JPH01215872A - Resin coating composition - Google Patents

Abstract

PURPOSE:To provide a resin coating compsn. improved in blocking resistance and drying properties, by blending a water-soluble resin with a specific particulate polymer and, if necessary, a crosslinking agent and/or a pigment. CONSTITUTION:Vinyl monomers (b) different in composition from the following component (a) (e.g., a mixture of styrene, p-methylstyrene and divinylbenzene) are emulsion-polymerized in the presence of an emulsion prepared by emulsion polymn. of vinyl monomers (a) (e.g., a mixture of styrene, methyl methacrylate, acrylonitrile and ethylene glycol dimethacrylate) to prepare a particulate hollow or porous polymer (B). 100pts.wt. (based on the solids content) water-soluble resin (A) completely soluble in water or semi-soluble in water to be in stable condition (e.g., a water-soluble epoxy-modified alkyd resin) is blended with 0.1-9,900pts.wt. component B and, if necessary, a crosslinking agent and/or a pigment (C).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a new and useful resin composition for paints, and more specifically, to a resin composition for paints that is made of a water-soluble resin and a specific composition and has hollow or porous particles inside. The present invention relates to a resin composition for coating material having excellent anti-blocking properties and drying properties, which contains a fine particle polymer having a structure as an essential component.

[Conventional technology and its problems] In recent years, from the viewpoint of popular pollution and toxicity to the human body,
The transition from traditional solvent-based paints to water-based paints is rapidly progressing. Among these, applied research on water-soluble resin paints, which have properties similar to solvent-based workability and coating film performance, is being actively conducted, mainly in the field of metal coating.

However, when used as a clear coating composition, the conventional type has the disadvantage of poor blocking resistance and hardness, and when used as a pigment-filled colored coating composition, it has poor blocking resistance and hardness. When diluted, the specific gravity of the pigment itself is high, so the sedimentation stability is insufficient, and the specific gravity of the paint increases, so the paint itself tends to become heavy. Furthermore, since most of the medium supporting the resin and the like is water, there is also the drawback that when the composition is coated, drying properties are poor.

In order to overcome these drawbacks, a technique has also been introduced in which a specific particulate polymer is included in the composition. For example, JP-A-59-138276, JP-A-61-7
No. 6559 discloses a technique for obtaining a high appearance with a baking composition using specific water-insoluble resin particles, JP-A-60
JP-A No. 1266, related to improving the stability of a composition containing a reactive powder during heating, JP-A-59-11
No. 7565 discloses a product in which the dispersibility of a specific powder is improved and the storage stability is improved.

However, it cannot be said that any of these compositions has satisfactory performance.

[Means for Solving the Problems] As a result of intensive studies in view of the above points, the present inventors have found that satisfactory performance can be achieved by using a specific fine particle polymer as an essential component as detailed below. The present inventors have discovered that the following can be obtained, and have completed the present invention.

That is, the present invention consists of: 100 parts by weight of a water-soluble resin (based on solid content) 0.1 to 9900 parts by weight of a fine particle polymer having a hollow or porous structure ■ A crosslinking agent if necessary ■ Pigments if necessary The present invention provides a resin composition for coating material comprising:

First of all, the water-soluble resin (■) that constitutes the present invention refers to resins that are completely soluble in water or are stable in a semi-soluble state, and are particularly suitable for those normally used for paints. I can use it without any problems. Specifically, there are water-soluble vinyl polymers such as polyvinyl alcohol, water-soluble fiber-based or polysaccharide-based polymers such as hydroxyethyl cellulose, and starch.

Further, partially or completely neutralized products of poly(condensation) polymers having acidic groups with organic or inorganic basic substances can also be used. Specific examples of poly(condensation) polymers having acidic groups include acrylic polymers, alkyd condensates, and polyester condensates, as well as modified products of these with not more than 50% of other resins. Typical examples of organic or inorganic basic substances include ammonia, morboline, triethylamine, butylamine, and the like. These are publicly known and
It can be prepared using agricultural methods.

