JPH05214194A - Aqueous emulsion of polymer fine particle - Google Patents

Abstract

PURPOSE:To provide an aqueous emulsion of polymer fine particle excellent in adhesivity, water resistance, etc., and having good weather resistance and good balanced properties. CONSTITUTION:An aqueous emulsion of polymer fine particle having a low surface tension contains polymer fine particles composed mainly of an acrylate ester monomer and/or a methacrylate ester monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer fine particle aqueous emulsion used for coating materials, water-based inks, mortar admixtures, paints, non-woven fabric binders and the like.

[0002]

2. Description of the Related Art Conventional coating materials used for coating metals, plastics, paper, cement concrete, plywood, slate, corrugated board, fibers, glass, leather, etc., are aqueous solutions, oil solutions, aqueous emulsions, Various types such as water-in-oil emulsions are known, but from the viewpoints of pollution prevention, fire safety, etc., water-based types that do not use organic solvents are rapidly advancing.
Nowadays, an aqueous acrylic emulsion mainly composed of an acrylic resin and / or a methacrylic resin is mainly used as a polymer material due to its good properties. However, although the aqueous acrylic emulsion is excellent in weather resistance, it has drawbacks in water resistance, adhesiveness, drying property, and the like, and when used in water-based ink, it has fast drying property, abrasion resistance, clear printing property, etc. There was a problem with. On the other hand, the coating material and the aqueous ink composition have an average particle diameter of 0.0
It has already been proposed to use an aqueous polymer fine particle emulsion having a particle size of 1 μm or more or 0.005 μm or more (for example, JP-A-2-73803 and JP-A-3-7).
9678), or in the inventions described in these publications, a special crosslinkable or reactive component must be used for the monomer and the emulsifier (JP-A-2-73803),
Only the average particle diameter of the polymer fine particle aqueous emulsion is focused on (Japanese Patent Laid-Open No. 3-79678), and the object of those inventions is to obtain the water resistance of the film,
Transparency, gloss, mechanical strength, etc. (JP-A-2-73803)
However, the desirable properties from the viewpoint of the coating material, the ink composition, etc., are improved in terms of drying properties, sharpness, jetting stability and the like of the ink composition (JP-A-3-79678). It was not always a well-balanced achievement.

[0003]

The present invention has been made as a result of earnest research on the relationship between the particle size and surface tension of polymer and the properties of emulsion against the background of the above-mentioned conventional technical problems. It is an object of the present invention to provide a polymer fine particle aqueous emulsion having excellent adhesion and water resistance as compared with an acrylic emulsion, good weather resistance and well-balanced properties.

[0004]

[Means for Solving the Problems] Means for solving the above-mentioned problems of the present invention are as follows:
Or 10 to 100% by weight of methacrylic acid ester monomer
And 90% by weight of another monomer, and polymer fine particles having an average particle diameter of 0.003 to 0.07 μm and a surface tension of 10 to 50 mN / m. It consists of an aqueous emulsion.

The acrylic acid ester monomer and the methacrylic acid ester monomer constituting the polymer fine particles of the polymer fine particle emulsion of the present invention are the acrylic acid and methacrylic acid which are commonly used in conventional aqueous acrylic emulsions. It is an ester of an acid with an unsubstituted aliphatic, alicyclic or aromatic alcohol. The term "unsubstituted" as used herein means having no group other than a hydrocarbon group. Examples of acrylic acid ester monomers and methacrylic acid ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate. , Isobutyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate,
Hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, octyl acrylate, octyl methacrylate, n-acrylate
Nonyl, isononyl acrylate, n-nonyl methacrylate, isononyl methacrylate, decyl acrylate, decyl methacrylate, undecyl acrylate, undecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, n-amyl acrylate, isoamyl acrylate, Examples include n-amyl methacrylate, isoamyl methacrylate, lauryl acrylate, lauryl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate. Preferred monomers are alkyl acrylates and methacrylic acid alkyl esters having an alkyl group having 4 to 12 carbon atoms, more preferably n-butyl acrylate, isononyl acrylate and 2-ethylhexyl acrylate, especially acrylic acid. 2-Ethylhexyl acid is preferred.
These monomers can be used alone or in combination of two or more.

