JP2662352B2 - Polymer latex composition containing silicone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to water repellency, pollution control,
The present invention relates to a polymer latex capable of forming a film having excellent weather resistance, pigment dispersibility, gloss, water resistance, and adhesion.
The polymer latex produced in the present invention is used as a paint, a base material for a building material, a finishing material for a building material, an adhesive, a pressure-sensitive adhesive, a paper processing agent, a fiber processing agent, and the like. It is useful.

[0002]

2. Description of the Related Art As a resin for water-based paints, polymer latex obtained by emulsion polymerization is widely used because it forms a film at room temperature or under heating and drying to form a film having relatively good durability. However, when exposed outdoors, the gloss of the film obtained from the polymer latex or a paint in which the pigment was blended with the polymer latex decreased quickly, and the level of gloss retention was low.

[0003] The introduction of silicones into polymers to solve the above problems is desirable, for example, to increase resistance to ultraviolet light, oxygen, water or various solvents and to improve durability. Prior art is a polymer latex prepared by emulsion polymerization of an ethylenically unsaturated monomer, and a silicone formed from a hydrolyzable silane compound coexists or chemically bonds in the copolymer. Latex or a method for producing the latex described in JP-A-60-181173 and JP-A-62-267374.
However, since the ethylenically unsaturated monomer and the hydrolyzable silane are simultaneously introduced into the reaction system, the resulting latex has poor dispersion stability. was there. Even if a dispersant or emulsifier is added as a stability improver to this latex and a film-forming aid or inorganic pigment is mixed, a film with excellent gloss can be obtained even if the latex can be mixed with or without coagulation. Could not. Further, since a large amount of a stability improver was required, a film having good water resistance could not be obtained.

Further, Japanese Patent Application Laid-Open Nos. 61-9463, 63-202630, 63-20263
No. 1, JP-A-3-45628 and JP-A-Hei-4
According to JP-A-57868, after emulsion polymerization of an ethylenically unsaturated monomer, the pH is adjusted to around 7, and then a hydrolyzable silane is introduced into the reaction system and polymerized. Agglomeration and latex agglomeration occur with the silane condensation reaction. It is difficult to stably obtain a high-concentration latex in industrial production, and many surfactants are required to prevent this. Alternatively, even when a latex is obtained, when the latex is mixed with a film-forming auxiliary and an inorganic pigment as a vehicle, the latex agglomerates, or a film having excellent gloss cannot be obtained even if it can be mixed without aggregating. To prevent this, many surfactants are required.
As a result, the coatings obtained from these latexes did not have good water resistance.

[0005]

As described above, the level of gloss immediately after coating of a coating obtained from a polymer latex containing a pigment is low, and the coating becomes glossy when exposed for a long period of time. There was a problem that it would be further reduced. The present invention can maintain the gloss of a film for a long time by introducing silicone into a polymer, and use no or no conventional surfactant in a large amount, or use a condensation catalyst and an interface of a hydrolyzable silane. Providing a polymer latex with excellent water resistance of the film by copolymerizing an ethylenically unsaturated monomer having a sulfonic acid group or a sulfuric ester group without using dodecylbenzenesulfonic acid, which also has an activator function. Is what you do.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have developed emulsion polymerization of an ethylenically unsaturated monomer having a sulfonic acid group or a sulfuric ester group, and also introduced silicone. As a result of intensive studies on the emulsion polymerization with a hydrolyzable silane, the present invention has been completed.

That is, the present invention provides emulsion polymerization of an ethylenically unsaturated monomer (A) having a sulfonic acid group or a sulfate group and another ethylenically unsaturated monomer (B) in an aqueous medium. And an ethylenically unsaturated monomer (C) having a sulfonic acid group or a sulfate group and another ethylenically unsaturated monomer (D), E) is a polymer latex composition containing silicone obtained by emulsion polymerization of (A) with (B) in a ratio of (A) of 0.05 to 20% by weight, (B) ) Is 80-9
9.95% by weight, and the ratio of (C) to (D) is 0.05 to 10% by weight for (C) and 90 to 9% for (D).
9.95% by weight, and the weight ratio of the polymer in the seed latex to the polymer formed from (C) and (D) is 1/99 to 99/1; The ratio of the polymer in the latex and the polymer formed from (C) and (D) to the silicone formed from (E) is 50/50 to 99/1; ) Is 0.5 to 50 ethylenically unsaturated monomers having a carboxyl group.
% By weight, and 50 to 99.5% by weight of an ethylenically unsaturated monomer having no carboxyl group. At least one of the compounds (E) has the following general formula (1): R ¹ —Si— (R ² ( ₃ ) (1) (wherein, R ¹ is hydrogen, an aliphatic hydrocarbon group having ^{1 to} 16 carbon atoms, an aryl group, a cycloalkyl group, a vinyl group, an alkyl acrylate group or an alkyl methacrylate group: R ² is 1) A polymer latex composition using a hydrolyzable silane represented by an alkoxy group, an acetoxy group, or a hydroxyl group having up to 8 carbon atoms, all of which may be the same or partially or entirely different. Is what you do.

