JPS6055063A - Polymer sealed dispersion solid and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION This invention relates to polymer-impregnated solids, such as pigments, and methods of making and using the same.

DETAILED DESCRIPTION OF THE INVENTION A dispersion of a non-dispersed non-mono-solid, ta++ solution is to provide a polymer-encapsulated pigment. Another object of the present invention is to prepare said polymer-encapsulated dispersed solids, such as t. v Polymerization A 4 Enclosed Face Nemi 1
To provide a manufacturing method. Really? The purpose of the Ming Dynasty is to provide uses for the polymer-encapsulated dispersed solids (eg, polymer-encapsulated pigments) and compositions containing the polymer-encapsulated dispersed solids (eg, polymer-encapsulated pigments). Other objects and advantages of the present invention are set forth in this specification or will be apparent to those skilled in the art from this specification.

The objects and benefits of the present invention are achieved by the methods and products of the present invention which incorporate 1+ dispersed solids such as polymeric encapsulated pigments.

In a broad sense, the present invention includes a simple method for producing uniformly 11-unit-encapsulated dispersed non-uniform solids. The process involves mixing in a reactor water, a finely divided solid, a nonionic protective colloid or stabilizer, and all or a portion of a nonionic IliEJl body having at least one monounsaturated 11 organo moiety. It's something you do. Solids have a low surface charge. A nonionic polymerization initiator is added to the mixture and the mixture is heated to initiate polymerization of the nonionic extender. Add all remaining nonionic catalyst and nonionic monomers to the mix.

Allow polymerization to proceed to completion or to the desired degree. Polymers with a high molecular weight of 1/2 are preferred, but lower molecular weight polymers can be used. A polymer-encapsulated solid dispersion is obtained. However, the new system of the present invention must be nonionic in nature.

The present invention includes a convenient and simple method for producing uniformly polymer-encapsulated pigments. The method involves mixing water, a finely divided pigment, a nonionic protective colloid or stabilizer, and all or a portion of a nonionic monomer having at least one monounsaturated organo moiety in a reactor. It is something. Pigments have the lowest surface charge.

A nonionic polymerization initiator is added to the mixture and the mixture is heated to initiate polymerization of the nonionic monomers. Add all remaining nonionic catalyst and nonionic monomers to the mix. Allow polymerization to proceed to completion or to the desired degree. Although high molecular weight polymers are preferred, lower molecular weight polymers can be used. Yield the polymer-encapsulated pigment dispersion. In the prior art, a solvent-based system precipitates a polymer onto a pigment. The system must be nonionic in nature. The product is called "Plastic Pigment 1 or 7 Opaque Polymer".

The inventive method of making the inventive polymer-encapsulated solids (eg, pigments) involves emulsion polymerization. The method is similar to some latex processes. Advantageously, the method
It is simple and versatile, allows the use of conventional latex reactors, has short (reduced) reaction times, and provides good heat transfer.

The reaction time to a given total solids is reduced by the preformed particle core (less monomer reacted).

(If some difficult-to-disperse pigments such as T102 and Ca(-03) cannot be purchased in a satisfactory slurry form, a preliminary dispersion step may be necessary. Can be micro-encapsulated.

t Dispersion monomer: This process is implemented using a monomer that acts as a dispersant (partial dispersant) for the pigment and also easily copolymerizes with the subsequent monomer raw materials. Vinylpyrrolidone is such a monomer, but its use with pigments having a hydrophilic surface is limited. For example, Ca C
O3 and ']"i Pure R-931 type TiO2 cannot be easily encapsulated with vinylpyrrolidone as the starting mass. Or, in other words, N-vinylpyrrolidone, vinyl acetate, butyl acrylate, etc. Certain monomers serve both as encapsulation polymer forming monomers and as dispersing monomers.

2. Surfactant grafting: When implementing this process, it is necessary to use nonionic surfactants with long ethylene oxide chains.

Igepal CO-990 (Noni/L/Pheno-#/
100 mole ethylene oxide (EO) serves this function. In this technique, it is clear that the hydrophilic parts of the soap are attracted to the pigment surface and either act as obvious polymerization sites or grafting occurs across the tertiary hydrogen in the nonyl group. It is. Although this system can accommodate both hydrophilic and hydrophobic types of pigments, the particle size of the pigment to be encapsulated is usually
limited by the approximate size of the O chain a).

In either process implementation, the surface charge of the polymer must be minimal, and any anionic components (surfactants, catalysts, monomeric acids, etc.) must be present during the early stages of polymerization.
However, if substantially included, encapsulation will be substantially or totally inhibited.

Stepwise polymerizations can be used, such as controlled polymerization techniques such as core/shell.

Some of the key elements of the emulsion polymerization process of the present invention to produce the polymeric pigments of the present invention are (1,1 non-ionic surfactant, (21) leaving minimal ionic residue in the amalgamation). (3) the use of the appropriate type or variety of pigment.

Although any suitable vinyl monomer can be used to make the encapsulated vinyl polymer, vinyl acetate or alkyl acrylates are preferably used. Encapsulation is demonstrated by film appearance and performance (gloss, scrub, etc.), stability, behavior in the reactor (no flocculation), incompatibility with conventional paints, microphotography.

The invention also includes polymer-encapsulated dispersed non-monomeric solids and suitable polymer-encapsulated solids.

The polymer-encapsulated solids or pigments of the present invention are also often described as solids or pigment dispersions. A dispersion is an apparently homogeneous material consisting of a visually heterogeneous mixture of two or more finely divided phases. Polymer encapsulated pigments can be incorporated into paints to produce very good appearance properties for the paints. The unique pigment dispersions of this invention are often more stable than the "pigment slurries" used in the paint industry today. Polymer-encapsulated pigments are useful in the production of paints or other coating materials and represent stable paint/coating intermediates. Polymer-encapsulated pigment dispersions form films according to typical emulsion polymer parameters of glass transition (Tg) and minimum film forming temperature (MFT). The films often exhibit better appearance properties such as gloss, image clarity and hiding than conventional dispersions. In one sense, the polymer-encapsulated pigment dispersion can be considered a pre-paint.

The polymer-encapsulated pigment dispersions of the present invention have better lz economy, gloss, hiding power, air drying time,
It can provide modulus, scrub resistance, color stability, and durability. The encapsulated pigment functions both as a binder and as a pigment. The present invention eliminates dispersion steps and equipment in producing paints and coatings. The polymer-encapsulated pigment dispersions can be used in commercial paints (eg gloss/semi-gloss, exterior home and interior paints), pigment slurries, paper coatings, roof coatings, coatings, adhesives, industrial coatings, textiles.

In addition to paints, there are other related uses for coatings and adhesives containing the polymer-encapsulated pigments.

Coating, paint, adhesive, etc.
It consists of four conventional non-facial components such as paints, adhesives, etc., plus the polymer pigments of this invention. The polymer-encapsulated pigment dispersion itself is a pigment slurry that can be used wherever slurries are used. There is reasonable stability at polymer contents as low as 10% based on 100% pigment. pigments/polymers using clay or calcium carbonate)
In JZ 9/1, typical colors for paper coating applications, ``models for coating colors.''

(Examples) Mica-encapsulated dispersions can be used in latex roof coatings to improve their water swelling and/or water permeation resistance, and can be used in latex caulking.

Latex adhesives, such as clay-filled paperboard sunbatch agents, can be achieved by utilizing a soft polymeric encapsulation layer. Industrial coating or baking are other areas where enamel is useful. Oven-dried samples of the polymer-encapsulated pigment dispersion were made and tested and the visual gloss appearance was significantly superior compared to typical latex enamels. Textile bonding or coating systems are a useful field similar to the paints, adhesives, and paper coatings cited above. The uses for the polymer-encapsulated dispersed non-monomer insoluble solids of the present invention are numerous.

The best and preferred method has been developed using polymer-embedded titanium dioxide in the paint and polymer-embedded calcium carbonate in the paper coating. The standard coated variety l' i 02 is difficult to control (opposite effect due to organic and heterogeneous-inorganic treatment), so the youngest pure TiO2 is preferred and cheaper. It is. ′
1 inert 4I4I' pigments are preferably used, but at least some 7 reactive 11 pigments may be encapsulated. Basically, titanium dioxide (TiO2) is pierced with vinyl acetate and/or acrylate with a nonionic surfactant and/or poly(vinylpyrrolidone) or vinylpyrrolidone monomer as stabilizer and redox catalyst. Enter.

One option is to first disperse the spider, qs@body, water, and stabilizer, and then add the catalyst. So, in addition to 1f coalescence, the pupil pressure probably includes a catalyst, a stable^1j, or a nonionic surfactant.

Since the method of the present invention may not be successful in encapsulating surface-treated pigments, the pigment should basically be pure pigment without surface treatment. Additionally, oxygen adsorbed on the surface of the pigment particles causes some inhibition of pigment encapsulation, and this condition should be avoided.

Another preferred embodiment of the invention includes preparing the encapsulation mixture prior to adding the nonionic polymerization initiator and nonionic catalyst. First mix the finely divided solid, non-ionic protective colloid or stabilizer (with water). Next, all or part of the nonionic monomer is added to the admixture.

(Example 17 shows that small amounts of initiator and reducer can be added to the admixture prior to monomer addition.

) DETAILED DESCRIPTION OF THE INVENTION Homopolymers or copolymers can be used to encapsulate pigments.

The monomers used in this invention have at least one monounsaturated organic moiety. Mixtures of monomers can be used.

A preferred type of monomer is one in which the monounsaturated organo moiety is an alkylene, aralkylene or cycloalkylene moiety. Preferably, the monomer has at least one reactive vinyl group R, R8C=CT19-1, a reactive hinyritene group n, n, c-rc and/or a reactive vinylene group-
Cn = r: Contains 10 11 R-. In the above formula, R7, T18, R9, 111o
, R41 are each lal hydrogen, (1)) carbon #1-4
algi #, (cl alkoxy having 1 to 4 carbon atoms, ("l
k alkylcarboxy having 1" to 12 carbon atoms, tel aryl having 6 to 10 carbon atoms, (g) alkoxycarbonyl having 2 to 12 carbon atoms, (g) halogen having at least 1111Iil, nitrile, argyl having 1 to 4 carbon atoms and/or or IN-substituted aryl having 6 carbon atoms substituted with alkoxy having 1 to 4 carbon atoms, (aralkyl having 1 to 4 carbon atoms in hl alkyl and 6 to 10 carbon atoms in aryl, (I) Substituted aralkyl in which the aryl has 6 to 10 carbon atoms and the substituent is halogen, alkyl having 1 to 4 carbon atoms, nitrile, and/or alkoxy having 1 to 4 carbon atoms, (
j) 2) IJ, substituted alkyl having 1 to 4 carbon atoms substituted with halogen and/or alkoxy having 1 to 4 carbon atoms, (k) substituted alkyl having 2 to 12 carbon atoms substituted with halogen and/or nitrile; Illll sialkylcarboxy has 2 to 1 carbon atoms substituted with halogen and/or di)
2-substituted alkoxycarbonyl, provided that allyl compounds excluding ethylene or substituted 1-olefins are 1-
Olefins do not fall within the scope of the above formula.

The term "vinyl monomer" as used in the present invention broadly refers to monomers containing at least one vinyl, vinylidene or vinylene group. Vinyl is HC= CH-, vinylidene is T-T2C= C=, vinylene is -Cn=
It is C11-. Each of the terms includes substituents.

Preferably, the monovinyl monomer is a vinyl monomer having the formula:

H2c = cr-I-n (wherein R is a hydrogen atom, a methyl group, an alkoxy group having 1 to 4 carbon atoms, an alkylcarboxyl group having 2 to 12 carbon atoms, preferably an alkyl carboxyl group having 2 to 10 carbon atoms, 2) IJ group , a halogen atom, preferably a chlorine atom, a phenyl group or a carbon number of 2 to 1
2, preferably an alkoxycarbonyl group having 2 to 9 carbon atoms. ) j4i- vinyl monomers and mixtures of vinyl monomers such as vinyl chloride-vinyl acetate, vinylidene chloride-vinyl chloride, vinylidene chloride-acrylonitrile can be used. The ten monovinyl monomers include styrene, 1 (2 R2 is alkyl and/or alkoxy having 1 to 6 carbon atoms), pt, fv, i.e., n, C6
115□, C11=c)-T2 (where n H: 1-
5 with Te, R is chlorine, fluorine, bromine, iodine, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, -CN
or -NO2); alkyl has 1 to 11 carbon atoms;
Preferably alkyl acrylate having 1 to 6 carbon atoms;
Alkyl has 1 to 11 carbon atoms, preferably 1. <Alkoxy acrylate with 1 to 6 carbon atoms; Algyl methacrylate with alkyl having 1 to 10 carbon atoms, preferably 1 to 2 carbon atoms; alkyl carbon X8 having 1 to 10 carbon atoms, preferably 1 to 1 carbon number Contains argyl methacrylate.

