JP2002187779A - Binder for ceramic and/or metallic material and method of manufacturing sintered compact - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binder for a ceramic and/or metallic material with which shape retention after demolding and volume retention after sintering are improved, a molding material dispersion liquid, a sintered compact and a method of manufacturing the sintered compact. SOLUTION: The binder for the ceramic and/or metallic material is composed of a vinyl polymer based heat reversible thickener (A) reversibly changeable from hydrophilicity to hydrophobicity at >=30 deg.C transition temperature (T) and a water dispersion based resin binder (B). The molding material dispersion liquid contains the binder and a powder ceramic and or a powdery metal. The sintered compact is formed by sintering a molding made of the molding material dispersion liquid. The method of manufacturing the sintered compact is performed by molding the molding material dispersion liquid containing the binder for the ceramic and/or metallic material composed of the vinyl polymer based heat reversible thickener (A) reversibly changeable from hydrophilicity to hydrophobicity at >=30 deg.C transition temperature (T) and the water dispersion based resin binder (B) at a temperature lower than T deg.C and heating to a temperature higher than the transition temperature to sinter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to ceramic and / or ceramic.
Also, the present invention relates to a binder for a metal material and a method for producing a sintered body, and more particularly to a binder for a ceramic and / or metal material using a thermoreversible thickener, and a sintered body using the binder. And a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as binders for ceramic and / or metal materials, polyvinyl alcohol (JP-B-51-17095), cellulose derivatives such as carboxymethylcellulose and methylcellulose (JP-B-56-114863), Examples include an ethylene-vinyl acetate copolymer (JP-A-59-121151), polyethylene (US Pat. No. 3,297,805), and polypropylene (JP-B-55-113510). Among them, methylcellulose that utilizes the fact that the viscosity changes with temperature is particularly exemplified.

[0003]

However, in order to increase the production speed when molding a dispersion of a molding material comprising a ceramic and / or metal material and a binder by a doctor blade method, an extrusion molding method, or the like, It is necessary to reduce the viscosity of these molding material dispersions containing alumina and the like. However, when the viscosity is reduced, the deformation of the molded body due to its own weight and the volume shrinkage due to drying increase. In order to prevent this, the viscosity of the molded body may be increased by heating after molding the molding material dispersion liquid and before demolding. Examples of the binder exhibiting such an effect include the above-mentioned methyl cellulose, but the thickening effect is not sufficient.
Sufficient shape retention cannot be obtained.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a binder containing a specific thermoreversible thickener (A) and a water-dispersed resin binder (B) is mixed with a ceramic and / or a binder. By using it as a binder for metal materials,
The inventors have found that the shape retention after demolding is excellent and the volume retention after sintering is high, and the present invention has been achieved. Particularly, it is very useful for fine ceramics, metal sintered bodies for electrode substrates, sintered high-speed steels for tools, etc., in which deformation is a major problem.

That is, the present invention provides a vinyl polymer-based thermoreversible thickener (A) whose hydrophilicity and hydrophobicity are reversibly changed at a transition temperature (T) of 30 ° C. or more, and a water-dispersible resin binder (B). A molding material dispersion containing the binder and the powdered ceramic and / or powdered metal; a firing material produced by sintering a molded body of the molding material dispersion. And a ceramic comprising a vinyl polymer-based thermoreversible thickener (A) whose hydrophilicity and hydrophobicity are reversibly changed at a transition temperature (T) of 30 ° C. or more and a water-dispersible resin binder (B). And / or a molding material dispersion containing a binder for a metal material is molded at a temperature lower than T ° C., and then heated to a temperature higher than a transition temperature to sinter.

[0006] The transition temperature (T) of the thermoreversible thickener (A) in the present invention is usually 30 ° C or higher, preferably 40 to 9 ° C.
The temperature is 5 ° C, more preferably 60 to 80 ° C. When the transition temperature is lower than 30 ° C., the viscosity of the binder containing the thermoreversible thickener (A) at room temperature becomes too high. The transition temperature is determined by gradually heating (1 ° C./min) an aqueous solution of 1% by mass of solid content of the thermoreversible thickener (A) and measuring the temperature at which the aqueous solution starts to become cloudy. Also,
The method of confirming that the thickening of (A) is thermoreversible is performed by cooling the aqueous solution turbid in the above measurement to T ° C. or less to eliminate the turbidity, and then heating the solution to T ° C. or more again to become turbid. And a method of confirming that the operation is performed.

The vinyl polymer thermoreversible thickener (A) of the present invention
Specific examples of (a) a (co) polymer [morpholinoethyl (M) having an essential monomer of a (meth) acrylic acid ester of an adduct of 1 to 40 mol of an alkylene (C2 to C4) oxide of a cyclic amine (Meth) acrylate polymers and the like described in JP-A-6-9848]; (ii) 1 to 40 moles of an adduct of an alkylene (2 to 4 carbon atoms) oxide of an acyclic amine having 5 or more carbon atoms (Co) polymers containing a (meth) acrylic acid ester as an essential monomer [diisopropylaminoethyl (meth) acrylate polymers and the like]; (c) (meth) of monoalkylamine or alkoxyalkylamine having 3 to 6 carbon atoms in total ) (Co) polymer containing acrylamide as an essential monomer [N-isopropyl (meth) acrylamide polymer, N-methoxypropyl (meth) acrylamide polymer (D) a dialkylamine having a total carbon number of 2 to 8, a dialkoxyalkylamine or a cyclic amine (meth) acrylamide as an essential monomer ( (Co) polymer [N, N-
Diethyl (meth) acrylamide polymer, N- (meth)
Acryloylpyrrolidine polymer, etc.
(E) No. 184]; (e) a (co) polymer having a vinyl monomer having a polyiminoethylene group (degree of polymerization of 2 to 50) as an essential monomer [tetraethyleneimine mono (meth) (F) a (meth) acrylamide having a cyclic amino group or an alkylamino group having 5 or more carbon atoms of an alkyl group as an essential monomer; (G) a (co) polymer [N-morpholino (meth) acrylamide polymer or the like]; (g) a polyoxyalkylene having 2 to 4 carbon atoms in the alkylene group (degree of polymerization: 3 to 40) monool or diol mono (meth) ) Acrylate as an essential monomer (co)
Polymer [tetraethylene glycol monoethyl ether mono (meth) acrylate polymer, pentaethylene glycol monobutyl ether mono (meth) acrylate polymer, trioxypropylene tetraoxyethylene glycol monomethyl ether mono (meth) acrylate polymer, tetrapropylene glycol Mono (meth) acrylate polymer of ethylene oxide 6 mol adduct); (h) polyoxyalkylene having 2 to 4 carbon atoms in alkylene group (degree of polymerization: 3 to 40) monool or diol monovinylphenyl ether is essential (Co) polymers as monomers (tetraethylene glycol monomethyl ether monovinyl phenyl ether polymer, pentaethylene glycol monoethyl ether monovinyl phenyl ether polymer, pen (Taoxypropylene tetraoxyethylene glycol monomethyl ether monovinyl phenyl ether polymer, monovinyl phenyl ether polymer of tetrapropylene glycol ethylene oxide 8 mol adduct, etc.); (li) alkyl (C1-6) vinyl ether polymer (methyl vinyl ether) And the like).

When (A) is a copolymer, the other monomer copolymerized with the above-mentioned essential monomer is mentioned as a monomer constituting a water-dispersed resin binder described later.
(1) nonionic monomer, (2) anionic monomer and (3)
Cationic monomers may be mentioned, and the copolymerization ratio of the essential monomer and the other monomer is usually based on the total number of moles of the essential monomer and the other monomer. Is 0.1 to 60% by weight,
Preferably it is 0.1 to 30% by weight.

Among (A), (A) to (H) are preferable in that they provide a large thickening effect, and (co) polymers selected from (A) to (D) are more preferable. Also, (A)
Has a weight average molecular weight of usually 1,000 to 50,000 by GPC (gel permeation chromatography).
00,000, preferably 2,000-500,000
It is.

(A) can be produced by a known radical polymerization method, and may be any method such as solution polymerization, bulk polymerization and emulsion polymerization. Further, (A) may be in any form such as an aqueous solution, a latex, and a lump. The solid content in the case of an aqueous solution or latex is usually 5 to 70% by weight, preferably 20 to 40% by weight, and the pH is usually 3 to 1%.
2, preferably 6 to 10.

