JP2003119397A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which can cover a substrate to give a coating film having a high grade and high strength without blisters in the coating film on heating and drying the coating film in a processing process, when used as a coating. SOLUTION: This resin composition comprising an aqueous resin dispersion having a solid content concentration of >=50 wt.% and an organopolysiloxane polyoxyalkylene glycol is characterized in that the molar ratio of the hydrogen atoms of the alkyl groups of the organopolysiloxane to the hydrogen atoms of the polyoxyalkylene glycol chain is 5/95 to 50/50 and that the polyoxyalkylene glycol chain is obtained from ethylene oxide and an alkylene oxide except the ethylene oxide.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition suitable for a coating agent for paper, fibers, plastics and the like. More specifically, the present invention relates to a resin composition capable of forming a coating film having an excellent coating film appearance without generating blisters in the step of heating and drying.

[0002]

2. Description of the Related Art Conventionally, emulsions have been used for various coating and impregnation processes, but in coating applications for forming thick films such as carpet backing, the film swells during film formation (hereinafter referred to as "blister"). Is caused, and the quality and physical properties of the processed product are deteriorated.

The cause of such blisters is that when the water-based coating agent is dried with hot air, the drying in the vicinity of the surface in direct contact with the hot air progresses before the inside, and the portion near the surface forms the film first. Therefore, it is considered that the water remaining inside the film evaporates later to cause the surface film to swell from the inside. It is known that blisters are likely to occur particularly when the surface coating film is thick, when the drying temperature is high, or when the air volume is strong.

As a method for suppressing the formation of blisters, for example, a method of adding a filler (seplite) (Japanese Patent Publication No.
(JP-A-65993), a large amount of filler is required to suppress blister, and the film-forming property of the film is deteriorated, and various physical properties such as film strength are deteriorated. In addition, a method of adding a silicone oil-based heat-sensitive gelling agent (Japanese Patent Publication No. 6-
No. 4935), it was still insufficient to suppress the formation of blisters.

[0005]

Therefore, an object of the present invention is to coat a base material when used as a coating agent (coating agent) without generating blister (blister of coating) during thermal drying in the processing step. And to provide a resin composition capable of obtaining a high-quality and high-strength coating film.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the solid content concentration is 50%.
The resin composition containing the water-based resin dispersion (A) and the specific organopolysiloxane polyoxyalkylene glycol (B) in an amount of at least wt% covers the base material without causing blister, and has high quality and high strength. The inventors have found that a film of 1) can be obtained, and completed the present invention.

That is, the present invention has a solid content of 50% by weight.
The above aqueous resin dispersion (A) and structural formula [1] and / or
Alternatively, in the resin composition containing the organopolysiloxane polyoxyalkylene glycol (B) represented by the structural formula [2], hydrogen of the alkyl group R ₁ of the organopolysiloxane represented by the structural formula [1] and the structural formula [2]. The molar ratio of atoms to hydrogen atoms in the polyoxyalkylene glycol chain is 5
/ 95 to 50/50 molar ratio, and the polyoxyalkylene glycol chain is obtained from ethylene oxide and an alkylene oxide other than ethylene oxide.

[0008]

[Chemical 5]

[0009]

[Chemical 6]

(In the above structural formulas [1] and [2], R ₁ is any alkyl group, R ₂ is any alkylene group, R ₃ ,
One of R ₄ has an ethylene residue and the other has 3 to 3 carbon atoms.
8 is an alkylene residue, R ₅ represents an alkyl group, an acetyl group or hydrogen, a and b each represent an integer of 1 or more, and m and n each represent an arbitrary integer. )

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Next, necessary items for carrying out the present invention will be specifically described below.

The resin composition of the present invention has a solid content of 5
In the resin composition containing 0% by weight or more of the aqueous resin dispersion (A) and the organopolysiloxane polyoxyalkylene glycol (B) represented by the structural formula [1] and / or the structural formula [2], [1] and structural formula [2]
The organopolysiloxane has a hydrogen atom of the alkyl group R ₁ and a polyoxyalkylene glycol chain having a hydrogen atom molar ratio of 5/95 to 50/50, and
The resin composition is characterized in that the polyoxyalkylene glycol chain is obtained from ethylene oxide and an alkylene oxide other than ethylene oxide.

[0013]

[Chemical 7]

[0014]

[Chemical 8]

In the above structural formulas [1] and [2], R ₁ is any alkyl group, R ₂ is any alkylene group, R ₃ and R
_4, one of which is an ethylene residue and the other has 3 to 8 carbon atoms
Alkylene residues, R ₅ represents an alkyl group, an acetyl group or a hydrogen, a and b represents an integer of 1 or more, respectively, m and n are each represents an arbitrary integer.