Next, the particulate polymer having a hollow or porous structure in (2) is obtained by emulsion polymerization of vinyl monomers with a specific composition. Monomers are emulsion-polymerized in advance, and then specific vinyl monomers having different compositions are emulsion-polymerized in the presence of the emulsion. Alternatively, it can be obtained by carrying out the manufacturing process in the presence of a solvent.

As such polymers, for example, the present inventors have previously disclosed Japanese Patent Application Laid-Open No. 62-79202@ and Japanese Patent Application No. 62-169.
Examples include those obtained by the method disclosed in No. 739g.

In other words, in the case of Japanese Patent Application Laid-Open No. 62-79202, it is as follows. A copolymer emulsion (C) obtained by emulsion polymerization of a polymerizable vinyl monomer (A) and, if necessary, a polyfunctional crosslinkable monomer (8), is used as a seed particle, and the above polymer (C) is added to this as a seed particle. By adding at least one type of α,β-ethylenically non-saturated saturated monomer (which can form a polymer with a contact angle of 1 to 110° high with respect to water) and carrying out emulsion polymerization, the desired hollow or porous structure can be formed. A fine particle polymer having a structure is obtained.

Examples of monomers used here include the following.

Among these, any composition that satisfies the above conditions may be used.

(meth)acrylic acid 1) Adducts of acid anhydride group-containing monomers such as acidic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid, maleic anhydride, and itaconic anhydride with glycol. Carboxyl group-containing monomers or dicarboxylic acids such as monocarboxylic acids containing saturated groups; maleic anhydride;
α, β- to dylenically unsaturated carboxylic acids such as polycarboxylic anhydride group-containing unsaturated monomers such as itaconic anhydride, 2
-Hydroxyethyl (meth)acrylate, ? -Hydroxib[]pyr (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate
Acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate-1, etc., hyaloxyalkyl ester of (meth)acrylic acid. Polyhydroxyalkyl esters containing unsaturated groups, such as dihydroxyalkyl esters of polyhydric carboxylic acids such as maleic acid and fumaric acid; Hydroxyl group-containing typified by hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether Monomers, carboxylic acid amides represented by (meth)acrylamide, N,+111 dimethyl(meth)acrylamide, N-alkoxymethylated (meth)acrylamide, diacetyl(meth)acrylamide, N-medyrol(meth)acrylamide, etc. Group-containing monomers, sulfonic acid amide group-containing monomers represented by styrene sulfonamide, tomethyl-p-styrene sulfonamide, N,N-dimethyl-p-styrene sulfonamide, etc., N,N- Dimethylaminoethyl (meth)acrylate-1~
N , N-dialkylaminoalkyl (meth)acrylates such as -1~ or polyhydric carboxylic acid anhydride group-containing monomers such as maleic anhydride and an active hydrogen group and a tertiary amine group that can react with each other. tertiary amino group-containing monomers represented by adducts with compounds that have cyano groups, cyano group-containing monomers represented by (meth)acrylonitrile, (meth)acrylic acid hydroxyalkyl esters α , monomers having a phosphoric acid ester group obtained by the condensation reaction of β-ethylenically unsaturated saturated carboxylic acid droxyalkyl esters and phosphoric acid derivatives, 2-acrylamido-2-methylpropanesulfonic acid Monomers with sulfonic acid groups such as methyl (meth)
Acrylate, ethyl (meth)acrylate, butyl (
C1-8 styrene such as meth)acrylate, 2-ethylhexyl(meth)acrylate, and cyclohexyl(meth)acrylate, α-methylstyrene, and
Aromatic vinyl compounds such as styrene or its derivatives such as t-butyl styrene and methylstyrene, (substituted) aromatic nucleus-containing (meth)acrylic acid esters such as benzyl (meth)acrylate, maleic acid, fumaric acid, itacon Diesters of unsaturated dicarboxylic acids and monohydric alcohols such as acids, vinyl esters such as vinyl acetate, vinyl benzoate, "Beoba" (vinyl ester manufactured by Shell), "Viscoat 8F, 8FM, 3F, 3 groups" (fluorine-containing (meth)acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.), perfluorocyclohexyl (meth)acrylate
1, (per)fluoroalkyl group-containing vinyl esters such as diperfluorocyclohexyl fumarate or N-1-propyl perfluorooctane sulfonamide ethyl (meth)acrylate, vinyl chloride, vinylidene chloride, vinylizone fluoride, Olefin lambda such as vinyl fluoride, chlorotrifluoroethylene, ethylene, propylene, butadiene, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1-helimethylolpropane tri(meth)acrylate, divinylbenzene, Trivinylbenzene, divinyl 1-ethoxysilane, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropylmethyldime-1-oxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, Hydrolyzable silyl group-containing monomers such as T-(meth)acryloyloxypropylmethyljethoxysilane are required.