The proportion of these acrylic acid ester monomers and / or methacrylic acid ester monomers in the total monomers is 10 to 100% by weight, preferably 15
~ 100% by weight. The amount of acrylic acid ester monomer and / or methacrylic acid ester monomer used is 10
If it is less than 5% by weight, weather resistance, water resistance and the like are deteriorated.

In the present invention, the other monomer that can constitute the polymer fine particles is a monomer that can be copolymerized with an acrylic acid ester monomer and / or a methacrylic acid ester monomer. As the other monomer, an aromatic vinyl-based monomer,
Vinyl cyanide type monomer, ethylenically unsaturated carboxylic acid hydroxyalkyl ester monomer, ethylenically unsaturated carboxylic acid amide monomer, ethylenically unsaturated acid monomer,
Ethylenically unsaturated sulfonic acid ester monomer, ethylenically unsaturated alcohol or ester monomer thereof, ethylenically unsaturated ether monomer, ethylenically unsaturated amine monomer, ethylenically unsaturated silane monomer, Vinyl halide type monomers, aliphatic conjugated diene type monomers and the like are used.

Examples of the aromatic vinyl monomers are styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, α-chlorostyrene and p-chlorostyrene. Styrene, p-methoxystyrene, p-aminostyrene, p-acetoxystyrene, sodium styrenesulfonate, α-vinylnaphthalene, sodium 1-vinylnaphthalene-4-sulfonate, 2-vinylfluorene, 2-vinylpyridine, 4- There are vinyl pyridine and the like, and styrene is particularly preferable.

Examples of the vinyl cyanide-based monomer include acrylonitrile, α-chloroacrylonitrile, α-methoxyacrylonitrile, methacrylonitrile, α-chloromethacrylonitrile, α-methoxymethacrylonitrile, vinylidene cyanide and the like. And acrylonitrile is particularly preferable.

Examples of the ethylenically unsaturated carboxylic acid hydroxyalkyl ester monomer include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.

Examples of the ethylenically unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N-
Butoxymethyl acrylamide, N-butoxymethyl methacrylamide, N-butoxyethyl acrylamide,
N-butoxyethyl methacrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, Nn-propoxymethyl acrylamide, N
-N-propoxymethylmethacrylamide, N-methylacrylamide, N-methylmethacrylamide, N,
N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N
-Diethylmethacrylamide and the like.

As the ethylenically unsaturated acid monomer, ethylenically unsaturated carboxylic acid, ethylenically unsaturated sulfonic acid and the like are used. Examples of ethylenically unsaturated carboxylic acid, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, fumaric acid, maleic acid, maleic anhydride and the like, examples of ethylenically unsaturated sulfonic acid vinyl sulfonic acid, Examples include isoprene sulfonic acid. The ethylenically unsaturated acid monomer may be neutralized with, for example, an alkali metal. Examples of the ethylenically unsaturated sulfonic acid ester monomer include alkyl vinyl sulfonate and alkyl isoprene sulfonate.

The ethylenically unsaturated alcohol and its ester include allyl alcohol, methallyl alcohol, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, allyl acetate, methallyl caproate, allyl laurate, Examples include allyl benzoate, vinyl alkyl sulfonate, allyl alkyl sulfonate, vinyl aryl sulfonate, and the like.

The ethylenically unsaturated ether monomer may be methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether,
Examples include methyl allyl ether and ethyl allyl ether.

Examples of the ethylenically unsaturated amine include vinyldimethylamine, vinyldiethylamine, vinyldiphenylamine, allyldimethylamine, methallyldiethylamine and the like.

Examples of the ethylenically unsaturated silane include vinyltriethylsilane, methylvinyldichlorosilane, dimethylallylchlorosilane and vinyltrichlorosilane.

Examples of the vinyl halide monomer include vinyl chloride, vinylidene chloride, 1,2-dichloroethylene, vinyl bromide, vinylidene bromide and 1,2-dibromoethylene.

The aliphatic conjugated diene monomer is 1,3
-Butadiene, 2-methyl-1,3-butadiene, 2,
3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,2-dichloro-1,3-butadiene, 2,3-
Dichloro-1,3-butadiene, 2-bromo-1,3-
There are butadiene, 2-cyano-1,3-butadiene, substituted linear conjugated pentadienes, linear and side chain conjugated hexadienes and the like, with 1,3-butadiene being particularly preferred.

