JP3318000B2 - Method for producing aqueous dispersion type composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to, for example,
Automobiles, home appliance products, plastics and various painting, particularly weathering resistance, in the required application of the durability, for producing how an aqueous dispersion type composition having good film properties.

[0002]

2. Description of the Related Art In recent years, in the field of paints and adhesives, the use of organic solvents has been changed from water-soluble or water-dispersible resins to pollution control or resource saving. Attempted. However, the conventional aqueous dispersion type resin is manufactured by an emulsion polymerization method using an ionic or nonionic surfactant, and as a result, a coating film formed by the influence of the surfactant used for polymerization is formed. Had poor defects in weather resistance, water resistance, and stain resistance, and were inferior in gloss to the coating film as compared with the solvent system due to the difference in the film formation mechanism.

[0003] Various attempts have been made to improve this disadvantage, one of which is to use a water-soluble polymer compound such as maleated polybutadiene, maleated alkyd resin, water-soluble acrylic resin, etc. as a dispersion stabilizer. A method of conducting a polymerization reaction in an aqueous medium, and in order to improve water resistance and weather resistance, a functional group capable of reacting the silyl group in an aqueous solution of a water-soluble synthetic resin having a hydrolyzable silyl group. For producing an emulsion polymer, comprising emulsion-polymerizing a comonomer containing a vinyl monomer having
No. 01 publication) has been proposed. However, since the hydrolyzable silyl group is unstable, it tends to gel during the synthesis or storage of the emulsion polymer, and has a disadvantage that it cannot be produced stably.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that the general formula (I)
Synthesis of a water-soluble resin (A) having a silyl group represented by
Hydrolysable ester (C) or chain which is not a chain transfer agent
By performing in the presence of a non-transfer agent hydrolysable ester (C) and A Ruko <br/> Le (D), it is stabilized silyl groups in (A), in an aqueous solution of (A) It has been found that the dispersion polymerization of (B) can be carried out stably and there is no problem in the storage stability of the obtained emulsion, and the present invention has been achieved.

That is, the present invention provides a compound represented by the general formula (I):

[0006]

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(Wherein, R ¹ is a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group having 1 to 10 carbon atoms, X is a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, an aminoxy Group, phenoxy group,
A represents a monovalent group selected from a thioalkoxy group and an amino group, a represents 0, 1 or 2) in an aqueous solution of a water-soluble resin (A) having a silyl group represented by the general formula (I): Aqueous dispersion-type composition obtained by subjecting the represented silyl group-containing acrylic copolymer (B) to dispersion polymerization.
In the production of the product , the water-soluble resin (A) is obtained by polymerizing the water-soluble resin (A) with a hydrolyzable ester (C) that is not a chain transfer agent or a hydrolyzable ester (C) that is not a chain transfer agent and an alcohol (D).
The aqueous dispersion type composition according to claim Rukoto example carried out in the presence of
For the production how of things.

[0008]

The water-soluble resin (A) having a silyl group used in the present invention is a vinyl monomer having a silyl group (a-
1), a vinyl monomer having a group capable of generating a water-soluble group or a water-soluble group and (a-2) and these monomers and other copolymerizable vinyl monomer (a-3) a chain It's a transfer agent
There hydrolysable ester (C) (hereinafter, simply hydrolyzable et
Stele (C)) or hydrolysable ester (C)
And is e by water-solubilizing copolymerized if necessary in the presence of A alcohol (D).

