U.S. patent application number 13/639060 was filed with the patent office on 2013-04-18 for mineral wool fiber mats, method for producing same, and use.
This patent application is currently assigned to CELANESE EMULSIONS GMBH. The applicant listed for this patent is Paolo Bavaj, Christoph Deller, Martin Jakob, Paul Scott. Invention is credited to Paolo Bavaj, Christoph Deller, Martin Jakob, Paul Scott.
Application Number | 20130095719 13/639060 |
Document ID | / |
Family ID | 44121542 |
Filed Date | 2013-04-18 |
United States Patent
Application |
20130095719 |
Kind Code |
A1 |
Deller; Christoph ; et
al. |
April 18, 2013 |
Mineral Wool Fiber Mats, Method for Producing Same, and Use
Abstract
The invention relates to mineral wool fiber mats, which are
stabilized by means of a binder made of polymers funtionalized with
epoxy groups and/or with carboxyl groups and selected cross-linking
agents. Said mats can be used as an insulating material and are
characterized by low or no formaldehyde emissions.
Inventors: |
Deller; Christoph; (Mainz,
DE) ; Jakob; Martin; (Kelkheim, DE) ; Bavaj;
Paolo; (Frankfurt a. Main, DE) ; Scott; Paul;
(Epson, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Deller; Christoph
Jakob; Martin
Bavaj; Paolo
Scott; Paul |
Mainz
Kelkheim
Frankfurt a. Main
Epson |
|
DE
DE
DE
GB |
|
|
Assignee: |
CELANESE EMULSIONS GMBH
Krongberg/Ts
DE
|
Family ID: |
44121542 |
Appl. No.: |
13/639060 |
Filed: |
March 23, 2011 |
PCT Filed: |
March 23, 2011 |
PCT NO: |
PCT/EP2011/001434 |
371 Date: |
December 14, 2012 |
Current U.S.
Class: |
442/327 ;
264/128 |
Current CPC
Class: |
C08F 220/06 20130101;
C08L 25/14 20130101; C08L 79/02 20130101; C08F 212/08 20130101;
C08L 31/04 20130101; C08F 212/08 20130101; C08F 220/14 20130101;
C08L 31/04 20130101; D04H 13/00 20130101; Y10T 442/60 20150401;
C08L 71/02 20130101; C03C 25/285 20130101; C08F 212/08 20130101;
C08F 220/325 20200201; C08J 5/24 20130101; C08F 220/1804 20200201;
C08F 220/325 20200201; C08F 220/06 20130101; C08F 220/14 20130101;
C08F 220/06 20130101; C08F 220/06 20130101; C08L 2666/14 20130101;
C08F 220/1804 20200201; C08L 2666/14 20130101; C08F 220/325
20200201; C08F 220/06 20130101; C08F 220/1804 20200201; C08J 5/044
20130101; C08F 220/14 20130101; C08L 25/14 20130101; C08K 5/17
20130101; C08J 2300/10 20130101; C03C 25/26 20130101 |
Class at
Publication: |
442/327 ;
264/128 |
International
Class: |
D04H 13/00 20060101
D04H013/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 19, 2010 |
DE |
10 2010 015 575.6 |
Claims
1. A mineral wool fiber mat bound with a binder containing an epoxy
and/or carboxyl functionalized emulsion copolymer and an amine
and/or an amine derivative as crosslinker.
2. The mineral wool fiber mat according to claim 1 wherein the
epoxy and/or carboxyl functionalized emulsion copolymer is a
polyvinyl ester, a polyacrylate or a polyalkenyl aromatic including
interpolymerized units derived from glycidyl esters of
ethylenically unsaturated mono- or dicarboxylic acids, and/or
including interpolymerized units derived from ethylenically
unsaturated mono- or dicarboxylic acids, salts or anhydrides.
3. The mineral wool fiber mat according to claim 2 wherein the
epoxy and/or carboxyl functionalized emulsion copolymer derives
from alkenyl aromatics, preferably from styrene, and/or from esters
of acrylic acid and/or methacrylic acid and includes
interpolymerized units derived from glycidyl esters of
ethylenically unsaturated monocarboxylic acids, preferably from
glycidyl esters of acrylic acid and/or methacrylic acid, and/or
includes interpolymerized units derived from ethylenically
unsaturated mono- or dicarboxylic acids, salts or anhydrides.
4. The mineral wool fiber mat according to claim 2 wherein the
epoxy and/or carboxyl functionalized emulsion copolymer derives
from esters of .alpha., .beta.-ethylenically unsaturated
C.sub.3-C.sub.8-mono- or dicarboxylic acids and includes
interpolymerized units derived from glycidyl esters of
ethylenically unsaturated monocarboxylic acids, preferably from
glycidyl esters of acrylic acid and/or methacrylic acid, and/or
includes interpolymerized units derived from ethylenically
unsaturated mono- or dicarboxylic acids, salts or anhydrides.
5. The mineral wool fiber mat according to claim 2 wherein the
epoxy and/or carboxyl functionalized emulsion copolymer derives
from one or more vinyl esters and includes interpolymerized units
derived from glycidyl esters of ethylenically unsaturated
monocarboxylic acids, preferably from glycidyl esters of acrylic
acid and/or methacrylic acid, and/or includes interpolymerized
units from ethylenically unsaturated mono- or dicarboxylic acids,
salts or anhydrides, and/or includes interpolymerized units derived
from ethylenically unsaturated mono- or dicarboxylic acids, salts
or anhydrides.
6. The mineral wool fiber mat according to claim 5 wherein the
epoxy functionalized emulsion copolymer in addition to the
structural units derived from one or more vinyl esters contains
further structural units derived from esters of .alpha.,
.beta.-ethylenically unsaturated C.sub.3-C.sub.8-mono- or
dicarboxylic acids with C.sub.1-C.sub.8 alkanols, from .alpha.,
.beta.-ethylenically unsaturated C.sub.3-C.sub.8-mono- or
dicarboxylic acids, from olefins or from a combination of two or
more of these monomers.
7. The mineral wool fiber mat according to claim 2 wherein the
epoxy functionalized emulsion copolymer is selected from the group
of copolymers derived from vinyl esters of saturated carboxylic
acids and from glycidyl esters of ethylenically unsaturated
carboxylic acids, of copolymers derived from vinyl esters of
saturated carboxylic acids, from esters of acrylic acid and/or
methacrylic acid and/or fumaric acid and/or maleic acid with
C.sub.1-C.sub.8-alkanols and from glycidyl esters of ethylenically
unsaturated carboxylic acids, of copolymers derived from vinyl
esters of saturated carboxylic acids, from ethylene, from
ethylenically unsaturated carboxylic acids and and from glycidyl
esters of ethylenically unsaturated carboxylic acids, of copolymers
derived from vinyl esters, ethylene, esters of acrylic acid and/or
methacrylic acid and/or fumaric acid and/or maleic acid with
C.sub.1-C.sub.8-alkanols, from ethylenically unsaturated carboxylic
acids and from glycidyl esters of ethylenically unsaturated
carboxylic acids, of copolymers derived from esters of acrylic acid
and/or methacrylic acid, of ethylenically unsaturated carboxylic
acids and from glycidyl esters of ethylenically unsaturated
carboxylic acids, of copolymers derived from styrene with butadiene
and/or from esters of acrylic acid and/or methacrylic acid with
C.sub.1-C.sub.8-alkanols, from ethylenically unsaturated carboxylic
acids and from glycidyl esters of ethylenically unsaturated
carboxylic acids.
