrophilicity. A further objective is to provide a process for
preparing a surface treated filler material product featuring low
moisture pick up susceptibility. Even a further objective is to
provide a process for preparing a surface treated filler material
product having a high volatile onset temperature. A still further
objective is to provide a process for preparing a surface treated
filler material product featuring a limited quantity of total
volatiles evolved at temperatures of between 25 and 350.degree. C.
A further objective is to provide a process for preparing a surface
treated filler material product by using a surface treatment agent
which can be easily handled and features a high flash point. A
further objective is to provide a process for preparing a surface
treated filler material product that can be carried out under
cost-efficient and mild conditions, i.e. by avoiding an intensive
thermal treatment. Further objects can be gathered from the
following description of the invention.
[0034] The foregoing and other objectives are solved by the
subject-matter as defined herein in claim 1.
[0035] Advantageous embodiments of the inventive a process for
preparing a surface treated filler material product are defined in
the corresponding sub-claims.
[0036] According to one aspect of the present application a process
for preparing a surface treated filler material product with
succinic anhydride(s) is provided, the process comprising at least
the steps of: [0037] a) providing at least one calcium
carbonate-containing filler material having [0038] i) a weight
median particle size d.sub.50 value in the range from 0.1 .mu.m to
7 .mu.m, [0039] ii) a top cut (d.sub.98).ltoreq.15 .mu.m, [0040]
iii) a specific surface area (BET) of from 0.5 to 150 m.sup.2/g as
measured by the BET nitrogen method, and [0041] iv) a residual
total moisture content of from 0.01 to 1 wt.-%, based on the total
dry weight of the at least one calcium carbonate-containing filler
material, [0042] b) providing at least one mono-substituted
succinic anhydride and optionally at least one mono-substituted
succinic acid in an amount of from 0.1 to 3 wt.-%, based on the
total dry weight of the at least one calcium carbonate-containing
filler material of step a), [0043] c) contacting the surface of the
at least one calcium carbonate-containing filler material of step
a) under mixing, in one or more steps, with the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid of step b) such that a treatment
layer comprising the at least one mono-substituted succinic
anhydride and the optional at least one mono-substituted succinic
acid and/or salty reaction product(s) thereof is formed on the
surface of said at least one calcium carbonate-containing filler
material of step a), wherein the temperature before and/or during
contacting step c) is adjusted such that the temperature is at
least 2.degree. C. above the melting point of the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid.
[0044] The inventors surprisingly found out that the foregoing
process for preparing a surface treated filler material product
avoids the use of intensive thermal treatments and leads to a
surface treated filler material product providing a sufficient
hydrophilicity and very low moisture pick up susceptibility as well
as a high volatile onset temperature of at least 250.degree. C., a
limited quantity of total volatiles evolved at temperatures of from
25 to 350.degree. C., a high flash point and imparts improved
mechanical properties to fibers, filaments, films and/or threads
and the corresponding articles comprising said surface treated
filler material product. More precisely, the inventors found out
that the surface characteristics of a surface treated filler
material product being obtained by said process can be improved by
the addition of defined mono-substituted succinic anhydride(s).
[0045] It should be understood that for the purposes of the present
invention, the following terms have the following meanings:
[0046] For the purpose of the present invention, the term "filler
material" in the meaning of the present invention refers to
substances of mineral origin added to materials such as paper,
plastics, rubber, paints and adhesives, etc. to lower the
consumption of more expensive materials such as binders, or to
enhance technical properties of the products. The person skilled in
the art very well knows the typical filler materials used in the
respective fields. Furthermore, the term "calcium
carbonate-containing filler material" refers to a material that
comprises at least 80 wt.-% calcium carbonate, based on the total
dry weight of the calcium carbonate-containing filler material.
[0047] The term "surface treated filler material product" in the
meaning of the present invention refers to a calcium
carbonate-containing filler material which has been contacted with
a surface treatment agent such as to obtain a coating layer on at
least a part of the surface of the calcium carbonate-containing
filler material.
[0048] The term "succinic anhydride", also called
dihydro-2,5-furandione, succinic acid anhydride or succinyl oxide,
has the molecular formula C.sub.4H.sub.4O.sub.3 and is the acid
anhydride of succinic acid.
[0049] The term "mono-substituted" succinic anhydride in the
meaning of the present invention refers to a succinic anhydride
substituted with one substituent.
[0050] The term "mono-substituted" succinic acid in the meaning of
the present invention refers to a succinic acid substituted with
one substituent.
[0051] The term "dry" calcium carbonate-containing filler material
is understood to be a filler material having less than 0.3% by
weight of water relative to the filler material weight. The % water
(equal to residual total moisture content) is determined according
to the Coulometric Karl Fischer measurement method, wherein the
filler material is heated to 220.degree. C., and the water content
released as vapour and isolated using a stream of nitrogen gas (at
100 ml/min) is determined in a Coulometric Karl Fischer unit.
[0052] The term "salty reaction products" in the meaning of the
present invention refers to products obtained by contacting a
calcium carbonate-containing filler material with one or more
mono-substituted succinic anhydride(s). Said salty reaction
products are formed between the mono-substituted succinic acid
which is formed from the applied mono-substituted succinic
anhydride and reactive molecules located at the surface of the
calcium carbonate-containing filler material. Alternatively, said
salty reaction products are formed between the mono-substituted
succinic acid, which may optionally be present with the at least
one mono-substituted succinic anhydride, and reactive molecules
located at the surface of the calcium carbonate-containing filler
material.
[0053] The term "specific surface area" (in m.sup.2/g) of the
mineral filler in the meaning of the present invention is
determined using the BET method with nitrogen as adsorbing gas,
which is well known to the skilled man (ISO 9277:1995). The total
surface area (in m.sup.2) of the mineral filler is then obtained by
multiplication of the specific surface area and the mass (in g) of
the mineral filler prior to treatment.
[0054] As used herein and as generally defined in the art, the
"d.sub.50" value is determined based on measurements made by using
a Sedigraph.TM. 5100 of Micromeritics Instrument Corporation
(operating instrument software version 1.04) and is defined as the
size at which 50% (the median point) of the particle volume or mass
is accounted for by particles having a diameter equal to the
specified value. The method and the instrument are known to the
skilled person and are commonly used to determine grain size of
fillers and pigments. The measurement is carried out in an aqueous
solution of 0.1 wt.-% Na.sub.4P.sub.2O.sub.7. The samples are
dispersed using a high speed stirrer and supersonics.
[0055] Where the term "comprising" is used in the present
description and claims, it does not exclude other non-specified
elements of major or minor functional importance. For the purposes
of the present invention, the term "consisting of" is considered to
be a preferred embodiment of the term "comprising of". If
hereinafter a group is defined to comprise at least a certain
number of embodiments, this is also to be understood to disclose a
group, which preferably consists only of these embodiments.
[0056] Whenever the terms "including" or "having" are used, these
terms are meant to be equivalent to "comprising" as defined
above.
[0057] Where an indefinite or definite article is used when
referring to a singular noun, e.g. "a", "an" or "the", this
includes a plural of that noun unless something else is
specifically stated.
[0058] According to another aspect of the present invention, a
surface treated filler material product is provided, comprising
[0059] a) at least one calcium carbonate-containing filler material
having [0060] i) a weight median particle size d.sub.50 value in
the range from 0.1 to 7 .mu.m, [0061] ii) a top cut
(d.sub.98).ltoreq.15 .mu.m, [0062] iii) a specific surface area
(BET) of from 0.5 to 150 m.sup.2/g as measured by the BET nitrogen
method, and [0063] iv) a residual total moisture content of below 1
wt.-%, based on the total dry weight of the least one calcium
carbonate-containing filler material, and [0064] b) a treatment
layer on the surface of the at least one calcium
carbonate-containing filler material comprising at least one
mono-substituted succinic anhydride and mono-substituted succinic
acid and/or salty reaction product(s) thereof, wherein the surface
treated filler material product comprises the treatment layer in an
amount of from 0.1 to 3 wt.-%, based on the total dry weight of the
at least one calcium carbonate-containing filler material.
[0065] It is preferred that the molar ratio of the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid to the salty reaction product(s)
thereof is from 0.1:99.9 to 99.9:01, preferably from 30:70 to
10:90. It is also preferred that the salty reaction product(s) of
the at least one mono-substituted succinic anhydride and/or the at
least one mono-substituted succinic acid are one or more calcium
and/or magnesium salts thereof. It is further preferred that the
treatment layer further comprises at least one organic material
such as polysiloxanes. It is also preferred that the surface
treated filler material product comprises the treatment layer in an
amount of from 0.1 to 2.5 wt.-%, preferably in an amount of from
0.1 to 2 wt.-%, more preferably in an amount of from 0.1 to 1.5
wt.-%, even more preferably in an amount of from 0.1 to 1 wt.-% and
most preferably in an amount of from 0.2 to 0.8 wt.-% based on the
total dry weight of the at least one calcium carbonate-containing
filler material.
[0066] According to a further aspect of the present invention, a
polymer composition is provided, comprising at least one polymeric
resin and from 1 to 85 wt.-%, based on the total weight of the
polymer composition, of the surface treated filler material
product. It is preferred that the at least one polymeric resin is
at least one thermoplastic polymer, preferably a thermoplastic
polymer selected from the group comprising homopolymers and/or
copolymers of polyolefins, polyamides halogen-containing polymers
and/or polyesters. It is also preferred that the polymer
composition is a masterbatch, preferably the masterbatch comprises
the surface treated filler material product in an amount of from 50
to 85 wt.-%, preferably from 60 to 85 wt.-% and more preferably
from 70 to 80 wt.-%, based on the total weight of the
masterbatch.
[0067] According to a still further aspect of the present
invention, a fiber and/or filament and/or film and/or thread is
provided, comprising the surface treated filler material product
and/or the polymer composition. According to another aspect of the
present invention, an article comprising the surface treated filler
material product and/or a polymer composition and/or a fiber and/or
filament and/or film and/or thread is provided, wherein the article
is selected from the group comprising hygiene products, medical and
healthcare products, filter products, geotextile products,
agriculture and horticulture products, clothing, footwear and
baggage products, household and industrial products, packaging
products, construction products and the like. According to another
aspect of the present invention, the use of a mono-substituted
succinic anhydride for decreasing the hydrophilicity of a calcium
carbonate-containing filler material surface is provided. According
to a further aspect of the present invention, the use of a
surface-treated filler material product for initiating the
crosslinking reaction in epoxide resins is provided.
[0068] According to one embodiment of the present invention, the at
least one calcium carbonate-containing filler material of step a)
is selected from among ground calcium carbonate (GCC), precipitated
calcium carbonate (PCC), modified calcium carbonate (MCC) and
mixture thereof.
[0069] According to another embodiment of the present invention,
the at least one calcium carbonate-containing filler material of
step a) comprises at least one ground calcium carbonate (GCC)
selected from the group comprising marble, chalk, dolomite
limestone and mixtures thereof and/or at least one precipitated
calcium carbonate (PCC) selected from the group comprising one or
more of the aragonitic, vateritic and calcitic mineralogical
crystal forms and/or at least one modified calcium carbonate
(MCC).
[0070] According to yet another embodiment of the present
invention, the at least one calcium carbonate-containing filler
material of step a) has a weight median particle size d.sub.50 from
0.25 .mu.m to 5 .mu.m and preferably from 0.7 .mu.m to 4 .mu.m.
[0071] According to one embodiment of the present invention, the at
least one calcium carbonate-containing filler material of step a)
has a top cut (d.sub.98) of.ltoreq.12.5 .mu.m, preferably
of.ltoreq.10 .mu.m and most preferably of.ltoreq.7.5 .mu.m.
[0072] According to another embodiment of the present invention,
the at least one calcium carbonate-containing filler material of
step a) has a specific surface area (BET) of from 0.5 to 50
m.sup.2/g, more preferably of from 0.5 to 35 m.sup.2/g and most
preferably of from 0.5 to 15 m.sup.2/g as measured by the BET
nitrogen method.
[0073] According to yet another embodiment of the present
invention, the at least one calcium carbonate-containing filler
material of step a) has a residual total moisture content of from
0.01 to 0.2 wt.-%, preferably from 0.02 to 0.15 wt.-% and most
preferably from 0.04 to 0.15 wt.-%, based on the total dry weight
of the at least one calcium carbonate-containing filler
material.
[0074] According to one embodiment of the present invention, the at
least one calcium carbonate-containing filler material of step a)
is preheated before contacting step c) is carried out, preferably
the at least one calcium carbonate-containing filler material of
step a) is preheated at a temperature of from 50 to 200.degree. C.,
more preferably of from 80 to 200.degree. C., even more preferably
of from 90 to 150.degree. C. and most preferably of from 100 to
130.degree. C.
[0075] According to another embodiment of the present invention,
the at least one mono-substituted succinic anhydride and the
optional at least one mono-substituted succinic acid of step b) are
provided in a total amount of from 0.1 to 2.5 wt.-%, preferably in
an amount of from 0.1 to 2 wt.-%, more preferably in an amount of
from about 0.1 to 1.5 wt.-%, even more preferably in an amount of
from 0.1 to 1 wt.-% and most preferably in an amount of from 0.2 to
0.8 wt.-% based on the total dry weight of the at least one calcium
carbonate-containing filler material.
[0076] According to yet another embodiment of the present
invention, the at least one mono-substituted succinic anhydride of
step b) consists of succinic anhydride mono-substituted with a
group selected from a linear, branched, aliphatic and cyclic group
having a total amount of carbon atoms from C2 to C30, preferably
from C3 to C25 and most preferably from C4 to C20 in the
substituent.
[0077] According to one embodiment of the present invention, the at
least one mono-substituted succinic anhydride of step b) is at
least one alkyl mono-substituted succinic anhydride, preferably at
least one alkyl mono-substituted succinic anhydride selected from
the group comprising ethylsuccinic anhydride, propylsuccinic
anhydride, butylsuccinic anhydride, triisobutyl succinic anhydride,
pentylsuccinic anhydride, hexylsuccinic anhydride, heptylsuccinic
anhydride, octylsuccinic anhydride, nonylsuccinic anhydride, decyl
succinic anhydride, dodecyl succinic anhydride, hexadecanyl
succinic anhydride, octadecanyl succinic anhydride, and mixtures
thereof.
[0078] According to anther embodiment of the present invention, the
at least one mono-substituted succinic anhydride of step b) is at
least one alkenyl mono-substituted succinic anhydride, preferably
at least one alkenyl mono-substituted succinic anhydride selected
from the group comprising ethenylsuccinic anhydride,
propenylsuccinic anhydride, butenylsuccinic anhydride,
triisobutenyl succinic anhydride, pentenylsuccinic anhydride,
hexenylsuccinic anhydride, heptenylsuccinic anhydride,
octenylsuccinic anhydride, nonenylsuccinic anhydride, decenyl
succinic anhydride, dodecenyl succinic anhydride, hexadecenyl
succinic anhydride, octadecenyl succinic anhydride, and mixtures
thereof.
[0079] According to yet another embodiment of the present
invention, the at least one mono-substituted succinic anhydride and
the optional at least one mono-substituted succinic acid of step b)
are added in contacting step c) in a total amount of from 0.1 to 2
wt.-%, preferably of from 0.2 to 1.5 wt.-% and most preferably of
from 0.3 to 1 wt.-%, based on the total dry weight of the at least
one calcium carbonate-containing filler material of step a).
[0080] According to one embodiment of the present invention, the at
least one mono-substituted succinic acid of step b) is present in
an amount of.ltoreq.10 mol.-%, based on the molar sum of the at
least one mono-substituted succinic anhydride and the at least one
mono-substituted succinic acid.
[0081] According to another embodiment of the present invention,
contacting step c) is carried out at a temperature of from 30 to
200.degree. C., preferably of from 80 to 150.degree. C. and most
preferably of from 110 to 130.degree. C.
[0082] According to yet another embodiment of the present
invention, contacting step c) is carried out in a batch or
continuous process, preferably for a period of time from 0.1 to
1000 seconds. It is preferred that contacting step c) is a
continuous process and comprises one or several contacting steps
and the total contacting time is from 0.1 to 20 s, preferably from
0.5 to 15 s and most preferably from 1 to 10 s.
[0083] According to one embodiment of the present invention, the
salty reaction product(s) of the mono-substituted succinic acid
and/or the at least one mono-substituted succinic acid formed on
the surface of said at least one calcium carbonate-containing
filler material in step c) are one or more calcium salts and/or
magnesium salts thereof.
[0084] According to another embodiment of the present invention,
the process further comprises step d) of contacting the at least
one calcium carbonate-containing filler material of step a), in one
or more steps, with at least one organic material such as
polysiloxanes. It is preferred that contacting step d) is carried
out during and/or after contacting step c), preferably after
contacting step c). It is further preferred that contacting step d)
is carried out at a temperature of from 40 to 200.degree. C.,
preferably of from 50 to 150.degree. C. and most preferably of from
60 to 120.degree. C. It is also preferred that the at least one
organic material is added in contacting step d) in an amount of
from 100 to 1 000 ppm, preferably from 200 to 800 ppm and most
preferably from 300 to 700 ppm, based on the total dry weight of
the at least one calcium carbonate-containing filler material of
step a).
[0085] According to yet another embodiment of the present
invention, the obtained surface treated filler material product has
a water pick-up of from 0.1 to 0.8 mg/g, preferably of from 0.2 to
0.7 mg/g and most preferably of from 0.2 to 0.6 mg/g at a
temperature of 23.degree. C. (.+-.2.degree. C).
[0086] According to one embodiment of the present invention, the
obtained surface treated filler material product has a volatile
onset temperature of.gtoreq.250.degree. C., preferably
of.gtoreq.260.degree. C. and most preferably of.gtoreq.270.degree.
C.
[0087] According to another embodiment of the present invention,
the obtained surface treated filler material product has a
hydrophilicity of below 8:2 volumetric ratio of water:ethanol
measured at +23.degree. C. (.+-.2.degree. C.) with the
sedimentation method.
[0088] As set out above, the inventive process for preparing a
surface treated filler material product with succinic anhydrides
comprises at least the process steps of a), b) and c). In the
following, it is referred to further details of the present
invention and especially the foregoing steps of the inventive
process for preparing a surface treated filler material
product.