Examples of useful monovinyl monomers and l-vinyl halides, such as vinyl chloride, vinyl fluoride, vinyl iodine; vinyl esters of aliphatic monocarboxylic acids, such as vinyl acetate, vinyl propionate, and laurin. vinyl acid, vinyl decanoate, vinyl butyrate, vinyl isobutyrate, vinyl dimethylpropionate, vinyl ethylbutyrate, vinyl valerate, vinyl caproate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, Vinyl β-phenylbutyrate, vinyl cyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl naphthoate; vinyl ethers, e.g. tan-
Butyl vinyl ether, inbutyl vinyl ether, vinyl propyl ether, vinyl 2-ethylhexyl ether, methyl vinyl ether, butyl vinyl ether,
Hexyl vinyl ether, octyl vinyl ether, tesyl vinyl ether, ethylhexyl vinyl ether,
Methoxyethyl vinyl ether, ethoxyethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether; vinyl alkoxyalkyl ether; vinyl haloalkyl ether; vinyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone ; Styrene; Styrene rust conductor, such as α-propylstyrene;
α-ethylstyrene, α-methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, 2-fluorostyrene, 3- Fluorstyrene, 4-fluorstyrene, 4-nitrostyrene,
2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 0-methylstyrene (0-vinyltoluene), m-methylstyrene, p-methylstyrene, 2
．． 5-dipromostyrene, 2,5-dichlorostyrene,
2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,4゜6-trimethylstyrene, 4-methoxy-6
-Methylstyrene, 4-fluoro-3-trifluoromethylstyrene, 2-bromo-4-trifluoromethylstyrene, trifluorostyrene, dipromostyrene, iodostyrene, trimethylstyrene, ethylstyrene,
These include diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, tethylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, and ethoxymethylstyrene.

Further examples of useful monovinyl monomers include acrylic esters of -valent alkanols, such as methyl acrylate,
Ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, nibutyl acrylate, amyl acrylate, hexyl acrylate, acrylic Octyl acrylate, tertiary octyl acrylate, 2-phenoxyethyl acrylate, 2-chloroethyl acrylate, 2-promoethyl acrylate, chlorobutyl acrylate, cyanoethyl acrylate, 2-nitroethyl acrylate, benzyl acrylate, methoxy acrylate Benzyl, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-impropoxyethyl acrylate, 2-butoxyethyl acrylate, acrylic 2-(2-methoxyethoxy)ethyl acid, 2-(2-butoxyethoxy)ethyl acrylate; methacrylic esters of -valent alkanols, such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, Phenyl methacrylate, methyl α-chloroacrylate, n methacrylate
-Propyl, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, nibutyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorbenzyl methacrylate, octyl methacrylate, N methacrylate -ethyl-N-phenylaminoethyl, 2-(3-phenylpropyloxy)ethyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-propoxyethyl methacrylate, 2-ethoxyethyl methacrylate, Methacrylic acid 2
-Impropoxyethyl, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate:
Unsaturated nitriles, such as acrylonitrile (CH2=C
I(CN), methacrylonitrile, heterocyclic vinyl monomers such as N-vinylpyrrolidone, N-vinylcarbazole, 2-vinyl-5-ethylpyridine, vinylpyridine (2, 3 or 4), vinylpicoline, N-vinyltriazole, N-vinyl-3,5-dimethylpyrazole, N-vinylcarbazole, vinylthiophene, N-vinylpyrrolidone, N-vinylpiperitone, N-vinyl-
These include δ-caprolactam and N-vinyl-2-pyridine.

Useful divinyl monomers include conjugated dienes and substituted divinyl acrylic monomers (preferably p-divinyl-benzene).
is included. Examples of useful divinyl monomers include 0-1
m- and p-divinylbenzene; divinyl ether or vinyl oxide [(CI-T2=cH)20]; 3.
9-divinyl spirobemeth-dioxane; divinyl sulfone (('TT2=CIIS02CH=CrT2)
; dienes or conjugated diolefins, such as propadiene;
1.3-7'tadiene, 1.3-pentadiene (cis and trans), 1.5-hexadiene, 2-methyl-t
Examples include 3-butadiene (isoprene L2,3-methylbutadiene: dicyclobentadiene; 2-chloro-1,3-butadiene).

co%/-v with 3 vinyl or allyl reactive moieties
-1 example; c-td triallyl cyanurate, diallyl fumarate, diallyl maleate are also useful.

Although the vinyl-reactive moieties of the monomers can be substituted,
If the substituent is not alkyl or alkoxy, the substituent (eg, CI) should not be attached directly to one of the bonded carbon atoms of the vinyl group (ie, the -unsaturated organo group).

Pigments are substances that impart color, including black or white, to other materials. Pigments are generally considered to be insoluble in the vehicle in which they are applied. The present invention does not include dyes that are soluble in the application medium. Pigments usually have photorefractive properties. Dyes, on the other hand, usually only have light-absorbing properties. The present invention includes inorganic pigments and organic pigments. Pigments are used as finely ground or granulated solid particles. As used in the present invention and the prior art, the term pigment includes phosphorescent, luminescent, luminescent, metallic, and pearlescent dyes.

The pigment must be particulate, with an average particle size of approximately 0.01
It should range from about 100 microns, preferably from about 0.2 to about 50 microns. The most preferred average particle size for organic pigments is about 0.2 microns and the most preferred average particle size for inorganic pigments is about 2 microns. Particle size,
Particle size distribution and shape are dictated by the pigment selected. The present invention eliminates pigment aggregates or agglomerates. Pigment colors are well developed and high pigment loadings can be obtained.

Examples of pigments, depending on color, are: opaque white pigments;
Example'i LJ" Zinc white (ZnO), antimony oxide (S
b203), zirconium oxide (ZrO), titanium dioxide (TlO2), lithopone (BaSO, I about 6696
and ZnS (approximately 54%), titanium oxide (TlO2
25% and CaSO475%), titanium barium white (Ti
e.

25% and naso475π); red and orange pigments, such as lead white (Pb304), cadmium red ((, rdS(S
e)], antimony vermilion (Sb2S3), vermilion (■■gS
), red yellow lead (PbCr04゜Pb (OH) 21,
Molybdenum red [circle] (MOS +Cr, p) o4]
, cadmium red lithopone [Cd5(Se) and BaSO
4], and quinacridone red (C2o11,202N2)
: Yellow pigment, for example 1llu lead yellow (4Zt+0 ・4
('C03・!(20・ror-120), barium yellow (13acr04), cobalt yellow [(-oK3(NO
2) 6・H,,0), strontium yellow (S r("r
(''), ), Naples Yellow C (PI)
(St:10) IF, yellow lead (yen) Cr(') 4
), Power 5 42 Domium Huang (CdS), Mitsudya Monk ([)hO), Cadmium Zu (Litopon (CdS and [(as04), India”)
"+prr+aO++Mg 5H20); Green pigments, such as cobalt green (CoO-nZnO), viridian (Cr203 2N20), phthalocyanine green, emerald green [Cu(C2■■302)
)23CII(AsO2)2], chromium oxide green (
Cr203), chrome green/(Fe4[Fe(
CN) 6) 3 and PbCrQ), verdigris [C1
1 (C211302)2・2Cu(OH)2], malachite (Cu CO3・Cu (0l-I) 2 ':'
P violet pigment, for example cobalt violet [
C03(PO4)2], ultramarine violet, manganese violet [(甜4)2Mn2(P2O3)2], quinacridone violet (C2o■■1202N2); blue pigments, such as navy blue (Fe4[Fe(CN)6]3), Egyptian blue (CaO-CuO・4SI02), -q7 cancer blue (Ba
Mn04 and Ba5O4), cobalt blue (Co()-A
1203), blue copperite (2CuCO5Cu(OH)3),
Cerulean Blue (Coo-nsn02), Blue Green Blue [2Ct
+ COs ・Cu (OT-I) 2 ), phthalocyanine blue, ultramarine blue (Na8-1oA16S16S2-4)
; Black pigments, such as lamp black (C), bone charcoal [C and Cag(Fe4)2:], charcoal black (C), graphite (C
); brown pigments, such as sepia.

A more general list of organic and inorganic pigments that can be used in the present invention includes iron oxide red, zinc oxide, titanium dioxide,
Yellow lead, carbon black, red yellow lead, chrome green,
Non-lead chromate, red lead, lake, azob ξ cuttoner, phthalocyanine, aluminum hydrate, lake, iron oxide,
Lead white, titanium-containing pigment, calcium carbonate, aluminum oxide, ultra horn (111t rapone),
Lead comate, cadmium sulfide, cadmium selenide,
Barium sulfate, azo pigment, anthraquinone and Bat M
l"l, acrylamino yellow, magnesium oxide, yellow lead,
Contains antimony oxide, zinc sulfide, magnesium fluoride, and ground pallite. Benzoic acid facings are useful, examples of which are toner, lake. Examples of benzoic acid toners include yellow toner, benoid toner, etc.
) yellow, Hansa yellow; orange toners, such as Bat Orange 3; red toners, such as naphthol red; violet toner; blue toner; green toner; brown toner; black toner. Examples of benzoic acid lakes are yellow lakes such as Acid Yellow 2; orange lakes; red lakes; violet lakes; blue lakes such as Acid Blue 93; green lakes; brown lakes; black lakes such as Natural Black 3.

Metallic pigments can be used, an example of which is aluminum flakes. Mixtures of pigments can be used. Z
Note that +1 reactive 11 pigments such as nQ can be used.

Extender pigments are substances that are added to paints to provide Bain) K adducts, fixation, or opacity, or to serve as adulterating media, and are usually inert materials.

The present invention involves polymeric encapsulation of extender pigments. Examples of suitable extender pigments (also called inert white pigments or transparent white pigments) or fillers are talc (5MgO4SiO2H20), chalk (CaCo5), pallite (3aSO4)
, barium carbonate (BaC03), aluminum hydrate (
Al(OH)3], mica, diatom ± (Sin2), aluminum stearate [AI(C18■(5502)3]
, stone 'Ill' (CaSO4-2), T2O), anhydride (CaSO4), silica quartz (Sin2), kaolinite (A, 1203.2SiO2.2H20), other clays, and silica fillers.

Mixtures of pigments and/or extender pigments can be used.

Advantages for certain pigments are as follows.

(al Tie, - 1!!1llk at low pigment levels
Power increases.

This is due to the drying force, the buildup, the loss of surface area, and the hide.
) must occur to induce losses. Pigments surrounded by a plastic barrier layer cannot be collected again.

(bl) Pigment voids - This group can be encapsulated without filling the pigment voids with an encapsulating polymer, which is a negative aspect encountered in current microvoid technology.
111de), dust pick-up/staining, gloss-limiting rings], both conversion and humidity can be achieved at the expense of a portion of the main pigment.

(cl colored surface material - multi-3) - This is the first problem of paint chemists. The encapsulated colored pigments are colored, color receptivity (rul-up)'1, floating Dlnaling),
Eliminate problems such as flooding.

Non-monolithic solids are those that are insoluble in the vehicle in which they are applied. (1) The carrier solid can be organic or inorganic.

Reduce the water contained in the initial charge to a water/total solids ratio of 4/6 to
It can be easily varied over a range of 7/3, in which the total solids is equal to the monomer and non-monomer (pigment) content. Water is not a solvent in the present invention because pigments, monomers, etc. are insoluble in it. The water serves as a thermal control mechanism and forms the liquid phase of the emulsion. Small amount (e.g. 10% or less)
Non-aqueous solutions of can be used with water. Examples of such non-aqueous solutions are alcohols such as methanol, ethanol, n-propyl alcohol, n-butyl alcohol, amyl alcohol, isopropyl alcohol, sec-butyl alcohol, isobutyl alcohol, 4-methyl 2
-Pentanol; ethers, eg U-'[: thyl ether, diethyl cellosolve, butyl ether; anhydrides, eg benzaldehyde, furfural.