The water-dispersed resin binder (B) of the present invention
Is usually in the form of an aqueous latex or an aqueous dispersion of a resin powder, preferably an aqueous latex, and does not have a thermoreversible thickening action. The solubility of the resin component (B) in water at 25 ° C. is usually less than 5% by weight. (B) includes a water-dispersible vinyl resin binder (B1) (eg, a styrene-based resin, an acrylic resin, a butadiene-based resin, and an ethylene-based resin); a water-dispersible condensation or polyaddition-based resin binder (B2) (for example, a polyester-based resin, a polyamide-based resin, or the like as a condensation resin, or a urethane resin, for example, as a polyaddition-based resin);
Water-dispersed ring-opening polymer resin (B3) (for example, ring-opening polymer resin such as epoxy resin and alkylene oxide resin). Among these, (B1) is preferable.

Examples of the vinyl monomer constituting the water-dispersed vinyl resin binder (B1) include the following. (1) Nonionic monomer (1-1) Acrylic ester monomer: (cyclo) alkyl (C 1-22) (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate,
n-butyl (meth) acrylate, iso-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, etc.]; Aromatic ring-containing (meth) acrylate [benzyl (meth) acrylate, phenylethyl (meth) acrylate, etc.]; hydroxyl-containing (meth) acrylate [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (Meta)
Acrylate, glycerin mono (meth) acrylate,
Polyglycerin (degree of polymerization: 2 to 4) mono (meth) acrylate, etc.]; polyfunctional (meth) acrylate [(poly) ethylene glycol (the number of oxyethylene units = 1 to 10)
0) di (meth) acrylate, (poly) propylene glycol (number of oxypropylene units = 1 to 100) di (meth) acrylate, 2,2-bis (4-hydroxyethylphenyl) propanedi (meth) acrylate, trimethylol (1-2) (meth) acrylamide monomer: (meth) acrylamide or a derivative thereof [(meth) acrylamide, N, N-dibutyl (meth) acrylamide, cyclohexyl (meth) Acrylamide, N-methyl (meth)
Acrylamide, N-methylol (meth) acrylamide, diacetone acrylamide, etc.]; (1-3) cyano group-containing monomer: (meth) acrylonitrile, 2-cyanoethyl (meth) acrylate, 2-cyanoethylacrylamide, etc .; 4) Styrene monomer: styrene, α-methylstyrene, vinyltoluene, p-hydroxystyrene, divinylbenzene, etc .; (1-5) Diene monomer: butadiene, isoprene, chloroprene, etc .; (1-6) Vinyl ester monomers: vinyl acetate, vinyl propionate, vinyl butyrate, etc .; (1-7) epoxy group-containing monomers: glycidyl (meth) acrylate, allyl glycidyl ether, etc .; (1-7) monoolefins ethylene , Propylene, 1-butene, etc .; (1-8) Halogen-containing monomer: vinyl chloride, vinylidene chloride, etc .; Isomers: N-vinyl-2-pyrrolidone, N-methylolmaleimide, N-vinylsuccinimide, etc.); (1-10) unsaturated dibasic acid dialkyl esters: dialkyl maleate (C1-8) ester, itaconic acid (1-11) Silyl group-containing monomer: 3-trimethoxysilylpropyl (meth) acrylate, etc .; (2) Anionic monomer (2-1) Monocarboxylic acid Acid monomer: (meth) acrylic acid,
Crotonic acid, monoalkyl maleate (C1-8)
(2-2) dicarboxylic acid-based monomers: (anhydride) maleic acid, fumaric acid, itaconic acid, etc .; Monosulfonic acid monomer: vinylsulfonic acid,
(Meth) allyl sulfonic acid, styrene sulfonic acid, alkyl (1 to 10 carbon atoms) allyl sulfosuccinic acid and the like; (2-4) sulfate monomer: (meth) acryloyl polyoxyalkylene (degree of polymerization 2 to 15) Sulfates and the like; and salts thereof [alkali metal salts such as sodium salt and potassium salt, amine salts such as triethanolamine,
(3) Cationic Monomer (3-1) Tertiary Amino Group-Containing Acrylic Monomer: N, N-dimethyl Aminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-
Diethylaminoethyl (meth) acrylate, N, N-
Diethylaminopropyl (meth) acrylate, N, N
(3-2) Tertiary amino group-containing amide monomers: N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, etc. (3-3) Other cationic monomers: aromatic ring-containing cationic monomers [vinylaniline, p-aminostyrene, etc.];
Heterocycle-containing cationic monomers [N-vinylcarbazole, vinylimidazole, 2-vinylpyridine, etc.]; and salts thereof (inorganic acid salts such as hydrochloride and phosphate, organic acids such as formate and acetate) Salt); and combinations of two or more of these.

The vinyl resin constituting the water-dispersible vinyl resin binder (B1) in the present invention includes an acrylic resin, a styrene-acrylic resin, a styrene-butadiene resin, and a butadiene containing the above-mentioned monomer as a component. -Acrylic resin, butadiene-acrylonitrile resin, vinyl acetate resin, ethylene-vinyl acetate resin,
Ethylene-propylene resin, polybutadiene resin,
Radical polymer resins such as a styrene-maleic acid resin and a modified polystyrene resin are exemplified. When (B1) is a copolymer, the copolymerization ratio (mol%) of the monomer is usually nonionic monomer / anionic monomer / cationic monomer = 100 to 50/0. ３０30 / 0-20. In addition, among the monomers, hydrophilic monomers [(1-2), (2-
1), (2-2), (2-3), (2-4), (3-1), and (3-2)] as long as (B) maintains an aqueous dispersion. There is no particular limitation as long as it is present.
0 mol%.

Among (B1), preferred are those selected from the group consisting of alkyl (C1 to C22) (meth) acrylates, styrene monomers and diene monomers.
A resin composed of at least one kind, particularly a resin composed of a copolymer obtained by combining a diene monomer with an alkyl (meth) acrylate and / or a styrene monomer is particularly preferable.

When (B1) is a latex, (B1)
The amount of the surfactant in the aqueous phase in 1) is 0.01 mmol /
g (resin) or less is preferable because the temperature range from the start of thickening to gelation can be narrowed.
More preferably, it is not more than mmol / g. In addition,
The amount of the surfactant in the aqueous phase is a molar concentration based on the weight of the resin component in (B1). The amount of surfactant in the aqueous phase is (B
1) After diluting 50 g to a concentration of 10% by weight,
2.0 g of the supernatant centrifuged at 0 rpm × 30 minutes
It was sampled and quantified by high performance liquid chromatography.

The amount of the surfactant in the aqueous phase is 0.01 mmol /
As a method for producing a resin latex having a solubility in water, for example, a non-polymerizable emulsifier having low solubility in water (for example, HL
B value of 3 to 9, for example, amine or alkali metal salt of a fatty acid having 22 or more carbon atoms, ethylene oxide 1 to 6 of an aliphatic or aromatic alcohol having 15 or more carbon atoms
), A method of emulsion-polymerizing a monomer using an emulsifier having a radical polymerizable group, and a method of emulsion-polymerizing a water-soluble polymer as a protective colloid. After polymerizing a polymerizable monomer having an ion-forming group in an organic solvent by (co) polymerization to synthesize a polymer, the obtained polymer is neutralized with an acid or an alkali, and then water is added to emulsify the polymer. And the like.

Among these methods, emulsion polymerization is preferable in that a latex containing a high molecular weight resin is obtained, and emulsion polymerization of a polymerizable monomer using an emulsifier (D) having a radical polymerizable group is preferred. Is particularly preferred. Examples of the emulsifier (D) having a radical polymerizable group include a polymerizable emulsifier represented by the following general formula (1).

[0018]

Embedded image

Wherein Ar is an aromatic ring, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are monovalent hydrocarbon groups,
At least one of m R ² and n R ³ is a hydrocarbon group having an aromatic ring. m and n are such that m + n is 1
R ⁴ and R ⁵ are a hydrogen atom or a methyl group, M is a cation, and A is C 2 to C 4
And p and q are 0 or 1 to 40
Indicates an integer.