The above-mentioned other monomers can be used alone or in combination of two or more kinds, but an ethylenically unsaturated acid monomer and a monomer other than the ethylenically unsaturated acid monomer can be used. It is preferable to use the monomer together, and particularly preferable to use methacrylic acid and styrene together.

The proportion of the other monomer in the total monomers is 0 to 90% by weight. If the proportion exceeds 90% by weight, the weather resistance will decrease.

The polymer fine particle aqueous emulsion of the present invention is a polymer solution prepared by dissolving a polymer prepared in advance in a solvent,
It can also be produced by a method of inversion of a polymer solution or the like produced by solution polymerization into an aqueous emulsion, but in general, when an acrylic acid ester monomer and / or a methacrylic acid ester monomer is used, Is preferably produced by a method of emulsion polymerization with other monomers. Hereinafter, the emulsion polymerization method for producing the polymer fine particle aqueous emulsion of the present invention will be described.

Emulsion polymerization for producing the polymer fine particle aqueous emulsion of the present invention generally uses an emulsifier composed of a hydrocarbon type surfactant and / or a fluorine type surfactant and, if necessary, in the presence of a polymerization initiator. In the presence of a chain transfer agent, various electrolytes, a pH adjusting agent, etc., from 10 to 100% by weight of acrylic acid ester monomer and / or methacrylic acid ester monomer and 90 to 0% by weight of other monomer. It is carried out by polymerizing the monomer.

Among the emulsifiers used in the present invention,
As the hydrocarbon-based surfactant, an anionic surfactant,
Although there are nonionic surfactants, cationic surfactants, amphoteric surfactants, etc., anionic surfactants are preferable, and strong acid type anionic surfactants are more preferable. Examples of the hydrocarbon-based strong acid anionic surfactant include sulfuric acid ester salts of higher alcohols, polyoxyethylene / alkyl ether sulfates, polyoxyethylene / alkylphenyl ether sulfates, fatty acid sulfuric acid ester salts, aliphatic amines, or Sulfate of aliphatic amide, sulfonate of dibasic fatty acid ester, sulfonate of aliphatic amide, alkyl or alkenyl sulfonate, alkylaryl sulfonate, alkyl sulfosuccinate, formalin condensed naphthalene sulfonate , Phosphate ester salts of aliphatic alcohols, polyoxyethylene alkyl (phenyl) ether phosphate ester salts, and the like. The hydrocarbon strong acid type anionic surfactant in the present invention is preferably a sulfate ester salt or a sulfonate, and specific examples thereof include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium diphenyl ether disulfonate, and dialkyl succinate. Examples thereof include sodium sulfonate.

Among the other hydrocarbon surfactants, the nonionic surfactants include polyoxyethylene alkyl ester, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, glycerin fatty acid ester, sorbitan fatty acid ester,
A polyoxyethylene sorbitan fatty acid ester etc. can be mentioned.

Further, the fluorosurfactant that can be used in the present invention is one in which the lipophilic group is a fluorinated hydrocarbon. Its chemical structure is basically the same as that of ordinary surfactants, and it has an anionic surfactant having hydrophilic groups such as carboxylate, sulfate, sulfonate, and phosphate, and a hydrophilic group. Examples thereof include a nonionic surfactant having a polyoxyethylene group, a cationic surfactant having a group such as an amine salt or a quaternary ammonium salt as a hydrophilic group, and an amphoteric surfactant. Fluorosurfactants generally have high surface activity, and many of them exhibit a sufficient emulsifying action even if the lipophilic group has a smaller number of carbon atoms than general surfactants. As the fluorine-based surfactant, perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl phosphate ester,
Examples thereof include perfluoroalkyl trimethyl ammonium salt, perfluoroalkyl polyoxyethylene, perfluoroalkyl betaine and the like. In the present invention, it is preferable to use these fluorochemical surfactants as emulsifiers.