Among the monomers used here, preferably (8) and CD) contain less than 5% by weight of α,β-ethylenically unsaturated carbonic acid based on the total amount of monomers.

As for the preparation method, first, the copolymer emulsion (C) may be prepared by synthesizing the required amounts of each of the above monomer groups in the presence of an emulsifier, a polymerization initiator, and water by the emulsion polymerization method shown below. Examples of emulsifiers used in this case include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, other reactive emulsifiers, and substances with surfactant properties such as acrylolibon. Type a5 and anionic emulsifiers are preferred because they produce less aggregates during polymerization and provide stable emulsions. Typical nonionic emulsifiers include polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester, ethylene oxide-propylene oxide block copolymer, etc., and anionic emulsifiers include: Examples include alkylbensene sulfonic acid alkali metal salts, alkyl sulfate 1 to alkali metal salts, and polyoxyethylene alkylphenol sulfate alkali metal salts.

Furthermore, instead of or in combination with the above-mentioned anionic emulsifier, a water-soluble oligomer made of a polycarboxylic acid or a sulfonate can also be used. Furthermore, water-soluble polymeric substances such as polyvinyl alcohol and hydroxyethylcellulose can be used as protective colloids. The amount of the emulsifiers and the like used is approximately 0.1 to 10 wt% based on the total monomer amount.

Next, the initiator is not particularly limited as long as it is commonly used in emulsion polymerization, but specific examples include water-soluble inorganic peroxides such as hydrogen peroxide; ammonium persulfate, potassium persulfate, etc. persulfates such as; organic peroxides such as cumene hydroperoxide and benzoyl peroxide; azobisisobutyronitrile,
There are azo initiators such as azobiscyanovaleric acid, and these may be used alone or in combination. The amount used is preferably 0.1 to 2 wt% based on the total monomer amount. It goes without saying that a method known as the so-called redzu 12 = cous polymerization method, which uses these polymerization initiators together with metal ions and reducing agents, may also be used.

Then, in the presence of water, preferably ion-exchanged water, and an emulsifier if necessary, the α,β-ethylenically inert saturated monomers are reacted as they are or in an emulsified state, either collectively, dividedly, or continuously. Dropped into a container in the presence of the polymerization initiator at 0 to 100°C, preferably 30 to 90°C.
It is sufficient to polymerize at a temperature of . The ratio of total monomer amount to water is such that the final solid content is 5 to 65 wt%, preferably 15 to 55 wt%.
It is set so that it falls within the wt% range. In addition, in order to grow or control the particle size during emulsion polymerization, a seed polymerization method may be used in which emulsion particles are preliminarily present in an aqueous phase and polymerized (preparation of (C)).

Then, in the presence of the emulsion (C), only the α,β-ethylenically unsaturated saturated monomers) are additionally polymerized. In other words, on the surface of the previously synthesized emulsion (C), the α,β-ethylenically inert saturated monomers in the subsequent step are deposited and polymerized. To obtain the target product in this step, (C)
In the presence of 0.1 to 9 () parts by weight based on the solid content of the ingredients, (
10 to 99.9 parts by weight of the monomer mixture constituting component D) may be polymerized.