The most preferred stabilizer or protective colloid is '[”-])et
N-1007 (Pson-Howard), a 100-mole ethoxylate of nonylphenol. Typically (jgLLO8IVE, poly(vinylpyrrolidone)
, poly(vinyl alcohol) alone or T-Det
Can be used with N-1nn7.

Suitable stabilizer concentrations are from 0.5 to 45 parts based on solids (pigmented medium). For high surface area pigments, up to 10 parts based on total solids may be required. There are some cases where the monomer alone is sufficiently surface active to effect a dispersion of a pigment (or non-monomeric solid), and the encapsulating polymer can still maintain a stable dispersion. Examples include vinyl acetate or N-vinylpyrrolidone (GA
V-Pyrol). The presence of anionic surfactants as wetting agents or stabilizers is extremely detrimental to the stability of the dispersion. Usually, a system that effectively forms an initial dispersion of the pigment is advantageous;
Several cases of improved dispersion were observed during the early stages of j-coalescence formation. It is believed that oligomeric moldings of the polymer or their grafts contribute to the degree of dispersion and its stabilization in a manner similar to postulated similar processes for conventional latex polymerization. The pigment (or non-monomeric solid) to monolithic ratio is preferably 971 to 1/9.

A carboxylated polymer layer can be formed if a comonomer such as acrylic acid or methacrylic acid is added at the final stage of the process. In this case, the anionic character of such carboxyl monomers appears to be weakened by preforming of the polymer layer. Also, anionic surfactants can be added at the completion of encapsulation without causing dispersion instability. Polymerization temperatures ranging from 40° to 85°C are preferred. Many types of latex-type processes can be employed. Preferably, the monomer (5 to 10% of the total mass) is added initially, followed by the addition of the monomer raw material. Other processes that can be used in the present invention include (In:%
! Adiabatic system in which the whole thing is charged, and then the catalyst is charged (
2) staged feed systems or staged adiabatic systems; (3) core/shell type systems in which different monomers are fed sequentially or reacted adiabatically or employ a staged polymerization process. Suitable monomers include vinyl acetate, butyl, ethyl, 2-ethylhexyl and heinbutyl acrylate esters, styrene, acrylonitrile, methyl methacrylate, vinylpyrrolidone. (2) For example, a styrene/vinyl acetate copolymer is not easily formed, since the usual relationship of (-4) appears to prevail in chemical polymerization.

Even vinyl isobutyl ether is useful in copolymers. Applicable to conventional emulsion polymerization 1. Obtaining original J((!) is applicable as long as care is taken to keep the system as low as possible for the initial design.

The pigment should have good dispersibility and, if desired, be evenly distributed throughout the surface area or entire body to be colored. Since 11 (V, solid) is well dispersed in the polymer-encapsulated face 1 (or solid) dispersion, such behavior eliminates or minimizes the separate work of dispersing the pigment (or solid). do.

The present invention includes the use of at least 1s nonionic surfactant or wetting agent. Nonionic surfactants have essentially no charge when dissolved or dispersed in an aqueous medium. The hydrophilic tendency of nonionic surfactants is primarily due to the oxygen in the molecules being hydrated by hydrogen bonding to water molecules. Although the strongest hydrophilic moieties in nonionic surfactants are ether bonds and hydroxyl groups, hydrophilic ether and amide bonds are present in many nonionic surfactants.

Commercially available nonionic surfactants include ethoxylated alkylphenols, ethoxylated fatty alcohols, carboxyl esters, carboxylamides, polyoxyalkylene oxide block copolymers, and are useful within the scope of this invention.

Nonionic ethoxylated alkylphenols are typically C8
~012 Members or derivatives thereof, such as nonylphenoxypoly(ethyleneoxy)ethanol, dodecylphenoxypoly(ethyleneoxy)ethanol, and octylphenoxypoly(ethyleneoxy)ethanol. Examples of useful non-ionic ethoxylated alkylphenols or more particularly alkylphenoxypoly(ethyleneoxy)phenols (with alkyl groups shown in some examples) include Adsee 50, Advawet,
Agrimul 70A.

Atkaflo-E %Br1tes EQC-10 (
Linyl), Carboxane J)Q, Carbo
xane NW, IConco Nl-21 (nonyl)
,Depcopal,f)c,rgon,l)i
5pcrsant NI-0, Dispersani N
'I-W, h;5trnnon NT (:onc.

Examide-Q, TJipochem AIL-
1no, )) yonic PE-100, Iber
scour WConc, ■berwet W-1f
lo, 1gepa ICA-630 (octyl), Tg
epal CA-73n (octyl), Igepal
C0-210 (nonyl), Jlyepal CQ-4
30 (nonyl), Jgepal CQ-550 (nonyl), Igepal C0-630 (nonyl), Igep
al C0-710 (nonyl), Tgepal Co-
730 (nonyl), TgepalCo-850 (nonyl), 1', gepal CQ-880 (nonyl), Ig
epal DM-530 (Sialgyl), [IHepa
InM-73° (dialkyl), Tgepal i
, o-43o (a-alkyl), Igepal T,
0-520 (linear-f Lukil), it! epaIL
O-630 (linear alkyl), Igepal T, 0-
730 (linear alkyl), Pnlyterge
ll-35tl (nonyl), Polytergen
t a-3on (octyl), Pnlytergen
tG-400 (octyl), 1lenex 64B (
nonyl), 1(enex 650 (nonyl), Ren
ex 67B (nonyl), f (enex 690 (
nonyl), 74. etzanol NP-40, 1et
zanol NP-80,1letzanol NP-
i20,l(etzanolNP-200,Ret,z
anol NP-500, 3o1ar 4 Liqui
dConc,, (nonyl), 5olar 12 (nonyl), 5olar 53 (nonyl), 5olar N
P 100 (octyl), 5oLar NP Liqu
id Cone, (nonyl), 3o1ar NPO (nonyl), 5pOntO200, 3tandopon,
5urfonicN-40 (nonyl), 5urfon
ic N-60 (nonyl), 5urfonic N-9
5 (nonyl), 5orfonic N-120 (nonyl), 3orfonic N-200 (nonyl), 5ur
fonic N-ro0 (nonyl), 5ynthonon
100 (nonyl), T-DET N-4 (nonyl)
, T-DET N-6 (nonyl), T-T)l':T
N-9,5 (nonyl), T-DBT N-12,5 (nonyl), T-T)ET N-15 (nonyl), T-Dl
;'rN-20 (nonyl), ntexon NP-3
(nonyl), J, ewelene (nonyl), Lip
al 9N (nonyl), Mak on 4, Ma
kon 10, Makon 20, Makon 30,
Neopon NP-10, Neutronyx 60
0 (nonyl), Neutronyx 605 (isooctyl), Nevtronyx622 (nonyl), N
eutronyx (nonyl), Neutronyx
676 (nonyl), N1noxBl)Q, N1no
x13)”Q, Non1onic E-4 (linear alkyl), Non1onic E-10 (linear alkyl)
, Nnn i on icE-15 (W-alkyl)
, Nntrosan 'l'3 Conc.

(Nonyl), Polytergent l” (-300
(nonyl), Tergitol J, +2-P-6 (dodecyl), 'l'ergi tol 12-P-9 (dodecyl), T'ergitol 12-P-12 (dodecyl), 'l'ergi tol N+'- 14 (nonyl), Tpr 7 mouth 01NP-27 (nonyl), 'l
"erIyi tnl NI'-1+ (nonyl), T
ertitol NP-55() = Jl/ ) Te
rgitol NP-44 (nonyl), Triton
N-57 (nonyl), Triton N-101 (nonyl), Triton N-IN (nonyl), Trito
n X (5 (octyl), Tritnn X-45 (octyl), TrNnn X-100 (t-octyl),
'priton X-102 (t-octyl),'l''
riton X-114 (t-octyl), i'rit
on X-165 (octyl), Triton X-2
05 (octyl), 'priton X-305 (octyl), and 'JaIdet (nonyl).

Examples of useful non-ionic ethoxylated 111 fatty acid alcohols or, more particularly, alkyl poly(ethyleneoxy)ethanols (with alcohols shown in some examples) include A, Ifonj C12113-60 (73-grade, linear Alfonic 1012-60 (primary, linear), Alfonic 1014-60 (primary, linear), Alfnic 1480-(So (primary, linear), Al to 5cours] (B.

Antarox T3L-350, Antarox L
F-330,Arosur fJ'L-457
(Oreil), Arosurf JL-758 (Oreil), Azocrest, Tl1o 5oft E
A-10, T3rij 30 (Lauryl), 1lrij
35 (Lauryl), 13rij 52 (Cetyl),
[3rij 56 (cetyl), Br1j 58 (cetyl), Br1j 72 (stearyl), nrij
76 (stearyl), '(3rij 78 (stearyl), 13rij 92 (oleyl), Br1j 9
6 (oleyl), Br1j 98 (oleyl), Ca
rboxane TW-85, Cerfak.

Crestomul L, ])epconol 1
11, Dergopen rlN.

J) rupene VO-250, Emnon 695
4, Emulphogene BC-420 () lysocil), Emulphogene BC-610 (tridecyl), Emt, +Iphogene 13C-840 (
tridecyl), &nulphor 0N-870 (oleyl), I, 1pa130 SA (stearyl), L
ipa13TD (tridecyl),'[,1pal 6
TD () Lysocil), ], 1pal 10TD ()
Lysocil), Neodol 23-5 (C12-13
(Uniform linear), Neodol 23-6.5 (C1
215th - unified linear ), Ne0d01 2F)'!
'+ (C12-15 -grade - line 1 large), N
eodnl 25-7 (C42-1, 1st 4Jj -
H'l)''), Ne0d0125-9 (Cth unified linear), Ner+rlol 25-122-15 (C12-45th unified linear), Nutrosan U
-9, Plurafac A-38, Poly 'I'
ergenf, , T-2On (tridecyl), Po
1y 'I'ergent J-5n (1() Lysocil), Promulgen 1703, Mouth enex 30
(Tridecyl), Retzanol SN, 3ip
onic L-4 (lauryl), 5iponic TJ
-12 (Lauryl), 5iponic L-16 (Lauryl), 5iponic T, -25 (Lauryl), E
thosperse LA, -4 (Lauryl), Etb
osperseLA-12 (lauryl), Elhosp
erse LA, -23 (Lauryl), l・; th
o sp e r se QΔ-9 (Oleyl)
, Ethosperse TT) A-6()
Sil), FylllO'5perSeTDA-12 (
) Lysocil), Examide-1) A, , I°'
ory1100, Hyonic KO-<S20, Tg
epal A, (M-type alcohol-A/) Kyro
EOB, Lipal 610 () Lysocil), Lip
al 2 CA (Sechi 71/), i, 1pal 9
T, 8 (Lauryl), I, 1pal 4 T, A (
Lauryl), J, 1pal 12 LA (Lauril)
, Lipal 23 LA (Lauryl), T, +pa
l 4MA (myristyl), T, +pal 8 MA
(Myristil), Lipal 20A (Oleyl),
'[, 1pal 50A (Oreil), T, 1pal
100+A (Oreil), Lipal 20 OA
(Oreil), Lipal 50 OA (Oreil)
,:[,ipa! 20 SA (stearyl), St
andamul 18.5tandapon 209.
5urfonic JN-70 (n-alkyl), 3u
rfonic NY-50 (first control line), 5urf
onic NY-66 (first control line), 5urfon
icNY-150 (first control line), 5urfonic
NY-300 (first control line), Te1kanite
M, Tergitol3-A-6 (tridecyl),
'I'ergitnl 15-8-5 (Second Class, CN
-45),'l"ergitol 15-8-9 (M
Secondary C1, -45), Tergitol 15-8-1
2 (secondary, C11-15), Tergitol 1
5-8-1-5 (secondary, C11-1,),'per
gitol 45-8-9, Tergitol 44-8
-1o, 'I'ergitol TWN ()limethylnonyl), Triton X-67, VOJI) 03
(Oreil), VOl p.