In the general formula (1), examples of the aromatic ring of Ar include a hydrocarbon-based aromatic ring and an aromatic ring containing a hetero atom. Examples of the hydrocarbon group include a benzene ring and a naphthalene ring, and examples of the aromatic ring containing a hetero atom include a thiophene ring and a pyrrole ring. R ² and R ³ are monovalent hydrocarbon groups, for example, an alkyl group,
They are an alkenyl group, an aralkyl group, an alkyl-substituted aralkyl group, a styryl group, a polystyryl group and a fused benzyl group, and at least one of R ² and R ³ is an aromatic ring-containing hydrocarbon. The alkyl group has 1 to 1 carbon atoms.
24 linear and branched hydrocarbons (methyl group, ethyl group,
Examples of n- and i-propyl groups, neopentyl groups, hexyl groups, octyl groups, etc.) and alkenyl groups include straight-chain and branched hydrocarbons having 2 to 24 carbon atoms (an allyl group, a propenyl group, an octenyl group, a nonenyl group, A benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group or the like as an aralkyl group; and a polystyryl group obtained by condensing or adding 2 to 8 styrenes. Examples of the condensed benzyl group include groups obtained by condensing 2 to 8 benzyl chlorides. Among these, preferred are styryl group, polystyryl group, benzyl group and condensed benzyl group, and the total of m and n is preferably 2 to 7. A is an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a propylene group, and a 1,2-butylene group. p and q are 0 or an integer of 1 to 40, preferably 5 to 40, and the total of p and q is preferably 15 to 40. Examples of the cation of M include an alkali metal (sodium, potassium, lithium) cation, an ammonium cation, an organic amine (mono-, di- or trialkylamine having an alkyl group having 1 to 12 carbon atoms) cation, and a quaternary ammonium cation (carbon Having alkyl groups of numbers 1 to 8, the four alkyl groups may be the same or different)
And the like.

When at least one of m R ² and n R ³ is an aromatic ring-containing hydrocarbon, or when the sum of p and q is 5 or less, the emulsion stability during radical polymerization is excellent, The particle size of the resulting resin latex can be optimized. When the sum of p and q is 40 or less, the hydrophilicity of the polymerizable emulsifier does not become too large, and also in this case, the emulsion stability of the monomer during radical polymerization is excellent, and the particle size of the resulting resin latex is optimized. it can.

Examples of the compound of the general formula (1) include bis (polyoxyalkylene ether of polycyclic phenol) monomethacrylate sulfate, and bis (polyoxyalkylene ether of polycyclic phenol) includes Polycyclic phenols (for example, styrenated phenols, benzylated phenols, etc .; in this case, the number of moles of styrene or benzyl added is 0.2 to 4 per phenol ring, and the styrene or benzyl group is directly added to the phenol ring. Carbonyl compound (for example, formaldehyde, acetaldehyde, or a styrene or benzyl group attached to a phenol ring).
A product obtained by adding an alkylene oxide (hereinafter abbreviated as AO) to a condensate formed by acetone or the like, or a product obtained by styrenating or benzylating a phenol such as a bisphenol (for example, bisphenol A or bisphenol F) in the same manner as described above. To which AO is added. In addition, when bis (polyoxyalkylene polycyclic phenyl ether) is a formaldehyde condensate,
A condensate of three or more nuclei may be by-produced, and a sulfate salt of monomethacrylate other than the general formula (1) is generated. Those containing these by-products can also be used as (D). AO includes ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter P).
O), 1,2-, 2,3-, 1,3- and 1,4-butylene oxide and combinations thereof. The preferred AO is EO. In the case of combined use, the binding mode may be random or block.

As a method for producing the compound of the formula (1), polycyclic phenol is condensed with formaldehyde (condensation degree is 2 to 1) as described in JP-B-6-62685.
0), followed by an addition reaction of AO, dehydration and esterification with (meth) acrylic acid, sulfated with a usual sulfating agent, and then neutralized if necessary. . In the above production method, the polycyclic phenol may be a styrenated phenol having 1 to 5 moles of added styrene, the AO may be EO or PO, the added mole number of AO may be 2 to 100, and the sulfonating agent may be chlorosulfonic acid. , Sulfuric anhydride or sulfamic acid.

As the emulsifier (D), in addition to the above, CH
₂ ＣC (R ¹ ) COO (CH ₂ ) _m SO ₃ M [wherein R ¹ is a hydrogen atom or a methyl group, m is an integer of 1 to 24, M is an alkali metal ion, an ammonium ion or an aminium ion. Show. CH ₂ 2C (R ¹ ) COO
(AO) pSO ₃ M or CH ₂ ＣC (R ¹ ) COO (AO) p
CH ₂ COOM wherein R ¹ is a hydrogen atom or a methyl group,
AO is an oxyalkylene group having 2 to 4 carbon atoms, and p is 2 to 2
Integer of 00, M represents an alkali metal ion, ammonium ion or aminium ion. And the polymerizable emulsifiers described in JP-A-9-25454.

Of these, those of the general formula (1) are preferred in that they have good copolymerizability with various monomers, especially styrene.

The amount of the polymerizable emulsifier (D) used is (B1)
0.1 to 2 with respect to the resin content [not including (D)]
0% by weight, preferably 1 to 10% by weight.

In producing the water-dispersed vinyl resin binder (B1) by an emulsion polymerization method, a known polymerization initiator is used. Examples of the polymerization initiator include organic polymerization initiators (peroxides (cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramethane hydroperoxide, benzoyl peroxide, lauroyl peroxide, etc.), azo compounds (azobisisobutyrate). Lonitrile, azobisisovaleronitrile, etc.)]
Inorganic polymerization initiator [persulfate (sodium persulfate, ammonium persulfate, potassium persulfate, etc.), hydrogen peroxide, etc.]
And the like. The amount of the polymerization initiator to be used is generally 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the total amount of the monomer mixture.

A known chain transfer agent can be used for the purpose of adjusting the molecular weight of the resin component. Examples of the chain transfer agent include α-methylstyrene dimer (2,4-diphenyl-4-methyl-1-pentene and the like), terpinolene,
Terpinene, dipentene, alkyl mercaptan having 8 to 18 carbon atoms, alkylenedithiol having 8 to 18 carbon atoms,
Examples include alkyl thioglycolate, dialkyl xanthogen disulfide, tetraalkyl thiuram disulfide, chloroform, carbon tetrachloride and the like. These can be used alone or in combination of two or more. The amount of the chain transfer agent to be used is generally 0 to the total amount of the monomer mixture.
It is 15% by weight, preferably 0-5% by weight.

If necessary, a reducing agent [sodium pyrobisulfite, sodium sulfite, sodium hydrogen sulfate,
Ferrous sulfate, glucose, sodium formaldehyde sulfoxylate, L-ascorbic acid (salt)], chelating agent (glycine, alanine, sodium ethylenediaminetetraacetate, etc.), pH buffering agent (sodium tripolyphosphate, potassium tetrapolyphosphate, etc.) And the like may be used in combination. The amount of these additives is usually 0 to 5% by weight, preferably 0 to 3% by weight, based on the total amount of the monomer mixture.
It is.

The weight average molecular weight by GPC of (B1) is usually from 2,000 to 5,000,000, preferably from 3,000 to 2,000,000.

Examples of the resin component (B2) in the present invention include a urethane resin (U), a polyester resin (E), and a polyamide resin (M).

The urethane resin (U) is obtained by reacting an organic polyisocyanate (u1) and a polyol (u2) as essential components. As (u1),
Aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon atoms of the NCO group) [for example, 2,4- and / or 2,2-
6-tolylene diisocyanate (TDI), 4,4'-
And / or 2,4'-diphenylmethane diisocyanate (MDI) and the like; alicyclic diisocyanate having 4 to 15 carbon atoms [for example, isophorone diisocyanate (I
PDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), etc.], aliphatic diisocyanates having 2 to 18 carbon atoms [eg, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate], and 8 carbon atoms To 15 aromatic aliphatic diisocyanates [xylylene diisocyanate (XDI) and the like], and modified products of these diisocyanates [for example, urethane group, carbodiimide group, allophanate group, urea group, buret group, isocyanurate group and / or oxazolidone group] Modified product containing a).

Examples of (u2) include polyester polyol (u21), polyether polyol (u22), polyolefin polyol (u23), castor oil-based polyol (u24), low molecular weight polyol (u25), and a mixture of two or more of these. No.

As (u21), for example, a polycondensate of a polyol [(u25) and / or (u22)] with a polycarboxylic acid (c1) and a lactone to (u25) and / or (u23) c2) or a polyadduct of alkylene carbonate (c3).
(U25) includes dihydric to octahydric or higher alcohols, and examples of the dihydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, and 1,3-butane. Diol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,8-octanediol, 1,9-nonanediol, cyclohexanedimethanol, bishydroxyethoxybenzene, etc. Examples of the tri- to octahydric alcohols include glycerin, trimethylolpropane, pentaerythritol and the like, and a mixture of two or more of these can also be used.

As (c1), divalent to octavalent or higher polycarboxylic acids such as aliphatic polycarboxylic acids [adipic acid, succinic acid, sebacic acid, azelaic acid,
Fumaric acid, maleic acid, dimer acid, etc.], aromatic polycarboxylic acids (terephthalic acid, isophthalic acid, trimellitic acid, etc.) and mixtures of two or more of these. Examples of (c2) include lactones having 4 to 12 carbon atoms, such as 4-butanolide, 5-pentanolide, and 6-hexanolide. (C3) has 2 to 8 carbon atoms
Alkylene carbonates such as ethylene carbonate and propylene carbonate.