8. The mineral wool fiber mat according to claim 7 wherein the
polymer is an epoxy functionalized polyvinyl ester containing at
least 50% by weight of vinyl acetate monomer units.
9. The mineral wool fiber mat according to at least one of claim 1
wherein the binder is introduced in the form of an aqueous
dispersion of the polymer.
10. The mineral wool fiber mat according to at least one of claim 1
wherein the binder content is in the range from 0.1% to 10% by
weight and preferably in the range from 0.5% to 5% by weight.
11. The mineral wool fiber mat according to at least one of claim 1
wherein the crosslinker is selected from the group of mono- or
polyamines, preferably aliphatic mono- or diamines or aromatic
mono- or diamines.
12. The mineral wool fiber mat according to at least one of claim 1
wherein the crosslinker is selected from the group of amides having
one or more amide groups, more particularly polyaminoamides and
very particularly preferably the condensation products of
unsaturated aliphatic acids with polyamines.
13. The mineral wool fiber mat according to claim 12 wherein the
crosslinker is selected from the group of polyaminoamides having an
ASTM D 2073 amine number between 100 and 2000 mg of KOH/g of
crosslinker, preferably between 250 and 1000 mg of KOH/g of
crosslinker.
14. The mineral wool fiber mat according to claim 12 wherein the
crosslinker used is neither alkoxylated nor hydroxyalkylated.
15. The mineral wool fiber mat according to at least one of claim 1
wherein the crosslinker is used in amounts ranging from 0.1% to 10%
by weight, based on the binder, preferably between 1-10% by weight
and more particularly between 2-7% by weight.
16. A process for producing the mineral wool fiber mat according to
claim 1 comprising the steps of i) applying a crosslinkable
composition containing an epoxy and/or carboxylfunctionalized
emulsion copolymer and a crosslinker selected from the group of
amines or amine derivatives to mineral wool fibers, and ii)
consolidating the mineral wool fibers to form a bound mineral wool
fiber mat by crosslinking the binder.
17. The process according to claim 16 wherein the crosslinkable
composition is applied in the form of an aqueous dispersion.
18. The use of the mineral wool fiber mat according to any one of
claim 1 as an insulating material, more particular more
particularly for insulating, more particularly thermally insulating
built structures and structural objects of any kind, preferably for
insulating roofs.
Description
[0001] The present invention relates to mineral wool fiber mats
impregnated with a selected binder. These mats are useful for
example as insulants, for example for thermal insulation of
roofs.
[0002] Aqueous polymeric dispersions for use as binders for mineral
wool fiber mats are known per se. Mineral wool mats incorporating
crosslinked polymers as binders form part of the subject matter of
a wide variety of patent documents.
[0003] US-A-2008/0175997 describes binder compositions for glass
mats that include an emulsion of a carboxyl-functionalized polymer
and also a crosslinker having aziridine groups. Compared with
conventional systems, a formaldehyde-free dispersion is concerned.
It has comparable or even improved strength and flexibility
compared with known systems. This document mentions further known
binder systems for glass mats that derive from
carboxyl-functionalized polymers and include specific crosslinkers,
for example polyol compounds combined with phosphorus-containing
accelerator, compounds containing active hydrogen, such as polyol,
polyvinyl alcohol or polyacrylate, combined with fluoroborate
accelerator, or crosslinkers which promote the esterification
between COOH and OH groups in the polymer, or comprise epoxidized
oils.
[0004] EP-A-1,018,523 discloses a polymer dispersion comprising a)
dispersed addition polymer comprising 5-20% by weight
interpolymerized carboxylic acid units, b) dissolved addition
polymer comprising 60-100% by weight of interpolymerized carboxylic
acid units, and c) selected alkoxylated long-chain amine as a
crosslinker. This dispersion is useful as a binder for mineral wool
mats for example.
[0005] DE-T-699 21 163 describes an insulating product based on
mineral wool based on specific mineral fibers, the insulating
product bearing a size based on a thermosetting resin admixed with
a latex in order that mechanical strength after aging may be
improved, The latex used comprises in particular polymers having
hydrophilic groups, for example carboxyl, hydroxyl or carboxylic
ester groups. Phenolic resin is mentioned as a thermosetting
resin.
[0006] DE-A-197 38 771 and DE-A197 20 674 describe binders for
mineral wool containing a) a thermoplastic polymer crosslinkable
with phenolic resin, such as polyacrylate or polyvinyl ester, b)
phenolic resin and c) flame retardant.
[0007] EP-A-1 164 163 discloses a binder for mineral wool, obtained
by mixing a carboxylic acid and an alkanolamine under reactive
conditions. An example of the carboxylic acid used is polyacrylic
acid, polymethacrylic acid or a polymaleic acid.
[0008] WO-A-01/05,725 describes a binder for mineral wool, obtained
by reacting a mixture which does not contain a polymer but includes
an amine and also a first and a second anhydride. Typical
representatives of the reaction mixture are diethanolamine, cyclic
aliphatic anhydride, for example maleic anhydride succinic
anhydride or hexahydrophthalic anhydride, and an aromatic
anhydride, for example phthalic anhydride.
[0009] WO-A-2007/060,236 describes a formaldehyde-free binder for
mineral wool comprising a) an aqueous dispersion of a polymeric
polycarboxylic acid, b) a selected alkanolamine, for example
ethanolamine, and c) an activated silane obtained by reacting a
silane, for example alkoxysilane, with an enolizable ketone
comprising at least one carboxyl group or with a ketone having at
least one hydroxyl group, for example dihydroxyacetone or
acetylacetone.
[0010] DE-A-100 14 399 discloses a mixture of two polymeric systems
one of which bears mandatory carboxyl groups, while the second one
contains interpolymerized functional groups capable of reacting
with the carboxyl groups of the first polymeric system to form a
covalent bond.
[0011] DE-A-26 04 544 discloses binders for consolidating glass
fiber mats wherein a carboxyl-containing polymer is reacted with a
crosslinker selected from the group of polyepoxides or capped
isocyanates. The polymer basis for the binders used is restricted
to polymers constructed from ethylenically unsaturated esters of
acrylic or methacrylic acid.
[0012] JP-A-2006-089,906 describes a formaldehyde-free binder for
mineral wool comprising a vinyl copolymer having hydroxyl groups
and groups derived from an organic acid.
[0013] WO-A-2004/085,729 describes a formaldehyde-free binder for
mineral wool comprising a) a compound having at least 2 cyclic
ether groups and b) a copolymer having nucleophilic groups.
[0014] WO-A-2006/136,614 discloses a binder for mineral wool
comprising a) phenol-formaldehyde binder and b) a hydroxylamine or
an amino alcohol.
[0015] DE-A-40 24 727 discloses an agent for hydrophilicizing
mineral wool fibers which comprises a) phenol-formaldehyde binder
and, as hydrophilicizing agent, a mixture of b) water-soluble
nitrogen-carbonyl compound, e.g., urea, c) acrylic resin and d)
mixture of carboxyl-containing fatty acid condensation products
with organic phosphoric esters.