Characterization of Step a): Provision of at Least One Calcium
Carbonate-Containing Filler Material
[0089] According to step a) of the process of the present
invention, at least one calcium carbonate-containing filler
material is provided.
[0090] The at least one calcium carbonate-containing filler
material in the meaning of the present invention refers to a filler
material selected from among ground (or natural) calcium carbonate
(GCC), a precipitated calcium carbonate (PCC), a modified calcium
carbonate (MCC) and mixtures thereof.
[0091] GCC is understood to be a naturally occurring form of
calcium carbonate, mined from sedimentary rocks such as limestone
or chalk, or from metamorphic marble rocks and processed through a
treatment such as grinding, screening and/or fractionizing in wet
and/or dry form, for example by a cyclone or classifier. In one
embodiment of the present invention, the GCC is selected from the
group comprising marble, chalk, dolomite, limestone and mixtures
thereof.
[0092] By contrast, calcium carbonate of the PCC type include
synthetic calcium carbonate products obtained by carbonation of a
slurry of calcium hydroxide, commonly referred to in the art as a
slurry of lime or milk of lime when derived from finely divided
calcium oxide particles in water or by precipitation out of an
ionic salt solution. PCC may be rhombohedral and/or scalenohedral
and/or aragonitic; preferred synthetic calcium carbonate or
precipitated calcium carbonate comprising aragonitic, vateritic or
calcite mineralogical crystal forms or mixtures thereof.
[0093] "Modified calcium carbonate" in the meaning of the present
invention may feature a natural ground or precipitated calcium
carbonate with an internal structure modification or a
surface-reaction product. According to a preferred embodiment of
the present invention, the modified calcium carbonate is a
surface-reacted calcium carbonate.
[0094] In one preferred embodiment, the at least one calcium
carbonate-containing filler material is marble.
[0095] It is appreciated that the amount of calcium carbonate in
the at least one calcium carbonate-containing filler material is at
least 80 wt.-%, e.g. at least 95 wt.-%, preferably between 97 and
100 wt.-%, preferably between 98.5 and 99.95 wt.-%, based on the
total dry weight of the at least one calcium carbonate-containing
filler material.
[0096] The at least one calcium carbonate-containing filler
material is preferably in the form of a particulate material, and
may have a particle size distribution as conventionally employed
for the material(s) involved in the type of product to be produced.
In general, it is one specific requirement of the present invention
that the at least one calcium carbonate-containing filler material
has a weight median particle size d.sub.50 value in the range from
0.1 to 7 .mu.m. For example, the at least one calcium
carbonate-containing filler material has a weight median particle
size d.sub.50 from 0.25 .mu.m to 5 .mu.m and preferably from 0.7
.mu.m to 4 .mu.m.
[0097] A further requirement of the present invention is that the
at least one calcium carbonate-containing filler material has a top
cut (d.sub.98) of.ltoreq.15 .mu.m. For example, the at least one
calcium carbonate-containing filler material has a top cut
(d.sub.98) of.ltoreq.12.5 .mu.m, preferably of.ltoreq.10 .mu.m and
most preferably of.ltoreq.7.5 .mu.m.
[0098] It is further appreciated that the at least one calcium
carbonate-containing filler material has a BET specific surface
area of from 0.5 and 150 m.sup.2/g as measured by the BET nitrogen
method according to ISO 9277. For example, the at least one calcium
carbonate-containing filler material has a specific surface area
(BET) of from 0.5 to 50 m.sup.2/g, more preferably of from 0.5 to
35 m.sup.2/g and most preferably of from 0.5 to 15 m.sup.2/g as
measured by the BET nitrogen method according to ISO 9277.
[0099] In one embodiment of the present invention, the at least one
calcium carbonate-containing filler material is preferably a marble
having a median particle size diameter d.sub.50 value from 0.1
.mu.m to 7 .mu.m, preferably from 0.25 .mu.m to 5 .mu.m and most
preferably from 0.7 .mu.m to 4 .mu.m. In this case, the at least
one calcium carbonate-containing filler material exhibits a BET
specific surface area of from 0.5 to 150 m.sup.2/g, preferably of
from 0.5 to 50 m.sup.2g, more preferably of from 0.5 to 35
m.sup.2/g and most preferably of from 0.5 to 15 m.sup.2/g, measured
using nitrogen and the BET method according to ISO 9277.
[0100] It is preferred that the at least one calcium
carbonate-containing filler material is a dry ground material, a
material being wet ground and dried or a mixture of the foregoing
materials. In general, the grinding step can be carried out with
any conventional grinding device, for example, under conditions
such that refinement predominantly results from impacts with a
secondary body, i.e. in one or more of: a ball mill, a rod mill, a
vibrating mill, a roll crusher, a centrifugal impact mill, a
vertical bead mill an attrition mill, a pin mill, a hammer mill, a
pulveriser, a shredder, a de-clumper, a knife cutter, or other such
equipment known to the skilled man.
[0101] In case the at lest one calcium carbonate-containing filler
material is a wet ground calcium carbonate-containing filler
material, the grinding step may be performed under conditions such
that autogenous grinding takes place and/or by horizontal ball
milling, and/or other such processes known to the skilled man. The
wet processed ground calcium carbonate-containing filler material
thus obtained may be washed and dewatered by well known processes,
e.g. by flocculation, filtration or forced evaporation prior to
drying. The subsequent step of drying may be carried out in a
single step such as spray drying, or in at least two steps, e.g. by
applying a first heating step to the calcium carbonate-containing
filler material in order to reduce the associated moisture content
to a level which is not greater than about 0.5 wt.-%, based on the
total dry weight of the at least one calcium carbonate-containing
filler material. The residual total moisture content of the filler
can be measured by the Karl Fischer coulometric titration method,
desorbing the moisture in an oven at 195.degree. C. and passing it
continuously into the KF coulometer (Mettler Toledo coulometric KF
Titrator C30, combined with Mettler oven DO 0337) using dry N.sub.2
at 100 ml/min for 10 min. The residual total moisture content can
be determined with a calibration curve and also a blind of 10 min
gas flow without a sample can be taken into account. The residual
total moisture content may be further reduced by applying a second
heating step to the at least one calcium carbonate-containing
filler material. In case said drying is carried out by more than
one drying steps, the first step may be carried out by heating in a
hot current of air, while the second and further drying steps are
preferably carried out by an indirect heating in which the
atmosphere in the corresponding vessel comprises a surface
treatment agent. It is also common that the at least one calcium
carbonate-containing filler material is subjected to a
beneficiation step (such as a flotation, bleaching or magnetic
separation step) to remove impurities.
[0102] In one embodiment of the present invention, the at least one
calcium carbonate-containing filler material comprises a dry ground
calcium carbonate-containing filler material. In another preferred
embodiment, the at least one calcium carbonate-containing filler
material is a material being set ground in a horizontal ball mill,
and subsequently dried by using the well known process of spray
drying.
[0103] Depending on the at least one calcium carbonate-containing
filler material, the at least one calcium carbonate-containing
filler material has a residual total moisture content of from 0.01
to 1 wt.-%, preferably from 0.01 to 0.2 wt.-%, more preferably from
0.02 to 0.15 wt.-% and most preferably from 0.04 to 0.15 wt.-%,
based on the total dry weight of the at least one calcium
carbonate-containing filler material.
[0104] For example, in case a wet ground and spray dried marble is
used as the at least one calcium carbonate-containing filler
material, the residual total moisture content of the at least one
calcium carbonate-containing filler material is preferably of from
0.01 to 0.1 wt.-%, more preferably from 0.02 to 0.08 wt.-% and most
preferably from 0.04 to 0.07 wt.-% based on the total dry weight of
the at least one calcium carbonate-containing filler material. If a
PCC is used as the at least one calcium carbonate-containing filler
material, the residual total moisture content of the at least one
calcium carbonate-containing filler material is preferably of from
0.01 to 0.2 wt.-%, more preferably from 0.05 to 0.17 wt.-% and most
preferably from 0.05 to 0.10 wt.-%, based on the total dry weight
of the at least one calcium carbonate-containing filler
material.
Characterization of Step b): Provision of at Least One
Mono-Substituted Succinic Anhydride
[0105] According to step b) of the process of the present invention
at least one mono-substituted succinic anhydride and optionally at
least one mono-substituted succinic acid are provided.
[0106] It is appreciated that the expression "at least one"
mono-substituted succinic anhydride means that one or more kinds of
mono-substituted succinic anhydride may be provided in the process
of the present invention.
[0107] According, it should be noted that the at least one
mono-substituted succinic anhydride may be one kind of
mono-substituted succinic anhydride. Alternatively, the at least
one mono-substituted succinic anhydride may be a mixture of two or
more kinds of mono-substituted succinic anhydride. For example, the
at least one mono-substituted succinic anhydride may be a mixture
of two or three kinds of mono-substituted succinic anhydride, like
two kinds of mono-substituted succinic anhydride.
[0108] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride is one kind of mono-substituted
succinic anhydride.
[0109] It is appreciated that the at least one mono-substituted
succinic anhydride represents a surface treatment agent and
consists of succinic anhydride mono-substituted with a group
selected from any linear, branched, aliphatic and cyclic group
having a total amount of carbon atoms from C2 to C30 in the
substituent.
[0110] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride consists of succinic anhydride
mono-substituted with a group selected from a linear, branched,
aliphatic and cyclic group having a total amount of carbon atoms
from C3 to C20 in the substituent. For example, the at least one
mono-substituted succinic anhydride consists of succinic anhydride
mono-substituted with a group selected from a linear, branched,
aliphatic and cyclic group having a total amount of carbon atoms
from C4 to C18 in the substituent.
[0111] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride consists of succinic anhydride
mono-substituted with one group being a linear and aliphatic group
having a total amount of carbon atoms from C2 to C30, preferably
from C3 to C20 and most preferably from C4 to C18 in the
substituent. Additionally or alternatively, the at least one
mono-substituted succinic anhydride consists of succinic anhydride
mono-substituted with one group being a branched and aliphatic
group having a total amount of carbon atoms from C2 to C30,
preferably from C3 to C20 and most preferably from C4 to C18 in the
substituent.
[0112] Thus, it is preferred that the at least one mono-substituted
succinic anhydride consists of succinic anhydride mono-substituted
with one group being a linear or branched, alkyl group having a
total amount of carbon atoms from C2 to C30, preferably from C3 to
C20 and most preferably from C4 to C18 in the substituent.
[0113] For example, the at least one mono-substituted succinic
anhydride consists of succinic anhydride mono-substituted with one
group being a linear alkyl group having a total amount of carbon
atoms from C2 to C30, preferably from C3 to C20 and most preferably
from C4 to C18 in the substituent. Additionally or alternatively,
the at least one mono-substituted succinic anhydride consists of
succinic anhydride mono-substituted with one group being a branched
alkyl group having a total amount of carbon atoms from C2 to C30,
preferably from C3 to C20 and most preferably from C4 to C18 in the
substituent.
[0114] The term "alkyl" in the meaning of the present invention
refers to a linear or branched, saturated organic compound composed
of carbon and hydrogen. In other words, "alkyl mono-substituted
succinic anhydrides" are composed of linear or branched, saturated
hydrocarbon chains containing a pendant succinic anhydride
group.
[0115] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride is at least one linear or
branched alkyl mono-substituted succinic anhydride. For example,
the at least one alkyl mono-substituted succinic anhydride is
selected from the group comprising ethylsuccinic anhydride,
propylsuccinic anhydride, butylsuccinic anhydride, triisobutyl
succinic anhydride, pentylsuccinic anhydride, hexylsuccinic
anhydride, heptylsuccinic anhydride, octylsuccinic anhydride,
nonylsuccinic anhydride, decyl succinic anhydride, dodecyl succinic
anhydride, hexadecanyl succinic anhydride, octadecanyl succinic
anhydride, and mixtures thereof.
[0116] Accordingly, it is appreciated that e.g. the term
"butylsuccinic anhydride" comprises linear and branched
butylsuccinic anhydride(s). One specific example of linear
butylsuccinic anhydride(s) is n-butylsuccinic anhydride. Specific
examples of branched butylsuccinic anhydride(s) are
iso-butylsuccinic anhydride, sec-butylsuccinic anhydride and/or
tert-butylsuccinic anhydride.
[0117] Furthermore, it is appreciated that e.g., the term
"hexadecanyl succinic anhydride" comprises linear and branched
hexadecanyl succinic anhydride(s). One specific example of linear
hexadecanyl succinic anhydride(s) is n-hexadecanyl succinic
anhydride. Specific examples of branched hexadecanyl succinic
anhydride(s) are 14-methylpentadecanyl succinic anhydride,
13-methylpentadecanyl succinic anhydride, 12-methylpentadecanyl
succinic anhydride, 11-methylpentadecanyl succinic anhydride,
10-methylpentadecanyl succinic anhydride, 9-methylpentadecanyl
succinic anhydride, 8-methylpentadecanyl succinic anhydride,
7-methylpentadecanyl succinic anhydride, 6-methylpentadecanyl
succinic anhydride, 5-methylpentadecanyl succinic anhydride,
4-methylpentadecanyl succinic anhydride, 3-methylpentadecanyl
succinic anhydride, 2-methylpentadecanyl succinic anhydride,
1-methylpentadecanyl succinic anhydride, 13-ethylbutadecanyl
succinic anhydride, 12-ethylbutadecanyl succinic anhydride,
11-ethylbutadecanyl succinic anhydride, 10-ethylbutadecanyl
succinic anhydride, 9-ethylbutadecanyl succinic anhydride,
8-ethylbutadecanyl succinic anhydride, 7-ethylbutadecanyl succinic
anhydride, 6-ethylbutadecanyl succinic anhydride,
5-ethylbutadecanyl succinic anhydride, 4-ethylbutadecanyl succinic
anhydride, 3-ethylbutadecanyl succinic anhydride,
2-ethylbutadecanyl succinic anhydride, 1-ethylbutadecanyl succinic
anhydride, 2-butyldodecanyl succinic anhydride, 1-hexyldecanyl
succinic anhydride, 1-hexyl-2-decanyl succinic anhydride,
2-hexyldecanyl succinic anhydride, 6,12-dimethylbutadecanyl
succinic anhydride, 2,2-diethyldodecanyl succinic anhydride,
4,8,12-trimethyltridecanyl succinic anhydride,
2,2,4,6,8-pentamethylundecanyl succinic anhydride,
2-ethyl-4-methyl-2-(2-methylpentyl)-heptyl succinic anhydride
and/or 2-ethyl-4,6-dimethyl-2-propylnonyl succinic anhydride.
[0118] Furthermore, it is appreciated that e.g. the term
"octadecanyl succinic anhydride" comprises linear and branched
octadecanyl succinic anhydride(s). One specific example of linear
octadecanyl succinic anhydride(s) is n-octadecanyl succinic
anhydride. Specific examples of branched hexadecanyl succinic
anhydride(s) are 16-methylheptadecanyl succinic anhydride,
15-methylheptadecanyl succinic anhydride, 14-methylheptadecanyl
succinic anhydride, 13-methylheptadecanyl succinic anhydride,
12-methylheptadecanyl succinic anhydride, 11-methylheptadecanyl
succinic anhydride, 10-methylheptadecanyl succinic anhydride,
9-methylheptadecanyl succinic anhydride, 8-methylheptadecanyl
succinic anhydride, 7-methylheptadecanyl succinic anhydride,
6-methylheptadecanyl succinic anhydride, 5-methylheptadecanyl
succinic anhydride, 4-methylheptadecanyl succinic anhydride,
3-methylheptadecanyl succinic anhydride, 2-methylheptadecanyl
succinic anhydride, 1-methylheptadecanyl succinic anhydride,
14-ethylhexadecanyl succinic anhydride, 13-ethylhexadecanyl
succinic anhydride, 12-ethylhexadecanyl succinic anhydride,
11-ethylhexadecanyl succinic anhydride, 10-ethylhexadecanyl
succinic anhydride, 9-ethylhexadecanyl succinic anhydride,
8-ethylhexadecanyl succinic anhydride, 7-ethylhexadecanyl succinic
anhydride, 6-ethylhexadecanyl succinic anhydride,
5-ethylhexadecanyl succinic anhydride, 4-ethylhexadecanyl succinic
anhydride, 3-ethylhexadecanyl succinic anhydride,
2-ethylhexadecanyl succinic anhydride, 1-ethylhexadecanyl succinic
anhydride, 2-hexyldodecanyl succinic anhydride, 2-heptylundecanyl
succinic anhydride, iso-octadecanyl succinic anhydride and/or
1-octyl-2-decanyl succinic anhydride.
[0119] In one embodiment of the present invention, the at least one
alkyl mono-substituted succinic anhydride is selected from the
group comprising butylsuccinic anhydride, hexylsuccinic anhydride,
heptylsuccinic anhydride, octylsuccinic anhydride, hexadecanyl
succinic anhydride, octadecanyl succinic anhydride, and mixtures
thereof.
[0120] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride is one kind of alkyl
mono-substituted succinic anhydride. For example, the one alkyl
mono-substituted succinic anhydride is butylsuccinic anhydride.
Alternatively, the one alkyl mono-substituted succinic anhydride is
hexylsuccinic anhydride. Alternatively, the one alkyl
mono-substituted succinic anhydride is heptylsuccinic anhydride or
octylsuccinic anhydride. Alternatively, the one alkyl
mono-substituted succinic anhydride is hexadecanyl succinic
anhydride. For example, the one alkyl mono-substituted succinic
anhydride is linear hexadecanyl succinic anhydride such as
n-hexadecanyl succinic anhydride or branched hexadecanyl succinic
anhydride such as 1-hexyl-2-decanyl succinic anhydride.
Alternatively, the one alkyl mono-substituted succinic anhydride is
octadecanyl succinic anhydride. For example, the one alkyl
mono-substituted succinic anhydride is linear octadecanyl succinic
anhydride such as n-octadecanyl succinic anhydride or branched
octadecanyl succinic anhydride such as iso-octadecanyl succinic
anhydride or 1-octyl-2-decanyl succinic anhydride.
[0121] In one embodiment of the present invention, the one alkyl
mono-substituted succinic anhydride is butylsuccinic anhydride such
as n-butylsuccinic anhydride.
[0122] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride is a mixture of two or more
kinds of alkyl mono-substituted succinic anhydrides. For example,
the at least one mono-substituted succinic anhydride is a mixture
of two or three kinds of alkyl mono-substituted succinic
anhydrides.