In the present invention, the molar ratio of the hydrogen atom of the alkyl group R ₁ of the organopolysiloxane in the organopolysiloxane polyoxyalkylene glycol (B) to the hydrogen atom of the polyoxyalkylene glycol chain is ¹
It was measured by the 1 H-NMR method (measuring solvent: deuterated chloroform).

The cloud point of the organopolysiloxane polyoxyalkylene glycol (B) used in the present invention is 55.
The temperature is preferably not higher than 0 ° C, more preferably 30 to 5
It is 5 ° C. The "cloud point" referred to here is the temperature at which the 1 wt% aqueous solution of the organopolysiloxane polyoxyalkylene glycol (B) is gradually heated from room temperature and the aqueous solution becomes turbid by visual observation. .

The internal temperature of the resin composition during heat drying is maintained at 50 to 60 ° C. until the contained water completely evaporates. It is considered that the blister is generated by water vapor inside when the surface of the resin is dried and formed into a film. The resin composition containing the aqueous resin dispersion (A) and the organopolysiloxane polyoxyalkylene glycol (B) shows a phenomenon in which the viscosity increases at temperatures above the cloud point. By utilizing this phenomenon, the cloud point is lowered below 50-60 ° C., which is the temperature reached during drying, to increase the viscosity and make the resin hard to move, and suppress the occurrence of blister.

The organopolysiloxane polyoxyalkylene glycol (B) used in the present invention is, for example, N
UC SILWET FZ-2164, FZ-210
1 (manufactured by Nippon Unicar Co., Ltd.) and the like.

The method for producing the aqueous resin dispersion (A) used in the present invention includes, for example, water, a polymerizable monomer mixture, a polymerization initiator, and (if necessary, an emulsifier and a dispersion stabilizer. (Or good)) and polymerizing them all at once,
It can be produced by a so-called pre-emulsion method in which a mixture of water, a polymerizable monomer and an emulsifier is added in advance, a monomer dropping method, or the like.

Aqueous resin dispersion (A) used in the present invention
Is preferably an acrylic copolymer water dispersion.

In the present invention, the polymerizable monomer used for producing the aqueous resin dispersion (A) is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, β-carboxyethyl (meth) acrylate, 2- ( (Meth) acryloyl propionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, β- (meth)
Acryloyloxyethyl hydrogen succinate,
β- (meth) hydroxyethyl hydrogen phthalate and salts thereof, glycidyl (meth) acrylate,
Glycidyl group-containing polymerizable monomer such as allyl glycidyl ether; 2-hydroxyethyl (meth) acrylate,
Hydroxyl group-containing polymerizable monomer such as 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate; aminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate , N, N-
Amino group-containing polymerizable monomer such as dialkylaminoalkyl (meth) acrylate; N-methylol (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl Polymerizable monomer containing a methylolamide group such as (meth) acrylamide or its alkoxy compound; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloxy. Propyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ
-(Meth) acryloxypropyltriisopropoxysilane, N-β- (N-vinylbenzylaminoethyl)-
silyl group-containing polymerizable monomers such as γ-aminopropyltrimethoxysilane and its hydrochloride; aziridinyl group-containing polymerizable monomers such as 2-aziridinylethyl (meth) acrylate; (meth) acryloyl isocyanate Isocyanate group- and / or blocked isocyanate group-containing polymerizable monomer such as phenol or methylethylketoxime adduct of (meth) acryloyl isocyanate ethyl; 2-isopropenyl-2-oxazoline, 2-
Oxazoline group-containing polymerizable monomer such as vinyl-2-oxazoline; (meth) acrylamide, N-monoalkyl (meth) acrylamide, N, N-dialkyl (meth)
Amide group-containing polymerizable monomers such as acrylamide; cyclopentenyl group-containing polymerizable monomers such as dicyclopentenyl (meth) acrylate; allyl group-containing polymerizable monomers such as allyl (meth) acrylate; acrolein, diacetone Carbonyl group-containing polymerizable monomer such as (meth) acrylamide; acetoacetyl group-containing polymerizable monomer such as acetoacetoxyethyl (meth) acrylate, sulfonic acid group and / or sulfate group (and / or salt thereof), Phosphate group and / or phosphate ester group (and / or salt thereof)
Containing an ethylenically unsaturated monomer, vinyl sulfonic acid, vinyl sulfonic acid such as styrene sulfonic acid or a salt thereof, allyl sulfonic acid such as allyl sulfonic acid, 2-methylallyl sulfonic acid or a salt thereof, (meth ) Sulfonic acids containing a (meth) acrylate group such as 2-sulfoethyl acrylate and 2-sulfopropyl (meth) acrylate or salts thereof, (meth) acrylamide group-containing sulfonic acids such as (meth) acrylamide-t-butylsulfonic acid Alternatively, a salt thereof, or "ADEKA REASOAP PP-70, PPE-710" having a phosphoric acid group (manufactured by Asahi Denka Co., Ltd.)
Etc., ethylene glycol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, diallyl phthalate, divinylbenzene, Allyl (meth) acrylate etc. are mentioned. Examples of the ethylenically unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-. Ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclo (Meth) acrylic acid esters such as pentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3- Pentafluoro Fluorine-containing ethylenic compounds such as ropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3, -tetrafluoropropyl (meth) acrylate and β- (perfluorooctyl) ethyl (meth) acrylate. Saturated monomers; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl ether; (meth) Nitrile group-containing ethylenically unsaturated monomers such as acrylonitrile; styrene, α-
Methyl styrene, vinyl toluene, vinyl anisole,
vinyl compounds having an aromatic ring such as α-halostyrene, vinylnaphthalene and divinylstyrene; radically polymerizable monomers such as isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride and N-vinylpyrrolidone Mention may be made of one or a mixture of two or more thereof.