In the present invention, the ratio of the ethylenically unsaturated monomer (A) having a sulfonic acid group or a sulfate ester group to the other ethylenically unsaturated monomer (B) is such that the ratio of the sulfonic acid group or the sulfate ester The ethylenically unsaturated monomer having a group (A) has a content of 0.05 to 20% by weight and the other ethylenically unsaturated monomer (B) has a content of 80 to 99.95% by weight. 0.1 to 10% by weight of an ethylenically unsaturated monomer (A) having an ester group, and 90 to 99.9% by weight of another ethylenically unsaturated monomer (B)
Preferably, the monomer mixture is a seed latex prepared by emulsion polymerization in an aqueous medium. Except for this weight ratio, the latex cannot be obtained stably, or the film obtained from the latex has poor water resistance.

In the present invention, as the second step, the ratio of the ethylenically unsaturated monomer (C) having a sulfonic acid group or a sulfate group to the other ethylenically unsaturated monomer (D) is determined by the ratio of sulfonic acid 0.05 to 10% by weight of an ethylenically unsaturated monomer (C) having a hydroxyl group or a sulfate group, and 90 to 99.95 of another ethylenically unsaturated monomer (D).
% By weight, wherein the ethylenically unsaturated monomer (C) having a sulfonic acid group or a sulfate group is 0.1 to 5% by weight,
95-99. Other ethylenically unsaturated monomers (D).
It preferably comprises 9% by weight. If the weight ratio is out of the range, latex cannot be obtained stably, and the water resistance of the film obtained from the latex is poor.

In the present invention, a polymer in a seed latex prepared by subjecting a monomer mixture comprising (A) and (B) to emulsion polymerization in an aqueous medium, and (C) and (D) as a second step. ) Is from 1/99 to 99/1, preferably from 5/95 to 95/5. In the present invention, a polymer in a seed latex prepared by subjecting a monomer mixture comprising (A) and (B) to emulsion polymerization in an aqueous medium, and formed from (C) and (D) in the second step The ratio of the polymer to be formed and the organopolysiloxane formed from the hydrolyzable silane (E) is preferably 50/50 to 99/1.

The ethylenically unsaturated monomer having a sulfonic acid group or a sulfate group in the present invention means a compound having a radical polymerizable double bond and a sulfonic acid group or a sulfate group in the molecule. , (A) and (C) may be the same or different, and two or more kinds may be used in combination, and some or all may be different. The monomer having a sulfonic acid group or a sulfate group is preferably an ammonium salt, a sodium salt, or a potassium salt, and these are represented by the following general formulas (I), (II), (III), (IV),
Allyl sulfosuccinate represented by, for example, Latemul (trademark) S-120, S-180A manufactured by Kao Corporation,
S-180, Eleminol (trademark) J manufactured by Sanyo Chemical Industries, Ltd.
S-2, etc.

[0012]

Embedded image

(In the above formula, R ₁ is hydrogen or a methyl group, R ₂ is a hydrocarbon or a hydrocarbon group having a substituent or an organic group containing an oxyalkylene group, A is an alkylene group having 2 to 4 carbon atoms or A substituted alkylene group, n represents 0 or an integer, and M represents ammonium, sodium, potassium) or an alkylphenol ether represented by the following formula (V), for example, Aqualon manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (Trademark) HS-10, etc.

[0014]

Embedded image

Wherein R ¹ is an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms, R ² is hydrogen or an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms, R ³ is hydrogen or A propenyl group, A has 2 to 4 carbon atoms
An alkylene group of n, n is an integer of 1 to 200, M is ammonium, sodium, potassium) Further, as a compound represented by the following general formula (VI), for example, Adecaria Soap (trademark) SE1 manufactured by Asahi Denka Kogyo KK
025N and the like.

[0016]

Embedded image

Wherein R ¹ is hydrogen or a methyl group, R ² is an alkyl or acyl group having 8 to 24 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 0 to 20; Is 0
An integer of 50, M is ammonium, sodium, potassium) p-styrenesulfonate, methylpropanesulfonic acid acrylamide salt, acrylic acid sulfoalkyl ester salt, methacrylic acid sulfoalkyl ester salt, etc. However, the present invention is not limited to these.

In the present invention, the other ethylenically unsaturated monomers (B) and (D) may be the same or partially or entirely different, and may or may not have a carboxyl group. Examples of the ethylenically unsaturated monomer having no carboxyl group include acrylates and methacrylates [hereinafter sometimes simply referred to as (meth) acrylates. ], Aromatic monomers such as styrene and vinyltoluene, vinyl esters such as vinyl acetate, vinyl propionate and vinyl persate, vinyl cyanides such as (meth) acrylonitrile, and halogenations such as vinyl chloride and vinylidene chloride. Vinyls, butadiene, etc., and various functional monomers such as (meth)
Acrylamide, diacetone acrylamide, pinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, N-methylolacrylamide, N-butoxymethylacrylamide, acid phosphooxyethyl methacrylate, 3-chloromethacrylate -2-acid phosphooxypropyl, divinylbenzene, methyl vinyl ketone, (poly) oxyethylene mono (meth) acrylate, (poly) propylene glycol (meth) acrylate, allyl (meth) acrylate, (poly) oxyethylene di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like.