[0123] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride consists of succinic anhydride
mono-substituted with one group being a linear or branched alkenyl
group having a total amount of carbon atoms from C2 to C30,
preferably from C3 to C20 and most preferably from C4 to C18 in the
substituent.
[0124] The term "alkenyl" in the meaning of the present invention
refers to a linear or branched, unsaturated organic compound
composed of carbon and hydrogen. Said organic compound further
contains at least one double bond in the substituent, preferably
one double bond. In other words, "alkenyl mono-substituted succinic
anhydrides" are composed of linear or branched, unsaturated
hydrocarbon chains containing a pendant succinic anhydride group.
It is appreciated that the term "alkenyl" in the meaning of the
present invention includes the cis and trans isomers.
[0125] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride is at least one linear or
branched alkenyl mono-substituted succinic anhydride. For example,
the at least one alkenyl mono-substituted succinic anhydride is
selected from the group comprising ethenylsuccinic anhydride,
propenylsuccinic anhydride, butenylsuccinic anhydride,
triisobutenyl succinic anhydride, pentenylsuccinic anhydride,
hexenylsuccinic anhydride, heptenylsuccinic anhydride,
octenylsuccinic anhydride, nonenylsuccinic anhydride, decenyl
succinic anhydride, dodecenyl succinic anhydride, hexadecenyl
succinic anhydride, octadecenyl succinic anhydride, and mixtures
thereof.
[0126] Accordingly, it is appreciated that e.g. the term
"hexadecenyl succinic anhydride" comprises linear and branched
hexadecenyl succinic anhydride(s). One specific example of linear
hexadecenyl succinic anhydride(s) is n-hexadecenyl succinic
anhydride such as 14-hexadecenyl succinic anhydride, 13-hexadecenyl
succinic anhydride, 12-hexadecenyl succinic anhydride,
11-hexadecenyl succinic anhydride, 10-hexadecenyl succinic
anhydride, 9-hexadecenyl succinic anhydride, 8-hexadecenyl succinic
anhydride, 7-hexadecenyl succinic anhydride, 6-hexadecenyl succinic
anhydride, 5-hexadecenyl succinic anhydride, 4-hexadecenyl succinic
anhydride, 3-hexadecenyl succinic anhydride, and/or 2-hexadecenyl
succinic anhydride. Specific examples of branched hexadecenyl
succinic anhydride(s) are 14-methyl-9-pentadecenyl succinic
anhydride, 14-methyl-2-pentadecenyl succinic anhydride,
1-hexyl-2-decenyl succinic anhydride and/or iso-hexadecenyl
succinic anhydride.
[0127] Furthermore, it is appreciated that e.g. the term
"octadecenyl succinic anhydride" comprises linear and branched
octadecenyl succinic anhydride(s). One specific example of linear
octadecenyl succinic anhydride(s) is n-octadecenyl succinic
anhydride such as 16-octadecenyl succinic anhydride, 15-octadecenyl
succinic anhydride, 14-octadecenyl succinic anhydride,
13-octadecenyl succinic anhydride, 12-octadecenyl succinic
anhydride, 11-octadecenyl succinic anhydride, 10-octadecenyl
succinic anhydride, 9-octadecenyl succinic anhydride, 8-octadecenyl
succinic anhydride, 7-octadecenyl succinic anhydride, 6-octadecenyl
succinic anhydride, 5-octadecenyl succinic anhydride, 4-octadecenyl
succinic anhydride, 3-octadecenyl succinic anhydride, 2-octadecenyl
succinic anhydride. Specific examples of branched octadecenyl
succinic anhydride(s) are 16-methyl-9-heptadecenyl succinic
anhydride, 16-methyl-7-heptadecenyl succinic anhydride,
1-octyl-2-decenyl succinic anhydride and/or iso-octadecenyl
succinic anhydride.
[0128] In one embodiment of the present invention, the at least one
alkenyl mono-substituted succinic anhydride is selected from the
group comprising hexenylsuccinic anhydride, octenylsuccinic
anhydride, hexadecenyl succinic anhydride, octadecenyl succinic
anhydride, and mixtures thereof.
[0129] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride is one alkenyl mono-substituted
succinic anhydride. For example, the one alkenyl mono-substituted
succinic anhydride is hexenylsuccinic anhydride. Alternatively, the
one alkenyl mono-substituted succinic anhydride is octenylsuccinic
anhydride. Alternatively, the one alkenyl mono-substituted succinic
anhydride is hexadecenyl succinic anhydride. For example, the one
alkenyl mono-substituted succinic anhydride is linear hexadecenyl
succinic anhydride such as n-hexadecenyl succinic anhydride or
branched hexadecenyl succinic anhydride such as 1-hexyl-2-decenyl
succinic anhydride. Alternatively, the one alkenyl mono-substituted
succinic anhydride is octadecenyl succinic anhydride. For example,
the one alkyl mono-substituted succinic anhydride is linear
octadecenyl succinic anhydride such as n-octadecenyl succinic
anhydride or branched octadencenyl succinic anhydride such
iso-octadecenyl succinic anhydride, or 1-octyl-2-decenyl succinic
anhydride.
[0130] In one embodiment of the present invention, the one alkenyl
mono-substituted succinic anhydride is linear octadecenyl succinic
anhydride such as n-octadecenyl succinic anhydride. In another
embodiment of the present invention, the one alkenyl
mono-substituted succinic anhydride is linear octensylsuccinic
anhydride such as n-octenylsuccinic anhydride.
[0131] If the at least one mono-substituted succinic anhydride is
one alkenyl mono-substituted succinic anhydride, it is appreciated
that the one alkenyl mono-substituted succinic anhydride is present
in an amount of.gtoreq.95 wt.-% and preferably of.gtoreq.96.5
wt.-%, based on the total weight of the at least one
mono-substituted succinic anhydride provided in step b).
[0132] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride is a mixture of two or more
kinds of alkenyl mono-substituted succinic anhydrides. For example,
the at least one mono-substituted succinic anhydride is a mixture
of two or three kinds of alkenyl mono-substituted succinic
anhydrides.
[0133] If the at least one mono-substituted succinic anhydride is a
mixture of two or more kinds of alkenyl mono-substituted succinic
anhydrides, one alkenyl mono-substituted succinic anhydride is
linear or branched octadecenyl succinic anhydride, while each
further alkenyl mono-substituted succinic anhydride is selected
from ethenylsuccinic anhydride, propenylsuccinic anhydride,
butenylsuccinic anhydride, pentenylsuccinic anhydride,
hexenylsuccinic anhydride, heptenylsuccinic anhydride,
nonenylsuccinic anhydride, hexadecenyl succinic anhydride and
mixtures thereof. For example, the at least one mono-substituted
succinic anhydride is a mixture of two or more kinds of alkenyl
mono-substituted succinic anhydrides, wherein one alkenyl
mono-substituted succinic anhydride is linear octadecenyl succinic
anhydride and each further alkenyl mono-substituted succinic
anhydride is selected from ethenylsuccinic anhydride,
propenylsuccinic anhydride, butenylsuccinic anhydride,
pentenylsuccinic anhydride, hexenylsuccinic anhydride,
heptenylsuccinic anhydride, nonenylsuccinic anhydride, hexadecenyl
succinic anhydride and mixtures thereof. Alternatively, the at
least one mono-substituted succinic anhydride is a mixture of two
or more kinds of alkenyl mono-substituted succinic anhydrides,
wherein one alkenyl mono-substituted succinic anhydride is branched
octadecenyl succinic anhydride and each further alkenyl
mono-substituted succinic anhydride is selected from
ethyenylsuccinic anhydride, propenylsuccinic anhydride,
butenylsuccinic anhydride, pentenylsuccinic anhydride,
hexenylsuccinic anhydride, heptenylsuccinic anhydride,
nonenylsuccinic anhydride, hexadecenyl succinic anhydride and
mixtures thereof.
[0134] For example, the at least one mono-substituted succinic
anhydride is a mixture of two or more kinds of alkenyl
mono-substituted succinic anhydrides comprising one or more
hexadecenyl succinic anhydride, like linear or branched hexadecenyl
succinic anhydride(s), and one or more octadecenyl succinic
anhydride, like linear or branched octadecenyl succinic
anhydride(s).
[0135] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride is a mixture of two or more
kinds of alkenyl mono-substituted succinic anhydrides comprising
linear hexadecenyl succinic anhydride(s) and linear octadecenyl
succinic anhydride(s). Alternatively, the at least one
mono-substituted succinic anhydride is a mixture of two or more
kinds of alkenyl mono-substituted succinic anhydrides comprising
branched hexadecenyl succinic anhydride(s) and branched octadecenyl
succinic anhydride(s). For example, the one or more hexadecenyl
succinic anhydride is linear hexadecenyl succinic anhydride like
n-hexadecenyl succinic anhydride and/or branched hexadecenyl
succinic anhydride like 1-hexyl-2-decenyl succinic anhydride.
Additionally or alternatively, the one or more octadecenyl succinic
anhydride is linear octadecenyl succinic anhydride like
n-octadecenyl succinic anhydride and/or branched octadecenyl
succinic anhydride like iso-octadecenyl succinic anhydride and/or
1-octyl-2-decenyl succinic anhydride.
[0136] If the at least one mono-substituted succinic anhydride is a
mixture of two or more kinds of alkenyl mono-substituted succinic
anhydrides, it is appreciated that one alkenyl mono-substituted
succinic anhydride is present in an amount of from 20 to 60 wt.-%
and preferably of from 30 to 50 wt.-%, based on the total weight of
the at least one mono-substituted succinic anhydride provided in
step b).
[0137] For example, if the at least one mono-substituted succinic
anhydride is a mixture of two or more kinds of alkenyl
mono-substituted succinic anhydrides comprising one or more
hexadecenyl succinic anhydride(s), like linear or branched
hexadecenyl succinic anhydride(s), and one or more octadecenyl
succinic anhydride(s), like linear or branched hexadecenyl succinic
anhydride(s), it is preferred that the one or more octadecenyl
succinic anhydride(s) is present in an amount of from 20 to 60
wt.-% and preferably of from 30 to 50 wt.-%, based on the total
weight of the at least one mono-substituted succinic anhydride
provided in step b).
[0138] It is also appreciated that the at least one
mono-substituted succinic anhydride may be a mixture of at least
one alkyl mono-substituted succinic anhydrides and at least one
alkenyl mono-substituted succinic anhydrides.
[0139] If the at least one mono-substituted succinic anhydride is a
mixture of at least one alkyl mono-substituted succinic anhydrides
and at least one alkenyl mono-substituted succinic anhydrides, it
is appreciated that the alkyl substituent of the at least one
alkenyl mono-substituted succinic anhydrides and the alkenyl
substituent of the of at least one alkenyl mono-substituted
succinic anhydrides are preferably the same. For example, the at
least one mono-substituted succinic anhydrides is a mixture of
ethylsuccinic anhydride and ethylsuccinic anhydride. Alternatively,
the at least one mono-substituted succinic anhydride is a mixture
of propylsuccinic anhydride and propenylsuccinic anhydride.
Alternatively, the at least one mono-substituted succinic anhydride
is a mixture of butylsuccinic anhydride and butenylsuccinic
anhydride. Alternatively, the at least one mono-substituted
succinic anhydride is a mixture of triisobutyl succinic anhydride
and triisobutenyl succinic anhydride. Alternatively, the at least
one mono-substituted succinic anhydride is a mixture of
pentylsuccinic anhydride and pentenylsuccinic anhydride.
Alternatively, the at least one mono-substituted succinic anhydride
is a mixture of hexylsuccinic anhydride and hexenylsuccinic
anhydride. Alternatively, the at least one mono-substituted
succinic anhydride is a mixture of heptylsuccinic anhydride and
heptenylsuccinic anhydride. Alternatively, the at least one
mono-substituted succinic anhydride is a mixture of octylsuccinic
anhydride and octensylsuccinic anhydride. Alternatively, the at
least one mono-substituted succinic anhydride is a mixture of
nonylsuccinic anhydride and nonenylsuccinic anhydride.
Alternatively, the at least one mono-substituted succinic anhydride
is a mixture of decyl succinic anhydride and decenyl succinic
anhydride.
[0140] Alternatively, the at least one mono-substituted succinic
anhydride is a mixture of dodecyl succinic anhydride and dodecenyl
succinic anhydride. Alternatively, the at least one
mono-substituted succinic anhydride is a mixture of hexadecanyl
succinic anhydride and hexadecenyl succinic anhydride. For example,
the at least one mono-substituted succinic anhydride is a mixture
of linear hexadecanyl succinic anhydride and linear hexadecenyl
succinic anhydride or a mixture of branched hexadecanyl succinic
anhydride and branched hexadecenyl succinic anhydride.
Alternatively, the at least one mono-substituted succinic anhydride
is a mixture of octadecanyl succinic anhydride and octadecenyl
succinic anhydride. For example, the at least one mono-substituted
succinic anhydride is a mixture of linear octadecanyl succinic
anhydride and linear octadecenyl succinic anhydride or a mixture of
branched octadecanyl succinic anhydride and branched octadecenyl
succinic anhydride.
[0141] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride is a mixture of nonylsuccinic
anhydride and nonenylsuccinic anhydride.
[0142] If the at least one mono-substituted succinic anhydride is a
mixture of at least one alkyl mono-substituted succinic anhydrides
and at least one alkenyl mono-substituted succinic anhydride and
the at least one alkenyl mono-substituted succinic anhydride is
between 90:10 and 10:90 (wt.-%/wt.-%). For example, the weight
ratio between the at least one alkyl mono-substituted succinic
anhydride and the at least one alkenyl mono-substituted succinic
anhydride is between 70:30 and 30:70 (wt.-%/wt.-%) or between 60:40
and 40:60.
[0143] Optionally, at least one mono-substituted succinic acid is
provided according to step b) of the inventive process.
[0144] It is appreciated that the expression "at least one"
mono-substituted succinic acid means that one or more kinds of
mono-substituted succinic acid may be provided in the process of
the present invention.
[0145] Accordingly, it should be noted that the at least one
mono-substituted succinic acid may be one kind of mono-substituted
succinic acid. Alternatively, the at least one mono-substituted
succinic acid may be a mixture of two or more kinds of
mono-substituted succinic acid. For example, the at least one
mono-substituted succinic acid may be a mixture of two or three
kinds of mono-substituted succinic acid, like two kinds of
mono-substituted succinic acid.
[0146] In one embodiment of the present invention, the at least one
mono-substituted succinic acid is one kind of mono-substituted
succinic acid.
[0147] It is appreciated that the at least one mono-substituted
succinic acid represents a surface treatment agent and consists of
succinic acid mono-substituted with a group selected from any
linear, branched, aliphatic and cyclic group having a total amount
of carbon atoms from C2 to C30 in the substituent.
[0148] In one embodiment of the present invention, the at least one
mono-substituted succinic acid consists of succinic acid
mono-substituted with a group selected from a linear, branched,
aliphatic and cyclic group having a total amount of carbon atoms
from C3 to C20 in the substituent. For example, the at least one
mono-substituted succinic acid consists of succinic acid
mono-substituted with a group selected from a linear, branched,
aliphatic and cyclic group having a total amount of carbon atoms
from C4 to C18 in the substituent.
[0149] It is appreciated that the at least one mono-substituted
succinic anhydride and the at least one mono-substituted succinic
acid may comprise the same or different substituent.
[0150] In one embodiment of the present invention, the succinic
acid molecule of the at least one mono-substituted succinic acid
and the succinic anhydride molecule of the at least one
mono-substituted succinic anhydride are mono-substituted with the
same group selected from any linear, branched, aliphatic and cyclic
group having a total amount of carbon atoms from C2 to C30,
preferably from C3 to C20 and most preferably from C4 to C18 in the
substituent.
[0151] If the at least one mono-substituted succinic anhydride is
provided in combination with at least one mono-substituted succinic
acid, the at least one mono-substituted succinic acid is present in
an amount of.ltoreq.10 mol.-%, based on the molar sum of the at
least one mono-substituted succinic anhydride and the at least one
mono-substituted succinic acid. For example, the at least one
mono-substituted succinic acid is present in an amount of.ltoreq.5
mo.-%, preferably of.ltoreq.2.5 mol.-% and most preferably
of.ltoreq.1 mol.-%, based on the molar sum of the at least one
mono-substituted succinic anhydride and the at least one
mono-substituted succinic acid.
[0152] In one embodiment of the present invention, at least one
mono-substituted succinic anhydride and at least one
mono-substituted succinic acid are provided in method step b).
[0153] If at least one mono-substituted succinic anhydride and at
least one mono-substituted succinic acid are provided in method
step b), the at least one mono-substituted succinic anhydride and
the at least one mono-substituted succinic acid are preferably
provided as a blend.
[0154] It is one requirement of the present invention that the at
least one mono-substituted succinic anhydride and the optional at
least one mono-substituted succinic acid are provided in a total
amount of from 0.1 to 3 wt.-%, based on the total dry weight of the
at least one calcium carbonate-containing filler material.
[0155] For example, the at least one mono-substituted succinic
anhydride and the optional at least one mono-substituted succinic
acid are provided in an amount of from 0.1 to 2.5 wt.-%, preferably
in an amount of from 0.1 to 2 wt.-%, more preferably in an amount
of from 0.1 to 1.5 wt.-%, even more preferably in an amount of from
0.1 to 1 wt.-% and most preferably in an amount of from 0.2 to 0.8
wt.-% based on the total dry weight of the at least one calcium
carbonate-containing filler material.
[0156] Additionally, or alternatively, the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid of the present invention are
preferably provided in a quantity such that the total weight of
said at least one mono-substituted succinic anhydride and the
optional at least one mono-substituted succinic acid on the surface
of the at least one calcium carbonate-containing filler material is
less than 5 mg/m.sup.2 of the at least one calcium
carbonate-containing filler material provided in step (a).
[0157] In one embodiment of the present invention, the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid of the present invention are
preferably provided in a quantity such that the total weight of
said at least one mono-substituted succinic anhydride and
mono-substituted succinic acid and/or salty reaction product(s)
thereof on the surface of the at least one calcium
carbonate-containing filler material is less than 4.5 mg/m.sup.2
and most preferably less than 4.0 mg/m.sup.2 of the at least one
calcium carbonate-containing filler material provided in step
(a).