[Silyl group-containing vinyl monomer (a-
1)] The silyl group-containing vinyl monomer (a-1) used in the synthesis of the silyl group-containing water-soluble resin (A) is represented by the formula (I) and a polymerizable double bond in one molecule. There is no particular limitation as long as the compound contains a group. For example, CH ₂ ＣＨCHS
i (OCH ₃ ) ₃ , CH ₂ ＣＨCHSiCH ₃ (OC
H ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (OC
H ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ S
i (OCH ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH
₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCHC
OO (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ , CH
₂ ＣＨCHSi (CH ₃ ) Cl ₂ , CH ₂ ＣＨCHSiCl
₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ SiCl ₃ , CH
₂ = CHCOO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ , C
H ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ SiCl ₃ , C
H ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ )
Cl ₂ , CH ₂ ＣＨCHSi (OC ₂ H ₅ ) ₃ , CH ₂ ＝
_{CHSi (CH 3) (OC 2} H 5) 2, CH 2 = CHS
i (OC ₃ H ₇ ) ₃ , CH ₂ ＣＨCHSi (OC ₄ H ₉ )
₃ , CH ₂ ＣＨCHSi (OC ₆ H ₁₃ ) ₃ , CH ₂ CHCHSi (O
_{C 8 H 17) 3, CH} 2 = CHSi (O-isoC
_{3 H 7) 3, CH 2} = CHSi (O-isoC 4 H 9)
₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (OC
_{2 H 5) 3, CH 2} = C (CH 3) COO (CH 2) 3
Si (OC ₂ H ₅ ) ₃ , CH ₂ ＣＨCHCOO (CH ₂ )
₃ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , CH ₂ ＣC (CH
₃ ) COO (CH ₂ ) ₃ Si (CH ₃ ) (OC ₂ H ₅ )
₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (OC
₆ H ₁₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃
Si (OC ₆ H ₁₃ ) ₃ ,

[0010]

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And the like. One or two or more silyl group-containing vinyl monomers (a-1) may be used in combination, and 100 parts of a vinyl monomer mixture (parts by weight, the same applies hereinafter).
The amount is 1 to 50 parts , preferably 2 to 20 parts . If it is less than 1 part, the water resistance and weather resistance are inferior, and if it exceeds 50 parts, the stability of the emulsion decreases.

[Vinyl monomer having water-soluble group or group capable of forming water-soluble group (a-2)] Vinyl monomer having a water-soluble group or group capable of forming a water-soluble group used in the present invention As the body (a-2), (meth) acrylic acid,
Acids having a polymerizable double bond such as itaconic acid, crotonic acid, maleic acid, fumaric acid, styrene sulfonic acid, vinyl sulfonic acid; or salts thereof (alkali metal salts, ammonium salts, amine salts, etc.); maleic anhydride Acid anhydrides or half esters thereof with a linear or branched alcohol having 1 to 20 carbon atoms; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth)
(Meth) acrylates having an amino group such as acrylate; (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, acryloylmorpholine or the like Hydrochloric acid, acetate and the like.

The monomer (a-2) is copolymerized in an acid form,
Thereafter, a method of forming a salt by neutralization is preferable in terms of stabilization of the alkoxysilyl group.

(A-2) may be used singly or in combination of two or more, and is used in an amount of 0 to 30 parts , preferably 0.1 to 20 parts , based on 100 parts of the monomer mixture. When the amount exceeds 30 parts, the stability of the emulsion tends to decrease.

[Other copolymerizable vinyl monomers (a-
3)] Other copolymerizable vinyl monomers (a-3) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Derivatives of (meth) acrylic acid such as 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, glycidyl (meth) acrylate; 2-trifluoroethyl (meth) acrylate, 2,2,3
3,3-pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth)
Fluorine-containing vinyl monomer such as acrylate; 1- (3-
(Meth) acryloxypropyl) -1,1,3,3,3
-Pentamethyldisiloxane, 3- (meth) acryloxypropyltris (trimethylsiloxy) silane, AK
Siloxane-containing vinyl monomers such as -5 (a silicone macromer manufactured by Toa Gosei Chemical Industry Co., Ltd.); 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N- Methylol (meth) acrylamide, trade name Alonix 5700 (hydroxyl-containing monomer), 4-hydroxystyrene, manufactured by Toagosei Chemical Industry Co., Ltd., HE-10, HE-20, HP-10 manufactured by Nippon Shokubai Chemical Industry Co., Ltd. And HP-20 (acrylate oligomers each having a hydroxyl group at the end), Blemmer P manufactured by NOF Corporation
P series (polypropylene glycol methacrylate), Blemmer PE series (polyethylene glycol monomethacrylate), Blemmer PEP series (polyethylene glycol polypropylene glycol methacrylate), Blemmer AP-400 (polypropylene glycol monoacrylate), Blemmer AE-35
0 (polyethylene glycol monoacrylate), Blemmer NKH-5050 (polypropylene glycol polytrimethylene monoacrylate) and Blemmer GLM
(Glycerol monomethacrylate), Plaxel FA-1, FA-4, FM- manufactured by Daicel Chemical Industries, Ltd.
1. A hydroxyl-containing vinyl compound such as FM-4 and ε-
Hydroxyl-containing vinyl monomers such as ε-caprolactone-modified hydroxyalkylvinyl monomers obtained by reaction with caprolactone; AS-6, AN-, a macromonomer (reactive polymer) of Toa Gosei Chemical Industry Co., Ltd.
6, AA-6, B-6; aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, and vinyl toluene; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate, and diallyl phthalate; Other vinyl compounds such as methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, and N-vinylimidazole are exemplified.