10 (Oreil), VOll) 020 (Oreil),
TrycoL LA, T, -4 (lauryl), Tryc
ol LAL-8 (lauryl), Trycol LAT
J-i2 (lauryl), TrycolLA'TJ-2
3 (lauryl), 7ryCol TD/r-6 () lysocil), Trycol TT) A-9 () lysocil),
TrycolTDA-15 () lysocil),'l”ri
cnl 'rDA-18 (tridecyl), 'prico
l 0ATJ-23 (Oreyl), 5ternxAJ-
100 () lysosil), 5teros AP-1rll
l (tridecyl).

Nonionic carboxylic acid ester type surfactants are polyol-solubilizing, polyoxyethylene-solubilizing, or both, and are based on several different types of hydrophobes. Non-f-one carboxylic esters include glycerol ester, polyethyl/glycol ester, anhydrosorbitol ester, and ethoxylated anhydride! -1 sorbitol esters, ethylene and diethylene glycol esters, propane diol esters, and ethoxylated natural fats and oils. Examples of useful nonionic glycerol esters of fatty acids are A, ldo MC (monococcoate)
, Aldo ML (monolaurate), A, ldo
MR (monolysylate), Aldo MS, Na
1. ['or, (monostearate), Ar1acel
165 (monostearate), Atomo X (, Jt
mos) 150 (mono- and di-fatty acids), Atmul
80 (mono- and difatty acids), Atmul 124 (
(mono- and di-fatty acids), A-tmul 500 (mono- and di-fatty acids), Cerasynt Q (monostearate), Drewmulse CNO#70 (mono-y-coni-)),]) rewmulse GMO (mono-ole r--)), Drewmulse )-IM-1
00 (monostearate), Emcol MSC (monostearate), Therest 2400 (monostearate), ) Therest 2421 (monooleate), Flexricin 13 (monolysylate), ] (allc.

CPTr-x4-N (monolaurate), FTall
co CP)-T-35-N (monolysylate), T
-Jodag (LA conversion (monolaurate), Hada
g GN40 (monooleate), Hodag CE
SIR, (monolysylate), Hodag (1,s
(monostearate), Kessco Po5ter
(shade), Kessco Ester (monooleate), Kessc.

5ter (monostearate), Monofl
ake (monostearate), Myverol']
”ype 1B-45 (cotton seed, mono), Myverol
TY+) (418-98 (safflower oil, mono), 3
urfactol 13 (monolysylate), Un
iwax- (contains monostearate).

Polyethylene glycol-based nonionic surfactants are polyoxyethylene esters of cycloaliphatic carboxylic acids related to fatty acids and abietic acid.

Examples of useful nonionic polyethylene glycol ester fatty acids, resins, and tall oils (with the degrees of esterification and acids indicated) include Aldosperse ■'-14 (mono, lauric), Aldosperse Q-9 (mono,
olein), J, 1dosperse S-9 (mono,
Stearin), Aldgsperse 5-40 (mono, stearin), Arosurf TIPL-418
(q=), laurin), A, rosurfI-■FL-
714 (Mono, Laurin), Arosurf) 1FS
-546 (mono, stearin), Arosurf [I
F5-846 (mono, stearin), Arn5t+r
f TTF'l"-453 (mono, tall oil), Car
L>oxane 865 (mono, fat), Emcnl
H-31A (mono, olein), t)nest
2620 (mono, laurin), :・notification erest 2
622 (Di, Laurin), Emerest 264 [
1(-E-], stearin), 1'Mnere s
t2642 (di, stearin), 1knerest
2646 (mono, olein), Emerest 2
650 (Mono, Laurin), Emerest 2 (S
52 (Di, Laurin), Emerest 2660 (
mono, olein), Ernulfor VN-430
(mono, fat), Fmulsynt 60n (di, olein), EstexP4-0 (mono, olein)
, Estex R4-8 (mono, stearin), Estex
ex SE 750 (mono, laurin), Kessc
o Ester (mono, laurin), I<eSSCO
Ester (The, Olein), Kessco Est
er (mono, olein), KesSco Ester
(di, stearin), KeSSCO (mono, stearin), Kessco Ester (mono, laurin),
Lipal 300 DL (di-laurin), 7. i
pa+ 400 DS (di, stearin), Lipa
l 300s (mono, stearin), Moroso1
120 (mono, stearin), Morosol 3F
(mono, olein), to (orosol 4L (mono, laurin), ~1yrj 45 (mono, stearin), Myrij 52 (mono, stearin), Neu
tronyx 268 (di, stearin), I'Je
utronyx 330 (mono, soybean), Neutr
onyx 352 (mono, stearin), Neutr
onyx834 (mono, olein), Non1sol
100 (mono, laurin), Non1sol 200
(mono, olein), Non1sol 300 (mono, stearin), Nopalcnl6-L (mono, laurin), Nopalcnl 6-0 (mono, olein), Ethofat C/15 (mono, palm), E
thofat C/25 (mono, palm), Ett+n
fat 142. /20 (mono, tall oil), Etho
fat 242/25 (mono, tall oil), th
ofal: n/15 (mono, olein), Etho
fat C/20 (mono, olein), l'1hof
at60/15 (mono, stearin), 181. hnf
at 60/20 (mono, stearin), Ethofa
t 60/25 (mono, stearin), LTodag
2O-TJ (-E), laurin), )(odag
4O-TJ (mono, laurin), Hodag 4O-
0 (mono, olein), [(odag 40-8 (mono, stearin), J-Jodag 40-R (mono,
Ricinol), I (odag 42-T, (di, two 1
1), Horlag 42-8 (di, stearin)
, Horlag6 [1-TJ (mono, laurin), )
(odag 60-s (mono, stearin), 1.f
odag 7S2-0 (di, olein), Tlodag
62-8 (di, stearin), Hodag 150
-8 (mono, stearin), Hodag 15o-0
(di, olein), Keripon NC (%), fat), Kessco Ester (mono, laurin),
Kessco Ester (Laurin), Peg
osperse400-DL (di, laurin), Pe
gosperse 400-D.

(The, Olein), Pegosperse 4oO-D
S (di, stearin), Pegosperse 40
0-MoT (Mono, Thor), Pegosperse
200-ML (mono, laurin), Pegospe
rse 100-MR (mono, ricinol), Pego
sparse 100-MS (mono, stearin),
Pegosperse 1oo-0 (mono, olein)
, R6nex20 (mono, fat and rosin), RJT
Ba5e (mono, fat), 5oltex 3835
(mono, fat), Stearox
CD (-t=/, tall oil), 3urfactan
t ARj50 (mono, rosin), '17eox (
Trydet 5A-8 (mono, tall oil), Trydet 5A-8 (mono, stearin), Trydet 20 (mono, tall oil)
, ■arconicQ510 (mono, olein), Vi
sco], -N17 (%), stearin).

Commercially available polyoxyethylene fatty acid ester contains the following ingredients:
Monoester, RCOO(OCH2C'H2)nOH;
Six, x, seven-le, RCOO(OCI(2e%
).

00CR; Polyglycol, I((OCIi2C'I(
2) It is a mixture containing nOH in various proportions.

Sorbitan is a mixture of anhydrosorbitol.

Examples of useful nonionic fatty acid esters of sorbitan (with the esters indicated) are A, rtnot a nλm
(monolaurate), A, rmotan MO (monooleate), Armotan MS (monostearate 1), ]) revwnulse SML (monolaurate), ]) revwnulse SMO (monooleate), l) revmulse SMP (monopalmitate), l ) rewmulse SMS (monostearate), Emsorb 2500 (monooleate), 'Eknsorb 2505 (monostearate), Ems or b2510 (Mo/Ba A/
' fitate), Emsorb 25113 (trioleate), 5orb 2507 (tristearate), Estasorh L (monolaurate), E
stasorb P (monopalmitate), 1zst
asorh S (monostearate), Estasor
b Q (monooleate), Estasorb 'l
'S () Restearate), Estasorb To
() lyoleate), Glycomul TJ (monolau V-1-), Qlycomul O (monooleate), Glyconllll P C monopalmitate)
, Qlycomul'S (monostearate), H
odag S■” (monolaurate), Hodag
SMP (monopalmitate), Tlodag SMS
(monostearate), LTodag STS ()
listearate), I-Tod ag 5M0 (monooleate), Hodag STO (lioleate)
, 5pan 20 (monolaurate), 5pan 4
0 (monopalmite)), 5pan 60 (monostearate), 5pan 65 (restearate)
, 5pan8 (monooleate), 3pan 85 (
) lyoleate).

Useful ethoxylated anhydrosorbitol esters,
Or more specifically, examples of polyoxyethylene derivatives (with the indicated esters) of sorbitan fatty acid esters are A
rmotan PML-20 (monolaurate), A,
rrno tan PA, 40-20 (monooleate), Armotan PMs-20 (monostearate), :Qrewnmoe5ePQI>-8M0 (monooleate), ]) rewmu I se PQ
E-8ML (monolaurate), ]) rewmulse
POE-3MP (monopalmitate), I) rewm
ulse PQE-8FvfS (-E: nostearate), Drewmulse POE=STS ()listearate), lk++prite 61211 (monooleate-1-), Emrite 6125 (monostearate 1), Emri+e6127 (tristearate), +il ycnsper seI, -20 (monolaurate), (iricosperse n-20(
monooleate), ()1ycnsperse Q-5
(monooleate), (ilycoqperse P-
20 (Mononoku Lumitate), C (Lycospers
e S-4 (monostearate), Glycosper
se 5-20 (monostearate), Glycos
perse To-2n ()
), Glycosperse'rs-20 (tristearate), ■ (odagPSFvfT, -20
(monolaurate), llodagPSMO-20 (monooleate), tlorlag l'5M1)-20
(monopalmitate), T-1odag ljsMs-
20 (monostearate), Tlodag PSTS-
2n () IJ Sf'7 rate), T-T
odag 1'ST, 0-20 () IJ o vx
)), 5orbinox), -20 (monolaurate), 5nrbinoxO-5 (monooleate)
, S old + i mouth ox Q-2 [] (monooleate)
, 5orbinnx P-2n (monopalmitate)
, 3orbinox 5-20 (monostearate)
, 5orbinox TO-20 () lioleate),
5orl] 1noxTS-20 () Restearate),
'17wep, n 21 (monolaurate), Twe
en20 (monolaurate), Tween40 (monopalmitate), TXveen 61 (monostearate), Tween 60 (monostearate), 'l'
ween 65 () Listearate), 'J'Xve
enP1 (monooleate), TIvepn 80 (
monooleate), 'J'ween 85 () lyoleate).

Examples of useful glycol esters of fatty acids (with the indicated esters) are Cerasynt M (EG stearate), l) rewmulse EGMS (BG monostearate), l) rewmulse Eaos (
EG distearate), F7nerest 2350
(E(3 monostearate), J(allc.

37-N (EG monostearate), T-1oda
g EGS (EG monostearate), Kessco
Ester (EG distearate), Kessco
Ester (EG monostearate), Ceras
ynt W ('[)IIG monostearate), col CAD (D stearate), col 5
(DEG oleate), 1 cal RDCD (DE
G Cocoate), Etr+erest 23(So (
DEG monostearate), J (odag DGTJ
(DI2G monolaurate), Hodag'DGO
(DEG monoo vx-)), TIodag 'D('i
S (DI"+Q monostearate), Kess'c
o Ester (T'll et al. monostearate),
Cerasynt PA (P(↑monostearate)
,Drewlene 10 (PG monostair 1/-t) ,'DrevwnolsePCM, (G monolaurate), ■)rewmLIIseP(,'
l'Js (PGmo/X Thea L')), I'rnere
st 2WIH(P(f-r::nostea l/-))
, I:'rneres 1.2'58 (S (P(+distearate), Tlal lco CI) TI-32
(PG % nostearate), ) (odag P(NL
(P('f % nolaurate), Hndag PCM
5 (PG monostearate), Pegospersc
PS (P (3 stearate), 1 stearate, 1 stearate, DI (G is diethylene glycol, PG is propylene glycol) is a useful ethoxylated nonionic surfactant. natural oils,
The wax is ethoxylated castor oil.

Nonionic surfactants include carboxylamides, such as jetanolamine condensates, monoethanolamine condensates,
Contains Impropano-V amine condensate. Examples of useful fatty acid non-indicating diethanolamines are coco, laurin,
These are jetanolamines of olein, myristicin, stearin, and ricinoleic acid. Examples of useful nonionic monoalkanolamines of fatty acids are those of lauric, coco, oleic, stearic acids where the amine moiety is ethanol or isopropanol. Nonionic surfactants also include, for example, nonionic polyoxyethylene fatty acid amides of coco, lauric, and oleic acid.