[0158] For example, the at least one mono-substituted succinic
anhydride and the optional at least one mono-substituted succinic
acid of the present invention are preferably provided in a quantity
such that the total weight of the at least one mono-substituted
succinic anhydride and the optional at least one mono-substituted
succinic acid on the surface of the surface treated filler material
product is from 0.1 to 5 mg/m.sup.2, more preferably from 0.2 to 4
mg/m.sup.2 and most preferably from 1 to 4 mg/m.sup.2 of the at
least one calcium carbonate-containing filler material provided in
step a).
[0159] Additionally or alternatively, it is to be noted that the at
least one mono-substituted succinic anhydride and the optional at
least one mono-substituted succinic acid of step (b) of the
inventive process are provided as a liquid at room temperature,
i.e. said at least one mono-substituted succinic anhydride features
a viscosity of less than 5 000, preferably of less than 2 500, more
preferably of less than 1,000 mPas and most preferably of less than
500 mPas at +20.degree. C. (.+-.2.degree. C.), when measured with
the appropriate equipment e.g. Physica MCR 300 rheometer (Paar
Physica) equipped with the measuring cell TEZ 150 P-C and the CC
28.7 measuring system at a shear rate of 5 s.sup.-1 and at
+20.degree. C. (.+-.2.degree. C.).
Characterization of Step c): Contacting of the at Least One Calcium
Carbonate-Containing Filler Material with the at Least One
Mono-Substituted Succinic Anhydride
[0160] According to step c) of the inventive process, the at least
one calcium carbonate-containing filler material of step a) is
contacted under mixing, in one or more steps, with the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid of step b).
[0161] Step c) of contacting the at least one calcium
carbonate-containing filler material with the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid takes place under mixing conditions.
The skilled man will adapt these mixing conditions (such as the
configuration of mixing pallets and mixing speed) according to his
process equipment.
[0162] In one preferred embodiment of the present invention, the
inventive process may be a continuous process. In this case, it is
possible to contact the at least one calcium carbonate-containing
filler material with the at least one mono-substituted succinic
anhydride and the optional at least one mono-substituted succinic
acid in a constant flow, so that a constant concentration of the at
least one mono-substituted succinic anhydride and the optional at
least one mono-substituted succinic acid is provided during step
c).
[0163] Alternatively, the at least one calcium carbonate-containing
filler material is contacted with the at least one mono-substituted
succinic anhydride and the optional at least one mono-substituted
succinic acid of step (b) in one step, wherein said at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid is preferably added in one
portion.
[0164] In another embodiment of the present invention, the
inventive process may be a batch process, i.e. the at least one
calcium carbonate-containing filler material is contacted with the
at least one mono-substituted succinic anhydride and the optional
at least one mono-substituted succinic acid in more than one steps,
wherein said at least one mono-substituted succinic anhydride and
the optional at least one mono-substituted succinic acid is
preferably added in about equal portions. Alternatively, it is also
possible to add the at least one mono-substituted succinic
anhydride and the optional at least one mono-substituted succinic
acid in unequal portions to the at least one calcium
carbonate-containing filler material, i.e. in larger and smaller
portions.
[0165] According to one embodiment of the present invention,
contacting step (c) is carried out in a batch or continuous process
for a period of time from 0.1 to 1000 s. For example, contacting
step (c) is a continuous process and comprises one or several
contacting steps and the total contacting time is from 0.1 to 20 s,
preferably from 0.5 to 15 s and most preferably from 1 to 10 s.
[0166] When implementing the at least one mono-substituted succinic
anhydride and the optional at least one mono-substituted succinic
acid of step b), it features a workable viscosity at about room
temperature, i.e. the at least one mono-substituted succinic
anhydride and the optional at least one mono-substituted succinic
acid is in a liquid state. Therefore, the contacting of the at
least one calcium carbonate-containing filler material with the at
least one mono-substituted succinic anhydride and the optional at
least one mono-substituted succinic acid may be carried out at
lower treatment temperatures than that used in processes
implementing fatty acids and/or fatty acid salts having at least 10
chain carbon atoms. It is thus one requirement of the present
invention that the temperature is adjusted during contacting step
c) such that the at least one mono-substituted succinic anhydride
and the optional at least one mono-substituted succinic acid is
molten.
[0167] A "molten" or "liquid" state in the meaning of the present
invention is defined as the state in which a material is entirely
liquid, in other words is entirely melted. Whereas the phenomenon
of melting occurs at constant temperature on application of energy,
a substance is qualified as being molten as of the moment following
melting when the temperature begins to rise, as observed on a curve
plotting temperature versus energy input obtained by Dynamic
Scanning Calorimetry, DSC, (DIN 51005: 1983-11).
[0168] Accordingly, it is appreciated that the temperature before
and/or during contacting step c) is adjusted such that the
temperature is at least 2.degree. C. above the melting point of the
at least one mono-substituted succinic anhydride and the optional
at least one mono-substituted succinic acid. For example, the
temperature before contacting step c) is adjusted such that the
temperature is at least 2.degree. C. above the melting point of the
at least one mono-substituted succinic anhydride and the optional
at least one mono-substituted succinic acid. Alternatively, the
temperature before and during contacting step c) is adjusted such
that the temperature is at least 2.degree. C. above the melting
point of the at least one mono-substituted succinic anhydride and
the optional at least one mono-substituted succinic acid.
[0169] It is appreciated that the wording "melting point of the at
least one mono-substituted succinic anhydride and the optional at
least one mono-substituted succinic acid" refers to the melting
point of the at least one mono-substituted succinic anhydride or,
if the at least one mono-substituted succinic acid is present, to
the blend comprising the at least one mono-substituted succinic
anhydride and the at least one mono-substituted succinic acid.
[0170] In one embodiment of the present invention, the temperature
before and/or during contacting step c) is adjusted such that the
temperature is at least 5.degree. C., preferably, at least
8.degree. C. and most preferably at least 10.degree. C. above the
melting point of the at least one mono-substituted succinic
anhydride and the optional at least one mono-substituted succinic
acid. For example, the temperature before and/or during contacting
step c) is adjusted such that the temperature is from 2 to
50.degree. C., preferably from 5 to 40.degree. C., more preferably
from 8 to 30.degree. C. and most preferably from 10 to 20.degree.
C. above the melting point of the at least one mono-substituted
succinic anhydride and the optional at least one mono-substituted
succinic acid.
[0171] In one embodiment of the present invention, the contacting
of the at least one calcium carbonate-containing filler material
with the at least one mono-substituted succinic anhydride and the
optional at least one mono-substituted succinic acid is thus
carried out at a treatment temperature of below 200.degree. C. For
example, the contacting of at least one calcium
carbonate-containing filler material with the at least one
mono-substituted succinic anhydride and the operational at least
one mono-substituted succinic acid is carried out at a treatment
temperature of from 30 to 200.degree. C., preferably of from 80 to
150.degree. C. and most preferably of from about 110 to 130.degree.
C.
[0172] The treatment time for carrying out the contacting of the at
least one calcium carbonate-containing filler material with the at
least one mono-substituted succinic anhydride and the optional at
least one mono-substituted succinic acid of step (b) is carried out
for a period of 1 000 s or less, preferably for a period of 500 s
or less, more preferably for a period of 250 s or less and most
preferably from 0.1 to 1 000 s. For example, contacting step (c) is
carried out for a period of time from 0.1 to 20 s, preferably from
0.5 to 15 s and most preferably from 1 to 10 s. In general, the
length of contacting the at least one calcium carbonate-containing
filler material with the at least one mono-substituted succinic
anhydride and the optional at least one mono-substituted succinic
acid of step (b) is determined by the treatment temperature applied
during said contacting. For example, where a treatment temperature
of about 200.degree. C. is applied, the treatment time is as short
as, for example, about 0.1. If a treatment temperature of about
90.degree. C. is applied, the treatment time can be as long as, for
example, about 1 000 s.
[0173] It is appreciated that at least one mono-substituted
succinic anhydride and the optional at least one mono-substituted
succinic acid are added in contacting step c) in an amount of from
0.1 to 2 wt.-%, based on the total dry weight of the at least one
calcium carbonate-containing filler material of step a). For
example, the at least one mono-substituted succinic anhydride and
the optional at least one mono-substituted succinic acid is added
in contacting step c) in an amount of from 0.2 to 1.5 wt.-% or of
from 0.3 to 1 wt.-%, based on the total dry weight of the at least
one calcium carbonate-containing filler material of step a).
[0174] In one embodiment of the present invention, the at least one
calcium carbonate-containing filler material is preheated, i.e.
activated, before contacting step c) is carried out. That is to
say, the at least one calcium carbonate-containing filler material
is treated at a temperature of from 50 to 200.degree. C.,
preferably of from about 80 to 200.degree. C., more preferably of
from 90 to 150.degree. C. and most preferably of from 100 to
130.degree. C. before contacting step c) is carried out.
[0175] The treatment time for carrying out the preheating of the at
least one calcium carbonate-containing filler material is carried
out for a period of 30 min or less, preferably for a period of 20
min or less and more preferably for a period of 15 min or less.
[0176] In one embodiment of the present invention, the preheating
of the at least one calcium carbonate-containing filler material is
carried out at a temperature that is of about equal to the
temperature implemented during contacting step c).
[0177] The term "equal" temperature in the meaning of the present
invention refers to a preheating temperature that is at most
20.degree. C., preferably at most 15.degree. C., more preferably
10.degree. C. and most preferably at most 5.degree. C. below or
above the temperature implemented during contacting step c).
[0178] According to one embodiment of the present invention, the
process further comprises step (d) of contacting the at least one
calcium carbonate-containing filler material of step (a), in one or
more steps, with at least one organic material such as
polysiloxanes.
[0179] In case, the inventive process further comprises contacting
step (d), such contacting of the at least one calcium
carbonate-containing filler material with the at least one organic
material may be carried out during and/or after the contacting of
the at least one calcium carbonate-containing filler material with
the at least one mono-substituted succinic anhydride and the
optional at least one mono-substituted succinic acid of step (b).
In one embodiment of the present invention, such contacting with
the at least one organic material is carried out after the
contacting of the at least one calcium carbonate-containing filler
material with the at least one mono-substituted succinic anhydride
and the optional at least one mono-substituted succinic acid of
step (b). In this case, contacting step d) is preferably carried
out at temperatures of from 40 to 200.degree. C. For example,
contacting step d) is carried out at temperature of from 50 to
150.degree. C. or from 60 to 120.degree. C.
[0180] The at least one organic material such as polysiloxane is
added in contacting step d) in an amount of from 100 to 1 000 ppm,
preferably from 200 to 800 ppm and most preferably from 300 to 700
ppm, based on the total dry weight of the at least one calcium
carbonate-containing filler material of step a)
[0181] Additionally or alternatively, the at least one organic
material such as polysiloxane is preferably added such that the
amount of the at least one organic material on the surface of the
surface treated filler material product, i.e. in the treatment
layer, is less than 0.1 mg, more preferably less than 0.08 mg and
most preferably less than 0.07 mg of the total weight of the at
least organic material/m.sup.2 of the at least one calcium
carbonate-containing filler material provided in step a).
[0182] The treatment time for carrying out the contacting of the at
least one calcium carbonate-containing filler material with the at
least one organic material is carried out for a period of 0.00166
to 166.66 min. For example, the contacting of the at least one
calcium carbonate-containing filler material with the at least one
organic material is carried out for a contacting time from 0.0166
to 20 min, preferably from 0.0833 to 15 min and most preferably
from 0.166 to 10 min.
[0183] The length of contacting step d) is determined by the
treatment temperature applied during said contacting. For example,
where a treatment temperature of about 140.degree. C. is applied,
the treatment time is as short as, for example from about 0.166 to
1 min.
[0184] Thus, it is appreciated that the treatment layer formed on
the surface of the at least one calcium carbonate-containing filler
material comprises the at least one mono-substituted succinic
anhydride provided in step b) and the optional at least one
mono-substituted succinic acid, optionally provided in step b)
and/or obtained as reaction product from contacting the calcium
carbonate-containing filler material with the at least one
mono-substituted succinic anhydride(s), and/or salty reaction
product(s) thereof obtained from contacting the at least one
calcium carbonate-containing filler material with the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid. In such a case, the treatment layer
of the surface treated filler material product preferably comprises
salty reaction product(s) of the mono-substituted succinic acid
and/or the at least one mono-substituted succinic anhydride formed
on the surface of said at least one calcium carbonate-containing
filler material in step c). For example, salty reaction product(s)
such as one or more calcium salts and/or magnesium salts of the at
least one mono-substituted succinic acid and/or the at least one
mono-substituted succinic anhydride. In one embodiment of the
present invention, the treatment layer of the surface treated
filler material product further comprises at least one organic
material such as polysiloxane.
[0185] Thus, it is appreciated that the at least one calcium
carbonate-containing filler material product obtained in process
step c) and optionally after step d), i.e. the surface treated
filler material product, comprises, preferably consists of, at
least one calcium carbonate-containing filler material and a
treatment layer comprising at least one mono-substituted succinic
anhydride and at least one mono-substituted succinic acid and/or
salty reaction product(s) thereof. The treatment layer is formed on
the surface of said at least one calcium carbonate-containing
filler material of step a).
[0186] In case the treatment layer on the surface of the at least
one calcium carbonate-containing filler material comprises at least
one mono-substituted succinic acid, it is preferred that the at
least one mono-substituted succinic acid is formed from the applied
at least one mono-substituted succinic anhydride. That is to say,
the substituent of the at least one mono-substituted succinic acid
and the substituent of the at least one mono-substituted succinic
anhydride are the same.
[0187] Additionally or alternatively, the at least one
mono-substituted succinic acid is provided in a blend together with
the at least one mono-substituted succinic anhydride.
[0188] In one embodiment of the present invention, the treatment
layer formed on the surface of the at least one calcium
carbonate-containing filler material comprises the at least one
mono-substituted succinic anhydride provided in step b) and at
least one mono-substituted succinic acid or salty reaction
product(s) thereof obtained from contacting the at least one
calcium carbonate-containing filler material with the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid. Alternatively, the treatment layer
formed on the surface of the at least one calcium
carbonate-containing filler material comprises the at least one
mono-substituted succinic anhydride provided in step b) and at
least one mono-substituted succinic acid and salty reaction
product(s) thereof obtained from contacting the at least one
calcium carbonate-containing filler material with the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid.
[0189] The treatment layer is preferably characterized in that the
total weight of the at least one mono-substituted succinic
anhydride and at least one mono-substituted succinic acid and/or
salty reaction product(s) thereof on the surface of the surface
treated filler material product is from 0.1 to 5 mg/m.sup.2, more
preferably from 0.2 to 4 mg/m.sup.2 and most preferably from 1 to 4
mg/m.sup.2 of the at least one calcium carbonate-containing filler
material provided in step a).
[0190] The treatment layer is preferably characterized in that the
total weight of the at least one mono-substituted succinic
anhydride and at least one mono-substituted succinic acid and/or
salty reaction product(s) thereof on the surface of the surface
treated filler material product is from 0.05 to 1 wt.-%/m.sup.2,
more preferably from 0.1 to 0.5 wt.-%/m.sup.2 and most preferably
from 0.15 to 0.25 wt.-%/m.sup.2 of the at least one calcium
carbonate-containing filler material provided in step a)
[0191] In one embodiment of the present invention, the treatment
layer is characterized in that the total weight of the at least one
mono-substituted succinic anhydride and mono-substituted succinic
acid and/or salty reaction product(s) thereof and the optional at
least one organic material on the surface of the surface treated
filler material product is from 0.1 to 5 mg/m.sup.2, more
preferably from 0.25 to 4.5 mg/m.sup.2 and most preferably from 1.0
to 4.0 mg/m.sup.2 of the at least one calcium carbonate-containing
material provided in step a).
[0192] Additionally or alternatively, the treatment layer of the
surface treated filler material product comprises the at least one
mono-substituted succinic anhydride and the at least one
mono-substituted succinic acid and/or salty reaction product(s)
thereof in a specific molar ratio. For example, the molar ratio of
the at least one mono-substituted succinic anhydride and the at
least one mono-substituted succinic acid to the salt reaction
product(s) thereof is from 99.9:0.1 to 0.1:99.9, preferably from
70:30 to 90:10.
[0193] The wording "molar ratio of the at least one
mono-substituted succinic anhydride and the at least one
mono-substituted succinic acid to the salty reaction product(s)
thereof" in the meaning of the present invention refers to the sum
of the molecular weight of the at least one mono-substituted
succinic anhydride and the sum of the molecular weight of the at
least one mono-substituted succinic acid to the sum of the
molecular weight of the mono-substituted succinic anhydride
molecules in the salty reaction products thereof and the sum of the
molecular weight of the mono-substituted succinic acid molecules in
the salt reaction products thereof.
[0194] It is further appreciated that the obtained surface treated
filler material product comprises the treatment layer in an amount
of from 0.1 to 2.5 wt.-%, preferably in an amount of from 0.1 to 2
wt.-%, more preferably in an amount of from 0.1 to 1.5 wt.-%, even
more preferably in an amount of from 0.1 to 1 wt.-% and most
preferably in an amount of from 0.2 to 0.8 wt.-% based on the total
dry weight of the at least one calcium carbonate-containing filler
material.
[0195] The resulting surface treated filler material product
obtained according to the present invention has excellent surface
characteristics in comparison to mineral fillers treated with fatty
acids and/or fatty acid salts having at least 10 chain carbon
atoms, i.e. without the implementation of the at least one
mono-substituted succinic anhydride and the optional at least one
mono-substituted succinic acid.
[0196] In particular, it is appreciated that the surface treated
filler material product obtained by the inventive process features
a volatile onset temperature of.gtoreq.250.degree. C. For example,
the surface treated filler material product obtained by the
inventive process features a volatile onset temperature
of.gtoreq.260.degree. C. or of.gtoreq.270.degree. C.
[0197] Additionally or alternatively, the surface treated filler
material product obtained by the inventive process features a total
volatiles between 25 and 350.degree. C. of less than 0.25%, and
preferably of less than 0.23% by mass, e.g. of from 0.04 to 0.21%
by mass, preferably from 0.08 to 0.15% by mass, more preferably
from 0.1 to 0.12% by mass.