[0016] There are also a number of documents already describing
epoxy- or carboxyl-functionalized binders. Examples thereof are
given in US-A-2008/0214716, US-A-2006/0258248, DE-C-199 56 420 and
WO-A-03/104284. WO-A-03/104284 describes binder systems for
producing glass fiber products in which low molecular weight epoxy
compounds are crosslinked with functionalized polymeric compounds.
US-A-2006/0258248 discloses epoxidized oils combined with
multifunctionalized carboxylic acids or anhydrides as suitable
crosslinking binders. US-A-2008/0214716 discloses binders for
producing fiber weaves from a polymer based on ethylenically
unsaturated monomers, a water-soluble polymer based on
ethylenically unsaturated carboxylic acids and an alkoxylated or
hydroxyalkylated crosslinker. DE-C-199 56 420 describes the use of
water-soluble polymers based on ethylenically unsaturated
carboxylic acids and certain amines in the presence of a
crosslinking agent based on epoxy or acrylic resin for producing
shaped articles.
[0017] There is increasing commercial demand for products which are
formaldehyde-free in their formulations and emissions during
application while retaining the current performance
characteristics.
[0018] It is an object of the present invention to provide bound
mineral wool fiber mats bonded together by formaldehyde-free
binders and very useful as insulating materials.
"Formaldehyde-free" is to be understood in the context of this
description as meaning a composition having a formaldehyde content
of less than 10 ppm.
[0019] The present invention provides a mineral wool fiber mat
bound with a binder containing an epoxy and/or carboxyl
functionalized copolymer, more particularly containing an
appropriately functionalized emulsion copolymer, preferably in
dispersion form, and an amine and/or an amine derivative as
crosslinker.
[0020] In a preferred embodiment of the present invention, the
mineral wool fiber mats contain a biosoluble fiber material bonded
by a formaldehyde-free binder applied in a pH range in which the
fibers are not attacked. This range is ideally located above the
neutral point. This pH range is preferably 7.5-10.
[0021] The mineral wool fiber mats of the present invention contain
glass wool and/or rockwool and can in principle contain further
aggregates known to a person skilled in the art and/or further
fibers.
[0022] Glass wool can be produced using any of the foundation
stocks known from the glass industry. Quartz sand, sodium carbonate
and limestone are typically used; cullet can be admixed to these
raw materials, for example at up to 70% by weight of cullet. The
melt is fiberized in a conventional manner by centrifugal casting
or jetting.
[0023] Rockwool can be produced in a similar manner to glass wool.
Basalt, diabase, feldspar, dolomite, sand and limestone are
typically used; these raw materials may likewise be admixed with
cullet. The melt is fiberized in a conventional manner by
centrifugal casting. In addition to the customary starting
materials for producing rockwool, it is also possible to use slags
generated as waste products in combustion or production processes,
for example blast furnace slags. This form of rockwool known as
slag wool is similarly known to a person skilled in the art.
[0024] The glass wool or rockwool used is preferably selected to
have a high biosolubility. Biosolubility is to be understood as
meaning the ability of the fibers to be dissolved and degraded in
the body by endogenous substances.
[0025] The glass wool or rockwool fiber mats formed are additized
with a binder to ensure their dimensional stability. The fiber mat
is subsequently cured by heat treatment, for example in a hot air
stream. Volatile constituents are additionally removed from the
fiber mat in the course of the heat treatment. Web-forming
processes of this type are described for example in US 200810175997
A1.
[0026] Alternatively, mineral wool fiber mats can also be produced
by wet laying. To this end, fibers can be initially charged in an
aqueous slurry together with the binder and be laid down on a
moving support surface, for example a water-permeable conveyor
belt, to form a fiber mat. After dewatering, the fiber mat is cured
by heat treatment, for example in a hot air stream. Production
processes for mineral wool mats of this type are described for
example in DE 601 23 177 T2.
[0027] Mineral wool mats may also contain further customary added
substances. Mineral oils are frequently added, for instance, to
improve further processability and imbued the mineral wool mats
with improved water-rejecting properties. In addition, such mats
may be laminated with aluminum foil or fibrous nonwoven webs when
used as an insulating material in particular.
[0028] The mineral wool fiber mats of the present invention are
endowed with a specific binder which contains an epoxy and/or
carboxyl functionalized copolymer.
[0029] The epoxy and/or carboxyl functionalized copolymers are
preferably derived from one or more ethylenically unsaturated
compounds, such that at least one of these monomers must have one
or more epoxy groups and/or one or more carboxyl groups.
[0030] These embodiments comprise by way of reactive groups either
only interpolymerized epoxy groups or only interpolymerized
carboxyl groups or, in addition to the inter-polymerized epoxy
groups, additionally interpolymerized carboxyl groups, for example
from units derived from ethylenically unsaturated mono- or
dicarboxylic acids. The selection of these embodiments depends
inter alia on further additions to the binder formulation and/or on
the reaction conditions prevailing at application (at the binding
of the mineral wool in the binding process, for example).
[0031] In addition to these copolymers, it is also possible to use
homo- or copolymers derived completely or overwhelmingly from
carboxyl-containing ethylenically unsaturated monomers. Examples
thereof are polyacrylic acid or salts thereof and also
polymethacrylic acid or salts thereof, more particularly the alkali
metal salts of these polymers.
[0032] The epoxy and/or carboxyl functionalized copolymers
preferably comprise copolymers of vinyl esters and/or of esters of
.alpha.,.beta.-ethylenically unsaturated C.sub.3-C.sub.8-mono- or
dicarboxylic acids and/or of alkenyl aromatics, each polymerized
with ethylenically unsaturated comonomers comprising epoxy groups
and/or carboxyl groups or anhydrides thereof.
[0033] In addition to the epoxy-containing monomers and/or the
carboxyl-containing monomers, it is mainly the following groups of
monomers which are contemplated as a basis for the classes of
polymer mentioned:
[0034] One group is formed by vinyl esters of monocarboxylic acids
having one to eighteen carbon atoms, examples being vinyl formate,
vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl valerate,
vinyl valerate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl
decanoate, isopropenyl acetate, vinyl esters of saturated branched
monocarboxylic acids having 5 to 15 carbon atoms in the acid
moiety, more particularly vinyl esters of Versatic.TM. acids, vinyl
esters of relatively long-chain saturated or unsaturated fatty
acids such as for example vinyl laurate, vinyl stearate and also
vinyl esters of benzoic acid and of substituted derivatives of
benzoic acid such as vinyl p-tert-butylbenzoate. Among these,
however, vinyl acetate is particularly preferred for use as
principal monomer.