The nonionic surfactant is a polyalkylene oxide block copolymer such as Tergito from Union Carbide.
l XI (and
Contains 0.

The initiator or catalyst system appears to be important for pores resulting in polymer-encapsulated pigments (or non-monomeric solids). The most preferred system is t-butyl hydroperoxide with sodium formaldehyde sulfoxylate (redox system)
It is. Hydrogen peroxide/sodium formaldehyde sulfoxylate and hydrogen peroxide/ferrous ion systems are preferred.

Previous attempts to use hot potassium or ammonium persulfate or potassium persulfate/sodium formaldehyde sulfoxylate redox systems have been unstable. It is clear that the anionic character of such systems, like anionic surfactants, somehow prevents encapsulation.

The initiator can be a free radical initiator. Suitable free radical initiators are peroxides. Examples of useful peroxides are dialkyl peroxides such as di-1-butyl peroxide, lauroyl peroxide, decanoyl peroxide, 2-methylbentanoyl berooxide, acetyl peroxide, 2,5-dimethyl-2,5-di( t-butylperoxy)hexane, 2,5-dimethyl-2,5-
di(1-butylperoxy)hexyne-3; diaryl peroxides, such as benzoyl peroxide; alkaryl peroxides, such as dicumyl peroxide; sulfonyl peroxides, such as acetylcyclohexylsulfonyl peroxide, acetyl 5eC-hebutylsulfonyl peroxide; peracid esters , for example t-butylperbenzoate, t-butylperoxyneodecanoate, t-butylperoxypivalet), 1,1,3.
3-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-butylperoxy-2-ethyl-hexanoate, t-butylperoxy Isobutyrate, t-butylperoxymaleic acid, oo-t-butyl 0-inpropyl monoperoxycarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperacetate, di- t-Butyldiperoxyphthalate; peroxydicarbonates, such as di(inpropyl)peroxydicarbonate, diisopropyl peroxydicarbonate, di(5ee-butyl)peroxydicarbonate, di(2-ethylhexyl)ber Oxydicarbonate, dicyclohexylberoxydicarbonate, dibenzyl peroxydicarbonate; organometallic peroxides, such as vinyltris(t-butylperoxy)silane; hydroperoxides, such as t-butyl hydroperoxide, cumyl hydroperoxide, 1,1 .3.3
-tetramethylbutyl hydroperoxide, 2,5-dihydroperoxy-2,5-dimethylhegisane; azo compounds such as 2,2'-azobis(isobutyronitrile), 2,21-azobis(2,4-dimethyl Valeronitrile).

The polymer-encapsulated pigment (or non-monomeric solid) dispersions of the present invention are stable and do not separate upon centrifugation.

High speed agitation (eg, 3 or more cycles per minute of dispersion) during the preparation of the polymer-encapsulated pigments (or non-monomeric solids) of the present invention has the disadvantage of causing foaming. The present invention provides water-based dispersion coatings that can be KM'ed from non-ionic systems.

Other than the above limitations, water soluble monomers such as acrylic acid, methacrylic acid, etc. do not act as nonionic monomers within the scope of the present invention.

Reagents The following is information about some of the reagents used in the examples below.

(1) PMA-30 is a 30% solution of phenylmercuric acetate.

(2) Atomite is Ca Cox, a pigment manufactured by Thomson and Pineman.

(3) ASP-170 is a clay pigment manufactured by Engelhardt.

(4) Zopaque RCL-9 is Guriday (Q
It is a TiO2 pigment made by the Pigments Division.

(5) CBLLO8IZ, E■ is hydroxyethylcellulose manufactured by Union Carbide Co., Ltd.

(6) Igepal Co-99o is produced by GAF.

(7) Ti Pure R-931 is E, 1. It is a TiO2 pigment manufactured by DuPont Nemer.

(8) U CAR Latex 351 is a vinyl acetate/n-butyl acrylate resin manufactured by Union Carbide with 65% solids and a nonionic stabilizer system.

(9) Rhoplex AC-388 is Rohm and Haas's acrylic latex (used for paint)
It is.

(II Nytal 300 is Vanderbilt (■a
It is a talc pigment manufactured by Derbi It.

Ql) Tamol 751 is a Rohm and Haas dispersant.

(12+ Titanox 2020keNT, TiO2 pigment manufactured by Chemicals.

(13L-475Ant 0anl is silicone.

<14) UCA, R■TJateX 367 is a polymer of M acid bi=#7]% and n-butyl acrylate 22X.

α5'l'exanol is a fusion acid manufactured by Eastman.

06) R-900TiO2 is l-;, 1. Manufactured by the Dupont Nemmer Company.

C7) 0P-44Dnll is Union Carbide's GET, LOS I/? : ■Hydroxyethyl lucose.

O8GOLT) IJONI) 11 HashilJ There is power.

(11Celite 281 is John Mahbir (L'
silica-filled (
It is a drug.

KanColoids 581-13 is a surfactant.

(211Tronox CR-822 is a TiO2 pigment manufactured by Kerr-McGee.

f221NatrosoI is hydroxyethylcellulose-?ll-al manufactured by Hercules.

(23+ I-1212 is a 55% PVC internal pigment formulation published by Union Carbide.

C24) Na1co is an antifoam agent.

(25) 5atintone Nn 5 is clay.

C1bl Dowicil 75 is a formaldehyde release agent used as a biostatic agent.
t).

@T-DET-N-507 is a 100-mole ethoxylate of nonylphenol from Tompun-Howard.

The following examples illustrate the invention. All parts, percentages, ratios, and proportions used in the examples are by weight, unless otherwise stated or otherwise obvious to those skilled in the art.

Example 1 Finely divided precipitated CaCO3 was encapsulated with a vinyl acetate and n-butyl acrylate copolymer (80/20) similar to typical commercial or retail latex copolymers. The pigment-to-resin ratio was 25 to 75. A nonionic surfactant, a nonionic initiator, and a nonionic catalyst (redox type) were used.
a The presence of COs was confirmed by E DAX sharpness.

Example 2 A physical blend of particles of latex (R, hnplex A, C-388) and Merck (Nytal 300) at a polymer to pigment ratio of 4:1 was made. Shadow micrographs of the blends show that latex particles are predominant. This is an example of the prior art.

Example 3 11Joplex A-C-388 and talc (Nyta
A physical blend of the particles was made with a polymer pigment ratio of 1:4 (1:500). A shadow micrograph of the blend shows that the pigment particles are predominant. This is an example of the prior art. ' Example 4 Finely divided talc particles (Nytal 300) were encapsulated with poly(vinyl acetate) at a polymer encapsulation ratio of 4:1. A nonionic surfactant, a nonionic initiator, and a nonionic catalyst (redox type) were used. Examination of the SEM micrographs did not show any presence of spherical latex particles. The shape of the talc particles is such that latex particles are easily formed.

Example 5 Conventional Commercial Semi-Gloss Production Sample [Pigment Volume Concentration (PVC)]
2 (S%) SEM photograph and EDAX tracking were performed. SEM is scanning electron microscopy, and BDAX is SE
This is an analysis of the fluorescence pattern associated with M. 26-PVC
The paint was made as follows; 34.6 pounds of propylene glycol (15,7 to 9) and 2 gallons of water (81
Mixed with ri.

Tr-475 Antifoam 3 bond (1,4k
li'), Tamo1731 15 bond (6,a
kg), '[riton Gl't-72 Bond (o9
kg), Igepal CO-8804 lb (1,s
kg), rt-9no Tto, 240 bond (100
kg), PMA-900015 bond (o, n6skg
) were added continuously. The mixture was milled at high speed for 20 minutes. Two gallons (81) of water were used as a starting point. 40.5 ounces of water (153,11 liters, T, -475 Ant
ifoam 3 bond (1.4kg), QP-a4o
4 bonds of OT (1.8 kg) and 1 bond of 29% ammonia solution (0, 4 kg) were pre-mixed in order 11a.

The premix was dissolved and added to the main mixture in 41.4'l'L. [(hoplex A, (, r −
38029 [1,4 bond (16iaky), TJca
r@T, at+prex 367 B 1.27 bond (3
6,90 kg) were added continuously with stirring. Once all ingredients were added, the mixture was mixed for 3 minutes (excessive mixing time may cause foaming). 'l'1ta
nnx Near 0HI (NI-6 Engineering Y, Titanium Pigment Division, Titanium Dioxide) is written in -2 (i' i equivalent to S-PVC paint i' 02/-!I! Combined (resin) ratio (26
8 rows of vinyl acetate were encapsulated with a 16% polymer at %I''VC), and based on this, SEM imaging and l:1)AX tracking of the polymer-encapsulated pigment was performed.

In both paints, the TiO2 particle size (0.2 microns) is very similar to the latex size (~0.5 microns), so the comparison is even greater than in the above examples. Nevertheless, traditional paint (26-P
VC paint), the latex/pigment mixture is clearly visible, whereas in the paints containing polymer-encapsulated pigments only one type of encapsulated particles are evident.

Example 6 TiO2 (Titanox 2020) as a dispersant ('l”amol 731) used in conventional paint technology
to obtain an aqueous dispersion. This was a control. A real paint was made based on the following formulation.

Table 1 P V C X ladder (■, adder) TRONOX
CTl-822/11TJC. ATl”T, ATEX
36 (S pulverized material heavy goods department water 1800 QP-44110 4.

Tamol 731 1 2. n TERGITOT,■NPX 4 0 Cnlloids 581-132.0Nuosept
95 1.0 Titanox 2020 240.0 Propylene Glycol 400 '['exanol 1 2. .

UCAR■7, atex 566 389.11Tri
ton (xTl-7 1.0 water or 3XQl'-a4oo~851<[J 1 3
9. [IN1(40H1)II 8.5 The resulting paint had total solids 45X, PVC'2 5%. This was traditional paint.

At equivalent TlO2/polymer ratio (25% PVC)'
A polymer-encapsulated pigment was made by encapsulating l:'1tanox 2020 with poly(vinyl acetate). SEM micrographs were performed at three regular meetings. By comparing the photographs of the control TiO2 dispersion, ie, conventional pigment, and the polymer-encapsulated pigment, the difference of the polymer-encapsulated pigment versus the TiO2 pigment control and the paint mixture was very evident.

The polymer-encapsulated pigment appeared to consist of uniform encapsulation without the presence of latex particles, which was not the case with the control and paint mixtures.

Example 7 TiO2 was encapsulated with a co-M polymer of vinyl acetate and butyl acrylate (a4X-16X) - The ratio of Ti02 to copolymer was 50:50. 22 Polymer-encapsulated TiO2
%PvC paint had 2.1 pores per gallon)” (252! pores per liter) Ti02.S.
EM micrograph of 22-P with polymer-encapsulated pigment
Cross section of film with VC composition and commercial 26 PV of Example 5
A cross section of a film of pigment C was examined. Paint is 2.4 bond per gallon (288.9 per liter)'r
i (1,, had l,.

In the cross section of the film of the present invention, the film itself has fewer holes than in the cross section of a conventional paint film.
Moreover, it appears that each TlO2 core is evenly distributed in the cross section.

Example 8 A number of other observations provide indirect evidence that there are real differences between conventional paint and polymer-encapsulated #1 format. 6 mil (0
, 151111) A side-by-side comparison was made of the Wei type drawdown, and when the film was dried, the visual appearance,
Rin existed. Equivalent pigment/polymer ratio (+?j+-P
Although the measured gloss difference was not large when measured with a conventional 60 gloss meter at VC level), the polymer-encapsulated pigment film has similar clearness of image (DOI) properties not found in traditional paint films. Adds sexiness or shine. Most such comparisons are made with Leneta (Leneta).
ta) Chart or Reneta scrub-resistant panel. When the polymer-encapsulated pigment film was cast onto a metal surface (aluminum panel), it appeared to transfer the metal surface to a semi-gloss paint film.

Also, when performing comparative scrub resistance measurements of conventional semi-gloss paints compared to polymeric encapsulated pigment films, reasonable attempts are made to maintain a high molecular weight in the encapsulated pigment layer, which is done using conventional latex technology principles. In some cases, advantages have been seen for polymer-encapsulated pigment films. Also, a clear improvement in hiding of the polymer-encapsulated pigments compared to conventional paints was observed. These differences are largely due to competing plastic pigment technologies, such as Glidden and Durax (1) UL.
This is the size found in those techniques reported by (ux). The latter provides equivalent concealment of TiO2 levels of approximately .