The fluorine-containing vinyl monomer, the copolymerized siloxane-containing vinyl monomer to improve water repellency, water resistance,
The durability is improved. Hydroxyl-containing vinyl monomer or
When hydrophilic monomers such as polypropylene glycol methacrylate and polyethylene glycol monomethacrylate are copolymerized, the stability of the silyl group-containing water-soluble resin (A) increases, and water-soluble groups such as acrylic acid and dimethylaminomethyl (meth) acrylate Alternatively, the amount of the vinyl monomer (a-2) having a group capable of forming a water-soluble group can be reduced.

[Hydrolysable ester (C)] Examples of the hydrolyzable ester (C) include an orthocarboxylic acid ester and / or a hydrolyzable silicon compound which is not a chain transfer agent and / or a partial hydrolysis product thereof. These hydrolyzable esters (C) decompose water in the system by being present during the synthesis of the water-soluble resin (A), and stabilize the silyl group represented by the general formula (I) contained in (A). .

Specific examples of the orthocarboxylic acid esters include methyl orthoformate, ethyl orthoformate, propyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, methyl orthopropionate, ethyl orthopropionate, and orthopropionic acid. Propyl, methyl orthobutyrate, ethyl orthobutyrate, propyl orthobutyrate and the like.

Hydrolyzable silicon compounds which are not chain transfer agents include methyl silicate, ethyl silicate, tetraacetoxy silane, methyl trimethoxy silane,

[0020]

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Examples include ethyl silicate 40 and HAS-1 of Colcoat Co., Ltd., and products obtained by partially hydrolyzing these hydrolyzable silicon compounds with water. Among them, methyl orthoacetate is preferred from the viewpoint of dehydration effect and economy.

The hydrolyzable ester (C) is used in an amount of at least 1 part, preferably at least 2 parts, per 100 parts of the silyl group-containing water-soluble resin or monomer mixture. If it is less than 1 part, the dewatering effect is not sufficient. The hydrolysable ester (C) comprises (A)
It may be added at an early stage of the component polymerization, or may be added continuously by mixing with a monomer mixture. Further, it may be used as a polymerization solvent.

[Alcohol (D)] Alcohol (D)
Stabilizes the silyl group by an equilibrium reaction. Specific examples of alcohol include methanol, ethanol, n-propanol, iso-propanol, n-butanol,
Alcohols having 1 to 4 carbon atoms such as iso-butanol are preferred, and methanol is particularly preferred.

When the alcohol (D) is used, it is used in an amount of at least 1 part, preferably at least 2 parts, per 100 parts of the silyl group-containing water-soluble resin or monomer mixture. If it is less than 1 part, the stabilizing effect is insufficient. Alcohol (D) is (A)
It may be added at the beginning of the component polymerization, or may be added continuously by mixing with the monomer mixture. Further, it may be used as a polymerization solvent.