Examples of the anionic emulsifier used in the present invention include sulfuric acid esters of higher alcohols, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, and the like, and nonionic emulsifiers include, for example, Examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene-polyoxypropylene block copolymer, and the like, and one kind or a mixture of two or more kinds thereof can be used.

Further, in the present invention, it is also possible to use an emulsifier having a polymerizable unsaturated group in the molecule, which is generally called "reactive emulsifier". Examples of the reactive emulsifier that can be used in the present invention include "Latemur S-180" (manufactured by Kao Corporation) having a sulfonic acid group and a salt thereof, "Eleminol JS-2, RS-30" (Sanyo Chemical Industries ( Co., Ltd.)
Etc .; "Aqualon HS-1 having a sulfate group and a salt thereof.
0, HS-20 "(manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)," Adecaria Soap SE-10, SE-20 "(Asahi Denka Kogyo Co., Ltd.)
Manufactured by etc .; “New Frontier A-2 having a phosphoric acid group
29E "(manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.);" Aqualon RN-10, RN-20, RN- "having a nonionic hydrophilic group.
30, RN-50 "(manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like, and one kind or a mixture of two or more kinds thereof can be used.

In the present invention, other dispersion stabilizers other than the emulsifier that can be used include, for example, polyvinyl alcohol, fibrin ether, starch, maleated polybutadiene, maleated alkyd resin,
Examples include synthetic or natural water-soluble polymer substances such as polyacrylic acid (salt), polyacrylamide, aqueous acrylic resin, aqueous polyester resin, aqueous polyamide resin, and aqueous polyurethane resin, and one or a mixture of two or more thereof. Can be used.

In the present invention, the aqueous medium for polymerizing the polymer is not particularly limited, but water alone may be used, or a mixed solvent of water and a water-soluble solvent. May be used. As the water-soluble solvent used here, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol,
Examples thereof include alcohols such as ethyl cellosolve and butyl cellosolve, and polar solvents such as N-methylpyrrolidone, and one kind or a mixture of two or more kinds thereof can be used.

In the present invention, a radical polymerization initiator is used as a polymerization initiator used in polymerizing the polymer, and examples thereof include potassium persulfate and sodium persulfate.
Persulfates such as ammonium persulfate, diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, t-butyl cumyl peroxide, dialkyl peroxides such as dicumyl peroxide, t-butyl peroxide Peroxyesters such as laurate and t-butylperoxybenzoate, organic peroxides such as hydroperoxides such as cumene hydroperoxide, paramenthane hydroperoxide and t-butyl hydroperoxide, hydrogen peroxide Radical polymerization using only these peroxides, or the above-mentioned peroxides, ascorbic acid and its salts, erythorbic acid and its salts, tartaric acid and its salts, citric acid and its salts, formaldehyde sulfoxy. Rat's It can also be polymerized by a redox polymerization initiator system in combination with a reducing agent such as a metal salt, sodium thiosulfate, sodium bisulfite and ferric chloride, and also 4,4′-azobis (4-cyanovaleric acid). , 2,
It is also possible to use an azo-based initiator such as 2'-azobis (2-amidinopropane) dihydrochloride.
One kind or a mixture of two or more kinds can be used.