602, which makes it possible. There was also a special stability in the TiO2-based polymer encapsulated pigment dispersion.

84/16 50% based on TiO2 (RCL-9) encapsulated with vinyl acetate/butyl acrylate copolymer
Attempts to separate the supergenes by centrifuging solid, 15 PVC polymer-encapsulated pigment dispersions were unsuccessful. It was very stable and no separation occurred under the leftover conditions. A control 'r 1o 2 dispersion was not run, but it was run under conditions where significant separation was expected. Repeated observations were made during the preparation of the polymer-injected pigment dispersion which showed that very high degrees of dispersion were obtained. actual,
An optical microscope was used to check the dilution of the reaction mixture and the absence of large floraculates was often observed. The wetting action on the drawdown of multiple polymer-encapsulated pigment dispersions alongside conventional paints appeared to cause separation or demixing of the film. This apparent wetting incompatibility was eliminated by the addition of certain anionic wetting agents or by mixing conventional paints with polymeric pigment dispersions. All of these behavioral differences are 1
5 shows that there are substantial and potentially important differences between pigment technology and conventional paint technology or prior art related to plastic pigments.

Example 9 Zopaque RTJC-9TiO2 with excellent stability
(Glidden Pigment Division) Layer polymer-encapsulated pigment dispersion-15P
Type vC remained stable without syneresis after 6 months.

Tie2 for plastics rather than coating applications
Ti tanox2010, which is considered to be a variety of
(NL Kogyo, titanium pigment division), 97% TiO2
The best results were obtained with a content of 1% and traces (1%) of alumina (Al2O, .) surface treatment. A stable dispersion and good film quality were obtained and were reproduced from batch-to-batch preparation of polymer-encapsulated pigment dispersion 1c. Also, 'l'1tanox 2020, coating variety TiO2, has been used to make the polymer-encapsulated pigment dispersion. Trademark 'l'ron
Although TiO2 in OX CI(-822 (Kell-McGee) gave a stable dispersion, SEM photographs showed that the encapsulation was not uniform, and the polymer layer appeared to be asymmetrically unattached to the TiO2 particles. The film quality also deteriorated.

Water/TiO2 under the assumption that surface treatment exists.
Attempts were made to mix monomers, such as extraction with vinyl acetate. Severe foaming was observed without improving the encapsulation. In addition to the well-known alumina (A1203), silica (Sin2) treatments that are widely applied to coated varieties of TiO2, both organic surface treatments and pTT conditioning with ammonia, amines or alkali hydroxides are often employed, sometimes changes between lots. It is clear that the opposite effects occur from the organic and non-ionic surface treatment of many varieties of TiO2. Therefore, untreated, high purity Tho is preferred. A polymer-encapsulated pigment dispersion was prepared using Atomite (CaCO3) pigment and one vinyl acetate moiety with a pigment/polymer ratio of 90/111 and a total solids level of 71), 96'. A smooth, thick, but easily handled dispersion was obtained, but showed substantial syneresis after 1-2 days. This dispersion was made using 5 parts of T-Det N-10072 on solid. Improved stabilization occurs in 4-10 part solids. Pigment using polyvinyl acetate/
Polymer 1: 68% all-solid polymer of lZ90/10 untreated Qnyacarb to make a facial dispersion
CaC0s was used. No syneresis was observed even after 5 days. The viscosity was high but manageable, and the dispersion exhibited a low brushometer viscosity of 13 voids at high shear rates. Low shear rate viscosity or chicken tropism could possibly be lowered by adding anionic surfactants.

A 62% all solids polymer encapsulated pigment dispersion was made using vinyl acetate monomer plus clay (ASP-170) with a pigment to polymer ratio of 9/1. The dispersion remained stable even after one month, with no trace of syneresis and remained suitable for handling. In a screening experiment using red iron oxide, a very bright red dispersion was obtained. Screening tests with good results were carried out using zinc oxide, a reactive pigment.

Ti-Pure R-900 (DuPont, Ti02) did not easily disperse into the initial reaction mixture. Once the reaction has started, the 'I(-' 900) deagglomerates to give a smooth, stable dispersion.The film drawdown gives a variable appearance (gloss) after drying and and considerable variation was observed from pigment lot to pigment lot.'
1-Pure R-960 (DuPont) was readily dispersed in the initial reaction mixture containing the acetic acid monomer. The polymer-encapsulated pigment dispersion did not have significant stability and syneresis occurred after approximately one month. phenomenon (aqueous layer formation).Only one experiment was conducted using R-960.

The dispersion of j-Pure Tt-932 was poor under all conditions (no high quality polymer-encapsulated pigment dispersion could be produced).

R-931 is a NIψT i O211jI phase variety, and therefore poor dispersion was expected.

Using Beaverwhite 325 (talc) and vinyl acetate monomer, 70% pigment/polymer ratio of 9/1.
An all-solid polymer encapsulated facial Ne.1 dispersion was made. Substantial syneresis occurred within 1-2 days. An attempt was made to make a 56% all solids polymer encapsulated pigment dispersion of 325 mesh wet milled mica and again substantial syneresis occurred within 1-2 days.

Example 10 Concealment comparisons were also performed using the l,enet838 opacity chart for visual comparison. Equivalent content of TlO2 (
At 2,41 bS/gae (288 g/l)), the polymer-encapsulated pigment dispersion clearly provided better hiding power than the commercial paint formulation even when compared against tinted production material. Titanox2010
A number of visual comparisons were made of the polymer-encapsulated pigment rC based on the prior art over a wide range of polymer/pigment ratios. The highest attainable skin with conventional painting techniques is TiO in semi-gloss paints of 3. fl
~33”1s/gal, (359~395 Vl)
Extrapolation of visual comparisons shows that a polymer-encapsulated pigment dispersion produces an equivalent skin compared to TitanoX.
2.4~2.91h”/galt as 2010,
It was shown that it is possible to achieve a throat weight in the range of (2q o to 350 g/11). Uniform polymer layer, e.g. Ti
What is achieved with tanox 2010 is required.

Additionally, alternative techniques to increase hiding power, such as ()nya
fine particle pigment extender pigments such as carb Ul- or polystyrene plastic pigments such as those carried out by Glidden or styrene polyester encapsulated TiO of Dulux
From knowledge of the use of 2, the improvement in hiding that can be achieved with polymer-encapsulated pigment dispersions is at least 30% of the TiO2 content claimed and clearly achieved with these alternative techniques.
is determined to be equal to the reduction of .

Example 11 A comparison of the scrub resistance of the p-coallocated 11J pigment dispersion paint against the commercial paint from Example 5 is shown in Table 2. At equivalent binder acid content, the polymer-encapsulated pigment dispersion showed an approximately 4-fold increase in side-by-side comparison. For long-term (2 weeks) drying of the paint, the difference increased to about a 5-fold advantage for the polymer-encapsulated pigment dispersion. When preparing polymer-encapsulated pigment dispersions, it is recommended to use those techniques that maximize loading in typical latexes, such as low catalysts, low temperatures, and high elemental concentrations. Ba,
This maximizes scrub resistance. A comparative wet adhesion test to a glossy alkyd (aged Glidden shamrock green) was also performed on the same sample;
Neither the P E P dispersion (22PVC) nor the commercially produced paint from Example 5 exhibited significant wet adhesion.

Table 2 Scrub resistance comparative control - Production sample of commercial formulation No. 5851 (2 (S PVC) PBP = Vinegar m Vinyl 84% / Butyl acrylate 16
Encapsulated with % monomer formulation']”1tanox 20
10 Gardner Scrub Cycle PEP 46% PVC with 3/1 pigment/polymer ratio 250280 Control 27 [1300 (Bl) PEP 22% PVC with 1/1 pigment/polymer ratio
1095N47 Control 260 320 (PEI of 2nd batch with Q Pigment/Polymer ratio 1:1) 22% pvc 1095 1177 Control 21 245 0 PBP 7% of Pigment 7 ratio 1/6 PVC11651215 Control 245 280 Note 1 ) EP = Polymer-Encapsulated Pigment Example 12 For short-term drying, the block resistance of the polymer-encapsulated pigment dispersion as a semi-gloss paint was inferior to that of conventional paint technology.The water release rate was lower than that of the encapsulated pigment particles. However, 1/4 Zopaque RCL-9TiO
2 Pigments/84 q PVC film of a polymer-encapsulated pigment dispersion based on vinyl acetate-16% butyl acrylate copolymer. σ) Block resistance was excellent. The plush wrapping test gave a 20 minute lay time, an 8 hour tack time when equilibrated and a 24 hour dry to touch time. In one test, TlO2 was encapsulated with a 60X butyl acetate core 740% shell in several stages at a needle to polymer ratio of 1/4. The film of polymer-encapsulated pigment dispersion is 50
A 0 gram weight was released by pressing the film face-to-face overnight and then air drying. Even in the absence of conventional propylene glycol additives, the same slow water release was visibly observed giving the polymer-encapsulated pigment dispersion an improved air drying time compared to conventional semi-gloss paints. This improvement is 4-5 times (based on limited observations).

Example 16 This example demonstrates polymeric microencapsulation of pigments using standard emulsion polymerization techniques. The paint used was a 762% PVC paint similar to the commercial paint used in Example 15.

Water 4! l 09m, Igepal C0-997
57 gm, vinyl acetate 89 gm, n-butyl acetate 2
Paint A was made by mixing 5g in a reactor. The reactor charges were mixed for 15 minutes at 200 rpm at room temperature.

Ti Pure R902210Jim was added and the mixture was mixed for 15 minutes at 300 rpm at room temperature.

Add Ce1ite281.96 fln) and mix 4
Mixed for 15 minutes at 0 Orpm. (↑old Bon
dR3889m, water 2609m were added and the mixture was mixed for 15 minutes at 460 rpm at room temperature. A.S.
P-1702929m, water 2609m were added and the mixture was mixed for 15 minutes at 500 rpm at room temperature.

t~butyl hydroperoxide 1.39m, water 5. Zom
The mixture was mixed at room temperature after the temperature was raised to 50°C.

Sodium formaldehyde sulfoxy 1/-t 1,5
A premix of flm and 71 (8.0 gm) was added.

After the reaction was carried out at 68°C for 1 hour, (', n1loi
I have d581-B 29m. The mixture was cooled to room temperature and transferred.

Polymer-encapsulated pigment solids - sr hi, 551%, s)
−? (Stormer) Utilization is 93K (,],
ronkfield Viscosity (
The ICI high shear viscosity was 0.05 voids.

p■] was Z5. Contrast ratio (dry) is 0.
It was 99. Paint contrast ratio (wet) is 0
．． 985, Bain I film appearance (6 mil gap, 3
B chart) was smooth and non-granular.

Water 4309m, Igepal CQ-99715, 2g
m, vinyl acetate s3ym, n-butyl acrylate 25g
.

Paint B was made by mixing 25 gm of V-Pyrol in a reactor. The reactor charge was heated to 20°C at room temperature.
Mixed for 15 minutes at 0 rpm. Ti Pure 1l-
902210, qm was added and the mixture was stirred at room temperature for 3 hours.
Mixed for 15 minutes at 00 rpm. Celite 28
Add 196 gn= and mix the mixture at 40 Orpm.
Mixed for 5 minutes. BO1dI3ondl(38B 9
n., 260 gm of water was added and the mixture was heated to 4.5 gm at room temperature.
Mixed for 15 minutes at 60 rpm.

Add ASP-170292, 9m and 300 gm of water,
The admixture was mixed for 15 minutes at 500 rpm at room temperature. t-butylhydroperoxy)' 13 gm.

5 gm of water was added at room temperature and the mixture was mixed after increasing its temperature to 50°C. sodium formaldehyde sulfoxylate) 1.5 flm, water 8. Q gm premix was added. The reaction was allowed to run for 1 hour at 68°C. The mixture was then cooled to room temperature and transferred.

The solid weight of the polymer-encapsulated pigment is 52.1%, the viscosity is 1ooKU, the Bruffield viscosity (0.3r
pm) was 5600 cps, and ICI high shear viscosity was 05 voids. pH was 7.9. The contrast ratio (dry) was 0.99. The contrast ratio of the paint (wet) is 0.99, and the paint film appearance (6
The mill gap, 3B chart) was smooth and non-granular.