[0035] A further group of monomers is formed by esters of
.alpha.,.beta.-ethylenically unsaturated C.sub.3-C.sub.8-mono- or
dicarboxylic acids with preferably C.sub.1-C.sub.18-alkanols and
more particularly C.sub.1-C.sub.8-alkanols or
C.sub.5-C.sub.8-cycloalkanols. The esters of dicarboxylic acids may
be monoesters, or preferably, diesters. Examples of suitable
C.sub.1-C.sub.8-alkanols are methanol, ethanol, n-propanol,
i-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol,
n-hexanol and 2-ethylhexanol. Examples of suitable cycloalkanols
are cyclopentanol or cyclohexanol. Examples are esters of acrylic
acid, of methacrylic acid, of crotonic acid, of maleic acid, of
itaconic acid, citraconic acid or of fumaric acid such as methyl
(meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate,
n-butyl (meth)acrylate, isobutyl (meth)acrylate, 1-hexyl
(meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, di-n-methyl maleate or fumarate, di-n-ethyl maleate
or fumarate, di-n-propyl maleate or fumarate, di-n-butyl maleate or
fumarate, diisobutyl maleate or fumarate, di-n-pentyl maleate or
fumarate, di-n-hexyl maleate or fumarate, dicyclohexyl maleate or
fumarate, di-n-heptyl maleate or fumarate, di-n-octyl maleate or
fumarate, di-(2-ethylhexyl) maleate or fumarate, di-n-nonyl maleate
or fumarate, di-n-decyl maleate or fumarate, di-n-undecyl maleate
or fumarate, dilauryl maleate or fumarate, dimyristyl maleate or
fumarate, dipalmitoyl maleate or fumarate, distearyl maleate or
fumarate and diphenyl maleate or fumarate.
[0036] Preferred principal monomers of this group are selected from
the group of acrylates and methacrylates. Particular preference is
given to methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl
(meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate,
1-hexyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate.
[0037] A further group of monomers is formed by alkenyl aromatics.
The alkenyl aromatics in question are monoalkenyl aromatics.
Examples thereof are styrene, vinyl toluene, vinyl xylene,
.alpha.-methylstyrene or o-chlorostyrene. Styrene in particular
must be mentioned as a preferred monomer in this group.
[0038] The monomers mentioned generally form the principal monomers
which, in relation to the total amount of the monomers to be
polymerized, normally account for a proportion of more than 50% by
weight and preferably more than 75%.
[0039] A further group of monomers which can mainly be used
together with vinyl esters and/or esters of
.alpha.,.beta.-ethylenically unsaturated C.sub.3-C.sub.8-mono- or
dicarboxylic acids and/or alkenyl aromatics is formed by aliphatic,
monoolefinically or diolefinically unsaturated, optionally
halogen-substituted hydrocarbons, such as ethene, propene,
1-butene, 2-butene, isobutene, conjugated C.sub.4-C.sub.8-dienes,
such as 1,3-butadiene, isoprene, chloroprene, vinyl chloride,
vinylidene chloride, vinyl fluoride or vinylidene fluoride.
[0040] The monomers are preferably to be selected so as to form an
addition polymer or copolymer having good compatibility in common
formaldehyde-free binder formulations which additionally has
excellent binding properties in the production of mineral wool
mats.
[0041] Preferably used binder polymers are derived from the
following principal monomers or combinations thereof in addition to
the epoxy-containing monomers and/or the carboxyl-containing
monomers: [0042] copolymers based on one or more vinyl esters, more
particularly vinyl acetate; [0043] copolymer based on esters of
.alpha., .beta.-ethylenically unsaturated C.sub.3-C.sub.8-mono with
C.sub.1-C.sub.8-alkanols, more particularly esters of (meth)acrylic
acid; [0044] copolymers based on vinyl esters and esters of
.alpha., .beta.-ethylenically unsaturated C.sub.3-C.sub.8-mono- or
dicarboxylic acids with C.sub.1-C.sub.8-alkanols, more particularly
esters of (meth)acrylic acid and maleic/or fumaric acid; [0045]
copolymers based on vinyl esters, more particularly vinyl acetate,
with ethylene; [0046] copolymer based on esters of .alpha.,
.beta.-ethylenically unsaturated C.sub.3-C.sub.8-mono- or [0047]
dicarboxylic acids with C.sub.1-C.sub.8-alkanols, more particularly
esters of (meth)acrylic acid and maleic/or fumaric acid, with
ethylene; [0048] copolymers based on vinyl esters, ethylene and
esters of .alpha., .beta.-ethylenically unsaturated
C.sub.3-C.sub.8-mono- or dicarboxylic acids with
C.sub.1-C.sub.8-alkanols, more particularly esters of (meth)acrylic
acid and maleic/or fumaric acid; or [0049] copolymers based on
styrene and esters of .alpha., .beta.-ethylenically unsaturated
C.sub.3-C.sub.8-mono- or dicarboxylic acids with
C.sub.1-C.sub.8-alkanols, more particularly esters of (meth)acrylic
acid and optionally ethylene and/or butadiene.
[0050] The examples of preferred epoxy-containing monomers for
copolymerization with the principal monomers are allyl glycidyl
ether, methacryloyl glycidyl ether, butadiene monoepoxides,
1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene,
8-hydroxy-6,7-epoxy-1-octene, 8-acetoxy-6,7-epoxy-1-octene,
N-(2,3-epoxy)-propylacrylamide, N-(2,3-epoxy)-propylmethacrylamide,
4-acrylamidophenyl glycidyl ether, 3-acrylamidophenyl glycidyl
ether, 4-methacrylamidophenyl glycidyl ether,
3-methacrylamidophenyl glycidyl ether, N-glycidoxymethylacrylamide,
N-glycidoxypropylmethacrylamide, N-glycidoxyethylacrylamide,
N-glycidoxyethyl-methacrylamide, N-glycidoxypropylacrylamide,
N-glycidoxypropylmethacrylamide, N-glycidoxybutylacrylamide,
N-glycidoxybutylmethacrylamide,
4-acrylamidomethyl-2,5-dimethylphenyl glycidyl ether,
4-methacrylamidomethyl-2,5-dimethylphenyl glycidyl ether,
acrylamidopropyldimethyl-(2,3-epoxy)propylammonium chloride,
meth-acrylamidopropyldimethyl-(2,3-epoxy)-propylammonium chloride
and glycidyl methacrylate. Epoxy-containing monomers derived from
glycidyl esters of ethylenically unsaturated mono- or dicarboxylic
acids, such as glycidyl acrylate and glycidyl methacrylate for
example, are particularly preferred.
[0051] The weight fraction contributed by the epoxy-containing
monomers based on the total amount of the monomers to be
polymerized is below 50% by weight, preferably between 0.1% and 20%
by weight, more preferably between 1% and 10% by weight and most
preferably between 2% and 5% by weight.
[0052] In addition to the abovementioned principal monomers, the
binder polymers used according to the present invention may
additionally contain at least structural units derived from
carboxyl-containing monomers.
[0053] This group of monomers includes mainly
.alpha.,.beta.-monoethylenically unsaturated mono- and dicarboxylic
acids of 3 to 10 carbon atoms and their water-soluble salts, for
example their sodium salts, and also their anhydrides. Preferred
monomers from this group are ethylenically unsaturated
C.sub.3-C.sub.8-carboxylic acids and C.sub.4-C.sub.8-dicarboxylic
acids, e.g., maleic acid, fumaric acid, itaconic acid, crotonic
acid, vinyl acetic acid, 2-carboxylethyl (meth)acrylate,
acrylamidoglycolic acid and, more particularly, acrylic acid,
methacrylic acid and also the monoesters of maleic and fumaric
acids such as mono-2-ethylhexyl maleate and monoethyl maleate.
[0054] These carboxyl-containing monomers are normally
interpolymerized in amounts of less than 50% by weight, preferably
between 0.1% and 20% by weight, more preferably between 1% and 10%
by weight and most preferably between 2% and 5% by weight, based on
the total amount of the monomers to be polymerized.