The amount of the emulsifier used in the present invention is adjusted so as to achieve the required average particle diameter and surface tension by adjusting the stirring conditions and the like according to the type of each surfactant, the type and composition of the monomer, and the like. To be selected. The preferred amount of emulsifier used is generally 1 to 10 parts by weight per 100 parts by weight of the monomer. Further, when a hydrocarbon type strong acid type anionic surfactant and a fluorine type surfactant are used in combination, the monomer 10
With respect to 0 parts by weight, the hydrocarbon strong acid type anionic surfactant is 0.1 parts by weight or more, preferably 0.2 to 10 parts by weight, and the fluorine-containing surfactant is 0.01 parts by weight or more, preferably 0. 0.02 to 1.0 part by weight is used. If the amount of the emulsifier used is too small, the stability of the emulsion tends to decrease, such as coagulation, and if it is too large, the adhesion and water resistance of the coating film formed from the emulsion tend to decrease. ..

Polymerization initiators that can be used in emulsion polymerization for producing the polymer fine particle aqueous emulsion of the present invention include: persulfates such as potassium persulfate and ammonium persulfate; inorganic initiators such as hydrogen peroxide; Hydroperoxides such as cumene hydroperoxide, isopropylbenzene hydroperoxide, paramenthane hydroperoxide, benzoyl peroxide, di-t
-Butyl peroxide, dialkyl peroxide such as dilauroyl peroxide, sulfide, sulfinic acid,
Examples thereof include organic initiators such as azo compounds such as azobisisobutyronitrile, asobisisovaleronitrile, azobisisocapronitrile, and azobis (phenylisobutyronitrile). The amount of the polymerization initiator used is preferably 0.03 to 2% by weight with respect to all the monomers,
Particularly, 0.05 to 1% by weight is preferable.

Further, a reducing agent or a chelating agent may be added to accelerate the emulsion polymerization. Examples of the reducing agent include sodium pyrobisulfite, sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, glucose, formaldehyde sodium sulfoxylate, L-ascorbic acid and salts thereof, sodium hydrogen sulfite, and the like.
Examples of the chelating agent include glycine, alanine, sodium ethylenediaminetetraacetate and the like.

The chain transfer agent which can be used in the emulsion polymerization for producing the polymer fine particle aqueous emulsion of the present invention preferably contains 60% by weight or more of a 2,4-diphenyl-4-methyl-1-pentene component. Α-
Methyl styrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, tetremethylthiuram Monosulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide,
Examples include dipentamethylthiuram disulfide.
The amount of the chain transfer agent used is generally 15% by weight or less based on all the monomers.

In emulsion polymerization for producing the polymer fine particle aqueous emulsion of the present invention, generally 100 to 800 parts by weight of water is used with respect to 100 parts by weight of all monomers, and an emulsifier, a polymerization initiator and, if necessary, further. Chain transfer agent, reducing agent, chelating agent, electrolyte, pH adjusting agent and the like in an appropriate amount, generally 10 to 90 ° C, preferably 40 to 80 ° C.
Polymerization is usually performed at a polymerization temperature of C for 5 to 15 hours.

As a method of adding the above-mentioned monomer in the emulsion polymerization for producing the polymer fine particle aqueous emulsion of the present invention, any method such as a batch addition method, a divided addition method or a continuous addition method can be adopted. A particularly preferable addition method is a method in which the polymerization is started in the presence of 10% by weight or less of the total monomers, and the remaining monomers are continuously or dividedly added and polymerized. In the divided addition method or the continuous addition method, the monomer may be added in a divided or continuous manner together with other addition components such as a polymerization initiator, or the other addition components may be added in advance in a single amount. Only the monomer can be added dividedly or continuously. Further, the monomer added at this time can be emulsified in advance.

The polymer fine particle aqueous emulsion of the present invention has an average particle diameter of polymer fine particles of 0.003 to 0.07.
μm, and preferably 0.005 to 0.05 μm. The average particle diameter referred to herein is a value obtained by treating the polymer fine particle emulsion with uranyl acetate and osmic acid, taking an electron micrograph, and averaging the particle diameters of 100 or more polymer fine particles. The average particle size is 0.
When it exceeds 07 μm, the adhesion and penetration to the base material such as plastic, paper, concrete and the like are deteriorated, and the value of 0.
When it is smaller than 003 μm, it becomes difficult to maintain a stable dispersed state of the emulsion in the polymerization operation,
Not practical. In order to make the polymer fine particle aqueous emulsion of the present invention have a required average particle size, stirring is performed especially at the initial stage of polymerization depending on the type and amount of the emulsifier used, the viscosity of the monomer phase, and the like. The conditions etc. must be adjusted, but the appropriate conditions can be set sufficiently by experiments.