Example 14 Using the general method outlined in Example 13, the pigment system used in Union Carbide published formulation I-1212 was encapsulated using a vinyl acetate/n-butyl acrylate ratio of 78/22 (-day , PVC/15, and −Fl, PV(
, so). Portions of these two polymer-encapsulated pigments were then blended to provide the S n PVC system and the 55PVC system. As a control, 45PVC and 6
We made 0 PVC paints and blended some of them to make 4 5nPVC and 55PVC paints. The results of the evaluation of these systems are shown in Table 3.4.

Table 3 45 Contrast 0.974 0.9775 [1
n977 0.9F15 55 n, s'ao [1,991 60rl, 991 0.996 45 Nigrosint- 0
．． 922 061350 Stainability +1. n947
n, 56755 +), B77 0.576 60 0.7611+, 5n2 45 Giltonite resistance 0.995 n, 98550
(G eye sor+1te) fl, 992 0.7485
5 Stability 0.041 [+64360 rlJ
344 0.675 45 ASTM 1 side love 5n5 1950 (
202 43 55 248 39 60 72 14 Note: Gilt Night ((ii I snn i f e
) This is a test in which a stain is placed on the first stitch of paint, the stain is washed away, and the extent to which the paint is stained is determined by measuring the contrast ratio.

p1>p is a combined human pigment.

3 Table 4 Polymer encapsulation T; o,, pigment ('l”rnnox (,
A series of tests were carried out using paints with various pigment volume concentrations according to ``N-822''.
It was 0%. The results are shown in Table @5.

Table 5 15 Contrast ratio 0.981 n, 98325
0.981 n, 990 1560 Gloss 67% 49% 2519% 31% 1520 Gloss 26% 17% 252% 5% 15 pT-(7,57,0 91i"T", S 48.0 48.OKU 827
8 ■C■, Boys i, [] 0.89 25 7) IE-I 6.2 /1.3') 6'r, 8
4 B, 0 48. OKU 8.15 77 ■C■, Boy's 0.95 0.90 Blue Kufu ~ Yield (0,3 rpm), Cent Boy's (c p ) 72,0θ014. Cl0
EXAMPLE 15 This example demonstrates emulsion polymerization and latex that can be used to inject pigments.

Water 485 gm, rr2epal Cn-99712,
9m, Sodium Acetate 2.5'Jtn, Tgepa
I Co-99-/ 45lm, Na1co 7l-T
15 antifoaming agent 5 g, monomer mixture (of vinyl acetate 9069rn and n-butyl acrylate 2539m) 7D,
A latex was prepared by mixing 9+n in a reactor. The initial reactor assembly was added and mixed at room temperature. The reactor is a 51 jacketed II IIW with steam/water for heating and cooling instrumentation controlled using an electric stirrer motor with stainless steel shaft, single blade, and digital display of r pHl. The flask contained an initial charge of 13 gm of t-butyl hydroperoxide.
Added to the reactor at °C. Next, a solution of 1.39 m of monosodium formaldehyde sulfoxylate and 89 m of water was poured into a reactor at 35°C, and the temperature was raised to 70°C and maintained at that temperature. '11j (-The remainder of the temperature mixture was fed over 4 hours. A solution of 3.69 m of t-butyl hydroperoxide and 349 m of water, a solution of 2.4 gm of sodium formaldehyde sulfoxylate and 34 gm of water. The monomer mixture, catalyst solution were fed to the reactor separately over 4172 hours.The monomer mixture, catalyst solution were fed to the reactor together starting at the same time.The agitation was about 20 Orpm when the temperature reached 70°C, and the monomer and peaked below 30 Orpm when the catalyst addition began, increasing to about 100 Orpm at the end of the addition.The reaction mixture was then heated for 30 minutes after the catalyst was added.The reaction mixture was cooled and removed from the reactor. The total solids of the obtained latex was 6
At 615%, plush-o-meter viscosity u'! 3.2
Bruchfield viscosity (LVT mode) at 5 poise
, 6 D rpm) was 5.350 cps.

Example 16 This example demonstrates emulsion polymerization techniques and latexes that can be used to encapsulate pigments.

Water 38811m, l:gepal Co-9979,
6fjm, sodium acetate 2. Ojim, Igep
al CQ-997569m.

Na1co 7l-D5 antifoam 4.0 gm, (vinyl acetate 722.4 gm and n-butyl acrylate 204.4 gm)
f! A latex was made by mixing 56 gm of the monomer mixture (with Ni) in a reactor. Initial reactor charges were added and mixed at room temperature. The reactor was a 31 jacketed resin flask with steam/water for heating and cooling controlled by instrumentation and using a stainless steel shaft, single blade, electric stirrer motor with digital display of rpm. . t-Butyl hydroperoxide tO41m
of initial charge was added to the reactor at 35°C. Next, sodium formaldehyde sulfoxylate 1.09
A solution of gm and 6.4 gm of water was slowly added to the reactor at 35°C. The temperature was raised to 70°C and maintained at that temperature. The remainder of the monomer mixture was fed over 4 hours. t
-butyl hydroperoxide 2.88 gm water 21
A solution of 2 fjm, 929 m of sodium formaldehyde sulfoxylate i, and 27.2.9 m of water were separately fed into the reactor over a period of 4 m and 72 hours. The monomer mixture and catalyst solution were fed together to the reactor starting at the same time. Stirring reached 70℃ level special contract j 75
rpm, from about 200 to 24 Orpm when the monomer and catalyst additions began, increasing to about 75 Orpm at the end of the addition (and during cooling). A quantity of 350 d of latex TPX-+5108 BA4222 was fed over the same period of time as the monomer addition. (The reason was to study the effect of adding latex to the reaction mixture and its effect on viscosity.) The reaction mixture was heated after 30 minutes after the catalyst was added. The reaction mixture was cooled and removed from the reactor. The total solids of the obtained latex was 65.33X, the platform viscosity was 2.19 Boise, and the Bruffield viscosity (LVT mode V, 60 rpm) was 8.300.
It was cps.

Example 17 This example demonstrates polymeric microencapsulation of pigments using standard emulsion polymerization techniques.

The reactor was purged with nitrogen. 4859 ml of water was added to the reactor. Pigment 2649m (Ti Pure R-90
0269m and 5antintone #5 23B, 9
m) to the reactor and the admixture at a moderate level (approximately 20 m) to the reactor.
Orpm) and stirred. Add the admixture to a high level (2
50-270 rpm) for about 5 minutes.
yrnl 87.9m was added. Add the mixture to 27 Orp.
Stir for 5 minutes at mtx.

Gara T-DET-N-50751grn was added.

Then Na1co 71-D5 Antifoam 19rn was added. Add the initial reactor charges at room temperature and mix 1-. The reactor was a 31 jacketed resin flask with steam/lk for heating and cooling instrumented and using a stainless steel shaft, two blades, and an rpmS digital indicator. 13 gm of t-butyl hydroperoxide (70X aqueous) 1 liter of initial preparation and 5.09 r of distilled water
Add to the reactor at 35°C and mix for 5 minutes at 270 rpm. Next, a reducer solution such as sodium formaldehyde sulfoxide-1.1.3j)rn and water [3.7m] was added to the reactor at 50<0>C. Reactor crosstalk is 60
When the temperature reached ˜65° C., 1) Begin the catalyst/starting material with one mass. Vinyl acetate 550 grn, acrylic acid n
-Butyl 155, Mm, Na1co 7i-r)5
79m of the l4it mixture was recirculated in a negative line over a period of 4 hours. t-Butyl hydroperoxide (TnT
TP) catalyst solution of 3,63 jim and 34 gm of water,
sodium formaldehyde sulfoxylate (SFS)
) 24 gm of water and 4 gm of water were fed linearly into the reactor separately over 4 hours.The monomer mixture and the catalyst/reducer solution were started together and the reactor The temperature was maintained at 60° to 65°C during the reaction and the agitation level (speed) was increased as necessary to maintain swirl or good mixing. After feeding the catalyst, use minimal agitation. The reaction mixture was then heated at 700-75°C for 30 minutes.
wicil 750, 759m and 3.0 gm of distilled water were added to the reaction mixture. The reaction mixture was cooled and removed from the reactor to provide a latex (polymer-encapsulated pigment dispersion).

The following is a list of t-butyl hydroperoxide and sodium formaldehyde sulfoxide used in Example 17.

Add to TBHP SFS reactor t3. j9 Supplied during 1.3.9 implementation
666g2.5g Total waste 493g 3.6g There was 58ml of Ni957 XTBHP in the feed water. There were 354 6.59% SI''S in the feed water.

Example 18 Example 1 except for the case where no baffle plate was used in the reactor
7 over and over ■7. A polymer-encapsulated pigment dispersion with a total solids content of 664% was obtained.

Procedural Arrest J11 October 1983 311'1 Commissioner of the Japan Patent Office Kazuo Wakasugi Indication of the case 1982 Patent Application No. 159142 Title of the invention Relationship with the case of the person who makes amendments to the Togo Group Enclosed Dispersed Solid and Manufacturing Process Patent Name of applicant Union Carbide Corporation Agent Contents of Masa Ura's column of claims and detailed description of the invention As shown in Attachment 1 The scope of claims is amended as follows.

1. A solid composition that is essentially a solid dispersion, consisting of non-monophylic insoluble solid particles uniformly arranged and encapsulated by at least one monounsaturated organo moiety.

2. The solid composition according to claim 1, wherein the solid is a solid solid.

(5) The solid composition according to claim 1, wherein the solid is an inorganic solid.

4. A solid composition according to claim 1117, wherein a nonionic stabilizer or a residue thereof is present in said encapsulation 11 (during coalescence and/or on the surface of said non-monomeric solid).

5. The nonionic stabilizer is a nonionic surfactant, and the nonionic surfactant forms a hydrophilic portion that is attracted to the surface of the -Jli medium material! The lJ, 1-body composition according to item 4, in which the range of Pa requirements is set forth in item 4.

6 Special 1r in which the nonionic surfactant is 05 to 10 on the basis of total solids, i.e., monomers and non-monomeric solids.
1-11, the solid composition according to Scope Item 5.

5. The solid composition of claim 4, wherein the Z nonionic stabilizer is a dispersed moiety that readily copolymerizes with said nonionic monomer having at least one monounsaturated organo moiety.

8. The solid composition according to claim 4, wherein M<min is N-vinylpyrrolidone.

9 Said non-ionic l4iW! The solid composition according to claim 1, wherein the body has fiM reactive unsaturated groups.

10. The solid composition according to claim 1, wherein the nonionic mesomorph has one reactive unsaturated group.

1t free radical 1Jll initiator or its? Uki is 0.05 to 1 tonneki% based on the total resistance of medium acid bodies and non-monomeric solids.
Claim 1 present in said encapsulating polymer at
The solid composition described in .

12. The solid composition of claim 11, wherein the free radical initiator is a peroxide.

15. The solid composition according to claim 1, wherein the ratio of non-uniform solid to monomer is in the range of 9:1 to 1:9.

14. The ratio of water to total solids is in the range of 4:6 to 7:B,
A solid composition according to claim 1, wherein the solids are monomeric and non-monomeric rigid solids.

15.+a) Water, a particulate non-monomeric solid with minimal surface loading, a non-ionic colloid or stabilizer, and a non-ionic monomer having at least one monounsaturated organo moiety. fb) add a nonionic polymerization initiator to mixed material (a), heat mixed material a) for 7 Ju to initiate polymerization of the nonionic monomer, Homogeneous vehicle coalescence consisting of adding the ionic catalyst and all the remainder of said non-ionic monomers to mixture ib) and advancing the chassis to the desired degree or degree to obtain a solid dispersion encapsulated. I-dependence method for encapsulated fractional solids.

16. Add the rest of the nonionic monomer over time.
16. The method of claim 15, wherein the nonionic stabilizer is a nonionic surfactant and the monomer solid is a pigment.

1Z Nonionic surfactant is all solid, Mllchi, 1￥L
0.5 to 10 parts by weight based on solid and non-uniform Q solids.The method according to claim 16cfJ.

18. The method of claim 15, wherein the initiator is a free radical initiator and is present in an amount of 0.05 to 1% based on the total weight of monomer and pigment.