As a specific example of (u21), for example,
Polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyneopentyl adipate diol, polyneopentyl terephthalate diol, poly (3-methylpentylene adipate) diol, polycaprolactone diol, polyvalerolactone diol, polyhexamethylene carbonate Diols and the like.

Number average molecular weight of (u21) and (u22) described below (measured by GPC, hereinafter abbreviated as Mn)
Is usually 300 to 6,000, preferably 500 to 5,
000. If it is less than 300, the obtained polyurethane resin is hard and brittle, and if it exceeds 6,000, the resin becomes soft and the strength is reduced.

As AO, ethylene oxide (hereinafter referred to as E)
O), propylene oxide (hereinafter referred to as PO), 1,2-, 2,3-, 1,3- and 1,4-butylene oxide or a combination of two or more thereof (random addition and / or block Addition) is included.

Examples of (u22) include polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene propylene polyol, and bisphenol EO and / or PO adducts. If Mn is less than 300, the resulting polyurethane resin is hard and brittle, and if it exceeds 6,000, the resin becomes soft and the strength is reduced.

(U23) includes polyalkadiene-based polyols such as 1,2 and / or 1,4-polybutadiene diol and hydrogenated polybutadiene diol; and acrylic polyols such as hydroxyethyl (meth) acrylate and other Monomer [styrene,
Alkyl (1-8 carbon atoms) (meth) acrylate, etc.]
And copolymers thereof.

Examples of (u24) include castor oil, a transesterified product of castor oil with (u25) and / or (u22), and an EO (4 to 30 mol) adduct of castor oil.

In the present invention, by using a compound (d) containing a hydrophilic group and an active hydrogen atom-containing group in the molecule in at least a part of the polyol (u2), an aqueous dispersion of the self-emulsifying polyurethane resin can be obtained. It can be a system resin binder. The hydrophilic group in (d) includes an anionic group, a cationic group and a nonionic group.
Examples of the anionic group include a sulfonic acid group, a sulfamic acid group, a phosphoric acid group, a carboxyl group, and salts thereof. As the active hydrogen atom-containing group in (d),
Examples include a hydroxyl group, a carboxyl group and an amino group. Among (d) having an anionic group, compounds having a sulfonic acid group include sulfonic acid diol [3-
(2,3-dihydroxypropoxy) -1-propanesulfonic acid, etc.], sulfopolycarboxylic acid [sulfoisophthalic acid, sulfosuccinic acid, etc.] and aminosulfonic acid [2-aminoethanesulfonic acid, 3-aminopropanesulfonic acid, etc.] Is mentioned. Examples of the compound having a sulfamic acid group include sulfamic acid diol [N,
N-bis (2-hydroxyalkyl) sulfamic acid (alkyl group having 1 to 6 carbon atoms) or its AO adduct (where AO is 1 to 6 moles of AO, such as EO or PO): For example, N, N- Bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 mol adduct, etc.]. As the compound having a phosphate group, bis (2
-Hydroxyethyl) phosphate and the like.
Examples of the compound having a carboxyl group include dialkylol alkanoic acids [eg, 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid,
2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid, etc.] and amino acids (2-aminoethanoic acid, etc.)
Is mentioned. These salts include amines (triethylamine, alkanolamine, morpholine, etc.)
And / or salts such as alkali metal hydroxides (such as sodium hydroxide). Specific examples of the aqueous dispersion binder containing an anionic group-containing urethane resin include those described in JP-B-42-24192 and JP-B-43-9076. (D) containing a cationic group includes N-methyldiethanolamine,
Neutralized products or quaternizing agents (such as dimethyl sulfate) with acids (such as acetic acid) such as N, N-dimethylethanolamine
(D) having a nonionic group, such as polyethylene glycol and polyethylene propylene glycol (Mn = 100 to 3,000). (D) may be used in combination with a nonionic compound and an anionic compound or a cationic compound. In the case where (d) is an ionic compound, the content of (d) in the water-dispersed resin binder of the self-emulsifying urethane resin is preferably such that the equivalent of the hydrophilic group based on the weight of the urethane resin is 0.01 to 2 meq / g, preferably 0.1
In the case where (d) is a nonionic compound, the weight of the hydrophilic group is preferably 3 to 30% by weight based on the weight of the urethane resin [(a21) or ( a22), and when it contains a polyoxyethylene chain (additional mole number of 2 or more), the weight thereof is also included], preferably 5 to 20% (% in the following)
Represents weight% unless otherwise specified).

As a method for producing the self-emulsifying type aqueous dispersion of (U), for example, an isocyanate group (hereinafter referred to as N
CO group is abbreviated), and in the presence or absence of an organic solvent that is non-reactive with the above (u1), (u2) containing (d) and, if necessary, a terminator (e), To give a urethane prepolymer, which is then hydrophilized (neutralized or quaternized) with a base [if (d) is an anionic compound] or an acid or quaternizing agent [if (d) is a cationic compound]. Or 10 ° C. to 60 ° C., preferably 20 ° C.
40 ° C., if necessary, a chain extender (f) and a crosslinking agent (h)
And / or an aqueous solution containing a terminating agent (e) to form an aqueous dispersion, an elongation reaction, a crosslinking reaction and / or a termination reaction until the NCO group disappears, and an organic solvent is distilled off as necessary. it can. The hydrophilization (neutralization or quaternization) may be performed after the formation of the aqueous dispersion.

In the production of the prepolymer, the equivalent ratio of isocyanate groups / active hydrogen-containing groups (excluding carboxyl groups) is usually 1.01-2, preferably 1.1-1.6.
It is. The reaction temperature for prepolymerization is usually 20 ° C to 1 ° C.
The temperature is 50 ° C, preferably 60 ° C to 110 ° C, and the reaction time is 2 to 10 hours. The end point of prepolymerization is that the free isocyanate (NCO) group content is usually 0.5 to 5% by weight.
It is the time when it became.

As organic solvents, ketones (acetone,
Methyl ethyl ketone, methyl isobutyl ketone),
Esters (ethyl acetate, butyl acetate, ethyl cellosolve acetate, etc.), ethers (dioxane, tetrahydrofuran, etc.), hydrocarbons (n-hexane, n-hexane, etc.)
-Heptane, cyclohexane, tetralin, toluene,
Xylene, etc.), chlorinated hydrocarbons (dichloroethane,
Trichloroethane, trichloroethylene, perchloroethylene and the like, amides (dimethylformamide, dimethylacetamide and the like), N-methylpyrrolidone and the like can be used.

As the chain extender (f) and the optional crosslinking agent (h), water, polyamine [having 2 to 2 carbon atoms]
16, aliphatic polyamines (ethylenediamine, hexamethylenediamine, diethylenetriamine, etc.), alicyclic polyamines (isophoronediamine, 4,4′-dicyclohexylmethanediamine, etc.), aromatic polyamines (4,4′-diaminodiphenylmethane, etc.), Araliphatic polyamines (xylylenediamine, etc.), hydrazine or derivatives thereof], blocked products of these polyamines [ketones having 3 to 8 carbon atoms (such as acetone, methyl ethyl ketone, methyl isobutyl ketone) as blocking agents], And hydrazine derivatives [hydrazine, carbodihydrazide, adipic acid dihydrazide, etc.] The amount of the chain extender (f) except for water and the amount of the cross-linking agent (h) used as required depends on the amount of the isocyanate remaining in the prepolymer. The amount is such that the primary amino group and the secondary amino group of (f) and (h) are usually 0.5 to 2 equivalents, preferably 0.9 to 1.2 equivalents to 1 equivalent of the nate group. .

Further, a terminating agent (e) optionally used
Examples thereof include compounds having 1 to 12 carbon atoms having one active hydrogen-containing group in the molecule, for example, monoalcohols (such as methanol and butanol) and monoamines (such as butylamine and dibutylamine). Terminating agent (e)
The amount of (e) active hydrogen-containing group is usually 0.5 equivalent to 1 equivalent of isocyanate group remaining in the prepolymer.
Equivalent to 2.0 equivalents, preferably 0.9 equivalent to 1.2 equivalents.
The amount is equivalent.