In the present invention, when it is necessary to adjust the molecular weight of the polymer, a compound having a chain transfer ability may be added as a molecular weight adjusting agent. Examples of the molecular weight adjusting agent include lauryl mercaptan, Examples thereof include mercaptans such as octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid and thioglycerin, and α-methylstyrene dimer.

In the present invention, the basic substance used as the neutralizing agent is, for example, sodium hydroxide,
Alkali metal compounds such as potassium hydroxide; Alkaline earth metal compounds such as calcium hydroxide and calcium carbonate; Ammonia; Monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanol Amine, diethanolamine,
Examples thereof include water-soluble organic amines such as triethanolamine, ethylenediamine, and diethylenetriamine, and one kind or a mixture of two or more kinds thereof can be used. Among these, particularly when it is desired to further improve the water resistance of the obtained coating, it is preferable to use ammonia which is easily scattered at room temperature or by heating.

In the present invention, the polymerization temperature at the time of polymerizing the polymer is different depending on the kind of the monomer used, the kind of the polymerization initiator and the like, but it is usually 30 to 90 when the polymerization is carried out in an aqueous medium. It is preferably carried out in the range of ° C.

Further, a water-soluble or water-dispersible thermosetting resin, for example, a phenol resin, a urea resin, a melamine resin, a polyester resin, a polyamide resin, a urethane resin or the like can be mixed and used.

Further, if necessary, known pigments, pH adjusters, film-forming aids, leveling agents, thickeners, water repellents, antifoaming agents, etc. are used within a range that does not impair the desired effects of the present invention. Those can be used by appropriately adding them.

Aqueous resin dispersion (A) obtained by the above method
When the solid content concentration is less than 50% by weight, since it contains a large amount of water, not only is the drying property inferior, but the film formation near the surface progresses during heat drying, and blisters easily occur. Is preferably 50% by weight or more.

As described above, the mechanism of blister generation during heat drying is faster than the case where water in the aqueous resin dispersion is completely volatilized, and the blister is generated because the vicinity of the surface of the coating agent dries and forms a film. Conceivable.

The average particle diameter of the aqueous resin dispersion (A) used in the present invention is preferably in the range of 250 to 2000 nm, more preferably 300 to 1500 nm. When the average particle diameter of the aqueous resin dispersion (A) is within such a range, water volatilizes from the gaps between the particles at the initial stage of heat drying to promote internal drying, and heat fusion between particles occurs at the latter stage of heat drying. It is preferable because a film is formed. When the average particle size of the aqueous resin dispersion (A) is less than 250 nm,
Since heat fusion between particles precedes in the initial stage of heat drying, a film is formed and blisters are likely to occur, which is not preferable.

In the present invention, the average particle size is a value measured by the dynamic light scattering method, and the value of the volume average particle size measured by Microtrac UPA type particle size distribution measuring device manufactured by Nikkiso Co., Ltd. is calculated. It was

In the present invention, the aqueous resin dispersion (A) having a solid content concentration of 50% by weight or more and the organopolysiloxane polyoxyalkylene glycol (represented by the structural formula [1] and / or the structural formula [2] ( In the resin composition containing B) and the inorganic filler (C), the hydrogen atom of the alkyl group R ₁ of the organopolysiloxane represented by the structural formulas [1] and [2] and the hydrogen atom of the polyoxyalkylene glycol chain. The molar ratio of 5/95 to 50/50,
Moreover, the resin composition is characterized in that the polyoxyalkylene glycol is obtained from ethylene oxide and an alkylene oxide other than ethylene oxide.

[0038]

[Chemical 9]

[0039]

[Chemical 10]

In the above structural formulas [1] and [2], R ₁ is any alkyl group, R ₂ is any alkylene group, R ₃ and R
_4, one of which is an ethylene residue and the other has 3 to 8 carbon atoms
Alkylene residues, R ₅ represents an alkyl group, an acetyl group or a hydrogen, a and b represents an integer of 1 or more, respectively, m and n are each represents an arbitrary integer.

The inorganic filler (C) used in the present invention is not particularly limited, but for example, calcium carbonate,
Magnesium carbonate, barium sulfate, aluminum hydroxide, talc, diatomaceous earth, mica, kaolin, titanium oxide,
Alumina, silica, calcium silicate, carbon black, attapulgite, shirasu balloon, pearlite, etc. may be mentioned, and these may be used alone or in admixture of two or more.