19. The method of claim 18, wherein the free radical initiator is an Amide.

20. The method according to claim 15, wherein the initiator and catalyst are redox based.

21 1111 llIr of the patent claim that heats up and starts Ik coupling and makes it work! Item 15, Item 22, Claim 15 Kii's method, wherein the polymerization is carried out at a blackness of 25° to 300″C.

23. The method according to claim 15, wherein the ratio of non-uniform solids to medium solids is in the range of 9:1 to 1:9. 24. The ratio of water to total solids is 4:6 to 7. :3, and the total solid is solid to monomers and non-monomers.Claim 1
The method described in Section 5.

25. The method of claim 15, wherein the nonionic stabilizer is a dispersed moiety that readily copolymerizes with said nonionic monomer having at least one monounsaturated organo moiety.

26. Special FW in which the fractional monomer is N-vinylpyrrolidone or a polymer of N-vinylpyrrolidone Claim 25
The method described in section.

16. The method of claim 15, wherein the 2Z nonionic stabilizer is a nonionic surfactant having a hydrophilic moiety that is attracted to nonmonomeric solid surfaces.

28, lfJ nonionic t\L-mer has at least one reactive vinyl group R1R8C-CR111-1 reactive vinylidene group R7R, c=c? and/or reactive vinylene group-
CR1 (1"CR++ - [wherein, R7, R@, R@
, R10%R11 are respectively fa) hydrogen, lbl carbon r! i1-4 alkyl, C(1) alkoxy having 1-4 carbon atoms, (d) alkylcarboxy having 2-12 carbon atoms,
1e) Aryl having 6 to 10 carbon atoms, (f) Carbon i number 2 to 1
2 alkoxycarbonyl, (g)'l>tt with at least one halogen, nitrile, alkyl having 1 to 4 carbon atoms and/or alkoxy having 1 to 4 carbon atoms! Number of carbons converted: 6
Substituted aryl, +b) aralkyl where alkyl has 1 to 4 carbon atoms and aryl has 6 to 10 carbon atoms, +1) alkyl has 1 to 4 carbon atoms and aryl has 6 to 10 carbon atoms,
(j) nitrile, halogen and 7/or alkoxy having 1 to 4 carbon atoms; Substituted alkyl having 1 to 4 carbon atoms, Ik)...rogen and 7/or (
, 1 nitrile-substituted alkylcarboxy having 2 to 12 carbon atoms, and 1d-substituted alkoxycarbonyl having 2 to 12 carbon atoms in which halogen and /-74 have been replaced by 100 with tolyl. +Eit, , ethylene or G goti
f 1 History Allyl compounds other than 1-olefins and 1-olefins are III! of the above formula! Do not enter the area. ] 11't 17 bodies, claim 15
The method described in section.

29. The method according to claim 28, wherein the nonionic 141 mer has an approximate number of reactive unsaturated groups.

29. The method according to claim 28, wherein the nonionic io,m-form has one anti-monodically unsaturated group.

31. Claim 1, wherein the pigment is an organic solid.
The method described in Section 5.

32. The method according to claim 15, wherein the pigment is an inorganic solid.

35. The mixture of step fa) is first mixed with water, particulate non-monomeric solids, and non-ionic protective colloids or stabilizers, and then all or part of the non-ionic monomers are added to the initial mixture. 16. A method as claimed in claim 15, comprising mixing and introducing the mixture into a mixture. 2. Insert "warm" after "glass transition" in line 5 from the bottom of Specification 131.

6. Correct "of the variety" in the 4th line of the 16th stroke to "for" 0 4. Correct "preferably the number of carbon atoms" in the 10th to 9th lines, 8th, 6th, and 4th lines from just below the 20th stroke. Corrects the number of carbon atoms in argyl to be 1.

5. [(PbCrO4' pb(on
)t ) J r (PbCr0.Pb(OH)t
') Correct to J.

6. Lines 4-5 of 3010, “Ultra horn
apbone ) Delete J.

Z Lines 9 to 13 from the bottom of the white space [benol
d) Yellow, ] is deleted.

8. In line 3214, ``hi'' is corrected to ``Yiyi-1''.

9 Revise "Humidity" in the 10th and 8th rows from the bottom to [Wet Processing-1].

1α 9 lines from the bottom of the same page [Transformation-1 to 1 dry + i1m
Correct to -1.

11 33L1M line) l'-CEL'LO8TVE
, 1 't[CELLO8IZE J ni revise.

12. At the bottom of the 37th stroke, 1 linyl 1 in [) 2 lines is changed to [nonyl 1
Correct to.

15. f-Lewe l er on the bottom of the 39th picture or on the C97 line
Correct +e l to [T, evelene -l.

14. Revise [NevtronYX J in the 4th line from the bottom of the blank space to [Neutronyx-1].

15, 1 (nonyl) 'f'ergit in the same 40μ8 line
ol 1 to [(nonyl), TergiLol −1 by Nr dE.

16. Correct ``-1 in tree 11'' to ``-rosin'' in line 7 of the same 46th mountain.

17 [Tall oil] Tryde in 7 lines from 4900 below
Correct t j to "tall oil), Trydet j".

18. On the 6th line from the bottom of page 55, ``1 hole result'' is corrected to ``Good result.''

19 On page 61, line 7, "internal pigment" is corrected to "interior paint."

2α Insert the following sentence between the 5th and 4th line from the bottom of the same page.

[“Drawdown-1” in the following examples refers to a film-making technique performed in the following manner: A solution or dispersion is poured onto a smooth surface, such as a glass plate, and a doctor blade ( A knife blade, which is arranged to slide over a sharpened surface, is placed in a pool of solution and then pulled tentatively along it. This creates a flat film that stretches the solution." 21 Ibid. 62 Correct ``go'' in negative 8 lines to ``take a photo''.

22. On page 67, line 3 and bottom line 1, ``I went'' was corrected to ``I took a photo.''

23, page 7o, line 11, after “demixing” [(deml
Insert the xing month.

24. Correct 1 type-1 in line 71011 to 1'.

25. On the bottom line of the same page, [1 of the variety is corrected to ``Yo-1.

26, line 7311 “(brushomet*r)
After l, insert [(viscosity measuring device'g commercially available from Gardnerne 1) -1.

27 75 drunkenness lines 3 and 7 [skin + fi-r el
m (hide) Correct to J.

Claims (1)

Claims: 1. A solid composition consisting of non-mono-collectively insoluble solid particles uniformly coated and encapsulated by at least one monounsaturated organo moiety and which is essentially a solid dispersion. 2. The solid composition according to claim 1, wherein the solid is an organic solid. (v) The solid composition according to claim 1, wherein the solid is an inorganic solid. 4. The solid composition according to claim 1, wherein a nonionic stabilizer or a residue thereof is present in the encapsulating polymer and/or on the surface of the non-ionic polymer. The solid composition according to claim 4, wherein the nonionic stabilizer is a nonionic surfactant, and the nonionic surfactant has a hydrophilic moiety that is attracted to a non-QII surface. A solid composition according to claim 5, wherein the nonionic surfactant is present in an amount of 0.5 to 10 parts by weight based on total solids, i.e., mono- and non-Qi solids. 1. A solid composition according to claim 4, wherein the nonionic stabilizer is a dispersed moiety that readily copolymerizes with said nonionic compound having at least one monounsaturated organomoiety.s , the solid composition according to claim 4, wherein the dispersed moiety is N-vinylpyrrolidone. Solid composition. 10 One of the nonionic molecules is one reactive unsaturation, 111
A solid composition according to claim 1, having a group comprising: 11. The free radical initiator or its residue is present in the encapsulated 1L combination in an amount of 1 to 1% by weight based on the total weight of monomeric and non-monomeric solids. The solid composition according to item 1. 12. The solid composition of claim 11, wherein the free radical initiator is a peroxide. 13. A solid composition according to claim 1, wherein the ratio of non-monomeric solids to monomer is in the range of 9:1 to 1:9. 14 The water to total solids ratio is in the range of 4:6 to 7:3;
The solid composition according to claim 1, wherein the solid is one monomer and one non-monomer. 15, (at water, a particulate non-monomeric solid with a low surface charge, a non-ionic protective colloid or stabilizer, and a non-ionic monomer having at least one monounsaturated organo moiety) (bl nonionic polymerization initiator is added to the mixed material fat, mixed material fal is heated to 11[]) to start polymerization of the nonionic 41-mer, fcl nonionic a homogeneously polymer-encapsulated solid dispersion consisting of adding the catalyst and all the remainder of said non-ionic monomers to the mixture FBL and allowing the polymerization to proceed to completion or to the desired degree to obtain a polymer-encapsulated solid dispersion. Method for producing a dispersed solid. 16. Adding the remainder of the nonionic monomer over time,
the nonionic stabilizer is a JIE ionic surfactant,
16. The method of claim 15, wherein said non-ionic solid is a pigment. 1z Nonionic surfactant is based on total solids, that is, single phase and non-monomeric solids K 1. 05 to 10 parts by weight. 18. The method of claim 15, wherein said initiator is a free radical initiator and is present in an amount of 0.005 to 1% by weight, based on the total weight of I4i-mer and pigment. 19 The free radical initiator is a peroxide! frF
18. The method according to item 18. 20. The method according to claim 15, wherein the initiator and catalyst are 17 dox types. 2t heating to initiate and carry out polymerization
The method according to claim 15. 22. The method according to claim 15, wherein the polymerization is carried out at a range of 25° to '500°C. 23. The method of claim 15, wherein the ratio of non-monomeric solids to J)1 is in the range of 9:1 to 1:9. 24 Claim 15, wherein the ratio of water to total solids is from 4:6 to 7:3, and the total solids are monomeric and non-monomeric solids.
The method described in section. 25. The method of claim 15, wherein the nonionic stabilizer is a dispersed moiety that readily copolymerizes with said nonionic monomer having at least one monounsaturated organo moiety. 26. The method according to claim 25, wherein the dispersed monomer is N-vinylpyrrolidone or a polymer of N-vinylpyrrolidone. 27. The method of claim 15, wherein the nonionic stabilizer is a nonionic surfactant having a hydrophilic moiety that is attracted to the nonmonomeric solid surface. 28. The nonionic monomer has at least one reactive hinyl group R, R8C=Cn, -, reactive vinylidene group R
7R8C' = C and/or reactive vinylene group -C
Rlo-CR11- [wherein, R7, R8, R2, Rlo
lRll is (al hydrogen, tbl alkyl having 1 to 4 carbon atoms, (C) alkoxy having 1 to 4 carbon atoms, (d1 alkylcarboxy having 2 to 12 carbon atoms, (e) alkyl having 6 to 4 carbon atoms,
1n aryl, alkoxynonorbonyl having 2 to 12 carbon atoms, (gl 1-substituted with at least one halogen, nitrile, alkyl having 1 to 4 carbon atoms and/or alkoxy having 1 to 4 carbon atoms) Substituted aryl with 6 carbon atoms, (hl alkyl has 1 to 4 carbon atoms and aryl has 6 to 10 carbon atoms)
aralkyl, (11 alkyl has 1 to 4 carbon atoms, aryl has 6 to 10 carbon atoms, substituent is halogen, alkyl having 1 to 4 carbon atoms, di) II and/or carbon number 1 to
substituted aralkyl which is alkoxy of 4; substituted aralkyl of 1 to 4 carbon atoms substituted with rj-nitrile; halogen and/or alkoxy of 1 to 4 carbon atoms; substituted with lkl halogen and/or 2) carbon number 2-12
substituted alkylcarboxy, or (1) halogen and/or
or a substituted alkoxycarbonyl having 2 to 12 carbon atoms substituted with nitrile. However, allyl compounds or 1-olefins other than ethylene or substituted 1-olefins do not fall within the scope of the above formula. 16. The method according to claim 15, which is a single unit containing the following. 29. The method of claim 28, wherein the nonionic monomer has a plurality of reactive unsaturated groups. 30. The method of claim 28, wherein said nonionic monomer has one reactive unsaturated group. 51 Claim 15, wherein the pigment is an organic solid
The method described in section. 32. The method according to claim 15, wherein the face 1 is an inorganic solid. 33. Step (mixing at first with water, particulate non-monomeric solid, and non-ionic protective colloid or stabilizer, then first mixing all or part of the non-ionic bulking material) 16. The method according to claim 15, wherein the method is mixed into a material.