The aqueous dispersion of (U) can be an emulsifier emulsified type (U) aqueous dispersion using an emulsifier [if necessary using (d)]. Emulsifier emulsifying type (U)
As a method for producing an aqueous dispersion of (a), for example, in the presence or absence of the organic solvent, (u1), (u2) and, if necessary, (d) and / or (e) are reacted under the same conditions as described above. The free NCO group content is usually 0.5-5
% By weight of a urethane prepolymer, after adding an emulsifier described below to the prepolymer, usually at 10 ° C. to 60 ° C., preferably 20 ° C. to 40 ° C., in the same manner as in the method for producing the self-emulsifying aqueous dispersion described above. If necessary, it is mixed with an aqueous solution containing (f), (h) and / or (e) to form an aqueous dispersion, and an elongation reaction, a crosslinking reaction and / or a termination reaction is carried out until the NCO group disappears. A method of removing the organic solvent is exemplified. The emulsifier may be added to either the prepolymer or water (solution) or to both. If the emulsifier is reactive with the prepolymer, it is preferably added to water. The amount of the emulsifier to be added is generally 0.2 to 10%, preferably 0.3 to 6%, based on the weight of the urethane prepolymer.

Examples of the emulsifier which can be used include anionic surfactants such as ether carboxylic acids or salts thereof, sulfates or ether sulfates and salts thereof, and sulfonates having a hydrocarbon group having 8 to 24 carbon atoms.
Sulfosuccinates, phosphates or ether phosphates and their salts, fatty acid salts, and acylated amino acid salts], nonionic surfactants [aliphatic alcohols (8 to 24 carbon atoms) AO (2 to 8 carbon atoms) ) Adducts, polyhydric (divalent to 10-valent or higher) alcohol fatty acid (8 to 24 carbon atoms) ester, fatty acid (8 to carbon atoms)
24) Alkanolamide, (poly) oxyalkylene (C2-8) alkyl (C1-22) phenyl ether, (poly) oxyalkylene (C2-8)
Alkyl (8-24 carbon atoms) amine, alkyl (8-24 carbon atoms) dialkyl (1-6 carbon atoms) amine oxide, cationic surfactant [quaternary ammonium salt type and amine salt type], Amphoteric surfactants [betaine-type amphoteric surfactants and amino acid-type amphoteric surfactants] and polymer-type emulsifying dispersants [polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, polyacrylic] Carboxyl group-containing (co) polymers such as acid soda and Mn = 1,000
To 50,000, those described in JP-A-11-193305, and the polymer-type dispersants having a urethane bond or an ester bond described in JP-A-7-133423 and JP-A-8-120041. ]
Is mentioned.

Preferred among these emulsifiers are:
A polymer type emulsifying dispersant and a nonionic surfactant are more preferable, and a polymer type emulsifying dispersant having a urethane bond or an ester bond described in the above publication is more preferable.

Preferred among the water-dispersed resin binders of the urethane resin are self-emulsifying resins from the viewpoint that the amount of the surfactant in the aqueous phase can be reduced.

The constituent components of the polyester resin (E) include polyols and polycarboxylic acids. Examples of the polyols include the same ones as exemplified in the above (u25). Of these, preferred are aliphatic dihydric alcohols, aliphatic trihydric alcohols, aliphatic tetrahydric alcohols, and combinations of two or more of these (particularly, combinations of dihydric alcohols with trihydric alcohols and / or tetrahydric alcohols). More preferred are neopentyl glycol, 2-butyl-2-ethyl-1,3-
A combination of a dihydric alcohol selected from propanediol and 1,6-hexanediol with trimethylolpropane and / or pentaerythritol. When used in combination, the mass ratio of dihydric alcohol to trihydric alcohol and / or tetrahydric alcohol is (99.5: 0.
5) to (70:30), especially (98: 2) to (80: 2)
0) is preferred. As polycarboxylic acids, those having 2 to 2 carbon atoms
10 aliphatic or cycloaliphatic dicarboxylic acids [eg oxalic acid, succinic acid, malonic acid, adipic acid, glutaric acid,
Azelaic acid, sebacic acid, hexahydrophthalic acid, nadic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid and the like]; an aromatic dicarboxylic acid having 8 to 18 carbon atoms [for example, phthalic acid, isophthalic acid, terephthalic acid and the like] An aliphatic or alicyclic polycarboxylic acid having 8 to 18 carbon atoms and having 3 to 4 or more valences [for example, methylcyclohexentricarboxylic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, etc.];
18 trivalent or higher polyvalent aromatic carboxylic acids [e.g., trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, etc.]; their ester-forming derivatives [e.g., acid anhydrides, lower alkyls (carbon number 1 to
4) Ester and the like], and a combination of two or more of these. Of these, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids, tri- or higher-valent or higher aromatic polycarboxylic acids (anhydrides), and combinations of two or more of these. Dicarboxylic acids, aromatic divalent to tetravalent carboxylic acids and combinations thereof are particularly preferred, and aromatic polycarboxylic acids selected from adipic acid and / or sebacic acid and isophthalic acid, terephthalic acid and (trimellitic anhydride) are particularly preferred. Combined use with acid [mass ratio (20-50) :( 80-50)].

The production method of (E) is not particularly limited, and it can be produced by emulsifying a polyester obtained by a usual esterification method or transesterification method. In the esterification or transesterification method, a catalyst and / or a solvent usually used for a polyesterification reaction may be used, if necessary, at a reaction temperature of 100 to 250 ° C. As the catalyst, for example, dibutyltin dilaurate, tin octylate,
Examples of the solvent such as paratoluenesulfonic acid and lithium naphthenate include aromatic solvents [toluene, xylene and the like] and ketone solvents [acetone, methyl ethyl ketone, methyl isobutyl ketone and the like].

The method of producing the water-dispersed resin binder of (E) is not particularly limited. However, when producing the self-emulsifying type aqueous dispersion of (E), the active agent of the above-mentioned (d) is used as a polyol. It can be produced by using a compound having a hydroxyl group as a hydrogen atom-containing group (eg, polyethylene glycol, dialkylol alkanoic acid, sulfonic acid diol) in combination. Further, it can be produced by using a polycarboxylic acid (d1) having an anionic group other than carboxylic acid (eg, sulfoisophthalic acid (salt) and an ester-forming derivative thereof) as a polycarboxylic acid. The preferred content of (d) in the self-emulsifying type (E) water-dispersed resin binder is the same as in the case where the synthetic resin is (U). In the case of the emulsifier emulsification type, the emulsifier can be produced in the same manner as in the case of (U) using the emulsifiers mentioned in the method for producing the emulsifier emulsification type of (U).

Among the water-dispersed resin binders of (E), the self-emulsifying type is preferred from the viewpoint that the amount of the surfactant in the aqueous phase can be reduced.

As the polyamide resin (M), a polyvalent carboxylic acid (eg, adipic acid, terephthalic acid, phthalic acid, trimellitic acid) and a polyvalent amine (eg, hexamethylenediamine, tetramethylenediamine, diethylenetriamine) are used as a solvent. And a resin obtained by dehydration-condensation in toluene or xylene or in the absence of a solvent.

Examples of the resin component of the water-dispersed ring-opening polymer resin binder (B3) of the present invention include epoxy resins and alkylene oxide resins.

Examples of epoxy resins include polyhydric phenols (bisphenol A, hydrogenated bisphenol A, phenol novolak, etc.), polyhydric amines (hexamethylene diamine, tetramethylene diamine, diethylene triamine, etc.) and polycarboxylic acids (adipic acid, Terephthalic acid,
Examples thereof include a resin obtained by reacting epichlorohydrin with phthalic acid and trimellitic acid in the presence of an alkali catalyst, and an epoxy resin described in US Pat. No. 5,238,767.

The alkylene oxide resin is obtained by ring-opening polymerization of AO having 2 to 12 carbon atoms (EO, PO, butylene oxide, tetrahydrofuran, styrene oxide, etc.) in the presence of an alkali or an acid catalyst. Can be If necessary, the polymerization can be carried out in the presence of a starting material (alcohols or amines having 1 or 2 to 6 active hydrogen atoms).

In order to adjust the gel content (described later) of (B2) or (B3), a crosslinking agent (an aldehyde-containing compound such as formaldehyde or glyoxal, a hydrazine or hydrazide-containing compound, an oxazoline or an oxazolidine-containing compound) is added to a resin. 0.01 to 1
0 mass%, preferably 1 to 5 mass% can be used.

In the method for producing the aqueous dispersion of (M) or (B3), the resin component should be 10 μm or less, preferably 3 μm or less.
m or less by a ball mill or the like, followed by dispersing in water in which a protective colloid such as polyvinyl alcohol or polyacrylate has been dissolved, and dissolving the resin component in a solvent to form a protective colloid such as polyvinyl alcohol or polyacrylate. 10 μm or less, preferably 3 μm, using a high-pressure homogenizer or a vortex, etc. in the dissolved water.
m or less, and then distilling off the solvent. In these cases, the amount of the surfactant in the aqueous phase of the water-dispersed resin binder (B2) or (B3) is substantially not contained, or the amount is 0.1% as in the case of the aqueous latex in (B1). It is preferably at most 0.01 mmol / g (resin).

