U.S. patent application number 10/466142 was filed with the patent office on 2004-03-25 for powdery pigment preparations for dyeing films.
Invention is credited to Balent, Robert, Beck, Dietmar, Ohleier, Heinfred.
Application Number | 20040059029 10/466142 |
Document ID | / |
Family ID | 7670904 |
Filed Date | 2004-03-25 |
United States Patent
Application |
20040059029 |
Kind Code |
A1 |
Balent, Robert ; et
al. |
March 25, 2004 |
Powdery pigment preparations for dyeing films
Abstract
The invention relates to a powdery pigment preparation
containing a pigment which is dispersed in an acrylate resin and
which is characterized in that the acrylate resin has an average
molar mass Mw ranging from 40000 to 80000 g/mol and is a copolymer
comprised of 50 to 65 mol % ethyl methacrylate, of 30 to 45 mol %
butyl methacrylate, and of 0.5 to 5 mol % methacrylic acid. The
powdery pigment preparation can be used for dying films,
particularly those made of polymethyl methacrylate. The films do
not have any specks nor holes.
Inventors: |
Balent, Robert; (Frankfurt
am Main, DE) ; Beck, Dietmar; (Bad Soden, DE)
; Ohleier, Heinfred; (Kelsterbach, DE) |
Correspondence
Address: |
CLARIANT CORPORATION
INTELLECTUAL PROPERTY DEPARTMENT
4000 MONROE ROAD
CHARLOTTE
NC
28205
US
|
Family ID: |
7670904 |
Appl. No.: |
10/466142 |
Filed: |
July 11, 2003 |
PCT Filed: |
January 15, 2002 |
PCT NO: |
PCT/EP02/00310 |
Current U.S.
Class: |
524/81 ; 524/186;
524/401; 524/430; 524/431; 524/86 |
Current CPC
Class: |
C08J 2433/00 20130101;
C09B 67/0061 20130101; Y10T 428/31507 20150401; C08J 3/226
20130101 |
Class at
Publication: |
524/081 ;
524/086; 524/186; 524/401; 524/430; 524/431 |
International
Class: |
C08L 023/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 18, 2001 |
DE |
101 02 019.8 |
Claims
1) A powderous pigment preparation comprising a pigment in
dispersion in an acrylate resin, wherein the acrylate resin has an
average molar mass Mw of between 40 000 and 80 000 g/mol and is a
copolymer of from 50 to 65 mol % ethyl methacrylate, from 30 to 45
mol % butyl methacrylate, and from 0.5 to 5 mol % methacrylic
acid.
2) A pigment preparation as claimed in claim 1, wherein the
acrylate resin has an average molar mass Mw between 50 000 and 70
000 g/mol.
3) A pigment preparation as claimed in claims 1 or 2, wherein the
acrylate resin is composed of from 55 to 60 mol % ethyl
methacrylate, from 35 to 40 mol % butyl methacrylate, and from 1 to
4 mol % methacrylic acid.
4) A pigment preparation as claimed in at least one of claims 1 to
3, wherein the butyl methacrylate is n-butyl methacrylate.
5) A pigment preparation as claimed in at least one of claims 1 to
4, wherein the weight ratio between the pigment and the acrylate
resin is from 70:30 to 30:70.
6) A pigment preparation as claimed in at least one of claims 1 to
5, wherein the pigment is a monoazo, disazo, laked azo pigment, azo
condensation pigment, benzimidazolone, naphthol, isoindolinone,
isoindoline, phthalocyanine, quinacridone, anthanthrone, perylene,
perinone, thioindigo, thiazineindigo, quinophthalone, dioxazine or
diketopyrrolopyrrole pigment or carbon black.
7) A pigment preparation as claimed in at least one of claims 1 to
5, wherein the pigment is a nickel titanate, chromium titanate,
iron oxide, ultramarine, chromium oxide or titanium dioxide.