In the polymerization of component (D), the use of emulsifiers should be avoided as much as possible since producing a large amount of particles of component (D) alone on a weight basis is contrary to the spirit of the present invention. If necessary, the amount used should be 5 wt% or less, preferably 2 wt% or less of the amount of component (D) used. If the amount used exceeds 5 wt %, a large amount of emulsion particles composed of component (D) alone will be produced as by-products, for example, an emulsion with two peaks will be formed when the particle diameter (b) is measured.

α and β in the emulsion particles produced in this way
- Ethylenically inert saturated monomer composition has a glass transition point of 5
It is sufficient to set the temperature to 0°C or higher.

Further, the method of Japanese Patent Application No. 169739/1982 as an alternative method is as follows. V, that is, in the presence of an organic titanate compound when producing an aqueous emulsion,
Emulsion (E) containing titanium atoms obtained by emulsion polymerization of at least one type of α, β-ethylenically unsaturated monomer
and then in the presence of the emulsion, α, β-
Only the ethylenically unsaturated monomers (F) are additionally polymerized. That is, α,β-ethylenically unsaturated monomers in the subsequent step are deposited and polymerized on the surface of the emulsion containing the previously synthesized organic titanium compound. When this manufacturing method is adopted, titanium atoms or titanium atoms bonded to organic compounds are reliably fixed in the final emulsion particles, and titanium atoms bonded to titanium atoms or organic compounds are fixed in the polymer in the subsequent process. Because of the strong bonding via atoms with the previously polymerized emulsion containing titanium atoms, a microparticle polymer emulsion having a completely hollow or porous structure is obtained by coating with the subsequent polymer.

The organic titanate compound that is an essential component includes the following compounds for boat fishing.

Tetraisopropyl titanate, tetrabutyl titanate, tetrastearyl titanate, 2-ethylhexyl titanate, isoprobyl tricumylphenyl titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, and tetra which is a condensate of titanates 1 to 1 above. Isopropyl rapeseed-1 polymer, organic titanium esters such as tetrabutyl titanate polymer, isopropyl tristearoyl titanate, isopropyl i-lioctanoyl titanate, isopropyl di(
Organic titanium acylates such as meth)acrylic isostearoyl titanate, diisostearoyl ethylene titanate, dicumylphenyloxyacetate titanate, isopropyl-1 to lith(dioctylpyrophosphate-1)
~) titanate 1 ~ and its organic amine salts, isopropyl tri(dioctyl phosphate) titanate, bis(
Organic titanium phosphate esters such as dioctyl pyrophosphate) oxyacetate titanate and its organic amine salts, bis(dioctyl pyrophosphate-1~) ethylene lentane-1~ and its organic amine salts, isoprobyl tridode'ylbenzene sulfonyl Organic titanium sulfonic acid esters such as titanates, titanium acetylacetonate, titanium lactate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl- Examples include organic titanium chelates such as 1-butyl)bis(ditridecyl)phosphite titanate.

The organic amine salt mentioned here refers to the active acidic hydroxyl group derived from the phosphate ester present in the organic titanium phosphate esters mentioned above, such as monoethylamine, diethylamine, triethylamine, butylamine, monoethanolamine, jetanol. The term refers to those neutralized with organic amines such as amine, triethanolamine, and morpholine. It is preferable to use organic amines that are volatile at room temperature. Neutralization can be carried out by blending the acidic hydroxyl group and the organic amine so that the molar ratio is at least equivalent (the organic amine or the organic amine may be in excess), and mixing at room temperature or after cooling.

In carrying out the present invention, organic titanium-phosphate esters are preferred among the above-mentioned compounds. The amount of the organic titanate compound to be used is 0.01 to 30 wt%, preferably 0.05 wt% based on the total amount of the organic titanate compound and the α,β-ethylenically unsaturated monomers used.
~25wt%.

In order to obtain a particulate polymer having a hollow or porous structure using this method, the first step is to add at least one type of α,β-ethylenically inert saturated monomer in the presence of the organic ditaneous compounds 1 to 1 described above. Emulsion polymerization may be carried out, or a mixture of an organic titanate compound and α,β-ethylenically unsaturated monomers may be simultaneously emulsion polymerized (preparation of (F)). Examples of the α,β-ethylenically inert saturated monomers used in this case include those mentioned above. In addition, the amount used is 70 to 99.99w based on the total amount of organic titanate 1 to compounds and α,β-ethylenically unsaturated monomers.
t%, preferably 75 to 99.95 wt%.