The resin other than the epoxy resin in (B) of the present invention preferably has a weight average molecular weight of 1,000 or more, more preferably 10,000 to 1, by GPC method.
Million or more. When (B) is an epoxy resin, the weight average molecular weight is preferably 300 or more, and more preferably 300 to 2,000. The weight average molecular weight is a weight average molecular weight obtained by measuring only a soluble component excluding an insoluble component in a gel content measurement described later.

The glass transition temperature (Tg) of (B)
Is usually -80 to 80C, preferably -50 to 50C. Tg was measured by flowing (B) into a glass mold.
This is a value obtained by measuring the film having a thickness of about 0.3 mm obtained by drying under reduced pressure at 8 ° C. for 8 hours under a condition of 20 ° C./min under nitrogen using a differential scanning calorimeter (DSC).

The gel content of (B) is usually from 5 to 95% by weight, preferably from 30 to 80% by weight. The gel content is the content of the toluene-insoluble component in the dried resin, and (B) was poured into a glass mold having a thickness of 1 mm to obtain a gel.
After drying under reduced pressure at ℃ for 24 hours, about 1 g of the obtained film was precisely weighed, left to dissolve in 400 ml of toluene for 48 hours, filtered with a filter paper of known weight, dried under the above conditions, and precisely weighed. It is a calculated value. Gel content (%) = [weight of toluene-insoluble matter on filter paper / weight of film before dissolving in toluene] × 100

The average particle size of (B) (arithmetic average; measured by laser Doppler method) is usually 0.02 to 10 μm, preferably 0.1 to 2 μm, more preferably 0.1 to 1 μm.
μm.

The solid content of (B) is usually 10 to 90% by weight, preferably 30 to 70% by weight, and the pH is usually 3 to 70% by weight.
-12, preferably 6-10.

In the water-dispersed resin binder (B),
What is used as a dispersion medium is usually water, a hydrophilic organic solvent [for example, a monohydric alcohol (eg, methanol, ethanol, isopropanol), a glycol (eg, ethylene glycol, propylene glycol, diethylene glycol)] or a trivalent or higher alcohol ( Glycerin, etc.), cellosolves (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.)
Etc.]. Among these, water is preferred, and when a hydrophilic organic solvent is used in combination, the amount of the hydrophilic organic solvent is usually preferably 10% by weight or less based on the total amount of the dispersion medium.

In the binder of the present invention, the weight ratio of (A) in terms of solid content is preferably 0.001 to 30%, more preferably, based on the total weight (solid content) of (A) and (B). 0.005 to 20%. (A) is 0.001%
If it is above, the thermo-reversible thickening is easily exerted, and if it is 30% or less, the viscosity of the binder at 25 ° C. does not become too high and it is easy to handle, so that it is preferable.

The binder in the present invention comprises a thermoreversible thickener (A) and a water-dispersed resin binder (B). If necessary, a known weight average molecular weight of 100 may be used.
It may contain 0 to 20,000,000 water-soluble polymer (C). Here, the water-soluble polymer has a solubility in water at 25 ° C. of 5% by weight or more, and specific examples thereof include polyvinyl alcohol and a modified product thereof (ethylene / ethylene).
Vinyl acetate = 50-80 mol% of vinyl acetate units of copolymer in a molar ratio of 2 / 98-30 / 70, 1-50 mol% of polyvinyl alcohol partially acetalized polyvinyl alcohol, etc.), starch and modified products thereof (Oxidized starch, phosphated starch, cationized starch, etc.), cellulose derivatives (carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, etc.), (meth) acrylamide polymer, (meth) acrylamide-
(Meth) acrylate copolymer, (meth) alkyl acrylate- (meth) acrylate copolymer, styrene-maleate copolymer, Mannich modified polyacrylamide, formalin condensation type resin (urea -Formalin resin, melamine-formalin resin, etc.), polyamide polyamine or dialkylamine-epichlorohydrin copolymer, polyethyleneimine, casein, soybean protein, synthetic protein, and mannangalactan derivative. Examples of the above-mentioned salts include alkali metal (sodium, potassium, lithium) salts, ammonium salts, organic amines (monomers having an alkyl group having 1 to 12 carbon atoms,
Di- or trialkylamine) salts, and quaternary ammonium salts (having an alkyl group having 1 to 8 carbon atoms, and the four alkyl groups may be the same or different). The content of the water-soluble polymer is usually 0 to 100 parts by weight, preferably 0.1 to 30 parts by weight, per 100 parts by weight of the total solid content of (A) and (B).

The solids content of the binder of the present invention [total of (A), (B) and optionally used (C)] is as follows:
It is usually 0 to 100 parts by weight, preferably 0.1 to 100 parts by weight, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total solid content of (A) and (B).

The dispersion of the molding material of the present invention contains the binder of the present invention and a powdered ceramic and / or a powdered metal. The particle size of the powder ceramic and powder metal is usually 100 μm or less, preferably 0.1 μm or less.
A powder having a particle size of from 01 to 30 μm, more preferably from 0.1 to 10 μm, may be mentioned. As powder ceramics, alumina, silica, zirconia, barium titanate, aluminum titanate, titanium oxide, ferrite, silicon nitride,
Examples include powders such as boron nitride, aluminum nitride, molybdenum disilicide, and silicon carbide, and mixtures of two or more thereof. Powder metal includes iron powder (carbonyl iron powder, atomized iron powder, reduced iron powder, etc.) nickel powder (carbonyl nickel powder, etc.), aluminum powder, copper powder, titanium powder, zirconium powder, zinc powder, chromium powder, molybdenum powder , Tungsten powder, beryllium powder, germanium powder, and other alloy powders (iron-nickel alloy powder, stainless steel powder,
Iron-silicon alloy powder, iron-boron alloy powder, etc.) and mixtures of two or more thereof. In addition to these, non-metallic powders such as silicon powder and boring powder can be included. Mixtures of powdered ceramics and powdered metals (tungsten carbide-cobalt, aluminum oxide-aluminum, etc.) can also be used. Examples of the mixture include a mixture of powder ceramic and powder metal and an alloy of powder ceramic and powder metal.

In the molding material dispersion of the present invention,
The binder of the present invention is usually used in an amount of 1 to 2 in terms of solid content with respect to 100 parts by weight of powder ceramic and / or powder metal.
0 parts by weight, preferably 5 to 10 parts by weight are used. If it is added in an amount of 1 part by weight or more, the strength of the molded article can be sufficiently exhibited. If the amount is 20 parts by weight or less, the deformation of the molded body after sintering is small, and cracks are less likely to occur.

Further, a deflocculant, a lubricant, a plastic dispersant, a drying aid and the like may be added to the molding material dispersion as required. Examples of peptizers include metal hydroxides such as sodium hydroxide and lithium hydroxide, sodium salts such as sodium silicate, sodium carbonate and sodium phosphate, lithium salts such as lithium carbonate, and ammonium salts such as ammonium oxalate. No. The amount of peptizer added is 0 to 3 parts by weight, preferably 0.1 to 0. 0 parts by weight, based on 100 parts by weight of the powdered ceramic and / or powdered metal.
5 parts by weight. Examples of the lubricant include hydrated magnesium silicate gel, stearate salts such as magnesium stearate and barium stearate, paraffin emulsion, wax emulsion having a melting point of 100 ° C. or lower, and cellulose acetate. The amount of the lubricant added is 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the powder ceramic and / or the powder metal. Examples of the plastic dispersant (which acts as both a plasticizer and a dispersant) include polyhydric alcohols such as glycerin and propylene glycol. The amount of the plastic dispersant added is 0 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the powdered ceramic and / or the powdered metal. Examples of the drying aid include carbonates such as ammonium carbonate and ammonium bicarbonate. The addition amount of the drying aid is 0 to 1 part by weight, preferably 0.1 part by weight, based on 100 parts by weight of the powder ceramic and / or the powder metal.
1 to 0.5 parts by weight. The total amount of these additives used is usually 0 to 20 parts by weight, preferably 0.1 to 1 part by weight, per 100 parts by weight of the powdered ceramic and / or powdered metal.
0 parts by weight.

The molding material dispersion of the present invention has a solid content (including the above-mentioned additives) of usually 60 to 90% by weight, preferably 70 to 80% by weight, and is in the form of an aqueous dispersion slurry.