Examples of the acrylate or methacrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, and the like. Specific examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and maleic anhydride. These ethylenically unsaturated monomers having a carboxyl group are also useful as catalysts for accelerating the hydrolysis and condensation reactions of hydrolyzable silanes.

In the present invention, the other ethylenically unsaturated monomer (B) comprises 0.5 to 50% by weight of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having no carboxyl group. It is preferable that the monomer comprises 50 to 99.5% by weight, the ethylenically unsaturated monomer having a carboxyl group is 1.0 to 20% by weight, and the ethylenically unsaturated monomer having no carboxyl group is 80%. ~ 9
More preferably, it comprises 9% by weight. Except for this weight ratio, the latex cannot be obtained stably, or the film obtained from the latex has poor water resistance. (A),
The carboxyl group in the seed latex prepared by subjecting the monomer mixture comprising (B) to emulsion polymerization in an aqueous medium is useful as a catalyst for accelerating the hydrolysis and condensation reactions of the hydrolyzable silane. .

In the present invention, the hydrolyzable silane (E)
At least one of the following general formulas (1): R ¹ —Si— (R ² ) ₃ (1) (wherein R ¹ is hydrogen, an aliphatic hydrocarbon group having ^{1 to} 16 carbon atoms, an aryl group, An alkyl group, a vinyl group, an alkyl acrylate group or an alkyl methacrylate group: R ² is an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group, all of which may be the same or partially or entirely different And R ¹ is a methyl group, a phenyl group, a vinyl group, γ- (meth)
An acryloxypropyl group is preferred, and R ² is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, or a hydroxyl group. Specific examples include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, vinylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane , Γ
-Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane and the like are preferably used, and one or more of these silanes may be used in combination.

Further, the compound which can be used in combination is represented by the following general formula (2): (R ³ ) _n -Si- (R ⁴ ) _4-n (2) (where R ³ is hydrogen and has 1 to 1 carbon atoms) 16 aliphatic hydrocarbon groups, aryl groups, cycloalkyl groups, vinyl groups, alkyl acrylate groups or alkyl methacrylate groups: R ⁴ is 1
An alkoxy group having from 8 to 8 carbon atoms, an acetoxy group, a hydroxyl group: n is 0 or a positive integer of 2, 3), and all or some of R ³ are the same or different. You may. Further, all of R ⁴ may be the same or part or all may be different. Among them, a methyl group and a phenyl group are particularly preferred as R ³ . R ⁴ is particularly preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, or a hydroxyl group. As specific examples of alkoxysilanes, dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane,
Examples include diphenyldiethoxysilane, methylphenyldimethoxysilane, trimethylmethoxysilane, and tetraethoxysilane. In addition, cyclic silanes, linear siloxanes, and chlorosilanes can be used in combination. Examples of the cyclic silane include octamethylcyclotetrasiloxane, octaphenylcyclosiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, and tetramethyltetrasiloxane. Vinyl cyclotetrasiloxane and the like can be used.

[0023]

[0024]

Further, as chlorosilanes, for example, methylchlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenylchlorosilane, vinylchlorosilane, γ- (meth) acryloxypropyltrichlorosilane, γ- (meth) acrylic Roxypropyldichloromethylsilane and the like.

In the present invention, the hydrolyzable silane (E)
Is represented by the following general formula (1), R ¹ —Si— (R ² ) ₃ (1) and the following general formula (5), (R ³ ) ₂ —Si— (R ⁴ ) ₂ (5) It is preferable to use those represented in combination. (1) / (5) is at least 1/10
0, preferably at least 10/100, more preferably at least 35/100.

In the present invention, a cyclic silane and / or a linear siloxane may be used in place of the hydrolyzable silane represented by the general formula (5), or may be used in combination. In the practice of the present invention, a normal emulsion polymerization method can be adopted. However, the hydrogen ion concentration (pH) during the first stage seed latex and the second stage emulsion polymerization is usually pH
It is carried out at a pH of 4.0 or less, preferably at a pH of 3.0 or less. That is, a feature of the present invention is that, in an emulsion polymerization system in which a seed latex is present, the condensation reaction of a hydrolyzable silane and the radical polymerization of an unsaturated monomer are simultaneously performed and / or after the condensation reaction of a hydrolyzable silane is preceded. An emulsion polymerization method for promoting the radical polymerization of a saturated monomer is used.Specifically, the emulsion polymerization method is not limited to the method described below. A method in which the hydrolyzable silane (E) is added after the step is completed, and the compound (C) and the compound (D) are introduced into the reaction system after the polymerization of the silane is completed, or a method in which the compounds are successively introduced.