[0198] Furthermore, the surface treated filler material product
obtained by the inventive process features a low moisture pick up
susceptibility. It is preferred that the moisture pick up
susceptibility of the surface treated filler material product
obtained by the inventive process is such that its total surface
moisture level is less than 0.8 mg/g of dry calcium
carbonate-containing filler material, at a temperature of about
+23.degree. C. (.+-.2.degree. C.). For example, the surface treated
filler material product obtained by the inventive process has a
moisture pick up susceptibility of from 0.1 to 0.8 mg/g, more
preferably of from 0.2 to 0.7 mg/g and most preferably of from 0.2
to 0.6 mg/g of dry calcium carbonate-containing material after at a
temperature of +23 C. (.+-.2.degree. C.).
[0199] Additionally or alternatively, the surface treated filler
material product obtained by the inventive process has a
hydrophilicity of below 8:2 volumetric ratio of water:ethanol
measured at +23.degree. C. (.+-.2.degree. C.) with the
sedimentation method. For example, the surface treated filler
material product has a hydrophilicity of below 7:3 volumetric ratio
of water:ethanol measured at +23.degree. C. (.+-.2.degree. C.) with
the sedimentation method.
[0200] In view of the very good results obtained, one aspect of the
present invention relates to the surface treated filler material
product comprising [0201] a) at least one calcium
carbonate-containing filler material having [0202] i) a weight
median particle size d.sub.50 value in the range from 0.1 .mu.m to
7 .mu.m, [0203] ii) a top cut (d.sub.98).ltoreq.15 .mu.m, [0204]
iii) a specific surface area (BET) of from 0.5 to 150 m.sup.2/g as
measured by the BET nitrogen method, and [0205] iv) a residual
total moisture content of.ltoreq.1 wt.-%, based on the total dry
weight of the at least one calcium carbonate-containing filler
material, and [0206] b) a treatment layer on the surface of the at
least one calcium carbonate-containing filler material comprising
at least one mono-substituted succinic anhydride and at least one
mono-substituted succinic acid and/or salty reaction product(s)
thereof, wherein the surface treated filler material product
comprises the treatment layer in an amount of from 0.1 to 3 wt.-%,
based on the total dry weight of the at least one calcium
carbonate-containing filler material.
[0207] In one embodiment of the present invention, the surface
treated filler material product is obtainable by the process of the
present invention.
[0208] With regard to the definition of the at least one calcium
carbonate-containing filler material, the at least one
mono-substituted succinic anhydride, the at least one
mono-substituted succinic acid, the salty reaction product(s)
thereof, the surface treated filler material product, and preferred
embodiments thereof, reference is made to the comments provided
above when discussing process steps a), b) and c), and optional
step d).
[0209] The surface treated filler material product is thus obtained
is advantageously implemented in polymer composition comprising at
least one polymeric resin and from 1 to 85 wt.-% of the surface
treated filler material product.
[0210] Accordingly, the polymer composition comprises at least one
polymeric resin. The polymer resin represents the backbone of the
composition and provides strength, flexibility, toughness and
durability to the final fiber and/or filament and/or film and/or
thread.
[0211] It is appreciated that the at least one polymeric resin
according to the present invention is not restricted to a specific
resin material as long as the polymer composition is suitable for
the preparation of fibers and/or filaments and/or films and/or
thread.
[0212] In one embodiment of the present invention, the at least one
polymeric resin is at least one thermoplastic polymer. Thus, it is
preferred that the at least one polymeric resin is a thermoplastic
polymer selected from the group comprising homopolymers and/or
copolymers of polyolefins, polyamides, halogen-containing polymers
and/or polyesters.
[0213] For example, if the at least one polymeric resin is a
polyamide the at least one polymeric resin is preferably nylon.
[0214] Additionally or alternatively, the at least one polymeric
resin is a homopolymer and/or copolymer of a polyolefin. For
example, the at least one polymeric resin is a homopolymer and a
copolymer of a polyolefin. Alternatively, the at least one
polymeric resin is a homopolymer or a copolymer of a
polyolefin.
[0215] It is appreciated that the at least one polymeric resin is
preferably a homopolymer of a polyolefin.
[0216] For example, the polyolefin can be polyethylene and/or
polypropylene and/or polybutylene. Accordingly, if the polyolefin
is polyethylene, the polyolefin is selected from the group
comprising homopolymers and/or copolymers of polyethylene like
high-density polyethylene (HDPE), medium-density polyethylene
(MDPE), low-density polyethylene (LDPE), very low-density
polyethylene (VLDPE), linear low-density polyethylene (LLDPE).
[0217] For example, the polyolefin is a homopolymer and/or
copolymer of polyethylene.
[0218] The expression homopolymer of polyethylene used in the
present invention relates to polyethylene comprising a polyethylene
that consists substantially, i.e. of more than 99.7 wt.-%, still
more preferably of at least 99.8 wt.-%, based on the total weight
of the polyethylene, of ethylene units. For example, only ethylene
units in the homopolymer of polyethylene are detectable.
[0219] In case the at least one polymeric resin of the polymer
composition comprises a copolymer of polyethylene, it is
appreciated that the polyethylene contains units derivable from
ethylene as major components. Accordingly, the copolymer of
polyethylene comprises at least 55 wt.-% units derivable from
ethylene, more preferably at least 60 wt-% of units derived from
ethylene, based on the total weight of the polyethylene. For
example, the copolymer of polyethylene comprises 60 to 99.5 wt.-%,
more preferably 90 to 99 wt.-%, units derivable from ethylene,
based on the total weight of the polyethylene. The comonomers
present in such copolymer of polyethylene are C.sub.3 to C.sub.10
.alpha.-olefins, preferably 1-butene, 1-hexene and 1-octene, the
latter especially preferred.
[0220] Additionally or alternatively, the polyolefin is a
homopolymer and/or copolymer of polypropylene.
[0221] The expression homopolymer of polypropylene as used
throughout the instant invention relates to a polypropylene that
consists substantially, i.e. of more than 99 wt.%, still more
preferably of at least 99.5 wt.-%, like of at least 99.8 wt.-%,
based on the total weight of the polypropylene, of propylene units.
In a preferred embodiment only propylene units are detectable in
the homopolymer of polypropylene.
[0222] In case the at least one polymeric resin of the polymer
composition comprises a copolymer of polypropylene, the
polypropylene preferably contains units derivable from propylene as
major components. The copolymer of polypropylene preferably
comprises, preferably consists of, units derived from propylene and
C.sub.2 and/or at least one C.sub.4 to C.sub.10 .alpha.-olefin. In
one embodiment of the present invention, the copolymer of
polypropylene comprises, preferably consists of, units derived from
propylene and at least one .alpha.-olefin selected from the group
consisting of ethylene, 1-butene, 1-pentene, 1-hexene and 1-octene.
For example, the copolymer of polypropylene comprises, preferably
consists of, units derived from propylene and ethylene. In one
embodiment of the present invention, the units derivable from
propylene constitutes the main part of the polypropylene, i.e. at
least 60 wt.-%, preferably of at least 70 wt.-%, more preferably of
from 80 wt.-%, still more preferably of from 60 to 99 wt.-%, yet
more preferably of from 70 to 99 wt.-% and most preferably of from
80 to 99 wt.-%, based on the total weight of the polypropylene. The
amount of units derived from C.sub.2 and/or at least one C.sub.4 to
C.sub.10 .alpha.-olefin in the copolymer of polypropylene, is in
the range of 1 to 40 wt.-%, more preferably in the range of 1 to 30
wt.-% and most preferably in the range of 1 to 20 wt.-%, based on
the total weight of the copolymer of polypropylene.
[0223] If the copolymer of polypropylene comprises only units
derivable from propylene and ethylene, the amount of ethylene is
preferably in the range of 1 to 20 wt.-%, preferably in the range
of 1 to 15 wt.-% and most preferably in the range of 1 to 10 wt.-%,
based on the total weight of the copolymer of polypropylene.
Accordingly, the amount of propylene is preferably in the range of
80 to 99 wt.-%, preferably in the range of 85 to 99 wt.-% and most
preferably in the range of 90 to 99 wt.-%, based on the total
weight of the copolymer of polypropylene.
[0224] Additionally or alternatively, the polyolefin is a
homopolymer and/or copolymer of polybutylene.
[0225] The expression homopolymer of polybutylene as used
throughout the instant invention relates to a polybutylene that
consists substantially, i.e. or more than 99 wt.-%, still more
preferably of at least 99.5 wt.-%, like of at least 99.8 wt.-%,
based on the total weight of the polybutylene, of butylene units.
In a preferred embodiment only butylene units are detectable in the
homopolymer of polybutylene.
[0226] In case the at least one polymeric resin of the polymer
composition comprises a copolymer of polybutylene, the polybutylene
preferably contains units derivable from butylene as major
components. The copolymer of polybutylene preferably comprises,
preferably consists of, units derived from butylene and C.sub.2
and/or C.sub.3 and/or at least one C.sub.5 to C.sub.10
.alpha.-olefin. In one embodiment of the present invention, the
copolymer of polybutylene comprises, preferably consists of, units
derived from butylene and at least one .alpha.-olefin selected from
the group consisting of ethylene, 1-propene, 1-pentene, 1-hexene
and 1-octene. For example, the copolymer of polybutylene comprises,
preferably consists of, units derived from butylene and ethylene.
In one embodiment of the present invention, the units derivable
from butylene constitutes the main part of the polybutylene, i.e.
at least 60 wt.-%, preferably of at least 70 wt.-%, more preferably
of at least 80 wt.-%, still more preferably of from 60 to 99 wt.-%,
yet more preferably of from 70 to 99 wt.-% and most preferably of
from 80 to 99 wt.-%, based on the total weight of the polybutylene.
The amount of units derived from C.sub.2 and/or C.sub.3 and/or at
least one C.sub.5 to C.sub.10 .alpha.-olefin in the copolymer of
polybutylene, is in the range of 1 to 40 wt.-%, more preferably in
the range of 1 to 30 wt.-% and most preferably in the range of 1 to
20 wt.-%, based on the total weight of the copolymer of
polybutylene.
[0227] If the at least one polymeric resin is a homopolymer and/or
copolymer of a halogen-containing polymer, the at least one
polymeric resin is preferably selected from polyvinylchloride
(PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride
(PVDF) and polytetrafluoroethylene (PTFE).
[0228] If the at least one polymeric resin is a homopolymer and/or
copolymer of polyester, the at least one polymeric resin is
preferably selected from polyethylene terephthalate (PET),
polytrimetethylene terephthalate (PTT), polybutylene terephthalate
(PBT), polyethylene aphthalate (PEN), but also degradable
polyesters, such as polylactic acid (polylactide, PLA).
[0229] In one embodiment of the present invention, the at least one
polymeric resin is a homopolymer of polyethylene and/or
polypropylene and/or polybutylene. For example, the at least one
polymeric resin is a homopolymer of polyethylene and polypropylene.
Alternatively, the at least one polymeric resin is a homopolymer of
polyethylene or polypropylene. In one embodiment of the present
invention, the at least one polymeric resin is a homopolymer of
polypropylene.
[0230] The expression "at least one" polymeric resin means that one
or more kinds of polymeric resin may be present in the inventive
polymer composition.
[0231] Full or partially based bio-based polymers are derived from
renewable biomass sources, such as vegetable fats and oils, corn
starch, pea starch or microbiota, aliphatic biopolyesters such as
polyhydroxyalkanoates (PHA), polyhydroxybutyrate (PHB),
polyhydroxyvalerate (PHV), polyhydroxyhexanoate (PHH), or
polyesters such as polyethylene terephthalate (PET).
[0232] Blends, Mixtures, Alloys and combinations of two or more of
the above mentioned polymers can be used as well in the present
invention.
[0233] Accordingly, it is appreciated that the at least one
polymeric resin may be a mixture of two or more kinds of polymeric
resins. For example, if the at least one polymeric resin is a
mixture of two or more polymeric resins, one polymeric resin is a
homopolymer or copolymer of polypropylene, while the second or
further polymeric resin is selected from the group comprising
homopolymers and/or copolymers of polyethylene, polybutylene,
polyamides, polyesters, halogen-containing polymers and mixtures
thereof, wherein the polymers can be fully or partially based
biopolymers.
[0234] In one embodiment of the present invention, the at least one
polymeric resin is one kind of polymeric resin. Preferably, the at
least one polymeric resin is a homopolymer of polyethylene or
polypropylene.
[0235] In one embodiment of the present invention, the at least one
polymeric resin has a melting temperature Tm of above 100.degree.
C., more preferably of above 150.degree. C., like of above
200.degree. C. For example, the melting temperature of the at least
one polymeric resin ranges from 100 to 350.degree. C., more
preferably ranges from 150 to 325.degree. C. and most preferably
ranges from 200 to 300.degree. C.
[0236] Furthermore, it is appreciated that the at least one
polymeric resin may be selected from polymeric resins having a
broad spectrum of melt flow rate. In general, it is preferred that
the at least one polymeric resin has a melt flow rate MFR
(190.degree. C.) of from 0.1 to 3 000 g/10 min, more preferably of
from 0.2 to 2 500 g/10 min. For example, the at least one polymeric
resin has a melt flow rate MFR (190.degree. C.) of from 0.3 to 2
000 g/10 min or from 0.3 to 1 600 g/10 min. Additionally or
alternatively, the at least one polymeric resin has a melt flow
rate MFR (230.degree. C.) of from 0.1 to 3 000 g/10 min, more
preferably of from 0.2 to 2 500 g/10 min. For example, the at least
one polymeric resin has a melt flow rate MFR (230.degree. C.) of
from 0.3 to 2 000 g/10 min or from 0.3 to 1 600 g/10 min.
[0237] For example, if the at least one polymeric resin is a
polyolefin being a homopolymer and/or copolymer of polypropylene,
it is preferred that the at least one polymeric resin has a melt
flow rate MFR (190.degree. C., 2.16 kg) of from 1 to 3 000 g/10
min, more preferably of from 3 to 2 500 g/10 min. For example, the
at least one polymeric resin which is a homopolymer and/or
copolymer of polypropylene has a melt flow rate MFR (190.degree.
C.) of from 5 to 2 000 g/10 min or from 10 to 1 600 g/10 min. It is
preferred that the at least one polymeric resin which is a
homopolymer and/or copolymer of polypropylene has a melt flow rate
MFR (230.degree. C.) of from 1 to 3 000 g/10 min, more preferably
of from 3 to 2 500 g/10 min. For example, the at least one
polymeric resin which is a homopolymer and/or copolymer of
polypropylene has a melt flow rate MFR (230.degree. C.) of from 5
to 2 000 g/10 min or from 10 to 1 600 g/10 min.
[0238] If the at least one polymeric resin is a polyolefin being a
homopolymer and/or copolymer of polyethylene, it is appreciated
that the at least one polymeric resin has a rather low melt flow
rate. Accordingly, it is preferred that the at least one polymeric
resin which is a homopolymer and/or copolymer of polyethylene has a
melt flow rate MFR (190.degree. C.) of from 0.5 to 20 g/10 min,
more preferably of from 0.7 to 15 g/10 min. For example, the at
least one polymeric resin has a melt flow rate MFR (190.degree. C.)
of from 0.9 to 10 g/10 min or from 0.9 to 5 g/10 min. Additionally
or alternatively, the at least one polymeric resin which is a
homopolymer and/or copolymer of polyethylene has a melt flow rate
MFR (230.degree. C.) of from 0.1 to 3 000 g/10 min, more preferably
of from 0.2 to 2 500 g/10 min. For example, the at least one
polymeric resin which is a homopolymer and/or copolymer of
polyethylene has a melt flow rate MFR (230.degree. C.) of from 0.3
to 2 000 g/10 min or from 0.3 to 1 600 g/10 min.
[0239] A further essential component of the present polymer
composition is the surface treated filler material product. With
regard to the definition of the surface treated filler material
product and preferred embodiments thereof, reference is made to the
comments provided above when discussing process steps a), b) and
c).
[0240] It is one requirement of the present invention that the
polymer composition comprises the surface treated filler material
product in an amount of 1 to 85 wt.-%, based on the total weight of
the polymer composition.
[0241] In one embodiment of the present invention, the polymer
composition comprises the surface treated filler material product
in an amount of from 5 to 85 wt.-% and preferably from 10 to 85
wt.-%, based on the total weight of the polymer composition. For
example, the polymer composition comprises the surface treated
filler material product in an amount of from 15 to 80 wt.-%, based
on the total weight of the polymer composition.
[0242] In one embodiment of the present invention, the polymer
composition is a masterbatch.
[0243] The term "masterbatch" refers to a composition having a
concentration of the surface treated filler material product that
is higher than the concentration of the polymer composition used
for preparing the final application product such as a fiber and/or
filament and/or film. That is to say, the masterbatch is further
diluted such as to obtain a polymer composition which is suitable
for preparing the final application product such as a fiber and/or
filament and/or film and/or thread.
[0244] For example, the masterbatch comprises the surface treated
filler material product in an amount of from 50 to 85 wt.-%,
preferably from 60 to 85 wt.-% and more preferably from 70 to 80
wt.-%, based on the total weight of the masterbatch.
[0245] According to one embodiment of the present invention, the
masterbatch is used to produce fibers and/or filaments and/or films
and/or threads.
[0246] According to a further embodiment, the polymer masterbatch
obtainable by the inventive process may be used in the manufacture
of polymer products, wherein said polymer products preferably
comprise polyolefin articles, such as woven fibers, non-woven
fibers, profiles, cables, films, or molded products.
[0247] The products comprising the polymer masterbatch according to
the present invention may be manufactured by any process known to
the skilled person.
[0248] In the art, many methods for the manufacture of polymer
products are known. These methods include, without being limited
to, melt processing techniques, for example, profile extrusion (for
pipes, sheets and hollow sheets), cable extrusion, film extrusion
(for cast films and blow films), molding (e.g., injection molding,
rotomolding, blow molding and thermoforming), fiber spinning (e.g.,
melt spinning, wet spinning, dry spinning and structural fibers),
co-kneading and pultrusion. The final articles may provide
mono-layer or multi-layer structures.