The molding material dispersion of the present invention includes a method in which a binder is prepared in advance and then a powder ceramic and the like are blended, and a method in which the components of the binder are blended and the dispersion is adjusted at the same time. It may be a method. Specifically, for example,
The following methods are mentioned. Conventionally, a thermoreversible thickener (A), a water-dispersible resin binder (B) and, if necessary, a water-soluble polymer (C) are added at a temperature lower than the transition temperature (T ° C.) of (A). Known mixers (Satake-type stirrer, propeller plunger, etc.)
To prepare a binder, and then add the powdered ceramic and / or powdered metal and, if necessary, other additives, and mix them with a mixer. (A), (B), (C),
Powder ceramic and / or powder metal, and other additives are each independently compounded at a temperature equal to or lower than the transition temperature (T ° C.) of (A), and the order of charging may be any. A method in which powder ceramic and / or powder metal and, if necessary, (C) or other additives are blended during the production of (A) or (B).

Normally, after the dispersion prepared as described above is further finely dispersed by a ball mill or the like,
After filtering through a filtration device (such as a stainless steel mesh) of ~ 400 mesh, defoaming is performed under reduced pressure to obtain a molding material dispersion.

As a method for molding and producing such molded articles from the molding material dispersion, molding methods such as a slurry casting method, a doctor blade method, a cold extrusion method and a dry pressing method can be mentioned. Specifically, the molding material dispersion liquid is transferred to a mold, a casting machine, an auger machine or a pressure press machine in accordance with each molding method, and molded into a predetermined shape. Immediately by a heating furnace such as a heating furnace, heat treatment and drying are performed at a transition temperature (T ° C.) or higher of (A). By increasing the viscosity of the binder of the present invention in this heat treatment and drying step,
Since shape retention is maintained, volume shrinkage due to drying is suppressed,
A ceramic and / or metal material with good dimensional stability is obtained.

The sintering of the compact is usually carried out under reduced pressure, normal pressure or increased pressure in an oxidizing, reducing or inert gas atmosphere.
00 to 2500 ° C, preferably 800 to 1200 ° C
And by holding it within 24 hours. When the molding material includes a metal material or a part of the metal material, degreasing may be performed before sintering. Degreasing after molding of the molded body,
Usually, under an oxidizing, reducing or inert gas atmosphere, under reduced pressure, normal pressure or pressurization, the temperature is usually 1 to 500 ° C / hr, preferably 1 to 200 ° C / hr at a heating rate of 200 to 500 ° C.
℃, 200 ~ 500 ℃ usually within 10 hours,
It is preferably carried out by holding for 5 hours or less.

The sintered body of the ceramic material thus obtained can be used as a capacitor, a semiconductor, a high dielectric and an IC.
Widely used in fields requiring dimensional stability, such as precision electronic materials such as packages, heat and wear resistant parts such as infrared rays, ultrasonic waves, sensors and minute squeeze rolls, minute bone filling agents, and minute tools such as minute drills. Available. Further, the metal material or the sintered body partially containing the metal material thus obtained can be widely used in fields such as electrode substrates of various secondary batteries and sintered high-speed steel for high-rigidity tools.

[0080]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the examples, parts are parts by weight and% is% by weight.

Production Example 1 (Thickener 1) 90 parts of morpholinoethyl methacrylate, 10 parts of methacrylic acid and 0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added to an ampoule, followed by freeze degassing. Thereafter, the mixture was sealed and polymerized at 50 ° C. for 8 hours to obtain “thickener 1” (transition temperature T ° C. = 65 ° C.).

Production Example 2 (Thickener 2) 100 parts of N-acryloylpyrrolidine and 2,2′-
Add 1 part of azobis (2,4-dimethylvaleronitrile) to the ampoule, freeze and deaerate, seal, polymerize at 50 ° C for 8 hours to obtain “thickener 2” (transition temperature T ° C = 56 ° C). Was.

Production Example 3 (Binder 1) A stirrer, a dropping cylinder, a nitrogen gas inlet tube and a thermometer were provided.
102 parts of water, 45 parts of styrene,
9 parts of tyl methacrylate, 4 parts of methacrylic acid, radical
As an emulsifier having a polymerizable group, bis (polycyclic phenol
Lioxyethylene ether) methacrylated sulfate
Terammonium salt [R in general formula (1) ¹Is a methyl group,
R^TwoAnd R^ThreeIs a styryl group or a polystyryl group and m +
n is 2 to 6 (5 on average), R^FourAnd R^FiveIs hydrogen,
Ar is a benzene ring, A is an ethylene group, M is ammonium
The sum of system, p and q is 23-25 (average 24)] 5
Parts, 1 part of sodium persulfate and lauryl mercaptan
After charging 0.2 parts and replacing the inside of the system with nitrogen gas while stirring,
37 parts of butadiene was press-fitted from a dropping cylinder and 3
The reaction was carried out for 0 hour and further at 85 ° C. for 5 hours. Then decompression
Strip the unreacted monomer under
By adjusting the pH to 9.5 with an aqueous solution of
Min 47.9%, emulsifier amount in aqueous phase 0.0008 mmol /
g (resin) of SBR resin latex (hereinafter referred to as “binder
-1 ").

Production Example 4 (Binder 2) Ammonium bis (polycyclic phenol polyoxyethylene ether) methacrylate sulfate as an emulsifier having a radical polymerizable group [In the general formula (1), R ¹ is a methyl group, R ^{2 is} R ³ is a benzyl group;
-6 (average of 5), R ⁴ and R ⁵ are hydrogen, Ar is a benzene ring, A is an ethylene group, M is ammonium, p and q
Of SBR resin latex having a solid content of 47.9% and an emulsifier amount of 0.0010 mmol / g (resin) in an aqueous phase in the same manner as in Production Example 3 except that 20 to 24 (average 22) was used. (Hereinafter referred to as "binder 2").

Production Example 5 (Binder 3) As a emulsifier having a radical polymerizable group, bis (polycyclic phenol polyoxyalkylene ether) methacrylated sulfate ammonium salt [In the formula (1), R ¹ is a methyl group, R ² and R ³ is a styryl group and a benzyl group; m + n is a total of 5 to 7 (6 on average); R ⁴ and R ⁵ are hydrogen; Ar is a benzene ring; A is an ethylene group and a propylene group having 18 to 20 ethylene groups; (Average 19),
Propylene group is 3 to 5 (on average, 4), M is ammonium, and the total of p and q is 20 to 24]. An SBR resin latex (hereinafter referred to as "binder 3") having an emulsifier amount of 0.0003 mmol / g (resin) was obtained.

Production Example 6 (Binder 4) A polymerizable emulsifier represented by the following formula (2) was used as an emulsifier having a radical polymerizable group, butyl methacrylate was used in place of styrene, and the amount of methyl methacrylate was 4
Acrylic resin latex having a solid content of 47.9% and an aqueous phase emulsifier amount of 0.0003 mmol / g (resin) in the same manner as in Production Example 3 except that butadiene injection was not performed. Binder 4 ").

[0087]

Embedded image

Here, Ar represents a phenylene group, and C ₉
H ₁₉ -is the p-position.

Production Example 7 (Binder 5) In a pressurized reaction vessel similar to that of Production Example 3, 102 parts of water, 15 parts of styrene, 37 parts of butyl methacrylate, 39 parts of methyl methacrylate, 4 parts of methacrylic acid, and a radical polymerizable group were added. As emulsifiers, bis (polycyclic phenol polyoxyethylene ether) methacrylated sulfate ammonium salt [in the general formula (1), R ² and R ³ are styryl groups and the number of substituents is 5 to 6 (average) 5.
5), R ⁴ and R ⁵ are hydrogen, Ar is a benzene ring, A is an ethylene group, p + q is a compound of 55 to 60 (58 on average)] 5 parts, 1 part of sodium persulfate and 0.2 part of lauryl mercaptan. After charging and replacing the inside of the system with nitrogen gas under stirring, the reaction was carried out at 50 ° C. for 30 hours and further at 85 ° C. for 5 hours. Then, the unreacted monomer was stripped under reduced pressure, and the pH was adjusted to 9.5 with an aqueous sodium hydroxide solution.
An acrylic resin latex of 018 mmol / g (resin) (hereinafter referred to as "binder 5") was obtained.

Production Example 8 (Binder 6) In a pressurized reaction vessel similar to that of Production Example 3, 102 parts of water, 45 parts of styrene, 20 parts of butyl methacrylate, 26 parts of methyl methacrylate, 4 parts of methacrylic acid, and a radical polymerizable group were added. As an emulsifier, 5 parts of sodium acryloyl polyoxypropylene (polymerization degree = 12) sulfate, 1 part of sodium persulfate and 0.2 part of lauryl mercaptan were charged, and the system was replaced with nitrogen gas under stirring, and then stirred at 50 ° C. for 30 minutes. The reaction was continued at 85 ° C. for 5 hours. The unreacted monomer was then stripped under reduced pressure, and the pH was adjusted to 9.5 with an aqueous sodium hydroxide solution to give a solid content of 47.9% and an emulsifier amount of 0.0080 mmol in the aqueous phase.
/ G (resin) of an acrylic-styrene resin latex (hereinafter referred to as "binder 6").