[0055] Particularly preferred binders for mineral wool fiber mats
contain an epoxy functionalized copolymer based on a polyvinyl
ester, on a polyacrylate or on a polyalkenyl aromatic that includes
interpolymerized units derived from glycidyl esters of
ethylenically unsaturated mono- or dicarboxylic acids, preferably
from glycidyl esters of acrylic or methacrylic acid.
[0056] Particularly preferred binders for mineral wool fiber mats
contain a carboxyl functionalized copolymer based on a polyvinyl
ester, on a polyacrylate or on a polyalkenyl aromatic that includes
interpolymerized units derived from ethylenically unsaturated mono-
or dicarboxylic acids, preferably from monoesters of fumaric or
maleic acid or from acrylic or methacrylic acid.
[0057] Particularly preferred binders for mineral wool fiber mats
contain an epoxy and carboxyl functionalized copolymer based on a
polyvinyl ester, on a polyacrylate or on a polyalkenyl aromatic
that includes interpolymerized units derived from glycidyl esters
of ethylenically unsaturated mono- or dicarboxylic acids,
preferably from glycidyl esters of acrylic or methacrylic acid, and
that includes interpolymerized units derived from ethylenically
unsaturated mono- or dicarboxylic acids, preferably from monoesters
of fumaric or maleic acid or from acrylic acid or methacrylic
acid.
[0058] A further particularly preferred embodiment of the binder is
based on epoxy functionalized copolymers derived from alkenyl
aromatics, preferably from styrene, or from esters of acrylic acid
and/or methacrylic acid, and includes interpolymerized units
derived from glycidyl esters of ethylenically unsaturated mono- or
dicarboxylic acids, preferably from glycidyl esters of acrylic acid
and/or methacrylic acid.
[0059] A further particularly preferred embodiment of the binder is
based on epoxy functionalized copolymers derived from esters of
.alpha.,.beta.-ethylenically unsaturated C.sub.3-C.sub.8-mono- or
dicarboxylic acids and includes interpolymerized units derived from
glycidyl esters of ethylenically unsaturated monocarboxylic acids,
preferably from glycidyl esters of acrylic acid and/or methacrylic
acid.
[0060] A further preferred embodiment of the binder is based on
epoxy functionalized copolymers derived from one or more vinyl
esters, more particularly vinyl acetate, and including
interpolymerized units derived from glycidyl esters of
ethylenically unsaturated monocarboxylic acids, preferably from
glycidyl esters of acrylic acid and/or methacrylic acid. The epoxy
functionalized copolymers mentioned may contain further structural
units derived from esters of .alpha.,.beta.-ethylenically
unsaturated C.sub.3-C.sub.8-mono- or dicarboxylic acids with
C.sub.1-C.sub.8-alkanols, from .alpha., .beta.-ethylenically
unsaturated C.sub.3-C.sub.8-mono- or dicarboxylic acids, e.g.,
acrylic acid, methacrylic acid or maleic acid or fumaric acid, from
olefins, e.g., ethylene or butadiene, or from a combination of two
or more of these monomers.
[0061] Selected epoxy and/or carboxyl functionalized copolymers
are: copolymers derived from vinyl esters of saturated carboxylic
acids and from glycidyl esters of ethylenically unsaturated
carboxylic acids or from ethylenically unsaturated mono- or
dicarboxylic acids, of copolymers derived from vinyl esters of
saturated carboxylic acids, from esters of acrylic acid and/or
methacrylic acid and/or fumaric acid and/or maleic acid with
C.sub.1-C.sub.8-alkanols and from glycidyl esters of ethylenically
unsaturated carboxylic acids or from ethylenically unsaturated
mono- or dicarboxylic acids, of copolymers derived from vinyl
esters of saturated carboxylic acids, from ethylene, from
ethylenically unsaturated carboxylic acids and and from glycidyl
esters of ethylenically unsaturated carboxylic acids or from
ethylenically unsaturated mono- or dicarboxylic acids, of
copolymers derived from vinyl esters, ethylene, esters of acrylic
acid and/or methacrylic acid and/or fumaric acid and/or maleic acid
with C.sub.1-C.sub.8-alkanols, from ethylenically unsaturated mono-
or dicarboxylic acids and from glycidyl esters of ethylenically
unsaturated carboxylic acids, of copolymers derived from esters of
acrylic acid and/or methacrylic acid, of ethylenically unsaturated
mono- or dicarboxylic acids and from glycidyl esters of
ethylenically unsaturated carboxylic acids, of copolymers derived
from styrene and optionally butadiene and/or from esters of acrylic
acid and/or methacrylic acid with C.sub.1-C.sub.8-alkanols, from
ethylenically unsaturated mono- or dicarboxylic acids and from
glycidyl esters of ethylenically unsaturated carboxylic acids.
[0062] It will be appreciated that the polymerization may
co-utilize further comonomers which modify the properties in a
specific manner. Such auxiliary monomers are normally
interpolymerized only as modifying monomers in amounts of less than
10% by weight, based on the total amount of the monomers to be
polymerized.
[0063] These monomers can have different functions; for example,
they can serve to stabilize polymer dispersions or they can improve
film cohesion or other properties by crosslinking during the
polymerization or during film formation, and/or react with the
crosslinker via a suitable functionality.
[0064] Monomers useful for further stabilization are generally
monomers which have an acid function and/or salts thereof. In
addition to the abovementioned carboxyl-containing monomers, which
likewise contribute to enhancing crosslink density in the binding
process of the mineral wool fiber mats, further monomers having
other acid functions, such as ethylenically unsaturated sulfonic
acids, ethylenically unsaturated phosphonic acids or dihydrogen
phosphates and water-soluble salts thereof, for example sodium
salts thereof, can also be used. Preferred monomers from this group
are vinylsulfonic acid and its alkali metal salts,
acrylamidopropanesulfonic acid and its alkali metal salts, and also
vinylphosphonic acid and its alkali metal salts.
[0065] Examples of crosslinking auxiliary monomers are monomers
having two or more vinyl radicals, monomers having two or more
vinylidene radicals, and also monomers having two or more alkenyl
radicals. Of particular advantage are the diesters of dihydric
alcohols with .alpha.,.beta.-monoethylenically unsaturated
monocarboxylic acids, among which acrylic acid and methacrylic acid
are preferred, the diesters of dibasic carboxylic acids with
ethylenically unsaturated alcohols, other hydrocarbons having two
ethylenically unsaturated groups, or the diamide of dihydric amines
with .alpha.,.beta.-monoethylenically unsaturated monocarboxylic
acids.
[0066] Examples of such monomers having two nonconjugated
ethylenically unsaturated double bonds are alkylene glycol
diacrylates and dimethacrylates, such as ethylene glycol
diacrylate, 1,2-propylene glycol diacrylate, 1,3-propylene glycol
diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol
diacrylates or methacrylates and ethylene glycol diacrylates or
methacrylates, 1,2-propylene glycol dimethacrylate, 1,3-propylene
glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
1,4-butylene glycol dimethacrylates, hexanediol diacrylate,
pentaerythritol diacrylate and also divinylbenzene, vinyl
methacrylate, vinyl acrylate, vinyl crotonate, allyl methacrylate,
allyl acrylate, diallyl maleate, diallyl fumarate, diallyl
phthalate, methylene bisacrylamide, cyclopentadienyl acrylate,
divinyl adipate or methylenebisacrylamide.