Adding a hydrolyzable silane (E),
A method of introducing the compound (C) and the compound (D) into the reaction system while the polymerization of the silane is in progress, or a method of sequentially introducing the compound (C) and the compound (D). A method of simultaneously introducing the hydrolyzable silane (E) and the compound (C) and the compound (D) into the reaction system, or a method of sequentially introducing the same. Etc., and it is also possible to carry out by combining the respective methods. Note that the second step may be performed in two or more steps as long as the above requirements are satisfied.

In the practice of the present invention, a radical polymerization catalyst which undergoes radical decomposition by heat or a reducing substance to cause addition polymerization of an ethylenically unsaturated monomer, and is a water-soluble or oil-soluble persulfate Salts, peroxides, azobis compounds and the like are used. Examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis (2-diaminopropane)
There are hydrochloride, 2,2-azobis (2,4-dimethylpareronitrile), etc., and potassium persulfate, which is also effective as a catalyst for accelerating the hydrolysis reaction and condensation reaction of hydrolyzable silane, Sodium sulfate,
Ammonium persulfate is preferred. The amount is usually 0.1 to 1% by weight based on the ethylenically unsaturated monomer. In addition, if it is desired to accelerate the polymerization rate and further polymerize at a low temperature, for example, sodium bisulfite, ferrous chloride,
A reducing agent such as ascorbate or Rongalite is used in combination with a radical polymerization catalyst.

If desired, a chain transfer agent for controlling the molecular weight, such as dodecyl mercaptan, can be added. In the present invention, the ethylenically unsaturated monomers (A) and (C) having a sulfonic acid group or a sulfate ester group are used.
In addition, a normal surfactant can be used in combination. For example, anionic surfactants such as fatty acid soaps, alkyl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl aryl sulfates, polyoxyethylene alkyl aryl ethers, and polyoxyethylene sorbitan fatty acid esters And nonionic surfactants such as oxyethyleneoxypropylene block copolymer, and nonionic surfactants copolymerized with an ethylenically unsaturated monomer called a reactive nonionic surfactant.

In the present invention, after the emulsion polymerization, as a curing catalyst at the time of film formation, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, tin octylate, tin laurate, iron octylate, lead octylate, tetraoctylate Metal salts of organic acids such as butyl titanate, n
-Hexylamine, 1,8-diazabicyclo [5,4,
An amine compound such as [0] -7-undecene can be added to the polymer latex.

When these curing catalysts are not water-soluble, they are preferably emulsified with a surfactant and water before use. The polymer latex produced according to the present invention is adjusted to a pH of 5 to 10 using amines such as ammonia, sodium hydroxide, potassium hydroxide, and dimethylaminoethanol in order to maintain long-term dispersion stability of the latex. Is preferred.

The polymer latex produced according to the present invention may optionally contain components which are usually added to water-based paints and the like, such as thickeners, defoamers, pigments, dispersants, dyes and preservatives. Is optional. When the above requirements of the present invention are not satisfied, a large amount of aggregates are generated during emulsion polymerization, a high-concentration latex cannot be produced stably, or a latex generates aggregates during pigment mixing. Or The film in which the pigment is mixed has poor gloss development, poor water resistance, and poor gloss retention.

[0034]

Next, the present invention will be described in detail with reference to examples and comparative examples, but it goes without saying that the scope of the present invention is not limited to these examples. The parts and percentages in the examples are by weight. The obtained polymer latex containing silicone was prepared according to the following test method by preparing a paint having the following composition.

(Coating composition) Pigment dispersion Water 82.5 parts Poise 530 Note 1 7.5 parts 5% aqueous solution of sodium tripolyphosphate 7.5 parts 3% aqueous solution of Daicel HEC SP-600 Note 2 25.0 parts Nopco 14.97VD * 3 2.5 parts TYPAKE R-930 * 4 375.0 parts Letdown polymer latex composition (in terms of solid content) 460.0 parts Ethylene glycol monobutyl ether 60.0 parts Ethylene glycol mono-2-ethylhexyl ether 0 parts Water 30.0 parts Nopco 1497VD 1.0 part (Note) * 1 Dispersant: manufactured by Kao Corporation * 2 Thickener: manufactured by Daicel Chemical Industries, Ltd. * 3 Defoaming agent: manufactured by San Nopco * 4 Rutile type titanium oxide: manufactured by Ishihara Sangyo Co., Ltd. (Test method) Initial gloss value, gloss retention rate No. Using 50, apply to a sulfated alumite plate and dry at room temperature for 30 days. The specular reflectance at 60 ° ─60 ° at that time was measured as an initial gloss value (this is defined as zero time). Sunshine type weatherometer (Suga Test Instruments Co., Ltd., WEL)
-SUN-DC) using an exposure test (rain cycle);
(12 minutes / hour, black panel temperature: 60 to 66 ° C.). The specular reflectance at 60 ° ─60 ° after 2000 hours of exposure was measured as a final gloss value, and the gloss retention was calculated by dividing the value by the initial gloss value.