The polymerization of the silyl group-containing water-soluble resin (A) comprises
It is possible to carry out any of the usual polymerization methods, that is, emulsion polymerization method, suspension polymerization method, solution polymerization method, etc., but from the viewpoint of simplicity of operation, the solution polymerization method is preferably used. .

In carrying out the solution polymerization, the solvent to be used is not particularly limited as long as it can dissolve the copolymerization product, but the polymer is dissolved in an aqueous medium and used as a dispersion stabilizer for polymerization. In such a case, it is preferable to use a water-soluble organic solvent because the operation is simpler without the need to collect the solvent. Alternatively, the solvent may be recovered, and polymerization may be performed using the isolated copolymer as a dispersion stabilizer.

As the solvent to be used, alcohol solvents having a straight and / or branched chain having 1 to 10 carbon atoms, HO
_{- (CH 2 CH 2 -O)} m -R 2 represented by (poly) ethylene glycol monoalkyl ether (R ² is an alkyl group having straight chain and (or) branched having 1 to 10 carbon atoms,
m is an integer of 1 to 5), R ² CO—O— (CH ₂ CH ₂ —
O) represented by _m -R ² (poly) ethylene glycol ether ester (R ² is straight-chain and (or 1 to 10 carbon atoms) alkyl groups having a branched alkyl group of both ends may be the same, different M is an integer of 1 to 5),
_{HO- (CH 2 CH 2 CH 2} -O) m -R 2 represented by (poly) propylene glycol monoalkyl ether (R ² is an alkyl group having straight chain and (or) branched having 1 to 10 carbon atoms, m Is an integer of 1 to 5), R ² CO—O—
_{(CH 2 CH 2 CH 2 -O} ) represented by _m -R ² (poly) propylene glycol ether ester (R ² is an alkyl group of the alkyl. Both ends with linear and (or) branched having 1 to 10 carbon atoms May be the same or different, and m is an integer of 1 to 5). In particular,
For example, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, hexyl alcohol, octyl alcohol; cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol Monoethyl ether, propylene glycol monobutyl ether,
Ethers such as propylene glycol monoisobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol isobutyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, and tripropylene glycol isobutyl ether; butyl cellosolve acetate , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, trippropi Ether esters such as glycol monoisobutyl ether acetate.

The polymerization initiator is not particularly limited as long as it is a commonly used initiator, and a redox initiator, an azo initiator, or a peroxide may be used. Among these initiators, azo initiators are preferred, and specific examples include:
For example, azo nitriles such as azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobismethylbutyronitrile, azobisdimethylmethoxyvaleronitrile; V-5
Azoamidines such as 0, VA004, VA-044, VA-061 (all manufactured by Wako Pure Chemical Industries, Ltd.); VA-080, VA-
Azoamidines such as VA-088, VA-088 (all manufactured by Wako Pure Chemical Industries, Ltd.); VA-080, VA-086, VA-088
Azoamides (such as those manufactured by Wako Pure Chemical Industries, Ltd.);
azoalkyls such as tert-octane and azodi-tert-butane; and cyanopropylazoformamide, azobiscyanovaleroyl acid, dimethylazobismethylpropionate and azobishydroxymethylpropionitrile. Further, if necessary, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ
-Mercaptopropylmethyldimethoxysilane, (CH
_{3 O) 3 Si-S-} S-Si- (OCH 3) 3, (CH
₃ O) ₃ Si- (CH ₂ ) ₃ -SS- (CH ₂ ) _{3-
Si- (OCH 3) 3, (} CH 3 O) 3 Si-S 8 -S
The molecular weight may be adjusted using a chain transfer agent such as i (OCH ₃ ) ₃ .

Regarding the polymerization conditions, it is desirable to carry out the polymerization at a polymerization temperature of usually 40 to 170 ° C., preferably 50 to 150 ° C., for 3 to 24 hours, preferably 4 to 20 hours.

[Water-solubilization of the silyl group-containing water-soluble resin (A)] In carrying out aqueous dispersion polymerization using the thus obtained silyl group-containing water-soluble resin (A), first, the polymer is converted into an aqueous medium. Need to be dissolved. The aqueous medium here means water or water in which a water-soluble organic solvent is dissolved. When the vinyl monomer having a group capable of forming a water-soluble group has a carboxyl group, for example, sodium hydroxide, sodium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monomethanol It can be achieved by neutralization with an amine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine or the like.