[0067] However, it is also possible to use monomers having more
than two double bonds, for example tetraallyloxyethane,
trimethylolpropane triacrylate or triallyl cyanurate.
[0068] A further group of auxiliary monomers is formed by auxiliary
monomers which are self-crosslinking or can be crosslinked via
carbonyl groups. Examples are diacetoneacrylamide, allyl
acetoacetate, vinyl acetoacetate and also acetoacetoxy-ethyl
acrylate or methacrylate.
[0069] A further group of auxiliary monomers are capable, under
selected conditions, of undergoing a crosslinking reaction either
by self-crosslinking or with a suitable monomeric reactant and/or
with the crosslinkers present: [0070] this group includes monomers
having N-functional groups, more particularly (meth)acrylamide,
allyl carbamate, acrylonitrile, methacrylonitrile,
N-methylol-(meth)acrylamide, N-methylolallyl carbamate and also the
N-methylol esters, -alkyl ethers or Mannich bases of
N-methylol(meth)acrylamide or of N-methylolallyl carbamate,
acrylamidoglycolic acid, methyl acrylamidomethoxyacetate,
N-(2,2-dimethoxy-1-hydroxyethyl)acrylamide,
N-dimethylaminopropyl(meth)acrylamide, N-methyl(meth)acrylamide,
N-butyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide,
N-dodecyl(meth)acrylamide, N-benzyl(meth)acrylamide,
p-hydroxyphenyl-(meth)acrylamide,
N-(3-hydroxy-2,2-dimethylpropyl)methacrylamide, ethyl-imidazolidone
(meth)acrylate, N-(meth)acryloyloxyethylimidazolidin-1-one,
N-(2-methacryloylamidoethyl)imidazolin-2-one,
N-[3-allyloxy-2-hydroxypropyl]amino-ethyl]imidazolin-2-one,
N-vinylformamide, N-vinylpyrrolidone or, N-vinylethyleneurea.
[0071] A further group of auxiliary monomers is formed by
hydroxyl-functional monomers such as the
C.sub.1-C.sub.9-hydroxyalkyl esters of methacrylic and acrylic
acids, such as n-hydroxyethyl acrylate, n-hydroxyethyl
methacrylate, n-hydroxypropyl acrylate, n-hydroxypropyl
methacrylate, n-hydroxybutyl acrylate, n-hydroxybutyl methacrylate
and also adducts thereof with ethylene oxide or propylene
oxide.
[0072] A further group of auxiliary monomers consists of monomers
comprising silane groups, e.g., vinyltrialkoxysilanes, such as
vinyltrimethoxysilane, vinyltriethoxysilane,
alkylvinyldialkoxysilanes or
(meth)acryloyloxyalkyltrialkoxysilanes, e.g.,
(meth)-acryloyloxyethyltrimethoxysilane, or
(meth)acryloyloxypropyltrimethoxysilane.
[0073] It is preferable in the context of the present invention to
ideally not use any functional monomers comprising free or bound
formaldehyde. If this is necessary as part of specific product
optimizations, the rule is to also use a compound that acts as a
formaldehyde scavenger. Pertinent examples thereof are N- or
S-nucleophiles such as urea or sodium bisulfite and also other
compounds described in the literature. The binders used according
to the present invention are obtainable by any method of
free-radical polymerization. Examples thereof are polymerization in
bulk, in solution, in suspension or, more particularly, emulsion
polymerization.
[0074] Preferably used binders contain aqueous polymeric
dispersions comprising the epoxy- and/or carboxyl-containing
copolymers described above. These dispersions are applied to the
mineral wool fiber mats without a solvent or almost without a
solvent.
[0075] In addition to the epoxy- and/or carboxyl-containing
polymers, the dispersions preferably used according to the present
invention contain protective colloids and/or emulsifiers.
[0076] Protective colloids are polymeric compounds which are
present during the emulsion polymerization and which stabilize the
dispersion.
[0077] Examples of suitable protective colloids are polyvinyl
alcohols, polyalkylene glycols, cellulose derivatives, starch
derivatives and gelatin derivatives or polymers derived from
N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole,
1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine,
4-vinylpyridine, acrylamide, methacrylamide, amino-bearing
acrylates, methacrylates, acrylamides and/or methacrylamides. A
comprehensive description of further suitable protective colloids
is given in Houben-Weyl, Methoden der organischen Chemie, Volume
XIV/1, Macromolecular substances, Georg-Thieme-Verlag, Stuttgart,
1961, pages 411 to 420.
[0078] Emulsifiers are low molecular weight and surface-active
compounds which are present during the emulsion polymerization and
which stabilize the dispersion. The dispersions used according to
the present invention may neutralize ionic and/or nonionic and/or
amphoteric emulsifiers, most preferably nonionic emulsifiers or
combinations of nonionic emulsifiers and anionic emulsifiers. A
list of suitable emulsifiers is given in Houben-Weyl, Methoden der
organischen Chemie, Volume XIV/I, Macromolecular substance,
Georg-Thieme-Verlag, Stuttgart, 1961, pages 192-208).
[0079] The proportion of protective colloids can be up to 20% by
weight, preferably in the range from 1% to 10% by weight and more
particularly in the range from 2% to 8% by weight, all based on the
dispersion.
[0080] The proportion of emulsifiers may likewise be up to 10% by
weight, based on the dispersion, preferably in the range from 1% to
6% by weight.
[0081] The binders used according to the present invention contain
at least one selected crosslinker from the group of amines, amine
derivatives, including preferably hydrophobically modified amines,
and amides, more particularly amidated amines. The amines or amine
derivatives used as crosslinkers shall not be alkoxylated or
hydroxyalkylated.
[0082] The crosslinkers used according to the present invention
comprise for example mono- or polyamines, more particular diamines,
preferably aliphatic mono- or diamines or aromatic mono- or
diamines. The amino groups of the crosslinkers used according to
the present invention can be primary, secondary and/or tertiary
amino groups. Preferably, the crosslinkers contain one or more
primary or secondary amino groups.
[0083] Preference for use as crosslinkers is given to amine
derivatives in which some of the amino groups were converted into
amide groups by reaction with hydrophobic acids. The amine
derivatives may have one or more amide groups.
[0084] Particular preference is given to using polyaminoamides.
Polyaminoamides are generally condensation products of unsaturated
aliphatic acids with polyamines. Products of this kind are
commercially available under the name of Versamid.RTM.. Examples of
such compounds are given in EP-A-1,533,331.
[0085] Preferred crosslinkers from the group of amine derivatives
having amidic structures are oligomeric or polymeric compounds
derived from a carboxylic acid, more particularly derived from
mono- or dicarboxylic acids or from a mixture of such carboxylic
acids including ethylenically unsaturated carboxylic acids and from
di-, oligo- or polyamines. The ethylenically unsaturated carboxylic
acids may form multimers, preferably of 2 to 10 carboxylic acid
units.
[0086] Particularly preferred crosslinking polymers are derived
from unsaturated carboxylic acids and diamines or from dimers of
ethylenically unsaturated carboxylic acids and di- or
oligoamines.
