Mitsubishi Yuka Badische Company, Ltd.

Masahiro Aoki

Takeo Tsukamoto

Takeshi Awata

Ryutaro Hayashi

Yoshinori Kato

Tadashi Abe

Toyoji Tomita

Tsunenori Takahashi

Naoyuki Katoh

An aqueous dispersed resin composition comprising (A) an aqueous dispersion of carbonyl-containing resin particles having an inner layer and an outermost layer, which is obtained by emulsion polymerization of a monomer mixture comprising (a) not less than 0.5% by weight of a carbonyl-containing monomer containing at least one aldo group or keto group and one polymerizable unsaturated double bond in the molecule thereof, (b) not less than 0.5% by weight of an ethylenically unsaturated carboxylic acid, (c) not more than 99% by weight of a monomer having a water-solubility of not more than 8 g/100 ml at 20.degree. C., and (d) not more than 99% by weight of an unsaturated monomer other than the monomers (a) to (c) in the presence of dispersed resin particles serving as an inner layer and (B) a hydrophilic compound comprising a hydrazine derivative containing at least two hydrazino groups in the molecule thereof, in which the resin constituting the outermost layer of the carbonyl-containing resin particles has a degree of solubilization of at least 5% by weight, and the resin constituting the inner layer has a degree of solubilization lower than that of the resin constituting the outermost layer. The composition provides a film excellent in water resistance, adhesion to a substrate, smoothness, gloss, and resistance to whitening on contact with water.

Aqueous dispersed resin composition

An aqueous dispersed resin composition is disclosed, comprising (A) an aqueous dispersion of carbonyl-containing resin particles having an inner layer and an outermost layer, which is obtained by emulsion polymerization of a monomer mixture comprising (a) not less than 0.5% by weight of a carbonyl-containing monomer containing at least one aldo group or keto group and one polymerizable unsaturated double bond in the molecule thereof, (b) not less than 0.5% by weight of an ethylenically unsaturated carboxylic acid, (c) not more than 99% by weight of a monomer having a water-solubility of not more than 8 g/100 ml at 20.degree. C., and (d) not more than 99% by weight of an unsaturated monomer other than the monomers (a) to (c) in an aqueous medium in the presence of dispersed resin particles serving as an inner layer, (B) a hydrophilic compound comprising a hydrazine derivative containing at least two hydrazino groups in the molecule thereof, and (C) an epoxy-containing compound containing at least two epoxy groups in the molecule thereof, in which the resin constituting said outermost layer of said carbonyl-containing resin particles has a degree of solubilization of at least 5% by weight, and the resin constituting the whole resin particles has a degree of solubilization of from 4 to 50% by weight. The composition is easily crosslinked at room temperature to provide a film excellent in water resistance, resistance to whitening on contact with water, antiblocking properties, heat resistance, solvent resistance, adhesion and hardness, and is particularly useful as an adhesive composition.

An aqueous crosslinking resin composition comprising (I) an aqueous resin dispersion obtained by emulsion polymerization of a monomer mixture consisting of (a) 2 to 50% by weight of an unsaturated carboxylic acid monomer, (b) 0.5 to 60% by weight of a carbonyl-containing unsaturated monomer containing at least one carbonyl group based on an aldo group or a keto group, and (c) the remainder of at least one monomer(s) selected from the group consisting of alkyl acrylates or methacrylates having from 1 to 8 carbon atoms in the alkyl moiety thereof, glycidyl methacrylate, glycol mono- or diacrylates, glycol mono- or dimethacrylates, aromatic vinyl compounds, vinyl halides, vinylidene chloride, acrylonitrile, methacrylonitrile, saturated carboxylic acid vinyl esters, unsaturated carboxylic acid amides, N-alkyl and/or N-alkylol compounds of unsaturated carboxylic acid amides, unsaturated sulfonic acids, and hydroxyl-containing unsaturated compounds, and (II) a hydrazine compound having at least two hydrazino groups (--NHNH.sub.2) per molecule, with the molar ratio of the hydrazino group in said hydrazine compound (II) to the carbonyl group in the resin of said aqueous resin dispersion (I) being from 0.05 to 5, and with the resin content in the aqueous resin dispersion (I) having been solubilized to a degree of at least 5% by weight by addition of sufficient amount of an alkali and/or water miscible organic solvent. The resin composition easily undergoes a crosslinking reaction at room temperature to provide a crosslinked film having excellent adhesion to a substrate, well-balanced resistance to water and solvents, excellent whitening resistance, and hardness.