[0249] According to one embodiment of the present invention, the
polymer masterbatch obtainable by the inventive process can
advantageously be used for the preparation of various shaped
articles for plastics applications. Examples include flexible
packaging for industrial and consumer applications, including roll
stocks, bags, pouches, labels, wraps, lidding, shrink sleeves and
stretch films; rigid packaging for industrial and consumer
applications including plastic bottles, cups and containers;
building and construction materials, including pipes and conduits,
cladding and profiles, insulation, seals and gaskets, geotextiles;
agriculture and horticulture materials including greenhouse
material, mulch films, tunnel, silage, bale wraps, boxes and
crates; transportation and automotive applications including
interior parts, such as instrument and door panels, consoles,
pillars and seating; exterior parts, such as bumper fascia,
fenders, tailgates as well as under the hood applications including
air ducts, air intake manifolds, radiators and cooling hoses;
electrical and electronic applications including CD players, DVD
systems, personal computers and TV sets, notebooks, tablets,
smartphones, cookers, refrigerators and freezers, washing machines,
dishwashers, tools and office equipment; medical and health
applications including disposable caps, gowns, masks, scrub suits
and shoe covers, drapes, wraps and packs, sponges, dressings and
wipes, bed linen, contamination control gowns, examination gowns,
lab coats, isolation gowns, diagnostic medical machinery and
medical devices; personal care products including absorbent hygiene
products (AHP), baby diapers, feminine hygiene products and adult
incontinence products, wipes, skin care products, depilatory
strips; household and furniture products, including wood
composites, decorative foils, floor coverings, flooring, kitchen
ware, cleaners, pet care, lawn and garden articles; toys, sports
and leisure articles including playhouses, building kits, play
vehicles, sports and fitness devices, shoes, clothing and
sportswear, safety equipment (helmets, kneepads), sports equipment,
and suit cases.
[0250] In another embodiment of the present invention, the polymer
composition used for preparing the final application product such
as a fiber and/or filament and/or film and/or thread comprises the
surface treated filler material product in an amount of from 1 to
50 wt.-%, preferably of from 5 to 45 wt.-% and most preferably from
10 to 40 wt.-%, based on the total weight of the polymer
composition. For example, the polymer composition used for
preparing the final application product such as a fiber and/or
filament and/or film comprises the surface treated filler material
product in an amount of from 15 to 25 wt.-%, based on the total
weight of the polymer composition.
[0251] In another embodiment of the present invention, the polymer
composition used for preparing the final application product such
as a fiber and/or filament and/or film and/or thread comprises the
at least one calcium carbonate-containing material in an amount of
from 1 and 10 wt.-%, based on the total weight of the polymer
composition. It is appreciated that the polymer composition
preferably comprises this amount when it is used as packaging
material for acidic food like citrus fruits or containers and/or
bottles for fruit juice.
[0252] If a masterbatch is used to produce fibers and/or filaments
and/or films and/or threads, it is preferred that the masterbatch
is diluted such as to obtain a polymer composition suitable for
preparing the final application product such as a fiber and/or
filament and/or film and/or thread. That is to say, the masterbatch
is diluted such as to comprises the surface treated filler material
product in an amount of from 1 to 50 wt.-%, preferably of from 5 to
45 wt.-% and most preferably from 10 to 40 wt.-%, based on the
total weight of the polymer composition.
[0253] A filter pressure test was performed in order to determine
the filter pressure value FPV of a LLDPE masterbatch as described
above and compared to the FPV a masterbatch comprising a mineral
material of the prior art.
[0254] The filter pressure test as herein described provides for
the Filter Pressure Value, in the present case, of dispersed
mineral material in LLDPE. The Filter Pressure Value FPV is defined
as the increase of pressure per gram filler. This test is performed
to determine the dispersion quality and/or presence of excessively
coarse particles or agglomerates of mineral materials in a
masterbatch. Low Filter Pressure Values refers to a good dispersion
and fine material, wherein high Filter Pressure Values refer to bad
dispersion and coarse or agglomerated material.
[0255] The Filter Pressure test was performed on a commercially
available Collin Pressure Filter Test, Teach-Line FT-E20T-IS,
according to the standard EN 13900-5. Filter type used was 14 .mu.m
and 25 .mu.m, extrusion was carried out at 200.degree. C.
[0256] According to another embodiment of the present invention,
the polymer composition is a fibre and/or filament and/or film
and/or thread. For example, the fiber and/or filament and/or film
and/or thread comprises the surface treated filler material product
in an amount of from 1 to 50 wt.-%, preferably from 5 to 45 wt.-%,
more preferably from 10 to 40 wt.-% and most preferably from 15 to
25 wt.-%, based on the total weight of the fiber and/or filament
and/or film and/or thread.
[0257] The surface treated filler material product according to the
present invention imparts excellent mechanical properties to final
application products such as fibers and/or filaments and/or films
and/or threads. In particular, the surface treated filler material
product imparts excellent mechanical properties to final
application products such as fibers and/or filaments and/or films
and/or threads, when the surface treated filler material product is
provided in form of the polymer composition of the present
invention.
[0258] Thus, the present invention refers in a further aspect to a
fibre and/or filament and/or film and/or threads comprising the
polymer composition as defined above and/or the surface treated
filler material product as defined above.
[0259] Furthermore, the present invention refers in another aspect
to a method for preparing a fibre and/or filament and/or film
and/or thread, the method comprising at least the steps of: [0260]
a) providing the polymer composition as defined above, and [0261]
b) subjecting the polymer composition of step a) to conditions
under which said polymer composition is converted into a fibre
and/or filament and/or film and/or thread.
[0262] Appropriate method conditions for preparing fibres and/or
filaments and/or films and/or threads are commonly known to the
skilled person and/or can be established by routine modifications
based on common general knowledge.
[0263] For example, the polymer composition of the present
invention may advantageously be implemented in a process of mixing
and/or extruding and/or compounding and/or blow moulding for
preparing fibers and/or filaments and/or films and/or threads,
wherein the at least one polymeric resin is preferably a
thermoplastic polymer selected from the group comprising
homopolymers and/or copolymers of polyolefins, polyamides and/or
polyesters.
[0264] The term "fiber" in the meaning of the present invention
refers to a linear structure forming textile fabrics such as
nonwovens which typically consist of fiber webs bonded together by
e.g. mechanical methods. Accordingly, the term "fiber" is
understood to refer to a finite structure.
[0265] The term "thread" in the meaning of the present invention
refers to a linear structure forming textile fabrics such as
nonwovens which typically consist of thread webs bonded together by
e.g. mechanical methods. Accordingly, the term "thread" is
understood to refer to a finite structure. The thread may be
constructed as mono-, bi- or multi-thread. If a bi- or multi-thread
is present, the composition of the single thread may be
substantially the same. That is to say, the compositions of the
single threads comprise substantially the same components, i.e. the
at least one polymeric resin and surface treated filler material
product, in the same amounts. Alternatively, the composition of the
single threads may be different. That is to say, the compositions
of the single threads may comprise the same components, i.e. the at
least one polymeric resin and surface treated filler material
product, in varying amounts or the compositions of the single
threads may comprise different components, i.e. the at least one
polymeric resin and/or surface treated filler material product may
be different, in the same amounts or the composition of the single
threads may comprise different components, i.e. the at least one
polymeric resin and/surface treated filler material product may be
different may be different, in varying amounts.
[0266] The term "filament" in the meaning of the present invention
refers to a structure that differs from fibers by its structure
length. Accordingly, the term "filament" is understood to refer to
endless fibers. It is further appreciated that the filament may be
constructed as mono-, bi- or multi-filament. If a bi- or
multi-filament is present, the composition of the single filaments
may be substantially the same. That is to say, the compositions of
the single filaments comprise substantially the same components,
i.e. the at least one polymeric resin and surface treated filler
material product, in the same amounts. Alternatively, the
composition of the single filaments may be different. That is to
say, the compositions of the single filaments may comprise the same
components, i.e. the at least one polymeric resin and surface
treated filler material product, in varying amounts or the
compositions of the single filaments may comprise different
components, i.e. the at least one polymeric resin and/or surface
treated filler material product may be different, in the same
amounts or the composition of the single filaments may comprise
different components, i.e. the at least one polymeric resin and/or
surface treated filler material product may be different may be
different, in varying amounts.
[0267] The cross-section of the filaments and/or fibers and/or
threads may have a great variety of shapes. It is preferred that
the cross-sectional shape of the filaments and/or fibers and/or
threads may be round, oval or n-gonal, wherein n is.gtoreq.3, e.g.
n is 3. For example, the cross-sectional shape of the filaments
and/or fibers and/or threads is round or trilobal, like round.
Additionally or alternatively, the cross-sectional shape of the
filaments and/or fibers and/or threads is hollow.
[0268] It is appreciated that the filaments and/or fibers and/or
threads may be prepared by all techniques known in the art used for
preparing such filaments and/or fibers and/or threads. For example,
the filaments and/or fibers and/or threads of the present invention
can be prepared by the well known melt-blown process, spunbonded
process or staple fibre production.
[0269] Further to this, said filled PP masterbatches were used by
melt extrusion processes to form fiber and filaments and continuous
filament nonwoven fabrics by means known to the skilled person.
[0270] In accordance with known technology such as the continuous
filament spinning for yarn or staple fiber, and nonwoven processes
such as spunbond production and meltblown production, the fibers
and filaments are formed by extrusion of the molten polymer through
small orifices. In general, the fibers or filaments thus formed are
then drawn or elongated to induce molecular orientation and affect
crystallinity, resulting in a reduction in diameter and an
improvement in physical properties. Spunmelt is a generic term
describing the manufacturing of nonwoven webs (fabrics) directly
from thermoplastic polymers. It encompasses 2 processes (spunlaid
and meltblown) and the combination of both.
[0271] In this process polymer granules are melted and molten
polymer is extruded through in a spinneret assembly which creates a
plurality of continuous polymeric filaments. The filaments are then
quenched and drawn, and collected to form a nonwoven web. Some
remaining temperature can cause filaments to adhere to one another,
but this cannot be regarded as the principal method of bonding.
There are several methods available for forming the collected web
of continuous filaments into a useful product by a bonding step,
which includes, but is not be limited to calendaring,
hydroentangling, needling and/or bonding by means of chemicals or
adhesives.
[0272] The spunlaid process (also known as spunbonded) has the
advantage of giving nonwovens greater strength. Co-extrusion of
second components is used in several spunlaid processes, usually to
provide extra properties or bonding capabilities. In meltblown web
formation, low viscosity polymers are extruded into a high velocity
airstream on leaving the spinneret. This scatters the melt,
solidifies it and breaks it up into a fibrous web.
[0273] It is known to those skilled in the art to combine processes
or the fabrics from different processes to produce composite
fabrics which possess certain desirable characteristics. Examples
of this are combining spunbond and meltblown to produce a laminate
fabric that is best known as SMS, meant to represent two outer
layers of spunbond fabric and an inner layer of meltblown fabric.
Additionally either or both of these processes may be combined in
any arrangement with a staple fiber carding process or bonded
fabrics resulting from a nonwoven staple fiber carding process. In
such described laminate fabrics, the layers are generally at least
partially consolidated by one of the bonding steps listed
above.
[0274] Processes are well known in the art, and are commercially
available, for producing spunbond fabric of polypropylene polymeric
resin. The two typical processes are known as the Lurgi process and
the Reinfenhauser process.
[0275] The Lurgi process is based on the extrusion of molten
polymer through spinneret orifices followed by the newly formed
extruded filaments being quenched with air and drawn by suction
through Venturi tubes. Subsequent to formation, the filaments are
disbursed on a conveyor belt to form a nonwoven web.
[0276] The Reifenhauser process differs from the Lurgi process in
that the quenching area for the filaments is sealed, and the
quenched air stream is accelerated, thus inducing more effective
entrainment of the filaments into the air stream.
[0277] In the above-described systems, nonwoven fabrics are
generally produced using polypropylene resins having a melt flow
index of about 25 to 40 grams/10 minutes. A Lurgi line was used to
produce polypropylene nonwovens. Extruder temperatures are between
230.degree. and 250.degree. C. The four spin beams are equipped
with melt pumps and spinnerets which contain 600 orifices each with
a diameter of 0.8 millimeters. The extruded filaments are formed to
a nonwoven web. The conveyor belt speed was adjusted to 20
meters/minute and hydroentangling was used to bond the nonwoven
web. Hydroentangling, also known as spunlacing, is a process which
employs high pressure water jets to entangle fibers in a loose web
thereby creating a fabric held together by frictional forces
between the said fibers. The final bonded nonwoven web with a width
of 100 cm has a fabric weight of 385 g/m2.
[0278] Samples of the said nonwoven fabrics comprising the CaCO3
according to the present invention and samples of nonwoven fabrics
comprising the prior art CaCO3 are compared hereafter in tables 5
and 6. Different amounts of the filled masterbatches were mixed
with further polypropylene (PP HF420FB, a homo-polypropylene with
MFR 19 g/10 min. (230.degree. C., 2.16 kg, ISO 1133) from Borealis)
and nonwoven fabrics were made from these mixtures.
[0279] The term "film" in the meaning of the present invention
refers to a structure that differs from filaments and/or fibers by
its dimensional structure. Accordingly, the term "film" is
understood to refer to a sheet.
[0280] It is appreciated that the films may be prepared by all
techniques known in the art used for preparing such films. For
example, the films of the present invention can be prepared by the
well known techniques used for preparing stretched/oriented films,
and preferably extrusion coating films, blown films, technical
blown films, monotapes, cast films and the like.
[0281] Accordingly, fibers and/or filaments and/or films and/or
threads according to the present invention are characterized in
that they contain said polymer composition and/or surface treated
filler material product and in that they have improved material
properties such as improved mechanical properties.
[0282] As another advantage, fibers and/or filaments and/or films
and/or threads according to the present invention cause lower
pressure decreases during film extrusion. In addition thereto, the
fibers and/or filaments and/or films and/or threads according to
the present invention further show good mechanical properties such
as tensile modulus, tensile test at yield and at break, elongation
at break and tear resistance.
[0283] In view of the very good results obtained with regard to the
hydrophilicity of the surface treated filler material product
treated with at least one mono-substituted succinic anhydride, as
defined above, a further aspect of the present invention is
directed to the use of the mono-substituted succinic anhydride for
decreasing the hydrophilicity of a calcium carbonate-containing
filler material surface. In particular, the at least one
mono-substituted succinic anhydride as defined above can be used to
decrease the hydrophilicity of the calcium carbonate-containing
filler material surface such that the surface treated filler
material product is suitable for use in fibers and/or filaments
and/or films and/or threads. A still further aspect of the present
invention is directed to the use of the surface treated filler
material product, as defined above, for initiating the crosslinking
reaction in epoxide resins.
[0284] Another aspect of the present invention is directed to an
article comprising the polymer composition as defined above and/or
the surface treated filler material product as defined above and/or
the fibre and/or filament and/or film and/or thread as defined
above. The article is preferably selected from the group comprising
hygiene products, medical and healthcare products, filter products,
geotextile products, agriculture and horticulture products,
clothing, footwear and baggage products, household and industrial
products, packaging products, construction products and the
like.
[0285] Preferably, the hygiene products are selected from the group
comprising absorbent hygiene products such as baby diapers or
nappies, feminine hygiene, adult incontinence products, depilatory
strips, bandages and wound dressings, disposable bath and face
towels, disposable slippers and footwear, top sheets or
coverstocks, consumer face masks, leg cuffs,
acquisition/distribution layers, core wraps, back sheets, stretch
ears, landing zones, dusting layers and fastening systems; and
wipes such as wet wipes, skin care wipes, baby wipes, facial wipes,
cleansing wipes, hand and body wipes, moist towelettes, personal
hygiene wipes, feminine hygiene wipes, antibacterial wipes and
medicated wipes.
[0286] Preferably, the medical and healthcare products are selected
from the group comprising medical products which can be sterilized,
medical packaging, caps like surgical disposable caps, protective
clothing, surgical gowns, surgical masks and face masks, surgical
scrub suits, surgical covers, surgical drapes, wraps, packs,
sponges, dressings, wipes, bed linen, contamination control gowns,
examination gowns, lab coats, isolation gowns, transdermal drug
delivery, shrouds, underpads, procedure packs, heat packs, ostomy
bag liners, fixation tapes, incubator mattress, sterilisation wraps
(CSR wrap), wound care, cold/heat packs, drug delivery systems like
patches.
[0287] Preferably, the filter products are selected from the group
comprising gasoline filters, oil filters, air filters, water
filters, coffee filters, tea bags, pharmaceutical industry filters,
mineral processing filters, liquid cartridge and bag filters,
vacuum bags, allergen membranes and laminates with nonwoven
layers.
[0288] Preferably, the geotextile products are selected from the
group comprising soil stabilizers and roadway underlayment,
foundation stabilizers, erosion control, canals construction,
drainage systems, geomembrane protection, frost protection,
agriculture mulch, pond and canal water barriers, said infiltration
barrier for drainage tile and landfill liners.
[0289] Preferably, the agriculture and horticulture products are
selected from the group comprising crop covers, plant protection,
seed blankets, weed control fabrics, greenhouse shading, root
control bags, biodegradable plant pots, capillary matting, and
landscape fabric.
[0290] Preferably, the clothing, footwear and baggage products are
selected from the group comprising interlinings like fronts of
overcoats, collars, facings, waistbands, lapels etc., disposable
underwear, shoe components like shoelace eyelet reinforcement,
athletic shoe and sandal reinforcement and inner sole lining etc.,
bag components, bonding agents, composition and (wash) care
labels.
[0291] Preferably, the packaging products are selected from the
group comprising interlinings like desiccant packaging, sorbents
packaging, gift boxes, file boxes, nonwoven bags, book covers,
mailing envelopes. Express envelopes, courier bags and the
like.
[0292] Preferably, the household and industrial products are
selected from the group comprising abrasives, bed linen like pocket
cloth for pocket springs, separation layer, spring cover, top
cover, quilt backing, duvet coverings, pillow cases etc.
blinds/curtains, carpet/carpet backings like scatter rugs, carpet
tiles, bath mats etc., covering and separation material, detergent
pouches, fabric softener sheets, flooring, furniture/upholstery
like inside lining, reverse fabric for cushions, dust cover, spring
covering, pull strips etc., mops, table linen, tea and coffee bags,
vacuum cleaning bags, wall-covering, wipes like household care
wipes, floor care wipes, cleaning wipes, pet care wipes etc.,
automotive building, cable wrapping, civil engineering, filtration
packaging, protection clothing, primary and secondary carpet
backing, composites, marine sail laminates, tablecover laminates,
chopped strand mats, backing/stabilizer for machine embroidery,
packaging where porosity is needed, insulation like fiberglass
batting, pillows, cushions, padding like upholstery padding,
batting in quilts or comforters, consumer and medical face masks,
mailing envelopes, tarps, tenting and transportation (lumber,
steel) wrapping, disposable clothing like foot coverings and
coveralls, and weather resistant house wraps.