8) A pigment preparation as claimed in at least one of claims 1 to
7, composed of a) from 30 to 70% by weight, preferably from 45 to
55% by weight, of a pigment; b) from 70 to 30% by weight,
preferably from 55 to 45% by weight, of the acrylate resin, c) from
0 to 8% by weight, preferably from 2 to 4% by weight, of a
lubricant, and d) from 0 to 10% by weight, preferably from 0 to 1%
by weight, of further customary additives, the sum of all
components being 100% by weight.
9) A process for producing a pigment preparation as claimed in one
or more of claims 1 to 8, which comprises dispersing the pigment in
the acrylate resin, plastifying the mixture at from 100 to
160.degree. C., and comminuting the plastic mass.
10) The use of a pigment preparation as claimed in one or more of
claims 1 to 8 to color plastics, especially polymethyl
methacrylate, paints, printing inks, electrophotographic toners,
and powder coating materials.
11) The use as claimed in claim 10 to color films, particularly of
polymethyl methacrylate.
Description
[0001] The invention relates to powderous pigment preparations
particularly suitable for coloring films of polymethyl methacrylate
(PMMA).
[0002] EP-A-0 718 327 describes poly(meth)acrylate copolymers used
as pigment dispersants in polymeric compounds for producing
extruded moldings.
[0003] U.S. Pat. No. 4,948,546 describes a method of producing
flexible sheets of PMMA colored with inorganic pigments. In that
method the pigments are used in the form of liquid or syrupy
dispersions in defined acrylic copolymers.
[0004] The coloring of thin films of PMMA confronts the skilled
worker with particular problems, since standard pigment
preparations have the effect of, or are unable to prevent, the
embrittlement of the film or the appearance of specks in the
colored film.
[0005] It was an object of the present invention to find powderous
pigment preparations capable of coloring thin PMMA films without
the resultant film exhibiting specks or holes.
[0006] It has been found that the pigment preparation below
comprising an acrylic resin of defined composition surprisingly
achieves the object proposed.
[0007] The present invention provides a powderous pigment
preparation comprising an organic or inorganic pigment in
dispersion in an acrylate resin, wherein the acrylate resin has an
average molar mass Mw of between 40 000 and 80 000 g/mol,
preferably 50 000 and 70 000 g/mol, in particular 55 000 to 65 000
g/mol, and is a copolymer of from 50 to 65 mol % ethyl
methacrylate, from 30 to 45 mol % butyl methacrylate, and from 0.5
to 5 mol % methacrylic acid.
[0008] Preference in the context of the present invention is given
to acrylate resins containing from 55 to 60 mol %, in particular
from 57 to 59 mol %, ethyl methacrylate, from 35 to 40 mol %, in
particular from 37 to 39 mol %, butyl methacrylate, and from 1 to 5
mol %, in particular from 2 to 4 mol %, methacrylic acid.
[0009] As butyl methacrylate it is preferred to use n- or iso-butyl
methacrylate. Particular preference is given to n-butyl
methacrylate.
[0010] Particularly suitable organic pigments include monoazo,
disazo, and laked azo pigments, azo condensation pigments,
benzimidazolone, naphthol, isoindolinone, isoindoline,
phthalocyanine, quinacridone, anthanthrone, perylene, perinone,
thioindigo, thiazineindigo, quinophthalone, dioxazine, and
diketopyrrolopyrrole pigment, and carbon black.
[0011] Examples are C.I. Pigment Brown 25, 41, P. Violet 19, P.Y.
17, 110, P.R. 101, 185, 254, P. Blue 15:1, 15:3, P. Green 7.
[0012] Particularly suitable inorganic pigments include nickel
titanates, chromium titanates, iron oxides, ultramarine, chromium
oxide, and titanium dioxide.
[0013] The weight ratio between the pigment and the acrylate resin
is preferably from 70:30 to 30:70, in particular from 55:45 to
45:55.