In the present invention, the above-mentioned inorganic filler (C)
The content of is preferably in the range of 5 to 50 parts by weight in terms of solid content relative to 100 parts by weight of solid content of the aqueous resin dispersion (A). When the content of the inorganic filler (C) is in such a range, the film strength is excellent.

Further, the inorganic filler (C) used in the present invention
The average particle size of is preferably in the range of 0.1 to 100 μm.

Examples of the dispersion stabilizer for the inorganic filler (C) used in the present invention include polyvinyl alcohol, fibrin ether, starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid (salt), polyacrylamide, Examples thereof include synthetic or natural water-soluble polymer substances such as water-soluble acrylic resin, and one kind or a mixture of two or more kinds thereof can be used.

In the present invention, the above dispersion stabilizer can be used for the purpose of improving the mixing stability and the storage stability of the inorganic filler (C), but it is used in view of the water resistance of the emulsion coating. It is preferable to minimize the amount. The amount of the dispersion stabilizer used is preferably 2 parts by weight or less in terms of solid content relative to 100 parts by weight of solid content of the aqueous resin dispersion (A).

In the resin composition containing the compositions (A), (B) and (C) of the present invention, the cloud point of a 1% by weight aqueous solution of the organopolysiloxane polyoxyalkylene glycol (B) is preferably 30 to. It is in the range of 55 ° C.

In the resin composition containing the compositions (A), (B) and (C) of the present invention, the average particle size of the aqueous resin dispersion (A) is preferably in the range of 250 to 2000 nm.

In the resin composition containing the compositions (A), (B) and (C) of the present invention, the aqueous resin dispersion (A) is preferably an acrylic copolymer water dispersion.

Aqueous resin dispersion (A) used in the present invention
Can be used by adding a water-soluble or water-dispersible crosslinking agent, if necessary. As the crosslinking agent in that case, for example, a polyfunctional epoxy compound, a polyfunctional melamine compound, a polyfunctional polyamine compound, a polyfunctional polyethyleneimine compound, a polyfunctional (block) isocyanate compound, a polyfunctional hydrazine compound, Metal salt compounds and the like can be mentioned, and one kind or a mixture of two or more kinds thereof can be used.

In addition to the above-mentioned cross-linking agent, a water-soluble or water-dispersible thermosetting resin such as phenol resin, urea resin, melamine resin, epoxy resin or urethane resin may be mixed and used. You can also

Further, if necessary, for example, a pigment, a pH adjusting agent, a film-forming auxiliary agent, a water-soluble solvent, a leveling agent, a thickening agent, a water repellent, and the like, as long as the desired effects of the present invention are not impaired. Known substances such as antifoaming agents can be appropriately added and used.

The resin composition of the present invention provides a high-quality coating film having excellent blister resistance, less surface blocking, and has a wide variety of uses. Coating, gluing,
For applications used in coating processing in applications such as textile industry resins (nonwoven fabric binders, etc.), paper processing resins, glass fiber processing resins (glass fiber sizing agents, glass paper binders, etc.), etc. As a result, it produces an extremely excellent effect.

As described above, the embodiment of the present invention is an aqueous resin dispersion (A) having a solid content of 50% by weight or more.
And a organopolysiloxane polyoxyalkylene glycol (B) represented by the structural formula [1] and / or the structural formula [2], the organopoly having the structural formula [1] and the structural formula [2]. The molar ratio of the hydrogen atom of the alkyl group R ₁ of the siloxane to the hydrogen atom of the polyoxyalkylene glycol chain is 5/95 to 50/50, and the polyoxyalkylene glycol chain has a molecular weight other than ethylene oxide and ethylene oxide. The present invention relates to a resin composition characterized by being obtained from alkylene oxide.

[0054]

[Chemical 11]

[0055]

[Chemical 12]

(In the above structural formulas [1] and [2], R ₁ is any alkyl group, R ₂ is any alkylene group, R ₃ ,
One of R ₄ has an ethylene residue and the other has 3 to 3 carbon atoms.
8 is an alkylene residue, R ₅ represents an alkyl group, an acetyl group or hydrogen, a and b each represent an integer of 1 or more, and m and n each represent an arbitrary integer. )

As another embodiment of the present invention, the above resin composition has a cloud point of a 1% by weight aqueous solution of the organopolysiloxane polyoxyalkylene glycol (B) in the range of 30 to 55 ° C. It is a thing.

As another aspect of the present invention, the average particle diameter of the aqueous resin dispersion (A) is 250 to 2000 nm.
The present invention relates to each of the above resin compositions in the range.