Further, the polymer fine particle aqueous emulsion of the present invention must have a surface tension of 10 to 50 mN / m. The surface tension referred to here is JIS K-2241.
It is a value measured according to (Dinui type surface tensiometer).
The preferred surface tension in the present invention is 15 to 37 mN / m.
Is. When the surface tension exceeds 50 mN / m, the permeability to various base materials deteriorates, and as a result, the adhesiveness also deteriorates. If the surface tension is less than 10 mN / m, the water resistance will decrease. The required surface tension of the aqueous emulsion of the present invention does not necessarily have to be achieved during emulsion polymerization and may be adjusted by further adding a suitable emulsifier after the polymerization. However, in this case, it is necessary to properly adjust the stirring conditions and the like so that the polymer fine particles have a required average particle size. Further, in order to adjust the surface tension, a water-soluble solvent such as alcohol, toluene, xylene, carbitol, dioctyl phthalate may be added.

The polymer fine particle aqueous emulsion of the present invention comprises 10 to 100% by weight of an acrylic acid ester monomer and / or a methacrylic acid ester monomer and 9% by weight of another monomer.
It can also be produced by inversion of a polymer solution of 0 to 0% by weight into an aqueous emulsion. In that case, the required amount can be obtained by adjusting the addition amount of an emulsifier, stirring conditions and the like. An emulsion having an average particle size and surface tension of

If desired, a silane compound may be added to the polymer fine particle aqueous emulsion of the present invention.
This can further improve the adhesion to a substrate such as a coating film formed from the polymer fine particle aqueous emulsion of the present invention. Specific examples of the silane compound include:
Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, Isopropyltrimethoxysilane, isopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,
3,3,3-tolufluoropropyltrimethoxysilane,
3,3,3-tolufluoropropyltriethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyl Triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, dimethyldimethoxysilane, dimethyldi Examples thereof include ethoxysilane and diethyldimethoxysilane. Preferred silane compounds are tetramexisilane, tetraexisilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane.

These silane compounds may be used alone or in admixture of two or more. The preferable addition amount is 0.1 to 80 parts by weight with respect to 100 parts by weight of the monomer. Further, the silane compound may be partially or wholly condensed after the addition.

The polymer fine particle aqueous emulsion of the present invention is excellent in adhesion to a substrate, water resistance and the like, and also has good weather resistance, and is made of paper, cardboard, plywood, metal, plastic, concrete, mortar, fiber, glass. It can be preferably used as a coating material for leather, water-based ink composition, cement admixture and the like. The aqueous emulsion further contains a filler, a defoaming agent, an antiseptic, an antifungal agent, a water-proofing agent, an antiaging agent, an ultraviolet absorber, a water-soluble solvent, a film-forming aid, etc., depending on its use. Then, the properties can be optimized.

The present invention will be described in more detail with reference to the following examples and comparative examples. In addition, part and% in these examples
Is weight basis unless otherwise specified.

EXAMPLES Examples 1 to 4, Comparative Examples 1 to 4 In a separable flask having an internal volume of 5 liters, the monomers and emulsifiers shown in Table 1 were used under a nitrogen gas atmosphere, and ammonium persulfate was used as a polymerization initiator. 0.5 parts, sodium ethylenediaminetetraacetate as a chelating agent 0.02
Parts and other polymerization stabilizers were added to prepare an emulsion in 250 parts of water, and emulsion polymerization was carried out at a polymerization temperature of 60 to 80 ° C. under stirring to prepare a polymer fine particle aqueous emulsion. The monomer was continuously added during the polymerization. In each of the examples, the polymerization conversion rate was 99.5% or more, the emulsion stability was good, and almost no coagulated product was observed. The following tests were carried out on the aqueous emulsions obtained in each example and each comparative example. The test results are shown in Table 1 (Examples 1 to 1
4) and Table 2 (Comparative Examples 1 to 4). Adhesion test: Slurry plate, ABS plate, and aluminum plate are coated twice with a polymer fine particle aqueous emulsion with a brush (application amount 300 g / m ² ), dried at room temperature for 48 hours, and then a razor blade is used to make a 2 mm square edge pattern. Then, a peeling test was performed with cellophane tape, and the number of peeled off lines (peeling number) was evaluated. The higher the number, the poorer the adhesion. (Evaluation Criteria) ◯ = Peeling number 10 or less, Δ = Peeling number 11 to 30, × = Peeling number 31 or more. Weather resistance test: After coating the polymer fine particle emulsion on an ABS plate, an aluminum plate, and a slate plate twice with a brush (coating amount 300 g / m ² ), a weather meter exposure test was conducted and the coating film after 1 month The discoloration was visually observed. The weather meter exposure conditions were carbon arc use, black panel temperature 63 ° C., and precipitation cycle 18 minutes / 120 minutes. (Evaluation Criteria) ◯ = Very good with no discoloration, Δ = slightly yellowing, × = fairly yellowing. Water resistance test: A test sample was prepared in the same manner as the weather resistance test, immersed in normal temperature water for 48 hours, and then the water absorption rate (weight increase ratio due to water absorption, unit%) was measured. The higher the water absorption rate, the poorer the water resistance.