[0087] Further preferred crosslinkers from polyaminoamides have an
ASTM D 2073 amine number between 100 and 2000 mg of KOH/g of
crosslinker and preferably between 250 and 1000 mg of KOH/g of
crosslinker.
[0088] Particular preference is given to using crosslinkers of the
Versamid.RTM. range (Cognis GmbH, Germany), e.g., Versamid.RTM. 150
or Versamid.RTM. 250.
[0089] The crosslinkers used according to the present invention are
typically present in amounts of 0.1% to 10% by weight, based on the
binder.
[0090] Preferred crosslinker concentrations are between 1-10% by
weight and more particularly between 2-7% by weight.
[0091] When carbonyl-containing auxiliary monomers are present in a
copolymer of the binder, crosslinking via these groups may also
take place in addition. Crosslinkers useful for this purpose
include compounds selected from the group of bis- or
polyoxazolines, bis- or polyiminooxazolidines, carbodiimides, bis-
or polyepoxides or blocked isocyanates (as described in
EP-A-206,059 for example).
[0092] It is further possible to use compounds having an at least
divalent metal ion for further crosslinking. The compounds in
question are capable of forming complexes or coordinative bonds
with the carboxyl groups of the binder polymer. This group
typically includes salts of Al.sup.3+, Zn.sup.2+, Sn.sup.2+,
Sn.sup.4+, Ti.sup.4+, TiO.sup.2+, Hf.sup.4+, HfO.sup.2+Zr.sup.4+,
ZrO.sup.2+ and further polyvalent ions. Ideally, these ions may
recruit further components of the binder into the crosslinking and
thereby increase crosslink density. The poly(vinylalcohol)
frequently used as a protective colloid is an example.
[0093] The binders used according to the present invention may
contain further customary additives. These include, for example,
film-forming auxiliaries to depress the minimum filming temperature
("MFT") presence, plasticizers, buffers, pH control agents,
dispersants, defoamers, fillers, dyes, pigments, silane coupling
agents, thickeners, viscosity regulators, solvents and/or
preservatives.
[0094] The binder used according to the present invention shall be
used in a formulation adjusted to a pH in an optimum range for
suitable reactivity of the functional groups of the polymeric
binder with the groups of the crosslinker. This pH range is
preferably located above the neutral point. Preferably, this pH
range is 7.5-10.
[0095] A suitable pH may already be obtained after the emulsion
polymerization for preparing the polymer dispersion or after
addition of the crosslinker, the amidated amine for example, or it
may be set subsequently in the formulation by adding pH control
agents.
[0096] The polymer dispersions particularly preferably used are
prepared under the customary continuous or batch procedures of
free-radical emulsion polymerization.
[0097] The conduct of a free-radically initiated aqueous emulsion
polymerization of ethylenically unsaturated monomers has been
extensively described and therefore is well-known to a person
skilled in the art [cf. for example Encyclopedia of Polymer Science
and Engineering, Vol. 8, pages 659 to 677, John Wiley & Sons,
Inc., 1987; D. C. Blackley, Emulsion Polymerisation, pages 155 to
465, Applied Science Publishers, Ltd., Essex, 1975; D. C. Blackley,
Polymer Latices, 2.sup.nd Edition, Vol. I, pages 33 to 415, Chapman
& Hall, 1997; H. Warson, The Applications of Synthetic Resin
Emulsions, pages 49 to 244, Ernest Bonn. Ltd. London, 1972; D.
Diederich, Chemie in unserer Zeit 1990, 24, pages 135 to 142,
Verlag Chemie, Weinheim; J. Piirma, Emulsion Polymerisation, pages
1 to 287, Academic Press, 1982; F. Holscher, Dispersionen
synthetischer Hochpolymerer, pages 1 to 160. Springer-Verlag,
Berlin, 1969 and patent document DE-A 40 03 422]. Typically, the
ethylenically unsaturated monomers are dispersed in an aqueous
medium, frequently with the aid of dispersant auxiliaries, and are
polymerized using at least one free-radical polymerization
initiator at least.
[0098] Water-soluble and/or oil-soluble initiator systems such as
peroxodisulfates, azo compounds, hydrogen peroxide, organic
hydroperoxides or dibenzoyl peroxide are used. They can be used
either on their own or combined with reducing compounds such as
Fe(II) salts, sodium pyrosulfite, sodium hydrogensulfite, sodium
sulfite, sodium dithionite, sodium formaldehydesulfoxylate,
2-hydroxyphenylhydroxymethyl-sulfonic acid or its sodium salt,
4-methoxyphenylhydroxymethylsulfinic acid or its sodium salt,
2-hydroxy-2-sulfinatoacetic acid or its disodium or zinc salt and
2-hydroxy-2-sulfinatopropionic acid or its disodium salt, or
ascorbic acid or its salts or isoascorbic acid or its salts, as
redox catalyst system.
[0099] Polymeric protective colloids and/or emulsifiers can be
added before or during the polymerization. An additional subsequent
addition of polymeric stabilizers and/or of emulsifiers is likewise
possible. This dispersion is then optionally further admixed with
the additives envisioned for the desired application.
[0100] The binders of the present invention can be formulated in
the apparatuses known by a person skilled in the art for this
purpose, for example stirred tanks and/or suitable mixers.
[0101] After the binder has been prepared, it is generally applied
directly to mineral wool fibers to produce the mineral woof fiber
mats. This can be done using relevant application methods known to
a person skilled in the art, for example spraying the fibers with
the dispersion. After application and thermal treatment of the
moist fibrous nonwoven web raw material, the reactive binder cures
and consolidates and thereby stabilizes the mineral wool fiber mat.
The curing reaction is preferably induced by raising the
temperature. The rate of curing, as will be known to a person
skilled in the art, can be influenced through further measures via
the formulation. Typical curing temperatures are preferably
70.degree. C.-250.degree. C. and more particular 130.degree.
C.-180.degree. C.
[0102] The invention also provides a process for producing the
above-defined mineral wool fiber mat comprising the steps of [0103]
i) applying a crosslinkable composition containing an epoxy and/or
carboxyl-containing copolymer and a crosslinker selected from the
group of amines or amine derivatives to an unbound mineral wool
fiber mat, and [0104] j) consolidating the mineral wool fibers to
form a bound mineral wool fiber mat by crosslinking the binder.
[0105] The mineral wool fiber mats of the present invention combine
comparable mechanical strengths and application properties with
very low and preferably no formaldehyde emissions.
[0106] The mineral wool fiber mats of the present invention are
particularly useful as an insulating material, more particularly
for insulating, more particularly thermally insulating built
structures and structural objects of any kind.
[0107] The examples which follow serve to illustrate the invention.
Parts and percentages in the examples are by weight, unless
otherwise stated.
EXAMPLES
Dispersion A
[0108] In a stirred glass tank equipped with stirring apparatus,
anchor stirrer, feed means and electronic temperature control, 2.97
parts of .RTM.Emulsogen EPN 287 nonionic emulsifier (from
Clariant), 0.5 part of .RTM.Emulsogen LS anionic emulsifier (from
Clariant), 0.25 parts of sodium acetate, 0.51 part of sodium
vinylsulfonate, 0.04 part of sodium metabisulfite and 0.00023 part
of ammoniumiron(II) sulfate (as 1% solution) were dissolved in 60
parts of deionized water to form the initial charge.