Examples 1 to 6 A stainless steel beaker was charged with 14 parts of a binder shown in Table 1 and 0.1 part of a 20% aqueous solution of a thickener, and mixed with a propeller plunger to obtain a binder. . To these binders were added 100 parts of easily sinterable fine-grained alumina having an average particle diameter of 2 μm (manufactured by Showa Light Metal Co., Ltd.), 4 parts of glycerin as a plastic dispersant, 2 parts of stearic acid as a lubricant and 30 parts of water, and 200 using a jar
The mixture was mixed at rpm for 30 minutes to obtain molding material dispersions of Examples 1 to 6.

Example 7 A stainless steel beaker was charged with 30 parts of water and 3 parts of polyvinyl alcohol (PVA-217: manufactured by Kuraray Co., Ltd.), heated to 70 to 90 ° C., and dissolved by stirring with a normal propeller type stirrer. After cooling to 30 ° C. or less,
4 parts and 0.1 part of a 20% aqueous solution of the thickener 1 were charged and mixed with a propeller plunger to obtain a binder. To this binder, 100 parts of easily sinterable fine-grained alumina (manufactured by Showa Light Metal Co., Ltd.) having an average particle diameter of 2 μm, 4 parts of glycerin as a plastic dispersant, and 2 parts of stearic acid as a lubricant were charged, and 30 parts were formed at 200 rpm using a propeller plunger. After mixing for 1 minute, the molding material dispersion of Example 7 was obtained.

Comparative Examples 1 and 2 In the same container as in Example 1, polyvinyl alcohol (PV
A-217: 7 parts of Kuraray Co., Ltd.) or methylcellulose (M-10000: Shin-Etsu Chemical Co., Ltd.) and 37 parts of water are charged.
Heat to 90 ° C, and in the case of methyl cellulose, 10 to 1
Cool at 5 ° C and dissolve with stirring with a normal propeller type stirrer.
Here, 100 parts of easily sinterable fine-grain alumina (manufactured by Showa Light Metal Co., Ltd.) having an average particle size of 2 μm, and glycerin 4 as a plastic dispersant
Parts and 2 parts of stearic acid as a lubricant were added and mixed at 200 rpm for 30 minutes using a propeller plunger to obtain molding material dispersions of Comparative Examples 1 and 2.

The dispersibility of the binder obtained in each of the examples and comparative examples and the shape retention and volume retention of the molding material dispersion were tested by the following evaluation methods. Table 1 shows the results.

Evaluation method of shape retention: Dispersion of molding material was measured with a blade-type sheet molding machine to obtain vertical, horizontal, and thickness = 10 cm × 10 cm.
A molded body having a size of × 3 mm was prepared and heat-treated with hot air at 80 ° C. to 90 ° C. for 3 minutes. The shape retention was evaluated by the following calculation formula. Shape retention (%) = ｛(thickness after heating / thickness before heating) × 1
00｝

Evaluation method of volume retention after sintering: The molded body produced by the evaluation of shape retention was sintered in an electric furnace at 1200 ° C. for 10 hours to obtain a sintered body. Measure the dimensions of the sintered body,
The apparent volume of the sintered body was calculated to determine the volume retention. Volume retention (%) = apparent volume after sintering / 15.7

Evaluation method of dispersibility in water: 50 g of ion-exchanged water was placed in a 100 ml beaker, and the temperature was adjusted to 25 ° C.
Using an electromagnetic stirrer with a length of 2 cm, under stirring (500 rpm
1 g of the binder was added to m), and the time until the whole became uniform was visually measured. However, polyvinyl alcohol was heated by heating ion-exchanged water to 70 to 90 ° C, and methylcellulose was evaluated by cooling ion-exchanged water to 10 ° C.

[0098]

[Table 1]

[0099]

The binder for a ceramic and / or metal material of the present invention can maintain good shape retention before and after sintering of a dispersion of a ceramic and / or metal material. The volume retention of the sintered body can be increased. Therefore, it is extremely effective for manufacturing minute parts made of ceramic and / or metal. Furthermore, since the binder of the present invention has good dispersibility in water and is easy to handle, the productivity can be improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 33:24) C04B 35/00 108 F term (Reference) 4G030 PA21 4J002 AA00W AB01Y AB04Y AB05Y AC02W AC03W AC07W AD00Y AD02Y BB15W BC04W BC05W BC07W BE02W BE02Y BE06Y BF02W BF03W BG00W BG01Y BG03Y BG072 BG12Y BG122 BG13Y BH01W BH01Y CC00Y CD13Y CL00Y CM01Y GT00

Claims (13)

[Claims] 1. A ceramic comprising a vinyl polymer-based thermoreversible thickener (A) whose hydrophilicity and hydrophobicity are reversibly changed at a transition temperature (T) of 30 ° C. or more and an aqueous dispersion resin binder (B). And / or a binder for metallic materials. 2. A thermo-reversible thickener (A) comprising a (co) polymer having a (meth) acrylate ester of an alkylene oxide adduct of a cyclic amine as an essential monomer, and a non-cyclic compound having 5 or more carbon atoms. (Co) polymer having (meth) acrylic acid ester of amine alkylene oxide adduct as essential monomer, and (co) polymer of (meth) acrylic acid amide of monoalkylamine or alkoxyalkylamine as essential monomer The polymer according to claim 1, which is at least one selected from the group consisting of a polymer and a (co) polymer having (meth) acrylamide of dialkylamine, dialkoxyalkylamine or cyclic amine as an essential monomer. Binder 3. The binder according to claim 1, wherein the water-dispersed resin binder (B) comprises a vinyl polymer resin. 4. The vinyl polymer resin is an acrylic resin, styrene-acrylic resin, styrene-butadiene resin, butadiene-acrylic resin, butadiene-acrylonitrile resin, vinyl acetate resin, ethylene-vinyl acetate resin. 4. The binder according to claim 3, wherein the binder is at least one resin selected from the group consisting of ethylene-propylene resin, polybutadiene resin, polyvinyl alcohol resin, styrene-maleic acid resin, and modified polystyrene resin. 5. The binder according to claim 1, wherein the amount of the surfactant in the aqueous phase of the aqueous dispersion resin binder (B) is 0.01 mmol / g (resin) or less. 6. The binder according to claim 1, wherein the water-dispersed resin binder (B) is a resin latex obtained by using a polymerizable emulsifier (D). 7. The polymerizable emulsifier (D) has the following general formula (1)
The binder according to claim 6, which is represented by the following formula: Embedded image Wherein Ar is an aromatic ring, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are monovalent hydrocarbon groups, and m
^At least one of ² and n R ³ is a hydrocarbon group having an aromatic ring. m and n are an integer of 0 or 1 to 4 in which m + n is 1 to 8, R ⁴ and R ⁵ are a hydrogen atom or a methyl group, M is a cation, A is an alkylene group having 2 to 4 carbon atoms, p and q represents 0 or an integer of 1 to 40. ] 8. The binder according to claim 1, wherein (A) is contained in a proportion of 0.001 to 30% by weight based on the total weight of the solid contents of (A) and (B). 9. Polyvinyl alcohol and a modified product thereof, starch and a modified product thereof, a cellulose derivative,
(Meth) acrylamide polymer, (meth) acrylamide- (meth) acrylate copolymer, alkyl (meth) acrylate- (meth) acrylate copolymer,
Styrene-maleate copolymer, Mannich-modified polyacrylamide, formalin condensed resin, polyamide polyamine or dialkylamine-epichlorohydrin copolymer, polyethyleneimine, casein, soybean protein, synthetic protein, and mannangalactan derivative The binder according to any one of claims 1 to 8, comprising at least one water-soluble polymer (C) selected from the group consisting of: 10. The content of the water-soluble polymer (C) is (A)
And 0.1 to 100 parts by weight of the total solid content of (B)
The binder according to claim 9, which is 100 parts by weight. 11. A molding material dispersion comprising the binder according to claim 1 and powdered ceramic and / or powdered metal. 12. A sintered body produced by sintering a molded body of the molding material dispersion according to claim 11. 13. A ceramic comprising a vinyl polymer-based thermoreversible thickener (A) whose hydrophilicity and hydrophobicity are reversibly changed at a transition temperature (T) of 30 ° C. or more and a water-dispersible resin binder (B). And / or a molding material dispersion containing a binder for a metal material is molded at a temperature lower than T ° C., and then heated to a temperature higher than a transition temperature to sinter.