As another embodiment of the present invention, the aqueous resin dispersion (A) relates to each of the above resin compositions which is an acrylic copolymer water dispersion.

Another embodiment of the present invention is represented by the aqueous resin dispersion (A) having a solid content concentration of 50% by weight or more and the structural formula [1] and / or the structural formula [2]. In the resin composition containing the organopolysiloxane polyoxyalkylene glycol (B) and the inorganic filler (C), a hydrogen atom of the alkyl group R ₁ of the organopolysiloxane represented by the structural formula [1] and the structural formula [2] The molar ratio of hydrogen atoms in the polyoxyalkylene glycol chain is 5/95
The resin composition is obtained in a molar ratio of about 50/50 and in which the polyoxyalkylene glycol is obtained from ethylene oxide and an alkylene oxide other than ethylene oxide.

[0061]

[Chemical 13]

[0062]

[Chemical 14]

(In the above structural formulas [1] and [2], R ₁ is an arbitrary alkyl group, R ₂ is an arbitrary alkylene group, R ₃ ,
One of R ₄ has an ethylene residue and the other has 3 to 3 carbon atoms.
8 is an alkylene residue, R ₅ represents an alkyl group, an acetyl group or hydrogen, a and b each represent an integer of 1 or more, and m and n each represent an arbitrary integer. )

As another embodiment of the present invention, the content of the inorganic filler (C) is 5 to 50 parts by weight based on 100 parts by weight of the solid content of the aqueous resin dispersion (A). The present invention relates to the above resin composition in the range of parts.

As another embodiment of the present invention, each of the above resin compositions wherein the cloud point of a 1% by weight aqueous solution of the organopolysiloxane polyoxyalkylene glycol (B) is in the range of 30 to 55 ° C. It depends on.

According to another aspect of the present invention, the average particle size of the aqueous resin dispersion (A) is 250 to 2000 nm.
The present invention relates to each of the above resin compositions in the range.

As another embodiment of the present invention, each of the above resin compositions in which the aqueous resin dispersion (A) is an acrylic copolymer water dispersion.

[0068]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited to these examples. In the following, unless otherwise specified, "%"
Means% by weight, and "part" means part by weight.

The evaluation method used in the present invention will be described below. [Evaluation method for blister (blister of coating)] 0.7 g of a resin composition containing a resin composition in a glass container having an inner diameter of 14 mm, a height of 30 mm, and a thickness of 1 mm, and 1 in the case of a product with a filler. After putting in 0.5g, put in a Tabai hot air dryer set at 90 ° C for 6 minutes, immediately put in a Tabai hot air dryer set at 150 ° C for 3 minutes, and visually observe the presence or absence of blister. It was judged according to the standard. ○: No change ×: Blister occurred

Synthesis Example 1 Synthesis of Aqueous Resin Dispersion (A-1) 210 parts of ion-exchanged water was charged into a polymerization vessel equipped with a stirrer, and the inside of the reaction vessel was stirred while stirring while feeding nitrogen gas. The temperature was raised to ° C. After the temperature was raised, 4 parts of the following monomer emulsion was added to the reaction vessel, and then 0.6 part of ammonium persulfate was added to start polymerization. Reaction vessel temperature 80
After the temperature was kept at 1 ° C. for 1 hour, the remaining 726 parts of the monomer emulsion and the following aqueous solution of the polymerization initiator were simultaneously dropped into the reaction vessel to carry out polymerization. The dropping time was 4 hours for the monomer emulsion and 4.5 hours for the polymerization initiator aqueous solution, and the polymerization was completed while maintaining the temperature in the reaction vessel at 80 ° C. After the completion of the polymerization, adjust the pH with aqueous ammonia to obtain a solid content of 60.
%, PH 8.0, and an average particle diameter of 350 nm to obtain an aqueous resin dispersion (hereinafter referred to as an aqueous resin dispersion (A-1)). Composition of monomer emulsion n-butyl acrylate 350 parts Methyl methacrylate 225 parts Methacrylic acid 15 parts Newcol 707SF (manufactured by Kao Corporation) 40 parts Ion-exchanged water 100 parts Composition of aqueous solution of polymerization initiator Ammonium persulfate 1.5 parts Ion-exchange 75 parts of water