Water resistance The above paint was coated with a wire coater No. Using No. 50, it was applied to a sulfated alumite plate and dried at room temperature for 2 hours. After further drying at 50 ° C. for 2 days, it was immersed in water at 40 ° C. for 30 days, and the state was visually determined. Judgment criteria ；: No blistering or shine is observed at all.

○: Some blistering was observed, but no gloss was observed. Δ: Blisters and gloss are observed. ×: The entire surface is blistered and gloss is remarkable.

[0038]

Example 1 A reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer was charged with 8 parts of methacrylic acid, 52 parts of methyl methacrylate, 40 parts of butyl acrylate, and 3 parts of water.
00 parts, Latemul ™ S-180A (ammonium sulfosuccinate diester having a double bond copolymerizable with an ethylenically unsaturated monomer in the molecule: manufactured by Kao Corporation)
20 parts of a 20% aqueous solution of
After raising to 8 ° C., 0.5 parts of ammonium persulfate are added and kept for 1 hour. As a result, the seed latex of the first stage was prepared, and the hydrogen ion concentration was measured.
It was 1.8. Next, 3 parts of methacrylic acid, 207 parts of methyl methacrylate, 190 parts of butyl acrylate, 33 parts of water
0 parts, 20 parts of a 20% aqueous solution of latemul S-180A, 1.0 part of ammonium persulfate, 2.5 parts of γ-methacryloxypropyltrimethoxysilane, 25 parts of dimethyldimethoxysilane, 25 parts of methyltrimethoxysilane
Part of the mixture into the reaction vessel from a separate dropping tank.
Let it flow in over time. During the inflow, set the temperature in the reaction vessel to 8
Keep at 0 ° C. After the inflow is completed, raise the temperature in the reaction vessel to 8
Maintain at 5 ° C. for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.1. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.02% of the total monomer.
The solid content of the obtained latex was 44.0%, and the average particle diameter was 980 °. This latex was blended with the paint described above and tested for initial gloss value, gloss retention and water resistance. The results are shown in Table 1.

[0039]

Comparative Example 1 A reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer was charged with 8 parts of methacrylic acid, 52 parts of methyl methacrylate, 40 parts of butyl acrylate, and 3 parts of water.
00 parts, 40% of sodium dioctyl sulfosuccinate
Aqueous solution (Perex (trademark) OT-P, manufactured by Kao Corporation)
4 parts of polyoxyethylene nonylphenyl ether 2
5% aqueous solution (Emulgen (trademark) 950, Kao Corporation)
1), raise the temperature in the reaction vessel to 78 ° C., add 0.5 parts of ammonium persulfate and maintain for 1 hour. Thus, a seed latex of the first stage was prepared, and the pH was 1.8 when the hydrogen ion concentration was measured. Next, 3 parts of methacrylic acid, methyl methacrylate 20
A mixed solution of 7 parts, 190 parts of butyl acrylate, 330 parts of water, 5 parts of a 25% aqueous solution of polyoxyethylene nonylphenyl ether (Emulgen 950, manufactured by Kao Corporation), 1.0 part of ammonium persulfate, and γ-methacrylic acid A mixed solution consisting of 2.5 parts of roxypropyltrimethoxysilane, 25 parts of dimethyldimethoxysilane and 25 parts of methyltrimethoxysilane is allowed to flow into the reaction vessel from separate dropping tanks over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.2. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.02% of the total monomer. The resulting latex has a solid content of 44.1% and an average particle size of 890 °.
Met. This latex was blended with the paint described above and tested for initial gloss value, gloss retention and water resistance. (Only ordinary surfactants were used instead of components (A) and (C).) The results are shown in Table 1.

[0040]

Comparative Example 2 A reaction vessel equipped with an agitator, a reflux condenser, a dropping tank and a thermometer was charged with 300 parts of water and Latemul S.
10 parts of a 20% aqueous solution of -180A was charged, the temperature in the reaction vessel was raised to 80 ° C, and then methacrylic acid 11
Parts, methyl methacrylate 259 parts, butyl acrylate 2
A mixture of 30 parts, 330 parts of water, 30 parts of a 20% aqueous solution of latemul S-180A, and 1.5 parts of ammonium persulfate;
γ-methacryloxypropyltrimethoxysilane 2.5
, 25 parts of dimethyldimethoxysilane and 25 parts of methyltrimethoxysilane are allowed to flow into the reaction vessel from separate dropping tanks over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured and was 2.3.
The pH was adjusted to 8 by adding a 25% aqueous ammonia solution, followed by filtration through a 100-mesh wire net. The dry weight of the filtered agglomerate was slightly higher at 0.35% of the total monomer. The solid content of the obtained latex was 44.0%, and the particle size was 900 °. This latex was blended with the paint described above and tested for initial gloss value, gloss retention and water resistance. (The production of the seed latex in the former stage and the reaction in the latter stage containing the seed latex were not divided.) The results are shown in Table 1.