[0039]

[Table 1]

[0040]

[Table 2]

As is clear from Table 1, by adopting the monomer composition, average particle size and surface tension in the present invention, a coating film having excellent adhesion, water resistance and weather resistance can be formed. On the other hand, when at least one of the monomer composition, the average particle size, and the surface tension is out of the range of the present invention, even if the polymer is mainly composed of an acrylic acid ester monomer and / or a methacrylic acid ester monomer. Even in such a case, the adhesion, water resistance and weather resistance are all deteriorated. This is because the average particle size of the polymer particles and the surface tension of the emulsion are extremely important from the viewpoint of the properties of the emulsion when the above-mentioned monomer is the main component,
It is shown that these conditions do not lead to a good aqueous emulsion until they are intimately bound, but such an effect was quite unexpected.

[0042]

INDUSTRIAL APPLICABILITY The polymer fine particle aqueous emulsion of the present invention has an average particle diameter and surface force of the polymer fine particles within a specific range, even though the ordinary monomer used in the aqueous acrylic emulsion is used. By adopting the above, it is possible to form a coating film which is excellent in adhesion, water resistance and weather resistance and which has a well-balanced property as a coating material. Further, due to its excellent properties, it can be suitably used for an aqueous ink composition, has a good affinity with the main cement material, and is also useful as a cement admixture having excellent weather resistance.

[Procedure amendment]

[Submission date] July 21, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

A silane compound may be added to the polymer fine particle aqueous emulsion of the present invention as necessary, whereby a silane compound and a base material such as a coating film formed from the polymer fine particle aqueous emulsion of the present invention can be added. Adhesion and the like can be further improved. Specific examples of the silane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and n.
-Propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-decyltrimethoxysilane, n
-Hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, hydroxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane , 3,3,3-Tolufluoropropyltrimethoxysilane, 3,3,3-Tolufluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryl Roxypropyltrimethoxysilane,
γ-methacryloxypropyltriethoxysilane, γ-
Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, 3,4-epoxycyclohexylethyl trimethoxysilane, 3,4-epoxycyclohexylethyl Examples thereof include triethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane and aminosilane. Preferred silane compounds are tetramethoxysilane, tetraethoxylan, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, part and% in these examples
Is weight basis unless otherwise specified.