[0014] Preferred powderous pigment preparations are those
consisting essentially of
[0015] a) from 30 to 70% by weight, preferably from 45 to 55% by
weight, of a pigment;
[0016] b) from 70 to 30% by weight, preferably from 55 to 45% by
weight, of said acrylate resin;
[0017] c) from 0 to 8% by weight, preferably from 2 to 4% by
weight, of a lubricant, and
[0018] d) from 0 to 10% by weight, preferably from 0 to 1% by
weight, of further customary additives, the sum of all components
being 100% by weight.
[0019] The acrylate resin used in accordance with the invention can
be prepared by customary methods, e.g., by techniques of solution
or emulsion polymerization that are known to the skilled
worker.
[0020] Component c) suitably comprises lubricants, such as
epoxidized soybean oils, fatty alcohol ethoxylates, and fatty acid
esters, for example.
[0021] Examples of suitable components d) include wetting agents,
dedusting agents, antifoams, and anticaking agents.
[0022] The pigment preparations of the invention can be produced by
dispersing the pigment in the acrylate resin, plastifying the
mixture at from 100 to 160.degree. C, preferably from 100 to
150.degree. C., in particular from 100 to 140.degree. C., and
comminuting the plastic mass.
[0023] The pigment, appropriately in powder form, is preferably
incorporated by dispersion into the acrylate resin or into a
mixture of components b), c) and/or d), and the mixture is
plastified by introduction of steam with a temperature of from 100
to 160.degree. C., preferably from 100 to 150.degree. C. This
incorporation takes place normally using a dispersion compounder.
During and after the introduction of steam the mixture is
appropriately kneaded. Subsequently, preferably with the addition
of a little water, the plastified mass is cooled to a temperature
of 60 to 80.degree. C. for its comminution. The brittle mass is
then fractionated in the compounder and ground in a mechanical
mill. It is also possible to adopt a procedure in which components
b), c) and/or d) are mixed first of all, then plastified as
described by the introduction of steam, and the pigment is
incorporated into the plastic mass by kneading.
[0024] The kneading time is appropriately from 10 to 60 minutes.
The particle size after grinding is generally from 100 to 200
.mu.m. The pigment preparation of the invention is free-flowing,
nondusting, and easy to meter.
[0025] The pigment preparations of the invention are suitable for
use as colorants for coloring high molecular mass materials, such
as plastics, paints, and printing inks, for example. With
particular advantage they are used for coloring PMMA, especially
for coloring PMMA films. This can be done by incorporating the
pigment preparation into thermoplastic PMMA to give a compounded
formulation with a pigment concentration of, for example, between
0.5 and 8% by weight, based on the overall weight of the
formulation. The incorporation can be carried out using
conventional kneading apparatus or extruders and preferably at
temperatures between 180 and 220.degree. C.
[0026] The compounded formulation produced in this way can be used
for further processing steps, an example being film production.
Films can be produced, for example, by melting the pigment
preparation of the invention together with PMMA carrier material,
or in the form of said compounded formulation, on one or more
plastifying units, and from 190 to 220.degree. C. for example, and
bringing the composition into film form by means of a downstream
tool. Suitable plastifying units include preferably extruders or
compounders.
[0027] As extrusion installations it is possible to use mono- or
coextrusion installations and also calenders. Depending on the
individual thicknesses, e.g., from 5 to 1000 .mu.m, preferably from
80 to 120 .mu.m, different dies/calender nips are used. Preferred
areas for use of the films of the invention are as laminating
foils.
[0028] A particular advantage of the pigment preparations of the
invention is that compounded PMMA formulations with a high pigment
concentration can be provided which can be processed directly to
thin films which are free from specks and holes.
[0029] The pigment preparations produced in accordance with the
invention are also suitable for use as colorants in
electrophotographic toners and developers, such as one- or
two-component powder toners (also called one- or two-component
developers), magnetic toners, liquid toners, polymerization toners,
and specialty toners, for example.