[0041]

Comparative Example 3 8 parts of methacrylic acid, 52 parts of methyl methacrylate, 40 parts of butyl acrylate, and 3 parts of water were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer.
Then, 00 parts and 20 parts of a 20% aqueous solution of latemul S-180A are charged, the temperature in the reaction vessel is raised to 78 ° C., and 0.5 parts of ammonium persulfate is added and maintained for 1 hour. Thereby, the seed latex in the first stage was adjusted, and the pH was 1.8 when the hydrogen ion concentration was measured. next,
3 parts of methacrylic acid, 207 parts of methyl methacrylate, 190 parts of butyl acrylate, 330 parts of water, Latemul S-18
20 parts of a 20% aqueous solution of 0A, ammonium persulfate 1.0
Parts of the mixed solution and 50 parts of dimethyldimethoxysilane are allowed to flow into the reaction vessel from separate dropping tanks over 3 hours.
During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours.
After cooling to room temperature, the hydrogen ion concentration was measured.
2.2. Add 25% aqueous ammonia and add p
After adjusting to H8, the mixture was filtered through a 100 mesh wire mesh.
The dry weight of the filtered agglomerate is 0.0
It was very slight at 2%. The solid content of the obtained latex was 44.0%, and the average particle diameter was 980 °. This latex was blended with the paint described above, and tested for initial gloss value, gloss retention and water resistance. (No hydrolyzable silane of the general formula (1) was used.) The results are shown in Table 1.
It was shown to.

[0042]

EXAMPLE 2 8 parts of methacrylic acid, 52 parts of methyl methacrylate, 40 parts of butyl acrylate, and 3 parts of water were placed in a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer.
Then, 00 parts and 20 parts of a 20% aqueous solution of latemul S-180A are charged, the temperature in the reaction vessel is raised to 78 ° C., and 0.5 parts of ammonium persulfate is added and maintained for 1 hour. Thus, a first stage seed latex was prepared, and the pH was 1.9 when the hydrogen ion concentration was measured. next,
γ-methacryloxypropyltrimethoxysilane 2.5
, 25 parts of dimethyldimethoxysilane, and 25 parts of methyltrimethoxysilane were charged over 5 minutes, followed by 210 parts of methyl methacrylate, 190 parts of butyl acrylate, 330 parts of water, and 2 parts of latemul S-180A.
A mixture of 20 parts of a 0% aqueous solution and 1.0 part of ammonium persulfate is allowed to flow into the reaction vessel from separate dropping tanks over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured and found to be pH 2.1. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.02% of the total monomer. The solid content of the obtained latex was 44.0%, and the average particle diameter was 980 °. This latex was blended with the paint described above and tested for initial gloss value, gloss retention and water resistance.
The results are shown in Table 1.

[0043]

Example 3 15 parts of methacrylic acid, 55 parts of methyl methacrylate, 30 parts of 2-ethylhexyl acrylate, 300 parts of water, 300 parts of lattemul S- were placed in a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer. 20% of 180A
20 parts of the aqueous solution is charged, the temperature in the reaction vessel is raised to 78 ° C., and 0.5 part of ammonium persulfate is added and maintained for 1 hour. Thus, the seed latex of the first stage was prepared, and the pH of the hydrogen ion concentration was measured to be 1.7. Subsequently, while maintaining the temperature in the reaction vessel at 60 ° C., 25 parts of dimethyldimethoxysilane and 25 parts of methyltrimethoxysilane After charging the mixed solution consisting of
Hold at 80 ° C. for 2 hours. Next, methyl methacrylate 230
Parts, 2-ethylhexyl acrylate 170 parts, water 330
Parts, 20 parts of a 20% aqueous solution of sodium p-styrenesulfonate, 20 parts of sodium dodecylbenzenesulfonate
A mixture of 2 parts of a 2% aqueous solution and 1.0 part of ammonium persulfate and 2.5 parts of γ-methacryloxypropyltrimethoxysilane are allowed to flow into the reaction vessel from separate dropping tanks over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the pH was measured to be 2.0. Add 25% aqueous ammonia and add p
After adjusting to H8, the mixture was filtered through a 100 mesh wire mesh.
The dry weight of the filtered agglomerate is 0.0
It was very slight at 2%. The solid content of the obtained latex was 44.0%, and the average particle diameter was 1090 °. This latex was blended with the paint described above and tested for initial gloss value, gloss retention and water resistance. The results are shown in Table 1.