Aqueous crosslinkable resin composition

A crosslinking aqueous pigment dispersion is disclosed, comprising (A) an aqueous resin dispersion, (B) a pigment, (C) a carbonyl-containing copolymer resin having an aldo group or a keto group, and (D) a hydrazine derivative having at least two hydrazino groups (--NHNH.sub.2) per molecule, in which said carbonyl-containing copolymer resin (C) is a copolymer resin obtained by copolymerizing a monomer mixture consisting of (a) from 1 to 30% by weight of a carbonyl-containing unsaturated monomer having an aldo group or a keto group, (b) from 10 to 65% by weight of an ethylenically unsaturated carboxylic acid monomer, (c) from 5 to 89% by weight of at least one unsaturated monomer selected from the group consisting of an alkyl acrylate or alkyl methacrylate having from 1 to 10 carbon atoms in the alkyl moiety thereof, an aromatic vinyl monomer, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, a vinyl halide, a vinylidene halide, butadiene, and ethylene, and (d) not more than 50% by weight of an unsaturated monomer other than the unsaturated monomers (a) to (c), and said carbonyl-containing copolymer resin (C) is present in an amount of from 0.1 to 10% by weight based on said pigment (B) and has been solubilized to a degree of at least 90% by weight by addition of an alkali and/or an organic solvent. The pigment dispersion provides a dry film excellent in gloss, water resistance, alkali resistance and weather resistance.

Crosslinking aqueous pigment dispersion

A process for producing an aqueous copolymer dispersion is disclosed, which comprises emulsion polymerizing 100 parts by weight of a vinyl monomer mixture comprising (A) from 60 to 99.8% by weight of an acrylic ester of an aliphatic saturated alcohol having from 4 to 8 carbon atoms, (B) from 0.2 to 10% by weight of a monomer selected from the group consisting of an .alpha.,.beta.-unsaturated carboxylic acid, an .alpha.,.beta.-unsaturated carboxylic acid anhydride, a 2-hydroxyalkyl acrylate, a 2-hydroxyalkyl methacrylate, acrylamide, methacrylamide, methylolacrylamide, and methylolmethacrylamide, and (C) up to 30% by weight of a vinyl monomer other than the monomers (A) and (B) in the presence of from 0.01 to 10 parts by weight of a compound having an allyl hydrogen atom, with a total amount of the monomers (A), (B) and (C) being 100% by weight. The resulting aqueous copolymer dispersion can form a film which exhibits excellent adhesion performance particularly to an adherend having small polarity and gives off no smell.

Process for producing aqueous copolymer dispersion from a vinyl monomer

A process for emulsion-polymerizing unsaturated monomer(s) is disclosed. When a hydrazine derivative having at least two hydrazine residues per molecule is added to the polymer dispersion obtained by said emulsion polymerization process, a polymer dispersion composition capable of forming a film which is excellent in blocking resistance, adhesiveness to an alkyd resin film, water-resistant adhesiveness to an alkyd resin film and water-resistant anti-whitening can be obtained.

Emulsion polymerization process

A process for producing a composite laminate comprising a insert part and an injection-molded resin part by coating the insert part with a primer comprising a copolymer aqueous emulsion having a glass transition point of not higher than 20.degree. C. which is obtained by emulsion polymerization of a monomer mixture consisting mainly of (a) from 35 to 75% by weight of an alkyl acrylate having from 1 to 8 carbon atoms in the alkyl moiety thereof, (b) from 10 to 50% by weight of an alkyl methacrylate having from 1 to 4 carbon atoms in the alkyl moiety thereof, (c) up to 15% by weight of styrene and/or acrylonitrile, the sum of the (b) and (c) components ranging from 15 to 55% by weight, (d) up to 5% by weight of a vinyl monomer selected from the group consisting of an .alpha.,.beta.-unsaturated acid or an anhydride thereof, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylamide, and methylol(meth)acrylamide, and (e) up to 30% by weight of other vinyl monomer(s), drying the primer, inserting the insert part into a cavity of an injection mold, injecting a molten resin into the cavity to thereby unite the insert part and the injected resin molded part into one body. The composite laminate is resistant to thermal shocks or electrical shocks.

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Mie, Japan

Masahiro Aoki