[0030] Suitable toner binders are addition polymerization resins,
polyaddition resins, and polycondensation resins, such as styrene,
styreneacrylic, styrenebutadiene, acrylic, polyester, and phenolic
epoxy resins, polysulfones, polyurethanes, individually or in
combination, and also polyethylene and polypropylene, which may
contain further ingredients, such as charge control agents, waxes
or flow assistants, or may be modified subsequently with such
additions.
[0031] The pigment preparations produced in accordance with the
invention are also suitable for use as colorants in powders and
powder coating materials, particularly in triboelectrically or
electrokinetically sprayable powder coating materials that are
employed for the surface coating of articles made for example of
metal, wood, plastic, glass, ceramic, concrete, textile material,
paper or rubber.
[0032] The resins used as powder coating resins are typically epoxy
resins, carboxyl- and hydroxyl-containing polyester resins,
polyurethane resins and acrylic resins, together with customary
curing agents. Combinations of resins also find application. For
example, epoxy resins are frequently used in combination with
carboxyl- and hydroxyl-containing polyester resins. Typical curing
components (depending on the resin system) are, for example, acid
anhydrides, imidazoles, and dicyandiamide and its derivatives,
capped isocyanates, bisacylurethanes, phenolic and melamine resins,
triglycidyl isocyanurates, oxazolines, and dicarboxylic acids.
[0033] The pigment preparations produced according to the invention
are additionally suitable for use as colorants in ink-jet inks,
both aqueous and nonaqueous, and in those inks which operate in
accordance with the hot-melt process, and also for "electronic
inks".
[0034] Furthermore, the pigment preparations produced in accordance
with the invention are also suitable for use as colorants for color
filters, for both subtractive and additive color generation.
[0035] The invention is illustrated by examples below. Parts denote
parts by weight.
EXAMPLE 1
[0036] In a dispersion compounder, 225 parts of acrylate resin
(consisting of 58 mol % ethyl methacrylate, 39 mol % n-butyl
methacrylate and 3 mol % methacrylic acid; molar mass 59 000 g/mol)
and 9 parts of epoxidized soybean oil are mixed at room
temperature. Then steam (130.degree. C.) is introduced and the mass
is plastified. 225 parts of C.I. Pigment Blue 15:1 are incorporated
in portions into the plastic mass over the course of 15 minutes,
followed by kneading at 110.degree. C. for 30 minutes more.
Thereafter the mass, with the addition of a little water, is
comminuted, the compounder is switched off, and the brittle mass,
after it has cooled, is fractionated in the compounder. It is
subsequently ground in a mechanical mill. This produces a powderous
pigment preparation.
EXAMPLE 2
[0037] In a dispersion compounder, 225 parts of acrylate resin
(consisting of 60 mol % ethyl methacrylate, 38 mol % n-butyl
methacrylate and 2 mol % methacrylic acid; molar mass 60 000 g/mol)
and 9 parts of epoxidized soybean oil are mixed at room
temperature. Then steam (130.degree. C.) is introduced and the mass
is plastified. 225 parts of C.I. Pigment Violet 19 are incorporated
in portions into the plastic mass over the course of 15 minutes,
followed by kneading at 110.degree. C. for 30 minutes more.
Thereafter the mass, with the addition of a little water, is
comminuted, the compounder is switched off, and the brittle mass,
after it has cooled, is fractionated in the compounder. It is
subsequently ground in a mechanical mill. This produces a powderous
pigment preparation.
EXAMPLE 3
[0038] In a dispersion compounder, 225 parts of acrylate resin
(consisting of 56 mol % ethyl methacrylate, 40 mol % n-butyl
methacrylate and 4 mol % methacrylic acid; molar mass 60 000 g/mol)
and 9 parts of fatty alcohol ethoxylate are mixed at room
temperature. Then steam (130.degree. C.) is introduced and the mass
is plastified. 225 parts of C.I. Pigment Red 254 are incorporated
in portions into the plastic mass over the course of 20 minutes,
followed by kneading at 110.degree. C. for 30 minutes more.