When the compound has a basic group, it is quaternized with an acidic compound such as hydrochloric acid or acetic acid. The neutralization is preferably adjusted to pH 5 to pH 10, preferably pH 6 to pH 7 by neutralization from the viewpoint of polymerization rate, polymerization stability and stability of the hydrolyzable silyl functional group.

When making the copolymer water-soluble, the copolymer may be dissolved in a water-soluble organic solvent and mixed with an aqueous medium, or the polymer may be recovered by distillation, reprecipitation, or the like. May be added.

[Silyl group-containing acrylic copolymer (B)
Polymerization] The water-soluble resin (A) thus obtained is used as a dispersion stabilizer to carry out a polymerization reaction in an aqueous medium to obtain an intended aqueous dispersion type composition (B).

As for the polymerization operation, a usual emulsion polymerization polymerization operation can be employed.

Silyl group-containing acrylic copolymer (B)
The group represented by the general formula (I) can be introduced by copolymerizing a vinyl monomer (a-1) having a silyl group with another vinyl monomer. Specific examples of (a-1) May be used as they are, or one or more of them may be used in combination. The amount of the vinyl monomer having a silyl group is 1 to 50 parts, preferably 2 to 20 parts, per 100 parts of the vinyl monomer mixture. If the amount is less than 1 part, the water resistance and the weather resistance are inferior. If the amount exceeds 50 parts, the stability of the emulsion decreases.

The other vinyl monomers copolymerizable with the vinyl monomer having a silyl group are not particularly limited, and specific examples thereof include the water-soluble resins mentioned as components of the water-soluble resin (A) containing a silyl group. A vinyl monomer (a-2) having a group capable of forming a group or a water-soluble group and another copolymerizable vinyl monomer (a-3) can be used.

In addition, a monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol dimethacrylate, ethylene glycol diacrylate, triallyl cyanurate, etc. is also used, and the resulting polymer is crosslinked. It is also possible to have

One or more of these monomers can be appropriately selected depending on the quality of the final product.
However, at least one of (a-1), (a-2) and (a-3) must be an acrylic monomer, and the acrylic monomer is contained in 100 parts of the vinyl monomer mixture. Includes more than 50 parts.

The amount of the water-soluble resin used in the dispersion stabilizer is from 1/20 to 1 by weight based on the total amount of the monomers to be polymerized.
/0.3 ratio, preferably 1/10 to 1/1.

As the aqueous medium in which the dispersion stabilizer is dissolved, water is usually used. However, when the dispersant resin is used in a state of being dissolved in an organic solvent, the amount of the organic solvent corresponding to the amount of the dispersant resin is consequently increased. Will be included in the system. In addition, for the purpose of increasing the solubility of the dispersant resin, it is possible to add a water-soluble organic solvent in an amount of 1/2 or less with respect to water.

As the polymerization initiator, any of a water-soluble or oil-soluble peroxide, an azo-based initiator, a redox initiator and the like which are usually used for radical polymerization can be used.
Preferably, a water-soluble initiator is used. Specific examples of the water-soluble initiator include, for example, sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, ter
t-butyl peroxide, cumene hydroperoxide,
Peroxides such as azodiisobutyric acid diamide, persulfates, and azo compounds, and redox initiators activated by a water-soluble reducing agent in an aqueous phase, and the like.

The amount of such an initiator is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on the weight of the monomer.

Further, the ionicity usually used for emulsion polymerization,
Although it is possible to use a nonionic surfactant in combination, it is preferable to use only a small amount from the viewpoints of water resistance and weather resistance. Specific examples of ionic and nonionic surfactants include, for example, potassium n-dodecylsulfonate, sodium isooctylbenzenesulfonate,
Sodium laurate, polyethylene glycol nonyl phenyl ether and the like.