[0293] Preferably, the construction products are selected from the
group comprising house wrap, asphalt overlap, road and railroad
beds, golf and tennis courts, wallcovering backings, acoustical
wall coverings, roofing materials and tile underlayment, soil
stabilizers and roadway underlayment, foundation stabilizers,
erosion control, canals construction, drainage systems, geomembrane
protection, frost protection, agriculture mulch, pond and canal
water barriers, and sand infiltration barriers for drainage
tile.
[0294] The following examples may additionally illustrate the
invention but are not meant to restrict the invention to the
exemplified embodiments. The examples below show the reduced total
volatiles, the reduced moisture pick up susceptibility and the
decreased hydrophilicity of the surface treated filler material
product and the good mechanical properties of the fiber and/or
filament and/or film and/or thread prepared from the polymer
composition according to the present invention.
EXAMPLES
Measurement Methods
[0295] The following measurement methods are used to evaluate the
parameters given in the examples and claims.
Measurement of the Total Volatiles
[0296] For the purpose of the present application, the "total
volatiles" associated with mineral fillers and evolved over a
temperature range of 25 to 350.degree. C. is characterized
according to % mass loss of the mineral filler sample over a
temperature range as read on a thermogravimetric (TGA) curve.
[0297] TGA analytical methods provide information regarding losses
of mass and volatile onset temperatures with great accuracy, and is
common knowledge; it is, for example, described in "Principles of
Instrumental analysis", fifth edition, Skoog, Holler, Nieman, 1998
(first edition 1992) in Chapter 31 pages 798 to 800, and in many
other commonly known reference works. In the present invention,
thermogravimetric analysis (TGA) is performed using a Mettler
Toledo TGA 851 based on a sample of 500+/-50 mg and scanning
temperatures from 25 to 350.degree. C. at a rate of 20.degree.
C./minute under an air flow of 70 ml/min.
[0298] The skilled man will be able to determine the "volatile
onset temperature" by analysis of the TGA curve as follows: the
first derivative of the TGA curve is obtained and the inflection
points thereon between 150 and 350.degree. C. are identified. Of
the inflection points having a tangential slope value of greater
than 45.degree. relative to a horizontal line, the one having the
lowest associated temperature above 200.degree. C. is identified.
The temperature value associated with this lowest temperature
inflection point of the first derivative curve is the "volatile
onset temperature".
[0299] The "total volatiles" evolved on the TGA curve is determined
using Star.sup.e SW 9.01 software. Using this software, the curve
is first normalised relative to the original sample weight in order
to obtain mass losses in % values relative to the original sample.
Thereafter, the temperature range of 25 to 350.degree. C. is
selected and the step horizontal (in German: "Stufe horizontal")
option selected in order to obtain the % mass loss over the
selected temperature range.
Particle Size Distribution (Mass % Particles with a Diameter<X)
and Weight Median Diameter (d.sub.50) of a Particulate Material
[0300] As used herein and as generally defined in the art, the
"d.sub.50" value is determined based on measurements made by using
a Sedigraph.TM. 5100 of Micromeritics Instrument Corporation and is
defined as the size at which 50% (the median point) of the particle
volume or mass is accounted for by particles having a diameter
equal to the specified value.
[0301] The method and the instrument are known to the skilled
person and are commonly used to determine grain size of fillers and
pigments. The measurement is carried out in an aqueous solution of
0.1 wt.-% Na.sub.4P.sub.2O.sub.2. The samples are dispersed using a
high speed stirrer and supersonics.
BET Specific Surface Area of a Material
[0302] Throughout the present document, the specific surface area
(in m.sup.2/g) of the mineral filler is determined using the BET
method (using nitrogen as absorbing gas), which is well known to
the skilled man (ISO 9277:1995). The total surface area (in
m.sup.2) of the mineral filler is then obtained by multiplication
of the specific surface area and the mass (in g) of the mineral
filler prior to treatment.
Moisture Pick-Up
[0303] The term "moisture pick-up susceptibility" in the meaning of
the present invention refers to the amount of moisture absorbed on
the surface of the mineral filler and is determined in mg
moisture/g of the dry treated mineral filler product after exposure
to an atmosphere of 10 and 85% of relative humidity, resp., for 2.5
hours at a temperature of +23.degree. C. (.+-.2.degree. C.). The
treated mineral filler product is first held at an atmosphere of
10% of relative humidity for 2.5 hours, then the atmosphere is
changed to 85% of relative humidity, where the sample is held for
another 2.5 hours. The weight increase between 10% and 85% relative
humidity is then used to calculate the moisture pick-up in mg
moisture/g of dry treated mineral filler product.
Hydrophilicity
[0304] The "hydrophilicity" of a mineral filler product is
evaluated at +23.degree. C. by determining the minimum water to
ethanol ratio in a volume/volume based water/ethanol-mixture needed
for the settling of the majority of said mineral filler product,
where said mineral filler product is deposited on the surface of
said water/ethanol-mixture by passage through a house hold tea
sieve. The volume/volume base is related to the volumes of both
separate liquids before blending them together and do not include
the volume contraction of the blend. The evaluation at +23.degree.
C. refers to a temperature of +23.degree. C..+-.1.degree. C.
[0305] A 8:2 volumetric ratio of a water/ethanol-mixture has
typically a surface tension of 41 mN/m and a 6:4 volumetric ratio
of a water/ethanol-mixture has typically a surface tension of 26
mN/m measured at +23.degree. C. as described in the "Handbook of
Chemistry and Physics", 84.sup.th edition, David R. Lid, 2003
(first edition 1913).
Dart Drop Test
[0306] The dart drop test is measured according to ASTM D
1709/A.
Residual Total Moisture Content Measurement of Calcium
Carbonate-Containing Material
[0307] The residual total moisture content of the filler is
measured according to the Karl Fischer coulometric titration
method, desorbing the moisture in an oven at 220.degree. C. and
passing it continuously into the KF coulometer (Mettler Toledo
coulometric KF Titrator C30, combined with Mettler oven DO 0337)
using dry N.sub.2 at 100 ml/min for 10 min. A calibration curve
using water has to be made and a blind of 10 min gas flow without a
sample has to be taken in account.
Measurements Done on Filament Samples
[0308] Titer or Linear Density [dtex] may be measured according to
EN ISO 2062 and corresponds to the weight in grams of 10'000 m
yarn. A sample of 25 or 100 meters is wound up on a standard reel
under a pretension of 0.5 cN/tex and weighted on an analytical
scale. The grams per 10'000 m yarn length are then calculated.
[0309] Tenacity is calculated from the breaking force and the
linear density, and expressed in centinewton per tex [cN/tex]. the
test is carried out on a dynamometer with a constant stretching
speed, applicable standards for this test are EN ISO 5079 and ASTM
D 3822.
[0310] Breaking force and elongation at break: The breaking force
is the force needed to be applied on a yarn to make it break. It is
expressed in Newton [N]. The elongation at break is the increase of
the length produced by stretching a yarn to its breaking point. It
is expressed as a percentage [%] of its initial length.
[0311] Tensile index is the product of tenancy [cN/tex] and the
square root of the elongation at break [%].
Measurements Done on Nonwoven Samples
[0312] Fabric weight or mass per unit are [g/m.sup.2] is measured
according to EN ISO 9864.
[0313] Tensile properties of geotextiles are measured according to
EN ISO 10319 using a wide-width strip with 200 mm width and 100 mm
length on a tensile testing machine.
[0314] Tensile strength [kN/m] and the elongation at maximum load
[%] are measured in machine direction (MD) and in cross machine
direction (CD). The energy value according to EN ISO 10319 is
calculated by the tensile strength (MD+CD)/2.
[0315] Static puncture resistance (CBR test) in [kN] is measured
according to EN ISO 12236. This method specifies the determination
of the puncture resistance by measuring the force required to push
a flat-ended plunger through geosynthetics.
[0316] Ash content in [%] of the fibers and the masterbatches is
determined by incineration of a sample in an incineration crucible
which is put into an incineration furnace at 570.degree. C. for 2
hours. The ash content is measured as the total amount of remaining
inorganic residues.
Example 1
[0317] This example relates to the preparation of a surface treated
filler material product in accordance with the process of the
present invention.
[0318] For the preparation of the surface treated filler material
product, lime stone from Omey, France was wet ground at 25 wt.-% in
tap water in a horizontal ball mill (Dynomill) and spray dried. The
obtained calcium carbonate-containing filler material features a
d.sub.50 of approximately 1.7 microns, a top cut (d.sub.98) of 5
.mu.m and a specific surfaced area of 4.1 m.sup.2/g and a residual
moisture content of 0.06 wt.-%.
[0319] The obtained spray dried calcium carbonate-containing filler
material was further treated as outlined in the following
tests:
Test 1 (Prior Art; PA1)
[0320] 500 g of the spray dried calcium carbonate-containing filler
material was added to an MTI Mixer and the sample was activated for
5 minutes at 180.degree. C. and 3000 rpm. Thereafter
polystyren-co-maleic anhydride having a Mn of 1600 (Aldrich number
442380) was introduced to the mixer in a quantity such as indicated
in Table 1. The contents of the mixer were mixed at 180.degree. C.
under a stirring speed of 3000 rpm for a period of 5 minutes.
[0321] The obtained surface treated filler material product was
stored in a closed plastic bag. For analysis purposes the sample
was taken out of the closed plastic bag and analyzed immediately.
The results are presented in table 2.
Test 2 (Prior Art; PA2)
[0322] 500 g of the spray dried calcium carbonate-containing filler
material was added to an MTI Mixer and the sample was activated for
5 minutes at 80.degree. C. and 3000 rpm. Thereafter,
1,2-cyclohexanedicarboxylic anhydride (Aldrich number 123463) was
introduced to the mixer in a quantity such as indicated in Table 1.
The contents of the mixer were mixed at 80.degree. C. under a
stirring speed of 3000 rpm for a period of 5 minutes.
[0323] The obtained surface treated filler material product was
stored in a closed plastic bag. For analysis purposes the sample
was taken out of the closed plastic bag and analyzed immediately.
The results are presented in table 2.
Test 3 (Prior Art; PA3)
[0324] 500 g of the spray dried calcium carbonate-containing filler
material was added to an MTI Mixer and the sample was activated for
5 minutes at 80.degree. C. and 3000 rpm. Thereafter, phenyl
succinic anhydride (Aldrich number 416622) was introduced to the
mixer in a quantity such as indicated in Table 1. The contents of
the mixer were mixed at 80.degree. C. under a stirring speed of
3000 rpm for a period of 5 minutes.
[0325] The obtained surface treated filler material product was
stored in a closed plastic bag. For analysis purposes the sample
was taken out of the closed plastic bag and analyzed immediately.
The results are presented in table 2.
Test 4 (Invention; IE4)
[0326] 500 g of the spray dried calcium carbonate-containing filler
material was added to an MTI Mixer and the sample was activated for
10 minutes at 120.degree. C. and 3000 rpm. Thereafter,
n-octadecenyl succinic anhydride having a purity of.gtoreq.96.5%
was introduced to the mixer in a quantity such as indicated in
Table 1. The contents of the mixer were mixed at 120.degree. C.
under a stirring speed of 3000 rpm for a period of 10 minutes.
[0327] The obtained surface treated filler material product was
stored in a closed plastic bag. For analysis purposes the sample
was taken out of the closed plastic bag and analyzed immediately.
The results are presented in table 2.
Test 5 (Invention; IE5)
[0328] 500 g of the spray dried calcium carbonate-containing filler
material was added to an MTI Mixer and the sample was activated for
10 minutes at 120.degree. C. and 3000 rpm. Thereafter, a mixture of
branched hexadecenyl succinic anhydrides (CAS #32072-96-1) and
branched octadecenyl succinic anhydrides (CAS #28777-98-2)
comprising an amount of branched octadecenyl succinic anhydrides of
about 40 wt.-%, based on the total weight of the succinic anhydride
mixture was introduced to the mixer in a quantity such as indicated
in Table 1. The contents of the mixer were mixed at 120.degree. C.
under a stirring speed of 3000 rpm for a period of 10 minutes.
[0329] The obtained surface treated filler material product was
stored in a closed plastic bag. For analysis purposes the sample
was taken out of the closed plastic bag and analyzed immediately.
The results are presented in table 2.
Test 6 (Invention; IE6)
[0330] 500 g of the spray dried calcium carbonate-containing filler
material was added to an MTI Mixer and the sample was activated for
10 minutes at 120.degree. C. and 3000 rpm. Thereafter,
n-butylsuccinic anhydride (TCI Europe N.V. product number B2742)
was introduced to the mixer in a quantity such as indicated in
Table 1. The contents of the mixer were mixed at 120.degree. C.
under a stirring speed of 3000 rpm for a period of 10 minutes
followed by the addition of 500 ppm of polydimethylsiloxane (Dow
Corning 200 Fluid 1000 CS) and mixing at 3000 rpm for 5 minutes at
120.degree. C.
[0331] The obtained surface treated filler material product was
stored in a closed plastic bag. For analysis purposes the sample
was taken out of the closed plastic bag and analyzed immediately.
The results are presented in table 2.
Test 7 (Invention; IE7)
[0332] 500 g of the spray dried calcium carbonate-containing filler
material was added to an MTI Mixer and the sample was activated for
30 minutes at 120.degree. C. and 3000 rpm. Thereafter,
n-octenylsuccinic anhydride (cis and trans mixture; TCI Europe N.V.
product number O0040) was introduced to the mixer in a quantity
such as indicated in Table 1. The contents of the mixer were mixed
at 120.degree. C. under a stirring speed of 3000 rpm for a period
of 20 minutes followed by the addition of 500 ppm of
polydimethylsiloxane (Dow Corning 200 Fluid 1000 CS) and mixing at
3000 rpm for 5 minutes at 120.degree. C.
[0333] The obtained surface treated filler material product was
stored in a closed plastic bag. For analysis purposes the sample
was taken out of the closed plastic bag and analyzed immediately.
The results are presented in table 2.
Test 8 (Invention; IE8)
[0334] 500 g of the spray dried calcium carbonate-containing filler
material was added to an MTI Mixer and the sample was activated for
10 minutes at 120.degree. C. and 3000 rpm. Thereafter, a mixture of
branched hexadecenyl succinic anhydrides (CAS #32072-96-1) and
branched octadecenyl succinic anhydrides (CAS #28777-98-2)
comprising an amount of branched octadecenyl succinic anhydrides of
about 40 wt.-%, was introduced to the mixer in a quantity such as
indicated in Table 1. The contents of the mixer were mixed at
120.degree. C. under a stirring speed of 3000 rpm for a period of
10 minutes followed by the addition of 500 ppm of
polydimethylsiloxane (Dow Corning 200 Fluid 1000 CS) and mixing at
3000 rpm for 5 minutes at 120.degree. C.
[0335] The obtained surface treated filler material product was
stored in a closed plastic bag. For analysis purposes the sample
was taken out of the closed plastic bag and analyzed immediately.
The results are presented in table 2.
TABLE-US-00001 TABLE 1 PA PA PA IE IE IE IE IE Test 1 2 3 4 5 6 7 8
treatment level 1.0 1.0 1.0 0.5 0.6 0.6* 0.6* 0.6* [wt.-%]
preheating 5/ 5/ 5/ 10/ 10/ 10/ 30/ 5/ Time/ 180 80 80 120 120 120
120 120 temperature ([min]/[.degree. C.]) treatment 5/ 5/ 5/ 10/
10/ 10/ 20/ 10/ time/ 180 80 80 120 120 120# 120# 180# temperature
([min]/[.degree. C.]) *comprises an additional treatment level of
0.05 wt.-% of siloxane, based on the total weight of calcium
carbonate-containing filler material. #comprises an additional
treatment step with siloxane for 5 min at 120.degree. C.
[0336] The results for the analysis of the surface treated filler
material product as described above are outlined in table 2.
TABLE-US-00002 TABLE 2 PA PA PA IE IE IE IE IE Test 1 2 3 4 5 6 7 8
Moisture pick-up -- -- -- 0.31 0.33 0.21 0.29 0.27 [mg/g] OST
[.degree. C.] -- -- -- 278 283 335 -- -- Hydrophilicity [vol/ 100
100 100 60 60 60 70 50 vol-%]
[0337] From the data given in Table 2, it can be gathered that the
surface treated filler material product prepared in accordance with
the present invention shows excellent properties. In particular, it
is shown that the surface treated filler material product prepared
in accordance with the present invention has a moisture pick up
susceptibility of less than 0.8 mg/g, a volatile onset temperature
of.gtoreq.250.degree. C., and a hydrophilicity of below 8:2
volumetric ratio of water:ethanol.
Example 2
[0338] This example relates to the preparation of a blown film
comprising the surface treated filler material product prepared in
accordance with the present invention and at least one polymeric
resin.
[0339] The details regarding the blown film polymer compositions,
based on the total weight of the obtained film, are described in
Table 3.
TABLE-US-00003 TABLE 3 Formulation [g/cm.sup.3] F0 F1 F2 F3 Polymer
resin 0.924 100 40 40 40 Treated carbonate A 2.7 60 IE4 2.7 60 IE5
2.7 60
[0340] The polymer compositions used for preparing the blown film
were afterward diluted to 20 wt.-% calcium carbonate-containing
material, based on the total weight of the obtained film.
[0341] Treated carbonate A is a stearic acid treated dry ground
calcium carbonate (marble from Italy) with a medium diameter
(d.sub.50) of 1.7 .mu.m and a top cut (d.sub.98) of 6.8 .mu.m, 57
wt.-% of the particles have a diameter of below 2 .mu.m. This
treated filler material is used as an internal reference.
[0342] Polymer resin relates to a linear low density polyethylene
resin (LLDPE) which is commercially available as Dowlex NG 5056G
from Down Chemical Company, Dow Europe GmbH, Horgen,
Switzerland.