As a preparation method, the above-mentioned organic titanate compounds and the required amounts of each of the above-mentioned monomer groups may be synthesized by the emulsion polymerization method shown below in the presence of an emulsifier, a polymerization initiator, and water.

As the emulsifier used in this case, those mentioned above) can be used. The amount of emulsifier used is 0.1 to 1% of the total monomer amount (including organic ditanate compounds; the same applies hereinafter).
It is about % by weight. Next, the polymerization initiator is also the same as that described above. The amount used is 0 based on the total monomer amount.
．． 1 to 2 wt% is preferable.

and an organic titanate compound and α in the presence of water, preferably ion-exchanged water, and optionally an emulsifier.

β-ethylenically unsaturated monomers are added individually, as they are or in an emulsified state, in batches or in portions, or continuously into a reaction vessel, or an organic titanate compound and α,β-ethylene are added to the reaction vessel. The mixture is mixed with the polyunsaturated monomers and added dropwise, as it is or in an emulsified state, into a reaction vessel either in batches, in portions, or continuously, and in the presence of the polymerization initiator, the temperature is preferably 0 to 100°C. is 30-9
The polymerization may be carried out at a temperature of 0°C. The ratio of total monomer amount to water is 1 to 60 wt%, preferably 15% by weight of the final solid content.
It should be set within the range of ~55W1%. Preferably, in order to grow or control the particle size during emulsion polymerization, a seed polymerization method may be used in which emulsion particles are pre-existing in an aqueous phase and polymerized.
(F) made by d Shu).

Then, only the α,β-ethylenically unsaturated monomers (F) are additionally polymerized in the presence of the emulsion (E). In order to obtain the desired product in this step, 50 to 99.9 parts of the monomer mixture constituting component (F) is added in the presence of 0.1 to 50 parts by weight based on the solid content of component (E). All you have to do is polymerize it. The additional emulsifiers used in the polymerization of the (') component are as described above.The composition of the α,β-ethylenically unsaturated monomers in the emulsion particles thus produced. The glass transition point may be set to 50°C or higher.

The thus obtained microparticles having a hollow or porous structure (1) can be pulverized by a known and commonly used drying method. For example, spray drying at a temperature of 100 to 250°C, tray drying at a humidity of 50 to 70°C, or fluidized bed drying can be carried out. The particle size of the obtained non-film-forming resin powder is generally an aggregate (secondary particles) of primary particles (fine particles with the same particle size as in emulsion), but if necessary, a dispersant such as an emulsifier, a protective It can be redispersed in water by adding colloids, etc. Therefore, it may be used in the form of a dry powder.

Although the details of how component (1) contributes to the improvement of blocking resistance and drying properties in the present invention are unknown, it can be inferred as follows.

That is, in general, blocking resistance and drying properties can be improved by increasing the glass transition point of the binder, or if the glass transition point is the same, by using a large amount of pigments, especially fillers such as extender pigments. However, in the case of a binder or a water-soluble resin as in the present invention, since most of the medium supporting the binder is water, the evaporation and volatilization of this water is rate-limiting. Here, if the above-mentioned polymer having a hollow or porous structure is used, the water to be volatilized will be supported in the hollow or porous structure, and when this composition is applied to a substrate, the absolute amount of water on the surface will be reduced. This results in an improvement in the blocking resistance and drying properties of the child rack. The supported water then evaporates slowly, but this process has little effect on performance.

The ratio of component (1) to component (2) can range from 0.1 to 9,900 parts by weight of (2) to 100 parts by weight of (2) on a solid content basis.

Next, the crosslinking agent (■) is added as necessary to cure and crosslink the water-soluble resin, which is the component (■) mentioned above. does not need to be added in particular. However, when higher performance is required, it is used as one that can react with the functional groups in component (1) or has the function of promoting the reaction of the functional groups in component (2).