Synthesis Example 2 Synthesis of Aqueous Resin Dispersion (A-2) A polymerization vessel equipped with a stirrer was charged with 200 parts of ion-exchanged water, and the inside of the reaction vessel was stirred while stirring while feeding nitrogen gas. The temperature was raised to ° C. After the temperature was raised, 15 parts of the following monomer emulsion was added to the reaction vessel, and then 0.6 part of ammonium persulfate was added to start polymerization. Reaction vessel temperature 8
After holding at 0 ° C for 1 hour, the remaining monomer emulsion 735
And the following polymerization initiator aqueous solution were simultaneously dropped into the reaction vessel to carry out polymerization. The dropping time was 4 hours for the monomer emulsion and 4.5 hours for the polymerization initiator aqueous solution, and the polymerization was completed while maintaining the temperature in the reaction vessel at 80 ° C.
After the completion of the polymerization, adjust the pH with aqueous ammonia to obtain a solid content of 60.
%, PH 8.0, and an average particle diameter of 218 nm to obtain an aqueous resin dispersion (hereinafter referred to as an aqueous resin dispersion (A-2)). Composition of monomer emulsion n-butyl acrylate 350 parts Methyl methacrylate 225 parts Methacrylic acid 15 parts Newcol 707SF (manufactured by Kao Corporation) 60 parts Deionized water 100 parts Composition of aqueous solution of polymerization initiator Ammonium persulfate 1.5 parts Ion exchange 75 parts of water

Example 1 100 parts of an aqueous resin dispersion (A-1) which is an acrylic acid ester copolymer emulsion (nonvolatile content 60%, average particle size 350 nm) was added to an organopolysiloxane polyoxyalkylene glycol (B). )
Manufactured by Nippon Unicar Co., Ltd. as FZ-2164 (cloud point 44 ° C.,
The hydrogen atom content of the alkyl group R ₁ of the organopolysiloxane was 22 mol%, a copolymer of ethylene oxide and propylene oxide was contained, and 1 part of the active ingredient) was added to obtain a resin composition of the present invention. The evaluation results are shown in Table 1. In the table, EO means ethylene oxide,
PO means propylene oxide.

Example 2 80 parts of an aqueous resin dispersion (A-1) which is an acrylic acid ester copolymer emulsion (nonvolatile content 60%, average particle size 350 nm) was added to an organopolysiloxane polyoxyalkylene glycol (B). ) As FZ-2164 manufactured by Nippon Unicar Co., Ltd. (cloud point 44 ° C., content of hydrogen atom of alkyl group R ₁ of organopolysiloxane 22 mol%, copolymer of ethylene oxide and propylene oxide, active ingredient 100%) 1 part As an inorganic filler (C), NS-200 manufactured by Nitto Dokuka Co., Ltd.
20 parts of (calcium carbonate) was added to obtain a resin composition of the present invention. The evaluation results are shown in Table 1.

Comparative Example 1 An aqueous resin dispersion (A-1) (nonvolatile content 60%, average particle size 350 nm), which is an acrylic ester copolymer emulsion, was obtained. The evaluation results are shown in Table 2.

Comparative Example 2 100 parts of an aqueous resin dispersion (A-2) which is an acrylic acid ester copolymer emulsion (nonvolatile content 60%, average particle size 218 nm) was added to 100 parts of an organopolysiloxane polyoxyalkylene glycol (B). 1 part of FZ-2164 manufactured by Nippon Unicar Co., Ltd. (cloud point 44 ° C., content of hydrogen atom of alkyl group R ₁ of organopolysiloxane 22 mol%, copolymer of ethylene oxide and propylene oxide, active ingredient 100%) Addition was performed to obtain a resin composition. The evaluation results are shown in Table 2.

Comparative Example 3 100 parts of an aqueous resin dispersion (A-1) which is an acrylic ester copolymer emulsion (nonvolatile content 60%, average particle diameter 350 nm) was added to 100 parts of organopolysiloxane polyoxyalkylene glycol (B). Manufactured by Nippon Unicar Co., Ltd., L-7604 (cloud point 49 ° C., hydrogen atom content of alkyl group R ₁ of organopolysiloxane 37 mol%, polyethylene oxide content, active ingredient 1
00%) 1 part was added to obtain a resin composition. The evaluation results are shown in Table 2.

Comparative Example 4 80 parts of an aqueous resin dispersion (A-1) which is an acrylic acid ester copolymer emulsion (nonvolatile content 60%, average particle size 350 nm) was added with organopolysiloxane polyoxyalkylene glycol (B). TPA-4380 manufactured by Toshiba Silicone Co., Ltd. (cloud point 38 ° C.,
Hydrogen atom content of the alkyl group R ₁ of the organopolysiloxane is 1.5 mol%, copolymer of ethylene oxide and propylene oxide is contained, active ingredient 33%) 3 parts, as an inorganic filler (C) manufactured by Nitto Koka Co., Ltd. 20 parts of NS-200 (calcium carbonate) was added to obtain a resin composition. The results are shown in Table 2.