[0044]

Examples 4 to 9 and Comparative Examples 4 to 8 Preparation of seed latex 5 parts of itaconic acid and 10 parts of methacrylic acid were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer.
Parts, 30 parts of methyl methacrylate, 15 parts of styrene, 40 parts of 2-ethylhexyl acrylate, 381.5 parts of water, Aqualon (trademark) HS-10 (a double bond copolymerizable with an ethylenically unsaturated monomer. 18 parts of a 25% aqueous solution of polyoxyethylene alkyl phenyl ether sulfate ammonium ester (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) in the molecule was charged, and the temperature in the reaction vessel was raised to 78 ° C., and then ammonium persulfate was added. Add 5 parts and keep for 1 hour. Thereby, a seed latex of the first stage was prepared, and the pH was 1.6 when the hydrogen ion concentration was measured.

Preparation of Latex, a to f, and A to A Next, the seed latex was added to a 25% aqueous solution of Aqualon HS-10 in an amount of 80 parts by weight as shown in Table 2 or Table 3.
, A mixed solution of 5 parts of ammonium persulfate, 655 parts of water, and other unsaturated monomer components shown in Table 2 or Table 3;
Alternatively, the hydrolyzable silane shown in Table 3 is allowed to flow into the reaction solution from a separate dropping tank over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the pH was measured and found to be in the range of 1.5 to 2.5. The pH was adjusted to 8 by adding a 25% aqueous ammonia solution, followed by filtration through a 100-mesh wire net. Except for Comparative Example 7, the dry weight of the filtered aggregate was 0.5% or less for all monomers. This latex was blended with the paint described above and tested for initial gloss value, gloss retention and water resistance. The results are shown in Tables 2 and 3.

Test Results Latexes a to f of Examples 4 to 9 are the latexes targeted by the present invention. Comparative Examples 4 and 5 do not contain a trialkoxysilane or a silane having a trisilanol group, which is an essential component, as a hydrolyzable silane, and therefore have poor gloss retention.

In Comparative Example 6, the amount of the hydrolyzable silane used was less than the range of the present invention, and the gloss retention was poor. Comparative Example 7 is an example in which the amount of the hydrolyzable silane used exceeded the range of the present invention, and a latex could not be obtained stably. In Comparative Example 8, the ratio of the seed latex to the polymer obtained from the unsaturated monomer in the second stage was out of the range specified in the present invention, and the gloss retention and water resistance were poor.

[0048]

Comparative Example 9 Aqualon HS- was added to 10,000 parts of the seed latex used in Examples 4 to 9 and Comparative Examples 4 to 8.
0.8 part of a 25% aqueous solution of 10 and ammonium persulfate 0.1 part.
05 parts, 6.6 parts of water, 3.5 parts of 2-ethylhexyl acrylate, 6.3 parts of methyl methacrylate, 0.2 part of methacrylic acid, 1 part of γ-methacryloxypropyltrimethoxysilane, dimethyl Diethoxysilane 10
And a mixed solution consisting of 10 parts of methyltriethoxysilane are allowed to flow into the reaction vessel from separate dropping tanks over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the pH was measured and found to be pH 1.9.
Met. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was 0.5
% Or less. This latex was blended with the above-mentioned paint and tested for initial gloss value, gloss retention and water resistance. The initial gloss value was 78%, the gloss retention was 25%, and the water resistance was x (poor). Was.

[0049]

Comparative Example 10 1000 parts of the seed latex used in Examples 4 to 9 and Comparative Examples 4 to 8 were added to Aqualon HS-
10 parts of a 25% aqueous solution, 2 parts of ammonium persulfate, 655 parts of water, 390 parts of n-butyl acrylate, 590 parts of methyl methacrylate, 20 parts of methacrylic acid, 45 parts of methyltriethoxysilane, 45 parts of dimethyldimethoxy When a mixed solution composed of 100 parts of silane was flowed into the reaction vessel from separate dropping tanks over 3 hours and kept at 80 ° C., the polymer latex aggregated.

[0050]

Comparative Example 11 1000 parts of the seed latex used in Examples 4 to 9 and Comparative Examples 4 to 8 were added to Aqualon HS-
520 parts of a 25% aqueous solution of 10 and ammonium persulfate 5
A reaction vessel containing a mixture of 485 parts of water, 485 parts of water, 390 parts of n-butyl acrylate, 590 parts of methyl methacrylate, and 20 parts of methacrylic acid, and a mixture of 45 parts of methyltriethoxysilane and 100 parts of dimethyldimethoxysilane. The mixture is allowed to flow through separate dripping tanks over 3 hours and kept at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature and measuring the pH,
pH 2.1. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered aggregate was 0.1% based on all monomers. This latex was blended with the paint described above and subjected to a water resistance test. The result was x (poor).

[0051]

Comparative Example 12 A reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer was charged with 10 parts of itaconic acid, 20 parts of methacrylic acid, 60 parts of methyl methacrylate, 30 parts of styrene, and 80 parts of 2-ethylhexyl acrylate. Part, water 7
63 parts and 0.2 parts of a 25% aqueous solution of Aqualon HS-10 were used, and the same procedure as in Examples 4 to 9 was carried out to prepare the first stage seed latex, and the hydrogen ion concentration was measured to be pH 1.9. Was. Next, Aqualon HS-10-2
80 parts of 5% aqueous solution, 5 parts of ammonium persulfate, 655 of water
Parts, a mixed solution consisting of 390 parts of n-butyl acrylate, 590 parts of methyl methacrylate, and 20 parts of methacrylic acid, and a mixed solution consisting of 45 parts of methyltriethoxysilane and 100 parts of dimethyldimethoxysilane were separately placed in a reaction vessel. After flowing over 3 hours from the drip tank and keeping it at 80 ° C,
The polymer latex has aggregated.