Specific examples include (1) polyvalent metal salts commonly referred to as driers, such as cobalt naphthenate, lead naphthenate, and zinc naphthenate, when the component has an unsaturated bond (group). or can be used. In addition, if the component contains a hydroxyl group, block polyisocyanate resin,
Can use aminoplast.

Specific examples of resins for block polyisocyanate-1 include:
Aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhex]nomethylene diisocyanate; cycloaliphatic diisocyanates such as xylylene diisocyanate and isoborone diisocyanate;
Adducts of organic diisocyanates such as aromatic diisocyanates such as tolylene diisocyanate and 4,4°-diphenylmethane diisocyanate with polyhydric alcohols or low molecular weight polyester resins or water, or polymers of the above-mentioned organic diisocyanates, and It is a product obtained by blocking isocyanate resin such as isocyanate-biuret using a known and commonly used blocking agent [Burnock D-550j (Jin Nippon Ink Chemical Industry (l wood products), [Takenate B815-N]
J “Propertool XC-910J (both manufactured by Narita Pharmaceutical Co., Ltd.
OL)\IXL-8U (Hoechst synthetic 0 wood product) etc.

Among these, "brominate X'C-
A block isocyanate resin such as ``910'' (manufactured by Takeshi Yakusho Kogyo (l wood products)) dispersed in water or emulsified using the above-mentioned emulsifier is suitable for use.

Aminoblast is a synthetic material obtained by reacting an amino group-containing compound component such as melamine, urea, acetoguanamine, steroguanamine, or spiroguanamine with an aldehyde compound component such as formaldehyde, paraformaldehyde, or glyoxal by a known and commonly used method. or their respective condensates with alcohol. Preferably,
Alcohols having 1 to 4 carbon atoms may be partially or completely etherified.

Specific examples include power 1 nomethoxymethyl melamine, l
Examples include \chilibutoxymemethymelamine, methoxib 1 to ximedylmelamine, methoxymethylmelamine, butoxymethylmelamine, or condensates thereof.

Among these, water-soluble substances such as hexabutoxymethyl melamine, hexabutoxymethyl melamine,
An aqueous dispersion of methoxymethylmelamine or butoxymethylmelamine using the above-mentioned emulsifier is preferable. The amount of these crosslinking agents to be used is 0 to 2 parts by weight per 100 parts by weight of the solid content of component (1).
00 parts by weight may be used.

Next, specific examples of the pigments in component (■) include heavy calcium carbonate, light calcium carbonate, magnesium carbonate, precipitated barium sulfate, mica, and titanium oxide, as well as kansui powder, powder, kaolin, clay, and fired pigments. leh, talc,
Silica sand, silica lime, ultrafine silica, white carbon, asbestos, pulp powder, dolomite powder, zinc white,
Inorganic pigments or fillers such as carbon black; organic pigments such as phthalocyanine, azo, and quinacridone pigments or their dispersion pigments. The amount of these pigments used can range from 0 to 400 parts by weight based on 100 parts by weight of the total solid content of components (1) and (2).

The composition of the present invention can be obtained using these four components, but in addition to these, various additives such as those shown below can also be blended.

methanol, ethanol, propatool, ethyl acetate,
Needles such as ethyl acetate, methyl ethyl ketone, methyl isomethyl ketone, toluene, xylene, bequinone, heptane, cellosolve arechie 1~: Phthalate esters such as dibutyl phthalate, dioctyl phthalate, dibdel glycol phthalate,] Aliphatic dibasic acid esters such as isodecyl succinate and dioquidyl adipate, phosphoric acid esters such as 1-licresyl phosphate, glycol esters such as diethylene glycolbenzene I-1, and epoxidized soybean oil Epoxy plasticizers such as
and chlorinated paraffins, and other Chisso' Noiser C3-12 (Chisso wood products), Bubur Calbi 1--
Luacetate 1~, phyllocellosolvebitol, hexylene glycol, cellosolve, benzyl alcohol,
Cyisopropyl succinate ester, Pyca194 (A
tlas Chemical Industries
), Dalyad A (Dow Chemical
Various plasticizers such as Co, ); various anionic and nonionic surfactants; salts of phosphoric acid derivatives such as pyrophosphoric acid, tripolyphosphoric acid, and hexamethanoic acid, salts of polycarboxylic acids, naphthalene sulfone Dispersants such as acid salts; drying agents such as mineral spirits and turpentine oil; freeze- or thaw-stability imparting agents such as ethylene glycol, propylene glycol, and glycerin; antifoaming agents such as silicone-based or acrylic oligomers; others Are preservatives included?The amount of these added depends on the conditions of use,
Determined according to purpose.