EXAMPLES Examples 1 to 5, Comparative Examples 1 to 4 In a separable flask having an internal volume of 5 liters, the monomers and emulsifiers shown in Table 1 were used under a nitrogen gas atmosphere, and ammonium persulfate was used as a polymerization initiator. 0.5 parts, sodium ethylenediaminetetraacetate as a chelating agent 0.02
Parts and other polymerization stabilizers were added to prepare an emulsion in 250 parts of water, and emulsion polymerization was carried out at a polymerization temperature of 60 to 80 ° C. under stirring to prepare a polymer fine particle aqueous emulsion. The monomer was continuously added during the polymerization. In each of the examples, the polymerization conversion rate was 99.5% or more, the emulsion stability was good, and almost no coagulated product was observed. The following tests were carried out on the aqueous emulsions obtained in each example and each comparative example. The test results are shown in Table 1 (Examples 1 to 1
5) and Table 2 (Comparative Examples 1 to 4). Adhesion test: A polymer fine particle aqueous emulsion is applied twice to a slate plate, an ABS plate, and an aluminum plate with a brush (application amount 300 g / m ² ), dried at room temperature for 48 hours, and then a razor blade is used to make a 2 mm square crevice. Then, a peeling test was performed with cellophane tape, and the number of peeled off lines (peeling number) was evaluated. The higher the number, the poorer the adhesion. (Evaluation Criteria) ◯ = Peeling number 10 or less, Δ = Peeling number 11 to 30, × = Peeling number 31 or more. Weather resistance test: After coating the polymer fine particle emulsion on an ABS plate, an aluminum plate, and a slate plate twice with a brush (coating amount 300 g / m ² ), a weather meter exposure test was conducted and the coating film after 1 month The discoloration was visually observed. The weather meter exposure conditions were carbon arc use, black panel temperature 63 ° C., and precipitation cycle 18 minutes / 120 minutes. (Evaluation Criteria) ◯ = Very good with no discoloration, Δ = slightly yellowing, × = fairly yellowing. Water resistance test: A test sample was prepared in the same manner as the weather resistance test, immersed in normal temperature water for 48 hours, and then the water absorption rate (weight increase ratio due to water absorption, unit%) was measured. The higher the water absorption rate, the poorer the water resistance.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

[0039]

[Table 1] ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 23, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, part and% in these examples
Is weight basis unless otherwise specified.

EXAMPLES Examples 1 to 5, Comparative Examples 1 to 4 In a separable flask having an internal volume of 5 liters, the monomers and emulsifiers shown in Tables 1 and 2 were used under a nitrogen gas atmosphere, and the polymerization initiator was used. 0.5 parts ammonium persulfate,
0.02 parts of sodium ethylenediaminetetraacetate as a chelating agent and other polymerization stabilizer are added to prepare an emulsion in 250 parts of water, and emulsion polymerization is carried out at a polymerization temperature of 60 to 80 ° C. under stirring to obtain polymer fine particles. An aqueous emulsion was prepared. The monomer was continuously added during the polymerization. In each of the examples, the polymerization conversion rate was 99.5% or more, the emulsion stability was good, and almost no coagulated product was observed. The following tests were carried out on the aqueous emulsions obtained in each example and each comparative example. The test results are shown in Table 1 (Examples 1 to 5) and Table 2 (Comparative Examples 1 to 4). Adhesion test: A polymer fine particle aqueous emulsion is applied twice to a slate plate, an ABS plate, and an aluminum plate with a brush (application amount 300 g / m ² ), dried at room temperature for 48 hours, and then a razor blade is used to make a 2 mm square crevice. Then, a peeling test was performed with cellophane tape, and the number of peeled off lines (peeling number) was evaluated. The higher the number, the poorer the adhesion. (Evaluation Criteria) ◯ = Peeling number 10 or less, Δ = Peeling number 11 to 30, × = Peeling number 31 or more. Weather resistance test: After coating the polymer fine particle emulsion on an ABS plate, an aluminum plate, and a slate plate twice with a brush (coating amount 300 g / m ² ), a weather meter exposure test was conducted and the coating film after 1 month The discoloration was visually observed. The weather meter exposure conditions were carbon arc use, black panel temperature 63 ° C., and precipitation cycle 18 minutes / 120 minutes. (Evaluation Criteria) ◯ = Very good with no discoloration, Δ = slightly yellowing, × = fairly yellowing. Water resistance test: A test sample was prepared in the same manner as the weather resistance test, immersed in normal temperature water for 48 hours, and then the water absorption rate (weight increase ratio due to water absorption, unit%) was measured. The higher the water absorption rate, the poorer the water resistance.

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─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI technical display location C09D 133/06 PFY 7921-4E (72) Inventor Yasuhisa Watanabe 2-11 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (3)

[Claims] 1. A polymer comprising 10 to 100% by weight of an acrylic acid ester monomer and / or a methacrylic acid ester monomer and 90 to 0% by weight of another monomer and having an average particle diameter of 0.003. An aqueous polymer fine particle emulsion containing polymer fine particles of .about.0.07 .mu.m and having a surface tension of 10 to 50 mN / m. 2. A coating material containing the polymer fine particle emulsion according to claim 1. 3. A polymer fine particle emulsion for aqueous ink, which comprises the polymer fine particle emulsion according to claim 1.