[0078]

[Table 1]

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[Table 2]

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EFFECTS OF THE INVENTION According to the present invention, in particular, the appearance of the coating film is excellent and the appearance is high without causing blister (blister of the coating film) during the heat drying step during the coating process on the paper, the fiber, the plastic substrate and the like. It is possible to supply a resin composition suitable for high-strength thick film coating and processing for forming a thick film coating.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 171/00 C09D 171/00 183/12 183/12 201/00 201/00 F term (reference) 4J002 BC03X BC04X BC09X BF02X BG01X BG04X BG05X BG07X BG09X BG11X BG12X BH02X CP18W FA08X GH01 HA06 4J038 CA061 CA062 CC061 CC062 CE051 CE052 CF051 CF052 CF091 CF092 CG141 CG142 CG171 CG172 CG191 CG192 CH031 CH032 CH041 CH042 CH071 CH072 CH121 CH122 CH171 CH172 CH201 CH202 CH251 CH252 DB221 DB222 DF021 DF022 DF041 DF042 DL151 DL152 GA06 KA03 KA08 LA02 MA08 MA10 MA12 MA14 NA11 NA12

Claims (9)

[Claims] 1. An aqueous resin dispersion (A) having a solid content concentration of 50% by weight or more and an organopolysiloxane polyoxyalkylene glycol (B) represented by structural formula [1] and / or structural formula [2]. In a resin composition containing
The molar ratio of the hydrogen atom of the alkyl group R ₁ of the organopolysiloxane represented by the structural formulas [1] and [2] to the hydrogen atom of the polyoxyalkylene glycol chain is 5/95 to 5
A resin composition characterized in that the molar ratio is 0/50, and the polyoxyalkylene glycol chain is obtained from ethylene oxide and an alkylene oxide other than ethylene oxide. [Chemical 1] [Chemical 2] (In the above structural formulas [1] and [2], R ₁ is an arbitrary alkyl group, R ₂ is an arbitrary alkylene group, and one of R ₃ and R ₄ is an ethylene residue, and the other is a carbon number of 3 to R ₅ is an alkyl group, an acetyl group or hydrogen, a and b each represent an integer of 1 or more, and m and n each represent an arbitrary integer.) 2. The cloud point of a 1% by weight aqueous solution of organopolysiloxane polyoxyalkylene glycol (B) is 3
The resin composition according to claim 1, which is in the range of 0 to 55 ° C. 3. The average particle diameter of the aqueous resin dispersion (A) is
The resin composition according to claim 1, which has a range of 250 to 2000 nm. 4. The resin composition according to claim 3, wherein the aqueous resin dispersion (A) is an acrylic copolymer water dispersion. 5. An aqueous resin dispersion (A) having a solid content concentration of 50% by weight or more and an organopolysiloxane polyoxyalkylene glycol (B) represented by structural formula [1] and / or structural formula [2]. And a resin composition containing an inorganic filler (C), the structural formula [1] and the structural formula [2]
The organopolysiloxane has a hydrogen atom in the alkyl group R _{1 and} a hydrogen atom in the polyoxyalkylene glycol chain in a molar ratio of 5/95 to 50/50, and the polyoxyalkylene glycol is ethylene oxide and ethylene oxide. A resin composition obtained from an alkylene oxide other than the above. [Chemical 3] [Chemical 4] (In the above structural formulas [1] and [2], R ₁ is an arbitrary alkyl group, R ₂ is an arbitrary alkylene group, and one of R ₃ and R ₄ is an ethylene residue, and the other is a carbon number of 3 to R ₅ is an alkyl group, an acetyl group or hydrogen, a and b each represent an integer of 1 or more, and m and n each represent an arbitrary integer.) 6. The content of the inorganic filler (C) is in the range of 5 to 50 parts by weight in terms of solid content relative to 100 parts by weight of solid content of the aqueous resin dispersion (A). Resin composition. 7. The cloud point of a 1% by weight aqueous solution of organopolysiloxane polyoxyalkylene glycol (B) is
The resin composition according to claim 5 or 6, which has a temperature range of 30 to 55 ° C. 8. The average particle diameter of the aqueous resin dispersion (A) is
The resin composition according to any one of claims 5 to 7, which has a range of 250 to 2000 nm. 9. The resin composition according to claim 5, wherein the aqueous resin dispersion (A) is an acrylic copolymer water dispersion.