Thereafter the mass, with the addition of a little water, is
comminuted, the compounder is switched off, and the brittle mass,
after it has cooled, is fractionated in the compounder. It is
subsequently ground in a mechanical mill. This produces a powderous
pigment preparation.
EXAMPLE 4
[0039] In a dispersion compounder, 225 parts of acrylate resin
(consisting of 58 mol % ethyl methacrylate, 39 mol % n-butyl
methacrylate and 3 mol % methacrylic acid; molar mass 59 000 g/mol)
and 18 parts of epoxidized soybean oil are mixed at room
temperature. Then steam (130.degree. C.) is introduced and the mass
is plastified. 225 parts of C.I. Pigment Yellow 17 are incorporated
in portions into the plastic mass over the course of 20 minutes,
followed by kneading at 110.degree. C. for 30 minutes more.
Thereafter the mass, with the addition of a little water, is
comminuted, the compounder is switched off, and the brittle mass,
after it has cooled, is fractionated in the compounder. It is
subsequently ground in a mechanical mill. This produces a powderous
pigment preparation.
EXAMPLE 5
[0040] In a dispersion compounder, 225 parts of acrylate resin
(consisting of 57 mol % ethyl methacrylate, 40 mol % n-butyl
methacrylate and 3 mol % methacrylic acid; molar mass 59 000 g/mol)
and 18 parts of fatty alcohol ethoxylate are mixed at room
temperature. Then steam (130.degree. C.) is introduced and the mass
is plastified. 225 parts of C.I. Pigment Red 185 are incorporated
in portions into the plastic mass over the course of 22 minutes,
followed by kneading at 110.degree. C. for 30 minutes more.
Thereafter the mass, with the addition of a little water, is
comminuted, the compounder is switched off, and the brittle mass,
after it has cooled, is fractionated in the compounder. It is
subsequently ground in a mechanical mill. This produces a powderous
pigment preparation.
EXAMPLE 6
[0041] In a dispersion compounder, 225 parts of acrylate resin
(consisting of 58 mol % ethyl methacrylate, 39 mol % n-butyl
methacrylate and 3 mol % methacrylic acid; molar mass 59 000 g/mol)
and 18 parts of epoxidized soybean oil are mixed at room
temperature. Then steam (130.degree. C.) is introduced and the mass
is plastified. 225 parts of C.I. Pigment Red 101 are incorporated
in portions into the plastic mass over the course of 20 minutes,
followed by kneading at 110.degree. C. for 30 minutes more.
Thereafter the mass, with the addition of a little water, is
comminuted, the compounder is switched off, and the brittle mass,
after it has cooled, is fractionated in the compounder. It is
subsequently ground in a mechanical mill. This produces a powderous
pigment preparation.
[0042] Use Example:
[0043] In a batchwise mixing operation polymethyl methacrylate
(PMMA), additives, such as lubricants, adhesion preventatives, heat
stabilizers and plasticizers, for example, and a powderous pigment
preparation from Examples 1 to 6 are mixed until the mixture is
homogeneous. The resultant compounded formulation is passed to a
planetary roll extruder under pressure and temperature and is
melted.
[0044] In the course of this operation the pigment preparations of
the invention are likewise melted and distributed to optimum effect
in the plastified material, so that coloring is homogeneous.
[0045] By the tool of the planetary roll extruder the plastified
and colored material is extruded onto a conveyor belt and so passes
to the calender rolls, where it is first of all melted further in
the nip between two corotating, heated metal rolls.
[0046] Further rolls downstream provide for additional
homogenization and corresponding adjustment to the thickness of the
sheetlike end product.
[0047] In this way colored PMMA films which are free from specks
and holes are obtained.
* * * * *