[0109] Under agitation, 5 parts of vinyl acetate were emulsified
into the initial charge. Thereafter, the initial charge was heated
to 65.degree. C. with a solution of 0.22 part of sodium persulfate
in 1.77 parts of deionized water being added at 40.degree. C. to
start the polymerization reaction.
[0110] Once the internal temperature of 65.degree. C. was reached,
the metered addition was commenced of 95 parts of vinyl acetate and
3 parts of glycidyl methacrylate and continued for 240 minutes.
During the reaction, the internal temperature was maintained at
65.degree. C. 30 minutes before completion of the metered addition
of monomer the temperature was raised from 65.degree. C. to
85.degree. C. in the course of 30 minutes and, concurrently, a
solution of 0.11 part of sodium persulfate in 1.77 parts of
deionized water was added over 30 minutes.
[0111] On completion of the metered addition of monomer the batch
was maintained at 85.degree. C. for 60 minutes and then cooled
down.
[0112] Solids content: 60.7%
[0113] Brookfield viscosity RVT (23.degree. C.), spindle 2, 20 rpm:
780 mPas
[0114] pH: 4.2.
Dispersions B
[0115] In a stirred glass tank equipped with stirring apparatus,
anchor stirrer, feed means and electronic temperature control, 0.25
part of .RTM.Disponil A 3065 nonionic emulsifier (from Cognis) was
dissolved in 31.5 parts of deionized water at the start to prepare
the initial charge.
[0116] Concurrently, in a separate vessel, 2.72 parts of
.RTM.Disponil A 3065 and 2 parts .RTM.Disponil FES 77 anionic
emulsifier (from Cognis) were dissolved in 55.6 parts of deionized
water. Under vigorous agitation, a monomer mixture of 30 parts of
methyl methacrylate, 10 parts of butyl acrylate, 60 parts of
styrene, 1.5 parts of glycidyl methacrylate, 2 parts of methacrylic
acid and 1 part of acrylic acid was emulsified into this solution
to prepare the monomer emulsion.
[0117] Furthermore, solutions were prepared of 0.195 part of sodium
persulfate in 2.92 parts of deionized water (=oxidant solution) and
0.1 part of sodium metabisulfite in 0.91 part of water (=reductant
solution).
[0118] The initial charge was heated to 80.degree. C. Subsequently,
2.85% (by weight) of the monoemulsion and also 22.8% (by weight) of
the reductant solution were added dropwise to the initial charge.
After 5 minutes, 33.3% of the oxidant solution were added to this
mixture to initiate the polymerization reaction. After a further 15
minutes the metered addition was commenced of monoemulsion and
initiator system (oxidant and reductant solutions), and continued
for 240 minutes in the case of the monoemulsion and for 225 minutes
in the case of the concurrent edition of the two solutions of the
initiator system. During reaction initiation and metering, the
internal temperature of the reactor was maintained at 80.degree.
C.
[0119] On completion of the metered addition of monomer a solution
of 0.023 part of .RTM.Tego Foamex 805 defoamer (from Evonik) in
0.13 part of deionized water was added during 5 minutes.
Immediately thereafter, 1 part of methyl methacrylate was added
dropwise to the polymer during 10 minutes. Following rapid addition
of a solution of 0.065 part of sodium persulfate and 0.21 part of
deionized water, the temperature rose to 85.degree. C. and was
maintained at 85.degree. C. for 90 minutes. Then, the internal
temperature was lowered to 65.degree. C. and a solution of 0.11
part of .RTM.Trigonox AW 70 (70% aqueous solution of tert-butyl
hydroperoxide from Akzo) in 0.42 part of deionized water was added.
After 15 minutes a solution of 0.11 part of sodium metabisulfite in
0.42 part of deionized water was added, followed by a delay time of
15 minutes. This operation was repeated immediately thereafter.
Following addition of 0.033 part of ammonia (as 25% solution) in
0.13 part of deionized water the internal temperature was brought
below 40.degree. C. and the dilute ammonia solution was used to set
a pH of 4.5.
[0120] Solids content: 53.1%
[0121] Brookfield viscosity RVT (23.degree. C.), spindle 1, 20 rpm:
120 mPas
[0122] pH: 4.5.
Determination of Crosslink Density in Mixtures of
Glycidyl-Functionalized Dispersions and Amidated Amines as
Crosslinkers
[0123] Producing mineral wool fibers according to the prior art
utilizes primarily phenol-formaldehyde resins which cure to form
close-meshed three-dimensional networks. The high crosslink density
is responsible for a plastic of very thermoset character being
formed. The combination of glycidyl-functionalized polymeric
dispersions and suitable crosslinkers, for example amidated amines,
which is described in this invention likewise cures to form highly
crosslinked polymeric systems having thermoset properties.
Therefore, crosslink density is hereinafter used as a measure of
the effectivity of the binding system.
[0124] Crosslink density was determined by determining insoluble
constituents in thermally treated thin films formed from mixtures
of dispersion and crosslinker. The method used is analogous to that
described in US-A-2008/0175997. The film thickness of the
substrates applied to planar-ground glass plates was 250 pm in all
cases, and N-dimethylformamide (DMF) was used as solvent. A Mathis
Labdryer LTE-S oven was used to heat-condition the films. The
heat-conditioning time was 10 minutes for the examples listed
hereinbelow. The temperatures to which the dried films were exposed
for this period were varied. The corresponding temperatures are
apparent from the table below, in which the investigated examples
according to the invention are shown.
[0125] The samples were prepared as follows before the films were
drawn down: the dispersions were admixed with 3% by weight and 6%
by weight (reckoned on the solids content of the dispersion) of the
appropriate crosslinker. The .RTM.Versamid 150 product from Cognis
was used in the examples listed herein. The amidated amine was used
as-supplied, and incorporated into the dispersion by slow stirring
for 5 minutes. Subsequently, the pH of the mixture was determined,
and found to be between 8 and 9.5 depending on the dispersion used
and the crosslinker quantity.
[0126] The dependence of the degree of crosslinking on the
temperature was determined for dispersions A and B in the
experiments. In the case of dispersion A, the dependence of the
degree of crosslinking on the amount of crosslinker was
additionally determined. The degree of crosslinking can be
influenced positively by higher temperature, longer
heat-conditioning times and an optimized concentration of
crosslinker. The amount of insoluble constituents from a film of
dispersion A and B without added crosslinker served as a
comparative example.
TABLE-US-00001 TABLE Amount of Insoluble Versamid 150 in
Temperature constituents Example Dispersion % by weight in .degree.
C. in % V1 A 0 210 7 V2 B 0 180 6 1 A 3 120 17 2 A 3 150 26 3 A 3
180 57 4 A 6 120 21 5 A 6 150 47 6 A 6 180 69 7 B 3 120 30 8 B 3
150 81 9 B 3 180 87
It is apparent from the table that using the suitable crosslinker
in the inventive examples as compared with the comparative examples
V1 and V2 (each without added crosslinker) increases the fraction
of insoluble constituents and hence the crosslink density as a
function of the amount of crosslinker added and of the temperature.
It is further apparent that the presence of the carboxyl groups in
dispersion B serves to enhance crosslink density as evidenced by
the increase in the percentage of insoluble constituents,
particularly clearly from a comparison of test 5 with test 8.
* * * * *