The polymerization can be carried out at a polymerization temperature of 30 to 90 ° C., preferably 40 to 80 ° C.

The monomer is copolymerized by the polymerization reaction to produce a silyl group-containing acrylic copolymer, but a part of the monomer is graft-polymerized to the water-soluble resin (A) as a side reaction. There is no problem.

The solid concentration in the aqueous dispersion composition is in the range of 20 to 70% by weight according to the method of the present invention.

[0047] When the solid concentration obtain ultra 70% by weight, or is difficult to remove the heat generated by the polymerization reaction since the viscosity of the system increases significantly, problems such as requiring a long time to retrieve from the polymerizer Is generated. When the solid content is less than 20% by weight, there is no problem in terms of polymerization operation, but the amount of resin generated by one polymerization operation is small, which is extremely disadvantageous from an economical point of view. In addition, if the concentration is less than 20% by weight, the film thickness of the coating film becomes thinner due to application requirements, resulting in deterioration of performance and disadvantageous in workability of coating.

The aqueous dispersion composition thus obtained is composed of ultrafine particles having a particle size of 0.02 to 0.1 micron, and as a result, has excellent film forming ability.

A solvent can be added for the purpose of assisting the formation of a film of the aqueous dispersion composition.
The amount of such a solvent to be added is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on the aqueous dispersion type resin composition. Specific examples of such a solvent include, for example, cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoethyl Ethers such as ether, dipropylene glycol monobutyl ether, dipropylene glycol isobutyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, and tripropylene glycol isobutyl ether; butyl cellosolve acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobu Ether acetate, dipropylene glycol monoethyl ether acetate,
Examples include ether esters such as dipropylene glycol monobutyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, and tripropylene glycol monoisobutyl ether acetate.

These solvents may be added at the time of polymerization of the aqueous dispersion type resin, may be added immediately after the completion of the polymerization, or may be added after cooling.

The curable composition for water-dispersed paints thus obtained does not need to use a curing catalyst. However, a catalyst may be used to promote the curability and to bring out the required physical properties. it can. Specific examples of such a curing catalyst include, for example, organic tin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate; phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl Phosphates or phosphates such as phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, didecyl phosphate; propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol, acrylic Glycidyl ether,
γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Yuka Shell Epoxy Co., Ltd. Reaction product of an epoxy compound such as Cardura (E), Epikote 828, Epikote 1001 and phosphoric acid and / or acid monophosphate ester;
Organic titanate compounds; organic aluminum compounds; organic zirconium compounds; maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, trimellitic acid, pyromellitic acid, their acid anhydrides, paratoluene sulfone Acidic compounds such as acids; amines such as hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine and dodecylamine;
Mixtures or reactants of these amines and acidic phosphate esters; and alkaline compounds such as sodium hydroxide and potassium hydroxide.

Among these curing catalysts, organotin compounds,
A mixture or reaction product of an acidic phosphate ester and an amine,
A saturated or unsaturated polycarboxylic acid or an anhydride thereof,
A reactive silicon compound, an organic titanate compound, an organic aluminum compound or a mixture thereof is preferred because of its high activity. More preferably, an organotin compound, an acidic phosphoric acid ester, or a mixture or a reaction product of an acidic phosphoric acid ester and an amine are preferred.

These curing catalysts may be used alone or in combination of two or more. The amount of the curing catalyst is not particularly limited, but is usually 0.01 to 20 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the solid content of the aqueous dispersion composition.
Use up to 10 parts by weight. If the amount exceeds 20 parts by weight, the appearance of the coating film tends to decrease.

If necessary, pigments (colored pigments such as white pigment carbon such as titanium dioxide, calcium carbonate, barium carbonate and kaolin, colored pigments such as red iron oxide and cyanine blue), a plasticizer, and the like may be added to the obtained aqueous dispersion type composition. Additives such as solvents, dispersants, thickeners, defoamers, preservatives, and ultraviolet absorbers, which are used in ordinary coating compositions, may be mixed and used.