[Effects of the Invention] The resin composition for coatings of the present invention has excellent blocking resistance when formed into a coating film using the component (1), which is a fine particle polymer having a hollow or porous structure, and has superior blocking resistance to that of conventional coatings. By partially replacing the pigment, a composition with excellent storage stability (sedimentation stability) and excellent drying properties can be obtained when used as a composition for drying at room temperature. Therefore, the composition of the present invention can be used for various purposes, for example, as a general or industrial water-based paint for wood and metal, or as a coating agent for paper and fiber processing. It is not particularly limited to these.

[Examples] Next, the present invention will be specifically explained by examples.
In the following, all parts and percentages are based on weight unless otherwise specified.

Production Example 1 (Production of ■Components) Into a reaction vessel equipped with a stirrer, reflux content 4, a dropping funnel, and a thermometer, 100 parts of water, 2 parts of emulsifier (1.0 parts of Emulgun 120 manufactured by Kao Corporation and 20 parts of Emul 20)
1.0 part of A) was added and stirred well.

Next, add styrene 12 to the reaction vessel, keeping the internal temperature at 80'C.
7 parts of methyl methacrylate (A), a mixture of 0.6 parts of acrylonitrile and 0.4 parts of σ ethylene glycol dimethacrylate, and 0.0 parts of ammonium persulfate.
A mixture of 5 parts of water and 4 parts of water was injected over about 1 hour to react, and the mixture was further aged for 1 hour. Thereafter, the internal temperature was maintained at 80'C, and 50 parts of styrene (ST) and 28 parts of p-methylstyrene were added.
5 parts of divinylbenzene (DVB) and 5 parts of divinylbenzene (DVB) and 5 parts of divinylbenzene (DVB). A mixture of 0.25 parts of tp ammonium and 5 parts of water was injected for about 1 hour to react, and then aged for 45 minutes.
I went for a minute. After that, cool it and use 25% ammonia aqueous solution 1
．． 0 parts was added to adjust the pH to 8.8.

The obtained emulsion had a solid content concentration of 48.6% and a viscosity of 1
3 cps (value of BM type rotational viscometer rotor No. 1, rotation speed 6 ° rpm, temperature 25 ° C), pH 8.8,
Zabu Micron Particle Analyzer (cou + ter'
N-4) and an average particle diameter of 0 measured using an electron microscope.
．． The diameter of microvoids in the particles was 0.21 parts m. This emulsion is called (A-1).

Production Example 2 (Production of component (■)) 580 parts of ion-exchanged water was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen introduction tube, and a thermometer, and the temperature was raised to 85°C. Next, ions = 29 = Dissolve 5 parts of sushilium dodecylbenzenesulfonate in 100 parts of exchanged water, 2 parts of bis(dioctylpyrophosphate)oxyacetate titanate, 186 parts of MHA, 10 parts of methacrylic acid (HAA), and ethylene glycol dimethacrylate. A mixture (consisting of 2 parts of EDHA) (the copolymer obtained from these α,β-ethylenically unsaturated monomers had a glass transition temperature of 110°C) was added and emulsified. A mixture of the emulsion, 2 parts of perf+MW ammonium, and 120 parts of ion-exchanged water was dropped into the reaction vessel for 2 hours to effect polymerization. The reaction is further maintained at the same temperature for 1 hour to complete the reaction. Thereafter, it was cooled to obtain the desired emulsion (A-2). The obtained emulsion had a solid content concentration of 20.5% and a pH of 5.
, the average particle size was 0.30 Yanagi.