[0343] Polymer composition F0 contains only the pure polymer resin,
no surface treated filler material product is included.
[0344] The blown film was prepared on a Collin blown film line with
a film grammage of 37.5 g/m.sup.2 and a film thickness of 40
.mu.m.
[0345] The fiber and/or filament and/or film and/or thread
comprising the inventive surface treated filler material product
prepared in accordance with the present invention show excellent
mechanical properties such as shown in FIG. 1.
[0346] FIG. 1 demonstrates clearly that fibers and/or filaments
and/or films and/or threads comprising the inventive surface
treated filler material product prepared in accordance with the
present invention show increased values in dart drop. In
particular, it is shown that the values determined for the dart
drop of the fibers and/or filaments and/or films and/or threads
comprising the inventive surface treated filler material product
prepared in accordance with the present invention are significantly
higher than the values determined for the sample consisting only of
the polymeric resin as well as for the reference sample.
[0347] It is further appreciated that the polymer composition
comprising the inventive surface treated filler material product
prepared in accordance with the present invention and which is used
for preparing the fiber and/or filament and/or film and/or thread
also shows an excellent filter pressure value (FPV) as can be
gathered from Table 4.
TABLE-US-00004 TABLE 4 Sample FPV, 16 g GCC, 14 .mu.m screen
[bar/g] F1 1.8 F2 0.7 F3 0.8
Example 3
[0348] This example relates to the preparation of a nonwoven fabric
comprising the surface treated filler material product prepared in
accordance with the present invention and at least one polymeric
resin.
[0349] Samples of the said nonwoven fabrics comprising the
CaCO.sub.3 according to the present invention and samples of
nonwoven fabrics comprising the prior art CaCO.sub.3 are compared
hereafter in tables 5 and 6. Different amounts of the filled
masterbatches were mixed with further polypropylene (PP HF420FB, a
homo-polypropylene with MFR 19 g/10 min. (230.degree. C., 2.16 kg,
ISO 1133) from Borealis) and nonwoven fabrics were made from these
mixtures.
TABLE-US-00005 TABLE 5 Formulation Norm Unit 1 2 3 4 Polypropylene
HF420FB 100 96 96 96 70% MB Invention 1 4 70% MB Invention 2 4 70%
MB Prior Art 1 4 Tests On Filaments Linear density dtex 9.3 10.1
9.3 9.7 Tenacity cN/dtex 2.26 2.08 2.03 2.09 Elongation % 252 251
239 229 Tensile index -- 359 330 314 316 On Nonwoven Fabric weight
EN ISO 9864 g/m.sup.2 372 388 367 387 Coefficient CBR EN ISO 12236
N/g 7.5 5.9 6.7 7.1 CBR EN ISO 12236 N 2766 2271 2449 2741 Tensile
Strength (MD + CD)/2 EN ISO 12319 N/g 10.6 9.5 10.2 9.3 Ash content
% 0 2.4 2.5 3.0 .sup.1MD refers to machine direction, .sup.2CD
refers to cross direction.
TABLE-US-00006 TABLE 6 Formulation Norm Unit 1 2 3 4 Polypropylene
HF420FB 100 90 90 90 70% MB Invention 1 10 70% MB Invention 2 10
70% MB Prior Art 1 10 Tests On Filaments Linear density dtex 9.3
10.4 10.0 10.0 Tenacity cN/dtex 2.26 1.97 1.99 1.87 Elongation %
252 244 239 226 Tensile index -- 359 308 308 281 On Nonwoven Fabric
weight EN ISO 9864 g/m.sup.2 372 405 385 401 Coefficient CBR EN ISO
12236 N/g 7.5 6.2 5.6 6.2 CBR EN ISO 12236 N 2766 2522 2142 2479
Tensile Strength (MD + CD)/2 EN ISO 12319 N/g 10.6 8.3 8.3 7.6 Ash
content % 0 5.9 5.9 7.0 .sup.1MD refers to machine direction,
.sup.2CD refers to cross direction
[0350] 70% MB Invention 1 refers to 70 wt % of a masterbatch of 28
wt % PP HH450 FB homo-polypropylene with MFR 37 g/10 min.
(230.degree. C., 2.16 kg, ISO 1133) from Borealis and 2 wt %
Irgastab FS 301, processing and thermal stabilizer from BASF and 70
wt % of CaCO.sub.3 according to the present invention, wherein the
treated CaCO.sub.3 has a median particles size diameter d50 of 1.7
.mu.m, a top cut of d98 of 6 .mu.m.
[0351] Treatment of the CaCO.sub.3: 0.5% of Hydrores AS 1000
(KEMIRA; CAS number 68784-12-3): 500 g of the spray dried calcium
carbonate-containing filler material was added to an MTI Mixer and
the sample was activated for 10 minutes at 120.degree. C. and 3000
rpm. Thereafter, Hydrores AS 1000 (Kemira) was introduced to the
mixer in a quantity of 0.5 wt %. The contents of the mixer were
mixed at 120.degree. C. under a stirring speed of 3000 rpm for a
period of 10 minutes.
[0352] The obtained surface treated filler material product was
stored in a closed plastic bag. For analysis purposes the sample
was taken out of the closed plastic bag and analyzed immediately. T
onset: 289.degree. C.; Water-pick-up: 0.7 mg/g
[0353] 70% MG Invention 2 refers to 70 wt % of a masterbatch of 28
wt % PP HH450 FB homo-polypropylene with MFR 37 g/10 min.
(230.degree. C., 2.16 kg, ISO 1133) from Borealis and 2 wt %
Irgastab FS 301, processing and thermal stabilizer from BASF and 70
wt % of CaCO.sub.3 according to the present invention, wherein the
treated CaCO.sub.3 has a median particles size diameter d50 of 1.7
.mu.m, a top cut of d98 of 6 .mu.m.
[0354] Treatment of the CaCO.sub.3: 0.6 wt % Hydrores AS 1100
(KEMIRA, CAS number 68784-12-3):
[0355] 500 g of the spray dried calcium carbonate-containing filler
material was added to an MTI Mixer and the sample was activated for
10 minutes at 120.degree. C. and 3000 rpm. Thereafter, Hydrores AS
1100 (Kemira) was introduced to the mixer in a quantity a quantity
of 0.6 wt %. The contents of the mixer were mixed at 120.degree. C.
under a stirring speed of 3000 rpm for a period of 10 minutes.
[0356] The obtained surface treated filler material product was
stored in a closed plastic bag. For analysis purposes the sample
was taken out of the closed plastic bag and analyzed immediately. T
onset: 300.degree. C.; Water-pick-up: 0.8 mg/g
[0357] 70% of MA PA1 refers to 70 wt % of a masterbatch of 28 wt %
PP HH450 FB homo-polypropylene with MFR 37 g/10 min. (230.degree.
C., 2.16 kg, ISO 1133) from Borealis and 2 wt % Irgastab FS 301,
processing and thermal stabilizer from BASF and 70 wt % of a wet
ground surface treated CaCO.sub.3 of the prior art, and the
CaCO.sub.3 has a median particle size diameter d50 of 1.7 .mu.m and
a top cut of d98 of 6 .mu.m.
[0358] As can be seen from the inventive examples 2 and 3 from
tables 5 and 6, samples of polypropylene nonwoven fabrics comprises
the CaCO.sub.3 according to the present invention and as seen in
example 4 from tables 5 and 6, samples of nonwoven fabrics
comprising the prior art CaCO.sub.3 can be produced in good quality
with slightly reduced mechanical properties compared to Example 1
being the unfilled polypropylene PP HF420FB.
[0359] It lies within the scope of the present invention that the
polypropylenes mentioned are not the only one and that other PP
polymers or PE polymers or a mix of PP and PE polymers are suitable
as well to be used for producing a masterbatch comprising the
CaCO.sub.3 of the present invention.
Example 4
[0360] This example relates to the preparation of multifilament
fibers comprising the surface treated filler material product
prepared in accordance with the present invention and at least one
polymeric resin.
[0361] Samples of the said multifilament fibers comprising the
CaCO.sub.3 according to the present invention and samples of
multifilament fibers comprising the prior art CaCO.sub.3 are
summarized hereafter in table 8 to 14. Different amounts of the
filled masterbatches were mixed with further polypropylene (Moplen
HP 561R, a homo-polypropylene with MFR 25 g/10 min. (230.degree.
C., 2.16 kg, ISO 1133) from LyondellBasell) and multifilament
fibers were made from these mixtures using a Collin Multifilament
Lab Line CMF 100 (produced by Dr. Collin GmbH, Ebersberg, Germany),
equipped with a single screw extruder with melt pump, spinneret
diameter 50 mm with 34 filaments O0.3 mm, Drawing conditions are
summarized in table 7. Limanol BF29 (from Schill+Seilacher GmbH,
Boblingen, Germany) is used as spinning oil.
TABLE-US-00007 TABLE 7 Drawing temperatures: Condition 1 Condition
2 Condition 3 Roll 1 80.degree. C. 100.degree. C. 110.degree. C.
Roll 2 85.degree. C. 105.degree. C. 115.degree. C. Roll 3
90.degree. C. 105.degree. C. 115.degree. C. Roll 4 90.degree. C.
110.degree. C. 120.degree. C.
TABLE-US-00008 TABLE 8 Inventive masterbatch Draw Elongation Linear
Ash temp. Draw Tenacity at max. density content Example Masterbatch
condition ratio [cN/dtex] load [%] [dtex] [%] 1 2% MB Inv. 3 1 2
1.23 223 754 1.3 2 5% MB Inv. 3 1 2 1.01 221 796 10.8 3 10% MB Inv.
3 1 2 1.14 171 742 9.7 4 15% MB Inv. 3 1 2 1.05 202 848 14.2 5 20%
MB Inv. 3 1 2 0.76 215 904 23.1 6 25% MB Inv. 3 1 2 0.73 180 962
28.0 7 30% MB Inv. 3 1 2 0.57 218 1012 30.6 8 40% MB Inv. 3 1 2
0.53 201 1042 38.9 9 10% MB Inv. 3 1 3 1.51 134 554 8.1 10 10% MB
Inv. 3 1 4 1.94 81 434 9.5 11 10% MB Inv. 3 1 5 2.35 38 355 10.9 12
10% MB Inv. 3 1 6 2.82 15 310 10.7 13 15% MB Inv. 3 1 3 0.89 99 578
17.0 14 15% MB Inv. 3 1 4 1.33 94 425 17.0 15 15% MB Inv. 3 1 5
1.74 76 350 16.5 16 15% MB Inv. 3 1 6 1.79 60 309 17.1 17 20% MB
Inv. 3 1 3 0.84 105 610 22.9 18 20% MB Inv. 3 1 4 1.09 111 449 19.8
19 20% MB Inv. 3 1 5 1.34 93 350 21.6 20 20% MB Inv. 3 1 6 1.78 58
293 19.4
TABLE-US-00009 TABLE 9 Inventive masterbatch Draw Elongation Linear
Ash temp. Draw Tenacity at max. density content Example Masterbatch
condition ratio [cN/dtex] load [%] [dtex] [%] 21 10% MB Inv. 3 2 2
0.54 219 792 9.7 22 10% MB Inv. 3 2 3 0.89 183 519 10.2 23 10% MB
Inv. 3 2 4 1.25 107 426 11.3 24 10% MB Inv. 3 2 5 1.71 77 350 12.7
25 15% MB Inv. 3 2 2 0.5 207 822 16.6 26 15% MB Inv. 3 2 3 0.79 152
560 18.2 27 15% MB Inv. 3 2 4 1.35 73 428 17.2 28 15% MB Inv. 3 2 5
1.9 74 359 16.1 29 20% MB Inv. 3 2 2 0.51 217 868 20.9 30 20% MB
Inv. 3 2 3 0.89 193 561 21.1 31 20% MB Inv. 3 2 4 1.17 112 451 22.8
32 20% MB Inv. 3 2 5 1.4 84 362 17.8
TABLE-US-00010 TABLE 10 Inventive masterbatch Draw Elongation
Linear Ash temp. Draw Tenacity at max. density content Example
Masterbatch condition ratio [cN/dtex] load [%] [dtex] [%] 33 10% MB
Inv. 3 3 2 0.91 196 678 10.5 34 10% MB Inv. 3 3 3 1.17 126 499 10.3
35 10% MB Inv. 3 3 4 1.2 104 390 9.5 36 10% MB Inv. 3 3 5 1.92 66
335 8.3 37 15% MB Inv. 3 3 2 0.89 170 679 12.0 38 15% MB Inv. 3 3 3
1.08 146 499 14.3 39 15% MB Inv. 3 3 4 1.73 97 402 15.5 40 15% MB
Inv. 3 3 5 1.82 19 362 16.0 41 20% MB Inv. 3 3 2 0.72 183 846 21.2
42 20% MB Inv. 3 3 3 1.11 117 572 21.1 43 20% MB Inv. 3 3 4 1.34 71
427 20.5 44 20% MB Inv. 3 3 5 1.66 66 348 19.2
TABLE-US-00011 TABLE 11 Prior art masterbatch Draw Elongation
Linear Ash temp. Draw Tenacity at max. density content Example
Masterbatch condition ratio [cN/dtex] load [%] [dtex] [%] 45 2% MB
PA2 1 2 1.36 223 736 1.8 46 5% MB PA2 1 2 0.95 222 774 4.6 47 10%
MB PA2 1 2 0.94 169 623 12.1 48 20% MB PA2 1 2 0.78 205 555 21.2 49
10% MB PA2 1 3 1.61 144 533 4.9 50 10% MB PA2 1 4 2.09 70 386 2.4
51 10% MB PA2 1 5 2.56 59 338 8.9 52 10% MB PA2 1 6 2.97 14 287
10.3 53 15% MB PA2 1 3 1.83 124 597 17.0 54 15% MB PA2 1 4 1.88 73
458 17.0 55 15% MB PA2 1 5 2.35 38 366 14.3 56 15% MB PA2 1 6 3.17
16 306 14.3 57 20% MB PA2 1 3 1.29 116 606 20.1 58 20% MB PA2 1 4
1.51 63 465 20.7 59 20% MB PA2 1 5 2.11 32 378 19.2 60 20% MB PA2 1
6 2.36 13 339 22.5
TABLE-US-00012 TABLE 12 Prior art masterbatch Draw Elongation
Linear Ash temp. Draw Tenacity at max. density content Example
Masterbatch condition ratio [cN/dtex] load [%] [dtex] [%] 61 10% MB
PA2 2 2 0.48 219 820 10.1 62 10% MB PA2 2 3 1.36 109 539 10.8 63
10% MB PA2 2 4 1.69 83 414 8.7 64 10% MB PA2 2 5 2.11 77 319 8.7 65
15% MB PA2 2 2 0.55 219 861 19.9 66 15% MB PA2 2 3 0.71 89 587 17.6
67 15% MB PA2 2 4 1.66 95 424 15.9 68 15% MB PA2 2 5 1.74 77 351
14.6 69 20% MB PA2 2 2 0.68 214 870 18.8 70 20% MB PA2 2 3 0.9 89
588 15.8 71 20% MB PA2 2 4 1.51 69 432 16.2 72 20% MB PA2 2 5 1.72
47 354 15.6
TABLE-US-00013 TABLE 13 Prior art masterbatch Draw Elongation
Linear Ash temp. Draw Tenacity at max. density content Example
Masterbatch condition ratio [cN/dtex] load [%] [dtex] [%] 73 10% MB
PA2 3 2 0.74 206 786 9.8 74 10% MB PA2 3 3 1.46 72 529 7.7 75 10%
MB PA2 3 4 1.96 85 406 6.7 76 10% MB PA2 3 5 2.2 17 326 8.5 77 15%
MB PA2 3 2 0.63 197 819 13.6 78 15% MB PA2 3 3 0.99 145 550 11.2 79
15% MB PA2 3 4 1.42 63 438 12.2 80 15% MB PA2 3 5 2.27 18 340 12.1
81 20% MB PA2 3 2 0.54 147 898 24.2 82 20% MB PA2 3 3 0.99 100 598
19.8 83 20% MB PA2 3 4 1.36 74 459 18.6 84 20% MB PA2 3 5 2.11 15
361 16.8
TABLE-US-00014 TABLE 14 neat polymer without masterbatch Draw
Elongation Linear Ash temp. Draw Tenacity at max. density content
Example Masterbatch condition ratio [cN/dtex] load [%] [dtex] [%]
85 None 1 2 1.34 210 732 0 86 None 1 3 1.99 151 530 0 87 None 1 4
2.56 92 409 0 88 None 1 5 2.66 49 356 0 89 None 1 6 3.57 15 286 0
90 None 1 7 4.03 15 234 0
[0362] 70% MG Invention 3 refers to 70 wt % of a masterbatch
produced on industrial scale wherein the treated CaCO.sub.3 has a
median particles size diameter d50 of 1.7 .mu.m, a top cut of d98
of 6 .mu.m. Treatment of the CaCO.sub.3: 0.5 wt % of Hydrores AS
1000 (KEMIRA; CAS number 68784-12-3). The precise filler content of
the masterbatch was determined by the ash content: 72.2 wt % and
the melt flow rate (MFR, 230.degree. C., 2.16 kg, ISO 1133) of the
masterbatch is 9.13 g/10 min.
[0363] 70% of MB PA2 refers to a masterbatch produced on industrial
scale wherein 70 wt % of a wet ground surface treated CaCO.sub.3 of
the prior art is used and the CaCO.sub.3 has a median particle size
diameter d50 of 1.7 .mu.m and a top cut of d98 of 6 .mu.m. The
precise filler content of the masterbatch was determined by the ash
content: 72.2 wt % and the melt flow rate (MFR, 230.degree. C.,
2.16 kg, ISO 1133) of the masterbatch is 9.04 g/10 min.
[0364] As can be seen in tables 8 to 10, samples of polypropylene
multifilament fibers comprises the CaCO.sub.3 according to the
present invention and as seen in tables 11 to 13, samples of
polypropylene multifilament fibers comprising the prior art
CaCO.sub.3 can be produced in good quality under various processing
conditions by varying the amount of CaCO.sub.3 addition, the draw
ratio and the draw temperatures. Table 14 shows the results of
polypropylene multifilament fibers comprising no CaCO.sub.3.
* * * * *