[0052]

Comparative Example 13 10 parts of itaconic acid, 20 parts of methacrylic acid, 60 parts of methyl methacrylate, 30 parts of styrene, 80 parts of 2-ethylhexyl acrylate were placed in a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer. , Water 60
0 parts and 300 parts of a 25% aqueous solution of Aqualon HS-10 are charged, the temperature in the reaction vessel is raised to 78 ° C., and 1.0 part of ammonium persulfate is added and maintained for 1 hour. Thus, a first stage seed latex was prepared, and the pH was 1.9 when the hydrogen ion concentration was measured. Next, 80 parts of a 25% aqueous solution of Aqualon HS-10, 5 parts of ammonium persulfate, 655 parts of water, and n-butyl acrylate 39
0 parts, 590 parts of methyl methacrylate, 20 methacrylic acid
Part of the mixed solution, and methyltriethoxysilane 45
Parts and a mixed solution consisting of 100 parts of dimethyldimethoxysilane are allowed to flow into the reaction vessel from separate dripping tanks over 3 hours, and kept at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the pH was measured to be 2.3. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerate was 0.2% based on all monomers. This latex was blended with the paint described above and subjected to a water resistance test. The result was x (poor).

[0053]

Comparative Example 14 Methyl methacrylate 9 was placed in a reaction vessel equipped with an agitator, a reflux condenser, a dropping tank and a thermometer.
0 parts, 30 parts of styrene, 80 parts of 2-ethylhexyl acrylate, 763 parts of water, and 36 parts of a 25% aqueous solution of Aqualon HS-10 were added, and the temperature in the reaction vessel was raised to 78 ° C. Add 0 parts and keep for 1 hour. Thus, a first-stage seed latex was prepared, and the pH was measured to be 2.3 when the hydrogen ion concentration was measured. Next, a 25% aqueous solution of Aqualon HS-10 80
, 5 parts of ammonium persulfate, 655 parts of water, 390 parts of n-butyl acrylate, 590 parts of methyl methacrylate, and 20 parts of methacrylic acid, and a mixture of 45 parts of methyltriethoxysilane and 100 parts of dimethyldimethoxysilane When the solution was allowed to flow into the reaction vessel from separate dropping tanks over 3 hours and kept at 80 ° C., the polymer latex aggregated. (No ethylenically unsaturated monomer having a carboxyl group was used.)

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

According to the present invention, the gloss of a film obtained from a conventional polymer latex or a film obtained from a paint in which a pigment is blended with the polymer latex decreases rapidly, and the gloss retention level is high. Was low. The polymer latex according to the present invention, in the presence of seed latex,
It is obtained by emulsion polymerization of a hydrolyzable silane and an unsaturated monomer, and can provide a film excellent in both gloss retention and water resistance, which cannot be achieved by a conventional polymer latex.

Claims (1)

(57) [Claims] An emulsion polymerization of an ethylenically unsaturated monomer (A) having a sulfonic acid group or a sulfate group and another ethylenically unsaturated monomer (B) in an aqueous medium. In the presence of a seed latex, an ethylenically unsaturated monomer (C) having a sulfonic acid group or a sulfate group and another ethylenically unsaturated monomer (D) are combined with a hydrolyzable silane (E). A polymer latex composition containing silicone obtained by emulsion polymerization, wherein the ratio of (A) to (B) is such that (A) is 0.05 to 2
0% by weight, (B) is 80 to 99.95% by weight, and the ratio of (C) to (D) is (C) is 0.05 to 1%.
0% by weight, (D) is 90 to 99.95% by weight, the polymer in the seed latex, (C) and (D)
Weight ratio with the polymer formed from 1/99 to 99
/ 1, and the ratio of the polymer in the seed latex and the polymer formed from (C) and (D) to the silicone formed from (E) is 50/50 to 99 / 1, wherein (B) is 0.5 to 50% by weight of an ethylenically unsaturated monomer having a carboxyl group, and 50 to 99.5% by weight of an ethylenically unsaturated monomer having no carboxyl group. Wherein at least one of (E) has the following general formula (1): R ¹ —Si— (R ² ) ₃ (1) (wherein R ¹ is hydrogen, an aliphatic carbon having ^{1 to} 16 carbon atoms) A hydrogen group, an aryl group, a cycloalkyl group, a vinyl group, an alkyl acrylate group or an alkyl methacrylate group: R ² is an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, a hydroxyl group, and all are the same or a part Or all may be different.) Polymer latex composition using that hydrolyzable silane.