Next, 274.9 parts of ion-exchanged water and (A-
2) Charge 195.1 parts and raise the temperature to 85°C. Next, 1 to 7 parts of lithium dodecylbenzene sulfonate were dissolved in 90 parts of ion-exchanged water, and 358 parts of ST, DVB
'The glass transition point of the copolymer obtained from the saturated monomers is 11.
5°C) and emulsify. The emulsion and
A mixture of 3.6 parts of ammonium persulfate and 80 parts of ion-exchanged water was dropped into the reaction vessel over 2 hours to carry out the reaction. After further holding at the same temperature for 1 hour, the emulsion particles containing the organic titanium compound were cooled.
A polymerized emulsion (A-3) was obtained. (
A-3) had a solid content concentration of 40.8%, a pH of 2.5, and an average particle diameter of 0.62.

A cross-sectional photograph of the thus obtained particle (A-, 3) taken by an electron microscope is shown in FIG. As shown in the figure (A-
It can be seen that the inside of the particle 3) has a hollow structure.

Examples 1 to 3 and Comparative Examples 1 to 3 The fine particle polymers obtained in Production Examples 1 and 2 and Watersol S-370 (Dainippon Ink Chemical Industry II product, water-soluble epoxy modified alkyd resin, Non-volatile content: 55, Gardner viscosity: 11, pH: 9.5) or Watersol S-701 (product of the same company, water-soluble acrylic resin, non-volatile content: 41.5', Gardner viscosity: Z,
p118.7), cobalt naphthenate or hexamethoxymethyl melamine as a crosslinking agent, carbon flak (IA-100, Mitsubishi Kasei Hama products) as a pigment, and dilution thinner in the composition shown in Table 1 using a conventional method. The mixture was mixed according to the instructions, and the paint was allowed to simmer.

Next, it was applied onto a glass plate using a 3 mil applicator, and the blocking resistance and drying properties were evaluated. In addition, the paint was diluted with thinner to a spray viscosity (20 seconds at Fort Cup 4) and stored at 50°C for 2 months to examine its storage stability. Include the results! are listed in the same table.

(Left below) Ei 1) 5% cobalt naphthenate, W type (Dainippon Ink & Chemicals Q not yet manufactured).

*2) Immediately before use, add 1 part of para-1 to luenesulfonic acid.

*3) (Water-soluble resin) ± (fine particle polymer) solid content, pigment type N concentration (pwc) is used by grinding in a sand mill in advance to a concentration of 3%.

*4) Water/butyl cellosolve-5015.0 (weight ratio)
Persimmon) In Examples 1 and 2 and Comparative Examples 1 and 2, it was applied to a glass plate and dried at room temperature for one day, and in Example 3 and Comparative Example 3, it was applied and forcedly dried at 40'C for 10 minutes. Curse was placed on a test plate, and a load of 500 g/cm 2 was applied for 5 minutes to evaluate traces of the case.

○: No trace of case at all △: There are some traces of case. ×: Traces of case are clearly recognized.

10) Example], 2, Comparative Examples 1 and 2, after drying at room temperature for 10 minutes, Example 3, Comparative Example 3 and 4 (
After forced drying at +'C for 10 minutes, the test plate was evaluated according to the following criteria (finger touch test).

○: No tack at all △: There is some tackiness, but it does not stick to your fingers at all. ×: There is tack, and it sticks to fingers.

Thurs. 7) ○: Very stagnant or numb at all / Good ×:
Sedimentation or caking will occur.

As can be seen from the table, the composition of the present invention has excellent anti-blocking properties and drying properties, and can be used as a coating material with excellent storage stability.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of particles taken by an electron microscope -C showing an example of a fine particle polymer having a hollow porous structure according to the present invention.

Claims (1)

[Claims] (1) [1] 100 parts by weight of water-soluble resin (based on solid content) [
2] Fine particle polymer having a hollow or porous structure0.
1 to 9,900 parts by weight [3] A crosslinking agent if necessary [4] A resin composition for a coating material, which contains pigments if necessary.