It is also possible to blend with commercially available water-based paints, for example, thermosetting acrylic paints such as acrylic paints and acrylic melamine paints, alkyd paints, and epoxy paints. Weather resistance, acid resistance, and solvent resistance can be improved.

It is also possible to add a melamine resin or an isocyanate compound as a cross-linking agent to achieve quick curing.

Next, the manufacturing method of the present invention will be described based on examples.

Production Examples 1 to 8 (Polymerization of Water-soluble Resin (A)) Isopropyl alcohol 60 was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction pipe and a dropping funnel.
After heating the temperature to 75 ° C while introducing nitrogen gas,
A mixture having the composition shown in Table 1 was dropped at a constant speed over a period of 5 hours using a dropping funnel. After the completion of dropping of the mixture, the mixture was reacted at 75 ° C. for 2 hours, and then (A-1) to (A-6) were cooled after adding 8.5 parts of ammonia, and (A-7) and (A-8) were cooled. After adding 2 parts of glacial acetic acid, the mixture was cooled to obtain a water-soluble resin having a number average molecular weight of 5,500. Further, isopropyl alcohol was added to the resin solution so that the solid content concentration became 60%.

[0059]

[Table 1]

Examples 1 to 5 and Comparative Examples 1 to 3 (Polymerization of Aqueous Dispersion Resin) 93 parts of deionized water was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet, and a dropping funnel. Preparation,
1 part of ascorbic acid and 0.1 part of ferrous sulfate were added, and the resin solutions (A-1) to (A-1) obtained in Production Examples 1 to 8 were further added.
Add 18.5 parts of -8), dissolve with sufficient stirring,
After the temperature was raised to 70 ° C. while introducing nitrogen gas, a mixture having the following composition was dropped at a constant rate over 5 hours using a dropping funnel.

Styrene 20 parts Butyl acrylate 20 parts Methyl methacrylate 55 parts γ-methacryloxypropyltrimethoxysilane 5 parts Cumene hydroperoxide 1 part Deionized water is added to the polymerization result and the obtained aqueous dispersion, The concentration was adjusted to 50%, and the storage stability test was conducted. The results are shown in Table 2.

[0062]

[Table 2]

[0063]

According to the present invention, when dispersing and polymerizing a silyl group-containing acrylic copolymer in an aqueous solution of a silyl group-containing water-soluble resin, the synthesis of the water-soluble resin is carried out using a hydrolyzable ester (C) or a hydrolyzable ester. (C) Oyo by carried out in the presence of beauty a alcohol (D), can be performed stably dispersed polymer may be the storage stability of the product.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-178301 (JP, A) JP-A-5-331408 (JP, A) JP-A-6-16735 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08F 30/08 C08F 2/44 C08F 20/02

Claims (5)

(57) [Claims] 1. A compound of the general formula (I): (Wherein, R ¹ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group;
Is a monovalent group selected from a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group and an amino group, and a represents 0, 1 or 2). prepared with water soluble <br/> solution, the general formula (I) silyl group-containing acrylic copolymer represented by by dispersion polymerization of water soluble dispersible composition (B) of the water-soluble resin (a) having When the water-soluble resin (A) is polymerized, the hydrolysable ester (C) which is not a chain transfer agent or the hydrolysable ester (C) which is not a chain transfer agent and an alcohol (D)
Producing how an aqueous dispersion type composition characterized in that that may be carried out in the presence of. 2. A hydrolysable ester which is not a chain transfer agent.
(C) is an orthocarboxylic acid ester, and (also
A) a hydrolyzable silicon compound that is not a chain transfer agent;
(1) The partial hydrolysis product thereof.
Manufacturing method. 3. The method according to claim 1, wherein the alcohol (D) is methanol.
The method according to claim 1. 4. The orthocarboxylic acid ester is orthoacetic acid.
3. An ester or orthoformate.
Manufacturing method. 5. The method according to claim 5, wherein the carboxyl group is converted to ammonia or
Use of a water-soluble resin (A) neutralized with an amine compound
The method according to claim 1, wherein: