JP3445238B2 - Cosmetic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a decorative material .

[0002]

2. Description of the Related Art Conventionally, (i) a vinyl chloride resin compounding agent containing a superabsorbent resin, a foaming agent and a polyolefin is applied to a base material as a decorative material for interior decoration for humidity control of wallpaper or the like, and then heated and foamed. Humidifying vinyl wall covering (Japanese Patent Laid-Open No. 62-231)
No. 740), and (ii) a cosmetic material having a moisture-absorbing / desorbing resin layer formed of a moisture-permeable urethane resin having a hydrophilic group in the molecule and activated clay, diatomaceous earth, a highly water-absorbing resin, etc.
No. 1-207854) is known.

[0003]

However, (i)
Is because there is not enough moisture permeability even if the wall material is moisture permeable,
It has poor moisture absorption and desorption properties, and cannot follow a change in humidity due to a change in temperature in a room, which may cause dew condensation. (Ii) is excellent in hygroscopicity, but has a low moisture release rate, so that when the room has low humidity, the room may further shift to a low humidity side and cause an overdry state.

[0004]

Means for Solving the Problems In view of the above problems, the present inventors have conducted intensive studies in order to obtain a moisture control cosmetic material having excellent moisture absorption / desorption properties and dew condensation prevention properties. Reached. That is, the present invention provides a cosmetic material substrate comprising the following water-absorbent resin dispersion (D), polyisocyanate (P) and
The solution obtained by mixing solvent, the impregnation and / or quotes Lee
For housing or comprising a humidity control resin layer made of a urethane resin (U) obtained by reacting after
It is a decorative material for furniture . Water-absorbent resin dispersion (D): The water-absorbent resin (B) polymerized and formed in (A) or its water-absorbing gel is dispersed in polyol (A) , and the dispersion is carried out .
(B) or the average particle diameter of the water-absorbing gel obtained is 0.
05~10μm der Ru absorbent resin dispersion.

The polyol (A) of the present invention includes polyether polyol, polyester polyol, polyether ester polyol, polyesteramide polyol, acrylic polyol, polyurethane polyol,
Epoxy polyols, epoxy-modified polyols, polymer polyols, polyhydroxyalkanes, oil-modified polyols, castor oil-based polyols, polyols whose main chain is composed of carbon-carbon bonds, etherified products in which the hydroxyl groups of the polyol are partially blocked with alcohols or carboxylic acids and At least one selected from the group consisting of esterified products and the like is included. These and other compounds include those described in "Polyurethane Resin Handbook" (editor: Keiji Iwata, Nikkan Kogyo Shimbun, published in 1987). Of these, polyether polyols, polyester polyols, polyether ester polyols, polyester amide polyols, acrylic polyols, polyurethane polyols, epoxy polyols, epoxy-modified polyols, polymer polyols, polyhydroxyalkanes, oil-modified polyols, castor oil-based polyols are preferred. And at least one selected from the group consisting of polyether polyols and polyester polyols.

[0006] Examples of the polyether polyol include a polyoxyalkylene polyol. As the polyoxyalkylene polyol, a compound having at least 2 (preferably 2 to 8) active hydrogen atoms (for example, a polyhydric alcohol, a polyhydric phenol, an amine, a polycarboxylic acid, phosphoric acid, or the like) has an alkylene oxide. Compounds with added structures and mixtures thereof are mentioned. Preferred among these are polyhydric alcohols. Examples of the polyhydric alcohol include C2 to C20 dihydric alcohol. Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol,
Alkylene glycols such as neopentyl glycol; dialkylene glycols such as diethylene glycol (having 1 to 20 carbon atoms in the alkylene group); diols in which the above diols have undergone a jump reaction with methylene chloride or the like; cyclohexanediol, cyclohexanedimethanol;
Xylylene glycol and diols having a cyclic group described in JP-B No. 45-1474; trihydric alcohols include glycerin, trimethylolpropane, trimethylolethane, hexanetriol and the like; tetrahydric alcohols Pentaerythritol, methylene glycoside, diglycerin; 5
Examples of the alcohol having a valency or higher include pentitol such as adonitol, arabitol, and xylitol; hexitol such as sorbitol, talitol and dulcitol; saccharides such as polyhydric alcohols such as glucose, mannose, fructose, and sorbose; , Oligosaccharides such as lactose and raffinose; glycols such as ethylene glycol and propylene glycol; triols such as glycerin, trimethylolpropane and hexanetriol; glycosides (such as glucoside); polyglycerins such as triglycerin and tetraglycerin; dipentaerythritol; Polypentaerythritol such as tripentaerythritol; tetrakis (hydroxymethyl) cyclohexanol

Examples of the polyhydric phenol include dihydric phenols having 6 to 40 carbon atoms, for example, monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A and bisphenol sulfone; condensation of phenol and formaldehyde (Novolak), for example, polyphenols described in US Pat. No. 3,265,641 and the like. Examples of the amines include ammonia, aliphatic amines having 1 to 8 carbon atoms and 1 to 20 carbon atoms, alicyclic amines, heterocyclic amines, and aromatic amines. Examples of the aliphatic amine include alkanolamines such as mono-, di- and tri-ethanolamine, isopropanolamine and aminoethylethanolamine; alkylamines having 1 to 20 carbon atoms; alkylenediamines having 2 to 6 carbon atoms such as ethylenediamine Propylenediamine, hexamethylenediamine; polyalkyleneamines such as diethylenetriamine and triethylenetetramine. Examples of the alicyclic amine include isophoronediamine, cyclohexylenediamine, dicyclohexylmethanediamine, and the like. Examples of the heterocyclic amine include aminoethylpiperazine and others described in JP-B-55-21044. Examples of the aromatic amine include aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, and diphenyletherdiamine.

As the alkylene oxide (hereinafter abbreviated as AO) to be added to the active hydrogen atom-containing compound, alkylene oxides having 2 to 4 carbon atoms, for example, ethylene oxide and propylene oxide (hereinafter referred to as EO,
PO), 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, and the like, and combinations thereof. Preferred are PO and combinations of EO and PO. The form of addition of the alkylene oxide is not particularly limited, and examples thereof include block addition and random addition, and the following addition modes. (I) Those added in the order of AO-EO (tipped) (ii) Those added in the order of AO-EO-AO-EO (balanced) (iii) Those added in the order of AO-EO-AO ' (Iv) block adducts such as those added in the order of PO-EO-PO (active secondary); and (v) random adducts in which EO and AO 'are mixed and added (vi JP-A-57-209920). (Vii) Random-block adducts such as those added in the order described in JP-A-53-13700, etc. AO ′ in (i) to (vii) above is an alkylene oxide other than EO. Represent.

The method for producing the polyoxyalkylene polyol may be a conventionally known method. As the catalyst to be used, in addition to an alkali catalyst (potassium hydroxide, sodium hydroxide, etc.), a complex metal such as BF ₃ complex, zinc hexacyanocobaltate, etc. Cyanide complexes and the like can be used. Also, PO, 1,
When an alkylene oxide such as 2-butylene oxide is added using these catalysts, the primary hydroxylation ratio of terminal hydroxyl groups is extremely low (for example, usually 2% or less when potassium hydroxide is used), and most terminals are secondary hydroxyl groups. is there. In this case, triphenylborane, triphenylaluminum,
When a ring-opening catalyst such as tris (pentafluorophenyl) borane or tris (pentafluorophenyl) aluminum is used, 40% or more of the terminal hydroxyl groups are primaryized. It is also possible to use such a polyoxyalkylene polyol.

[0010] Ether compounds (eg, methyl ether, isopropyl ether, phenyl ether, etc.) and ester compounds (eg, acetic acid ester and benzoic acid ester) in which hydroxyl groups of the polyoxyalkylene polyol are partially blocked with an alcohol or a carboxylic acid are further included. No. Examples of the polyester polyol include a reaction product of a polyhydric alcohol and a polybasic acid. Examples of the polyhydric alcohol include the same as those described for the polyether polyol. As polybasic acids, 2 to 8
Having a carbon number of 3 to 20, such as succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, and these acids And anhydrides. Further, polyester polyols obtained by subjecting lactones such as caprolactone and methylcaprolactone to ring-opening polymerization with glycol or the like are also suitable examples. These are obtained by reacting at 80 to 200 ° C.

Examples of polyether polyester polyols include those obtained by subjecting the above polyether to a raw material and subjecting it to the above-mentioned polybasic acid for a polyesterification reaction, and ring-opening copolymerization of an epoxide compound and an acid anhydride. Compounds having both segments of polyether and polyester in one molecule obtained by the reaction can be exemplified. Examples of the polyesteramide polyol include, for example, an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine, xylylenediamine, hydrogenated xylylenediamine, ethanolamine, or propanolamine in the molecule during the polyesterification reaction. It is obtained by using those having 5 and having 2 to 6 amino groups or 2 to 6 amino groups such as amine or amino alcohol having 2 to 20 carbon atoms.

Acrylic polyols can be synthesized by copolymerizing a polymerizable monomer having one or more hydroxyl groups in one molecule with another monomer copolymerizable therewith. Refers to known acrylic polyols.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (C2-6) (meth) acrylates, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid Monohydroxyl ester such as 2-hydroxybutyl,
Poly (2-octavalent) hydroxyalkyl (C2-20) such as trimethylolpropane monoacrylate
Poly (1- to 7-valent) (meth) acrylates and the like can be mentioned. Examples of the copolymerizable monomer include (meth)
Acrylic acid and its methyl, ethyl, propyl, butyl, 2-ethylhexyl esters, maleic acid, fumaric acid, itaconic acid and their corresponding esters, styrene, α-methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile, etc. And the like.

The polyurethane polyol includes, for example, a reaction product of a polyol and a polyisocyanate having a terminal hydroxyl group. Examples of the polyol include the same as the above-mentioned polyether polyol, polyester polyol, polyester ether polyol, polyesteramide polyol and polyhydric alcohol. Examples of the polyisocyanate include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group) (for example, 2,4- and / or 2,6-
Tolylene diisocyanate (TDI), crude TDI,
2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [condensation product of crude diaminophenylmethane} formaldehyde and aromatic amine (aniline) or a mixture thereof: diaminodiphenylmethane and a small amount ( A phosgenate of a mixture with a trifunctional or higher polyamine (for example, 5 to 20% by weight): polyallyl polyisocyanate (PAPI) or the like]; aliphatic polyisocyanate having 2 to 18 carbon atoms (for example, hexamethylene diisocyanate, lysine diisocyanate, etc.) Alicyclic polyisocyanate having 4 to 15 carbon atoms (eg, isophorone diisocyanate, dicyclohexylmethane diisocyanate);
5 aromatic aliphatic polyisocyanates (eg, xylylene diisocyanate); and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretonimine group, isocyanurate group, Oxazolidone group-containing modified products); and JP-A-61-7
No. 6517, other polyisocyanates described above;
And mixtures of two or more of these. Further, a part of the active hydrogen of the polyol is ethylenediamine, propylenediamine, hexamethylenediamine, xylylenediamine, bisaminomethylcyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, ethanolamine, or propanolamine. A product obtained by reacting with an amino compound can also be used as the polyurethane polyol. The ratio of active hydrogen to isocyanate is preferably equivalent to 2:
1 to 100: 99, more preferably 2: 1 to 50: 4
9 In the urethanization reaction, a urethanization catalyst described later is used.

The epoxy polyol includes, for example, a condensation type epoxy resin obtained by reacting the above-mentioned polyhydric phenol compound or its hydride with epichlorohydrin. In addition, for example, a fatty acid and an epoxy resin are reacted. Epoxy ester resins obtained by reaction with alkanolamines and modified epoxy resins obtained by reaction with alkanolamines can also be used.

Examples of the polymer polyol include those obtained by polymerizing one or more of the above-mentioned vinyl monomers in a polyol (the above-mentioned polyether polyol, polyester polyol, etc.) and finely dispersing the polymer. After completion of the polymerization, it is desirable to remove impurities such as organic solvents, decomposition products of the polymerization initiator, and unreacted monomers by conventional means. The polymer polyol thus obtained is usually 30 to 70%,
Preferably 40-60%, more preferably 45-55.
%, Particularly preferably 50-55% of the total monomer polymerized,
That is, it is a translucent or opaque white or tan dispersion in which the polymer is dispersed in a polyol. Castor oil-based polyols include castor oil and modified castor oil (castor oil modified with polyhydric alcohols such as trimethylolpropane and pentaerythritol). Examples of the polyoxyalkane include, for example, a polymer having a main chain composed of only carbon and having 2 to 30 hydroxyl groups, a vinyl acetate homopolymer or another copolymer having an ethylene bond. Examples thereof include a saponified copolymer of a monomer and a hydrogenated polybutadiene polyol. Further, as (A), a low molecular weight polyol (for example, the above-mentioned polyhydric alcohol, preferably a liquid at room temperature) may be used in combination. (A) has a molecular weight of usually 100 to 100,000, preferably 500 to 50000, and more preferably 1,000.
0 to 20,000.

The water-absorbent resin dispersion (D) in the present invention
Is obtained by dispersing a water-absorbent resin (B) polymerized in (A) or a water-absorbing gel thereof in a polyol (A). Examples of (B) include those formed by polymerization of a water-soluble vinyl monomer or a precursor thereof and a crosslinking agent. In the present invention, the water-soluble vinyl monomer includes at least one carboxylic acid (salt) group, sulfonic acid (salt) group, phosphoric acid (salt) group, hydroxyl group, amide group, amino group, quaternary ammonium base and the like. Examples include a polymerizable monomer having a hydrophilic group.

Examples of the monomer having a carboxylic acid (salt) group include (meth) acrylic acid, (anhydride) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itacone acid,
Carboxyl group-containing vinyl monomers such as itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, and cinnamic acid; and alkali metal salts (sodium salt, potassium salt, etc.) and alkaline earth thereof Metal salt (calcium salt, magnesium salt, etc.), amine salt, ammonium salt and the like can be mentioned. Examples of the monomer having a sulfonic acid (salt) group include aliphatic or aromatic vinyl sulfonic acids (salts) [eg, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, (meth) acryl sulfonic acid ( Sulfopropyl (meth) acrylate, 2
-Hydroxy-3- (meth) acryloxypropylsulfonic acid) and salts thereof (eg, alkali metal salts, ammonium salts, and amine salts). Phosphoric acid (salt)
Examples of the monomer having a group include, for example, hydroxyalkyl (meth) acrylate monoester [eg, 2-
Hydroxyethyl (meth) acryloyl phosphate,
Phenyl-2-acryloyloxyethyl phosphate, etc.), alkylphosphonic acid (meth) acrylates [eg, 2-acryloyloxyethylphosphonic acid (salt)
Etc.].

Examples of the monomer having a hydroxyl group include, for example,
Monoethylenically unsaturated alcohols such as (meth) allyl alcohol and the like; monoethylenically unsaturated esters or ethers of polyols such as alkylene glycol, glycerin, polyoxyalkylene glycol and the like [for example, hydroxyethyl (meth) acrylate] ,
Hydroxypropyl (meth) acrylate, triethylene glycol (meth) acrylate, poly-oxyethylene-oxypropylene (random or block) glycol mono (meth) allyl ether (terminal hydroxyl group may be etherified or esterified) Etc.]. Examples of the monomer having an amide group include (meth) acrylamide and N-alkyl (meth)
Acrylamide (for example, N-methylacrylamide and the like), N, N′-dialkylacrylamide [for example,
N, N'-dimethylacrylamide, N, N'-di-n
-Or i-propylacrylamide etc.], N-hydroxyalkyl (meth) acrylamide [for example, N-
Methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc .; N, N′-dihydroxy (meth) acrylamide [eg, N, N′-dihydroxyethyl (meth) acrylamide, etc.], vinyl lactams [eg, N-vinylpyrrolidone, etc.].

Examples of the monomer having an amino group include monoethylenically unsaturated mono- or di-carboxylic acid containing amino group-containing ester, dialkylaminoalkyl ester, dihydroxyalkylaminoalkyl ester, morpholinoalkyl ester and the like. Dimethylaminoethyl (meth) acrylate, diethylamino (meth) acrylate, morpholinoethyl (meth) acrylate, dimethylaminoethyl fumarate, etc.], heterocyclic vinyl compounds [eg, 2-vinylpyridine,
-Vinylpyridines such as N-vinylpyridine, N-vinylimidazole, etc.].
Examples of the monomer having a quaternary ammonium group include tertiary amino acids such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, and diallylamine. And quaternized amine group-containing vinyl monomers (quaternized using a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, and dimethyl carbonate).

The precursor includes a vinyl monomer which becomes water-soluble by hydrolysis, for example, a monomer having at least one hydrolyzable group (ester group, nitrile group, amide group, etc.). Examples of the monomer having an ester group include lower alkyl (C1-C3) esters of monoethylenically unsaturated carboxylic acids [for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Ethylhexyl (meth) acrylate, etc.] and esters of monoethylenically unsaturated alcohols [eg, vinyl acetate, (meth) allyl acetate, etc.]. Examples of the monomer having a nitrile group include (meth) acrylonitrile and the like. Of these, water-soluble vinyl monomers are preferred. More preferred are monomers having a carboxylic acid (salt) group and a sulfonic acid (salt) group, and particularly preferred are acrylic acid and / or acrylate. These polymerizable monomers may be used alone or, if necessary, in combination of two or more.

In (B), other vinyl monomers can be used together with the water-soluble vinyl monomer, if necessary. Other vinyl monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, hydroxystyrene, and chlorostyrene; unsaturated nitriles such as (meth) acrylonitrile; and alkyl groups having 1 to 30 carbon atoms. (Meta)
(Meth) acrylic esters such as alkyl acrylates and hydroxypolyoxyalkylene ether mono (meth) acrylates; olefins such as ethylene and propylene; fluorinated vinyl monomers such as perfluorooctylethyl methacrylate and perfluorooctylethyl acrylate Monomers; vinyl monomers containing amino groups such as diaminoethyl methacrylate and morpholinoethyl methacrylate; and vinyl-modified silicon at both terminals. Of these, aromatic vinyl monomers, unsaturated nitriles and (meth) acrylates are preferred from the viewpoint of copolymerizability and dispersion stability.

In the present invention, the crosslinking agent for obtaining (B) includes a copolymerizable crosslinking agent and other crosslinking agents. As the copolymerizable crosslinking agent, a compound having two polymerizable double bonds; and at least one functional group having at least one polymerizable double bond and being reactive with the water-soluble monomer. And compounds having the same.

Examples of the compound having two polymerizable double bonds include the following. Bis (meth) acrylamide; N, N-alkylene (c1-c6) bis (meth) acrylamide (for example, N, N-methylenebisacrylamide). Polyesters of polyols or polyepoxides with unsaturated mono- or polycarboxylic acids, such as those derived from ethylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol or cyclohexene diepoxide and (meth) acrylic acid or maleic acid Ruji
Or tri- (meth) acrylate and di- or trimaleate. Carbamyl ester: polyisocyanate [tolylene diisocyanate, hexamethylene diisocyanate,
4,4'-diphenylmethane diisocyanate and N
A carbamyl ester obtained by reacting a CO group-containing prepolymer (obtained by reacting the above polyisocyanate with an active hydrogen atom-containing compound) and hydroxyethyl (meth) acrylate. Polyvinyl compounds: divinylbenzene, divinyltoluene, divinylxylene, divinylether, divinylketone, trivinylbenzene and the like.

Di- or poly- (meth) allyl ether of polyol: Poly (meth) of polyols [alkylene glycol, glycerin, polyalkylene glycol, polyalkylene polyol, carbohydrate, etc.]
Allyl ethers such as polyethylene glycol diallyl ether, allylated starch and allylated cellulose. Polyallyl esters of polycarboxylic acids: diallyl phthalate, diallyl adipate and the like. Esters of unsaturated mono- or polycarboxylic acids with mono (meth) allyl etherified polyols: (meth) acrylates of polyethylene glycol monoallyl ether. Polyallyloxyalkanes: tetraallyloxyethane and the like.

Having at least one polymerizable double bond,
And at least one functional group reactive with the water-soluble monomer.
In the compound having two or more carboxyl groups, sulfonic acid groups, phosphoric acid groups, hydroxyl groups or hydroxyl groups in the water-soluble monomer, a hydroxyl group,
Epoxy groups and tertiary amine groups are exemplified. Examples of the compound include a hydroxyl group-containing ethylenically unsaturated compound [eg, N-methylol (meth) acrylamide and the like];
Epoxy group-containing ethylenically unsaturated compound [eg glycidyl (meth) acrylate etc.]; tertiary amino group-containing ethylenically unsaturated compound [eg dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate] And the like. Other crosslinking agents include polyvalent metal salts such as calcium oxide and zinc diacetate. Among these crosslinking agents, copolymerizable crosslinking agents are preferred, and N, N-methylenebisacrylamide, ethylene glycol diacrylate, trimethylolpropane triacrylate and tetraallyloxyethane are particularly preferred.

In the present invention, the water absorbent resin dispersion (D)
Can be obtained by the following method. The water-soluble vinyl monomer or its precursor is simply referred to as (1), the other vinyl monomer is referred to as (1 ′), and the crosslinking agent is referred to as (2). A liquid obtained by mixing (A) and, if necessary, an emulsifier is added dropwise to the aqueous solution or aqueous dispersion of (1), (2) and, if necessary, (1 ′), and if necessary, heated using a radical polymerization catalyst or irradiated Irradiation with an electron beam, ultraviolet rays, or the like. The aqueous solution or aqueous dispersion of (1), (2) and, if necessary, (1 ′) is added dropwise to (A), and the same operation is carried out using a radical polymerization catalyst and an emulsifier as necessary. The aqueous solution or aqueous dispersion of (1), (2) and, if necessary, (1 ′) is added dropwise to a mixture of (A) and water, and the same operation is carried out using a radical polymerization catalyst and an emulsifier as necessary. (A) A radical polymerization catalyst is optionally present in a dispersion comprising an emulsifier and water, and (1), (2) and (1 ′) are added dropwise as necessary, and the operation is carried out in the same manner as thereafter. When (1) is a precursor, a precursor which has been hydrolyzed in advance may be used or may be hydrolyzed at the time of polymerization.

(1), (2) and if necessary (1 ′)
Is usually from 2 to 120 based on the weight of (A).
%, Preferably 10 to 100%, more preferably 30%
~ 90%. The amount of (1) used is usually 50 based on the total weight of (1), (2) and if necessary (1 ′).
%, Preferably 60 to 99.9%, particularly preferably 75 to 95%. The amount of (2) used is (1),
Usually 0.001% to 50%, preferably 0.01 to 30%, based on the total weight of (2) and if necessary (1 ′).
%, Particularly preferably 0.1 to 10%. If the amount of (2) used is 0.001% or more, and if it is 50% or less, the humidity control property is sufficient. The amount of the other vinyl monomer (1 ′) is usually 0 to 20%, preferably 0 to 10%, based on the total weight of (1), (2) and, if necessary, (1 ′).
%, More preferably 0 to 5%.

The polymerization of the water-soluble vinyl monomer or the like is preferably carried out in the presence of water. The amount of water used should be 5 to 50% based on the weight of the dispersion, preferably 5 to 45%, more preferably 10 to 30%. When the amount of water used is 50% or less, and when it is 5% or more, the production of the dispersion becomes easy.

Examples of the radical polymerization catalyst include azo compounds [azobisisobutyronitrile, azobiscyanovaleric acid, 2,2'-azobis (2-aminodipropane) dihydrochloride, etc.], inorganic peroxides [hydrogen peroxide] ,
Ammonium persulfate, potassium persulfate, sodium persulfate, etc.], organic peroxides [benzoyl peroxide, di-t-
Butyl peroxide, cumene peroxide,
Redox catalysts [reducing agents such as alkali metal sulfites or bisulfites, ammonium sulfite, ammonium bisulfite, ascorbic acid, and alkali metal persulfate]; succinic peroxide, di (2-ethoxyethyl) peroxydicarbonate, etc. Consisting of a combination of an oxidizing agent such as a salt, ammonium persulfate, and peroxide]; and a combination of two or more of these. The amount of the catalyst used is usually 0.0005 to 5%, preferably 0.001 to 2%, based on the total weight of (1), (2) and if necessary (1 ′).

Examples of the emulsifier include nonionic surfactants such as lauryl alcohol ethylene oxide adduct, lauric acid ethylene oxide adduct, sorbitan lauric acid monoester, stearylamine ethylene oxide adduct, and nonylphenol ethylene oxide adduct. Cationic surfactants [lauryl alcohol sulfate, sodium alkylbenzene sulfonate, aerosol OT, dithiophosphate ester salts, etc.]; cationic surfactants [laurylamine acetate, triethanolamine monostearate formate, etc.]; Two or more of them may be used in combination. Preferred are nonionic surfactants. The amount of the emulsifier to be used is generally 0 to 20% by weight, preferably 0.1 to 10% by weight, based on the dispersion.

In the present invention, the content of (B) in (U) is usually from 1 to 70% by weight from the viewpoint of dispersibility of (B).
Preferably from 5 to 65% by weight, particularly preferably from 10 to 60% by weight.
% By weight. The content of (B) is adjusted within the above range according to the purpose of use as a cosmetic material. As a method of adjusting the content of (B), the content is adjusted to a target content when synthesizing a dispersion, or the content is adjusted when producing a urethane resin. For example, the content per unit area is controlled by controlling the expansion ratio. Is adjusted.

In the present invention, (U) is an organic polyisocyanate (P) obtained by removing (D) from water if necessary.
And, if necessary, in the presence of a urethane-promoting catalyst, a cross-linking agent, a foaming agent, a foam stabilizer, and the like, as described below, and further reacting by further adding a polyol. This production can be performed by a known method such as a one-shot method, a semi-prepolymer method, or a prepolymer method. Examples of the polyol used here include the same ones as those described in the above (A). The ratio of NCO (isocyanate) to active hydrogen is preferably from 0.7 / 1 to 10/1, more preferably from 0.8 / 1 to 5/1, particularly preferably from 0.1 / 1 to 5/1.
9/1 to 2/1. In addition, a foamed or non-foamed water-absorbent polyurethane molded product can be produced by reacting in a closed mold or an open mold using a low-pressure or high-pressure molding device.

As (P), those conventionally used in the production of polyurethane can be used. As such a polyisocyanate, the same polyisocyanate as used in synthesizing a polyurethane polyol can be used. . Preferred among these are polyisocyanates that are readily available commercially, such as 2,2.
4- and 2,6-TDI, and mixtures of these isomers, crude TDI, 4,4'- and 2,4'-MD
I, a mixture of these isomers, PAPI also referred to as crude MDI, and a modified polyisocyanate-containing urethane group, carbodiimide group, allophanate group, urea group, buret group, isocyanurate group-containing modified polyisocyanate. Isocyanates. In the present invention, the isocyanate index [NCO / equivalent ratio of active hydrogen atom-containing group × 10]
0] is usually 80 to 140, preferably 85 to 120,
Particularly preferably, it is 95 to 115. Further, the isocyanate index is set to be much higher than the above range (for example, 30
(0-1000 or more) Polyisocyanurates can also be introduced into the polyurethane. The active hydrogen in this case does not include the water in the hydrogel. The mass ratio of the other polyol and the crosslinking agent to (A) is not particularly limited, but preferably 0 to 200 parts by mass of the other polyol and 0 to 50 parts by mass of the crosslinking agent with respect to 100 parts by mass of (A). And more preferably 10 to 100 parts by mass of the other polyol and 1 to 20 parts by mass of the crosslinking agent.

As the urethane-promoting catalyst, a catalyst usually used for a polyurethane reaction [for example, an amine-based catalyst (triethyleneamine, N-ethylmorpholine, 1,8
3 such as diazabicyclo <5,4,0> undecene-7
Grade), tin-based catalysts (such as stannous octylate, dibutyltin dilaurate), and other metal catalysts (such as lead octylate). The amount of the catalyst used is about 0.001 to about 5% based on the total weight of the dispersion of the present invention and the organic polyisocyanate. Examples of the cross-linking agent include polyhydric alcohols, polyhydric phenols, alkanolamines, and polyamines such as polyhydric alcohols such as ethene glycol and diethylene glycol; and alkanols such as triethanolamine and diethanolamine. Amines, and these crosslinking agents can be used alone or in combination. The amount of the crosslinking agent varies depending on the type of the crosslinking agent, but is preferably 2 to 20 parts by mass, more preferably 3 to 10 parts by mass, per 100 parts by mass of the polyol.

Examples of the foaming agent include hydrocarbon compounds (methylene chloride, propane, petroleum ether, etc.), chlorofluorocarbons (monofluorotrichloromethane, etc.), azo compounds (diazoamino derivatives, azonitrile, azodicarboxylic acid derivatives, etc.), ammonium compounds ( Ammonium carbonate, ammonium bicarbonate, etc.), water and the like. The amount of the foaming agent used is preferably 0.1 to 80 parts by mass, more preferably 0.2 to 50 parts by mass, per 100 parts by mass of the polyol.
Parts by weight. Examples of the foam stabilizer include a silicone surfactant (polysiloxane-polyoxyalkylene copolymer). The amount of foam stabilizer used is preferably polyol 1
The amount is 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, per 100 parts by mass. Other additives that can be used in the present invention include a flame retardant, a reaction retarder,
Coloring agents, internal release agents, antioxidants, antioxidants (hindered phenolic and hindered amine antioxidants), plasticizers (ester plasticizers such as dibutyl phthalate and dioctyl adipate, and tar plasticizers such as tar) , A petroleum resin-based plasticizer, etc.), a bactericide, carbon black and other fillers.

In the present invention, the form (U) is not particularly limited, whether it is hard, semi-rigid, soft, resin (elastomer) or foam, and examples thereof include plate, needle, fiber, chip and the like. You. Further, another support (for example, synthetic fiber and / or natural fiber, nonwoven fabric, paper, synthetic resin, or the like) may be impregnated or coated. The humidity control resin layer of the present invention is made of (U), and the thickness of the layer when impregnated and coated can be arbitrarily adjusted according to the range where humidity control or dew condensation prevention is required. The average particle size of (B) dispersed in (U) is usually from 0. 0 in view of the moisture absorption rate .
It is from 0.05 to 10 μm, preferably from 0.1 to 5 μm . In the present invention, other moisture-absorbing and desorbing materials (for example, activated clay, sepiolite, diatomaceous earth, highly water-absorbing resin, etc.) may be used in combination when producing the moisture-controlling resin layer. The quantity is (U) 100
It is preferably 1 to 500 parts by mass, more preferably 5 to 250 parts by mass with respect to parts by mass.

The decorative material of the present invention may be composed of only the humidity-controlling resin layer in which (B) or its hydrogel is dispersed in (U). It may be formed on one or both sides to form a decorative material. The decorative material of the present invention is provided with a moisture proof (for example, on the back surface of the moisture control resin layer, or on one or both of the layers between the humidity control resin layer and the decorative material substrate, in order to prevent moisture and moisture coming from the decorative material substrate side. Polyethylene resin) and a waterproof (for example, fluorine resin) layer may be laminated. The thickness of the moisture-proof and waterproof layers is preferably 0 to
It is 50 μm, more preferably 1 to 20 μm.

The decorative material substrate may be in any form as long as it supports the humidity control resin, and examples thereof include plate-like and sheet-like forms. As the type of the base material, wood veneer, wood plywood, particle board, wood such as wood fiber board, metal such as iron, aluminum, polyvinyl chloride, acrylic resin, urethane resin, polyester resin,
Non-ceramic ceramic materials such as polyolefin resin, synthetic resin such as styrene resin, glass, ceramics such as ceramics, gypsum board, calcium silicate board and cement,
Fiber materials such as paper, cloth, woven fabric, and non-woven fabric are exemplified. When the decorative material of the present invention is used, for example, for decorative sheet paper for building materials (for example, wallpaper, ceiling material, indentation, etc.), as a decorative material substrate, high-quality paper having a basis weight of about 15 to 210 g / m ² , It is preferable to use paper such as thin paper, backing paper for wallpaper, Japanese paper, or a woven and / or nonwoven fabric made of glass fiber, asbestos, synthetic fiber and / or natural fiber.

The decorative material of the present invention is finished into a decorative material by the following method, for example. (I) After providing a decorative material base material (for example, a nonwoven fabric) for forming a humidity control resin layer on one or both surfaces of the decorative material base material (for example, a synthetic resin plate or the like), impregnating with the humidity control material for a decorative material /
Alternatively, a humidity control resin layer is formed by coating. (Ii) After one or both surfaces of the decorative material base material are impregnated and / or coated with a decorative material humidity control material, a resin layer surface is laminated with, for example, a moisture-permeable base material (eg, a nonwoven fabric); ) A support (for example, nonwoven fabric, synthetic resin plate, etc.) impregnated and coated with a humidity control material for decorative material is interposed between decorative paper and a decorative material base material (for example, synthetic resin plate, etc.); A humidity control material, in particular, a urethane foam-formed humidity control material for a cosmetic material is used as it is as a decorative material base material. Further, in (i), (ii) and (iii) of the above-mentioned cosmetic material production examples, the formation of the humidity control material layer for a cosmetic material is carried out according to (D) of the present invention.
After impregnating and / or coating with a solution in which isocyanate and, if necessary, a solvent or other additives are mixed, and then heating or the like is performed as necessary, thereby providing a humidity control material for a decorative material such as a ceiling material or a push-in material of the present invention ( U) . The humidity control material for a cosmetic material of the present invention has a water-absorbent resin uniformly dispersed in a urethane resin as fine particles having an average particle diameter of 10 μm or less, and has excellent humidity control properties and a moisture absorption / desorption rate.

The humidity control material for a cosmetic material obtained according to the present invention comprises:
Can easily impart moisture conditioning and anti-condensation properties to cosmetic materials,
As a result, it is possible to prevent various discomforts caused by a humid environment. Because of these effects, the decorative material using the humidity control material for decorative materials according to the present invention is useful as a decorative material for interior materials such as houses and furniture.

[0041]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Hereinafter, unless otherwise specified, parts in Examples are parts by weight. The compositions of the raw materials used in Synthesis Examples 1 to 3, Examples 1 to 3, and Comparative Examples 1 to 3 are as follows. Amine catalyst: Triethylenediaminetin catalyst (1): Stanas octoate tin catalyst (2): Cibutyltin dilaurate isocyanate (1): Crude tolylene diisocyanate (TDI-80) Isocyanate (2): Hexamethylene diisocyanate trimer foam stabilizer : X-20-1353 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone foam stabilizer) Water absorbent resin: Sunwet PA-200 (manufactured by Sanyo Chemical Industries, cross-linked sodium polyacrylate-based water absorbent resin)

[Volume-Based Particle Diameter Measurement Method] The water-absorbent resin dispersion was diluted with the polyoxyalkylene compound used in the water-absorbent resin dispersion so that the transmittance of the laser light became 70 to 90%. The particle diameter was measured by a distribution measuring device (laser diffraction / scattering type particle size distribution measuring device LA-700; manufactured by Horiba, Ltd.). (Unit: μm)

[Moisture Absorption and Release Test] The humidity control material for cosmetics of the present invention and the comparative humidity control material for cosmetics were subjected to a relative humidity of 90% (25%).
C) in a thermo-hygrostat, and the time-dependent change in the amount of absorbed moisture was measured. Thereafter, the sample was allowed to stand in a thermo-hygrostat at a relative humidity of 40% (25 ° C.), and the amount of released moisture was measured. The amount of moisture absorption and release is
The amount (g) of water absorbed and released per 100 g of the humidity control material for a cosmetic material is shown. [Humidity control test] A cosmetic material of the present invention, which will be described later, and a comparative cosmetic material were adjusted to 50 ° C. and 60% RH in advance.
It is adhered to the ceiling surface of an airtight container having a size of m (length) x 50 cm (width) x 100 cm (height) to make it tightly closed. Thereafter, the temperature around the closed container was changed, and the change in temperature and humidity in the container was captured by a temperature and humidity recorder (ST-400 manufactured by Nippon Shintech Co., Ltd.), and the value of the temperature and humidity at each time was measured.

Synthesis Example 1 350 parts of a 25% aqueous sodium hydroxide solution and 200 parts of acrylic acid were introduced at a temperature of 40 ° C. or lower into a 2 L four-necked flask equipped with a temperature controller, a vacuum stirring blade, a nitrogen inlet and an outlet. After stirring and mixing, 0.02 parts of methylenebisacrylamide was further added and mixed with stirring to obtain a uniform solution (1). In a 500 ml Erlenmeyer flask, P was added to glycerin.
Polyether polyol having a hydroxyl value of 34 to which O is added and then EO (EO content: 20%) (A-1) 400
And 4 parts of a nonionic emulsifier obtained by adding 14 mol of EO to a higher alcohol, were mixed and stirred to obtain a uniform solution (2). Then, the solution (2) was continuously charged over 1 hour while stirring the solution (1) at a temperature of 40 ° C. or less while blowing in a nitrogen solution, and W /
An O-type emulsion was prepared. Further, a solution prepared by dissolving 0.02 part of 2,2′-azobis (2,4-dimethylvaleronitrile) in 0.1 part of toluene was added in advance, and the mixture was stirred and stirred at 50 ° C. for 1 hour to disperse the water absorbent resin. Body (D
1) was synthesized.

Synthesis Example 2 In Synthesis Example 1, glycerin was replaced with P in place of (A-1).
A water-absorbent resin dispersion (D2) was prepared in the same manner as in Synthesis Example 1 except that 600 parts of a polyether polyol having a hydroxyl value of 50 (EO content: 70%) to which O was added followed by EO was used.
Polyol (B) synthesized from: Synthetic Example 3 A water-absorbent dispersion (D3) was prepared in the same manner as in Synthetic Example 1 except that 2-acrylamido-2-methylpropanesulfonic acid was used instead of acrylic acid in Synthetic Example 1. Synthesized.
Table 1 shows the particle diameters and viscosities of the dispersions (D1) to (D3) obtained in Synthesis Examples 1 to 3. The value of the particle diameter in Table 1 is
It shows the particle diameter corresponding to 50% of the cumulative distribution of the volume-based particle size distribution.

[0046]

【table 1】

Example 1 After 100 parts of the dispersion (D1) obtained in Synthesis Example 1, 0.1 part of tin catalyst (2), 3.8 parts of isocyanate (2) and 100 parts of toluene were mixed, the mixture was mixed. Basis weight 100g / m ²
Of polyester spunbond nonwoven fabric of 110
The composition was cured at 15 ° C. for 15 minutes and dried to prepare a humidity control material for decorative material K1. Table 2 shows the results of evaluating the moisture absorption / release properties of the obtained humidity control material K1 for cosmetics. Example 2 100 parts of the dispersion (D2) obtained in Synthesis Example 2, 0.1 part of a tin catalyst (2), 3.6 parts of isocyanate (2) and 60 parts of toluene were mixed, and the mixture was treated in the same manner as in Example 1. To prepare a humidity control material K2 for a cosmetic material. Table 2 shows the results of evaluating the moisture absorption / release properties of the obtained humidity control material K2 for cosmetics.

Example 3 100 parts of the dispersion (D3) obtained in Synthesis Example 3, 1 part of water,
0.3 part of the amine catalyst and 1 part of the foam stabilizer were mixed, and then adjusted to about 25 ° C. Next, 0.1 part of a tin catalyst (1) was added and mixed for 10 seconds. To the obtained mixture, 6 parts of isocyanate (1) at 25 ° C was added and mixed for 7 seconds to prepare a humidity control material K3 for a cosmetic material. The obtained humidity control material for cosmetics K3
Table 2 shows the results of evaluating the moisture absorption / release properties of the sample. Comparative Example 1 The water-absorbent resin 40 was added to 60 parts of (A-1) used in Synthesis Example 1.
Parts, tin catalyst (2) 0.1 part, isocyanate (2) 3.6
After mixing 60 parts with 60 parts of toluene, a comparative humidity control material K4 for a cosmetic material was prepared in the same manner as in Example 1. Table 2 shows the results of evaluating the moisture absorption / release properties of the obtained comparative humidity control material K4 for cosmetics.

Comparative Example 2 To 60 parts of (A-1) used in Synthesis Example 1, 40 parts of B-type silica gel, 1 part of water, 0.3 part of an amine catalyst and 1 part of a foam stabilizer were mixed. The mixture was adjusted to 25 ° C.
Next, 0.1 part of a tin catalyst was added and mixed for 10 seconds. 6 parts of isocyanate at 25 ° C. were added to the obtained mixture,
After mixing for 7 seconds, a comparative humidity control material K5 for a cosmetic material was prepared.
Table 2 shows the results of evaluating the moisture absorption / release properties of the obtained comparative humidity control material K5 for cosmetics.

[0050]

[Table 2]

Embodiment 4 100 parts of the dispersion (D1) obtained in Synthesis Example 1 and a tin catalyst
0.1 parts, isocyanate 3.8 parts and toluene 1
After mixing 00 parts, a decorative paper base material (basis weight 30 g / m ^TwoMakeup
60g / m basis weight on paper surface^TwoRayon non-woven fabric
On the non-woven fabric surface of
200g / m^TwoAfter coating so that
The composition was cured and dried at 10 ° C. for 15 minutes to prepare a decorative material. Profit
FIG. 1 shows the results of the humidity control test of the obtained decorative material H1.

Comparative Example 3 In Example 4, 100 parts of (D1) was replaced with (A-1) 6
Comparative cosmetic material H2 was prepared in the same manner as in Example 4 except that the mixture was changed to a mixture of 0 parts and 40 parts of zeolite. FIG. 2 shows the results of the humidity control test of the obtained comparative decorative material H2. Comparative Example 4 The decorative material H3 was obtained using the decorative paper used in Example 4 as it was.
And FIG. 3 shows the humidity control test result of the obtained decorative material H3.

[0053]

The cosmetic material of the present invention has an average particle size of the water-absorbing resin.
Fine particles having a particle diameter of 10 μm or less are uniformly dispersed in the urethane resin, and have excellent humidity control properties and moisture absorption / desorption rates.

[0054]

[Brief description of the drawings]

FIG. 1 shows the results of a humidity control test of Example 4.

FIG. 2 is a result of a humidity control test of Comparative Example 3.

FIG. 3 shows the results of a humidity control test of Comparative Example 4.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI B01J 20/26 B01J 20/26 A C08G 18/00 C08G 18/00 H 18/63 18/63 Z (C08G 18/00 C08G 101 : 00 101: 00) (56) References JP-A-11-207854 (JP, A) JP-A-11-57465 (JP, A) JP-A-11-62028 (JP, A) JP-A-2000-128947 ( JP, A) JP-A-2000-325217 (JP, A) JP-A-8-302218 (JP, A) JP-A-9-272806 (JP, A) JP-A 9-324119 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) B27M 3/00 B32B 21/08 E04B 1/64 E04B 2/56 B01D 53/28 B01J 20/26 C08G 18/00 C08G 18/63

Claims (8)

(57) [Claims] 1. A cosmetic material substrate comprising the following water-absorbent resin dispersion (D), polyisocyanate (P) and, if necessary, a solvent
Mixed solution of the impregnation and / or after the quotes Lee ring
A residential or furniture makeup having a humidity control resin layer made of a urethane resin (U) obtained by the reaction.
Wood . Water-absorbent resin dispersion (D): In polyol (A),
The water-absorbent resin (B) polymerized and formed in (A) or the water-absorbing gel thereof is dispersed and (B)
The average particle size of the water-absorbing gel is 0.05 to 10 μm.
Oh Ru water-absorbing resin dispersion. 2. The method according to claim 1, wherein (U) is obtained by heating.
The cosmetic material according to claim 1. 3. A water-absorbent resin (B), in (A), a cosmetic according to claim 1 or 2, wherein the water-soluble vinyl monomer or a precursor thereof and a crosslinking agent and is formed by polymerizing Wood . 4. A method according to claim 1, wherein the water-absorbent resin (B) comprises one or more vinyl monomers having a carboxyl group or a sulfonic acid group, a copolymerizable crosslinking agent, and optionally another 3. The cosmetic material according to claim 1, wherein the vinyl monomer is formed by polymerization . 5. The method according to claim 1, wherein (A) is a polyether polyol, a polyester polyol, a polybutadiene polyol, an acrylic polyol, a polyether ester polyol,
The cosmetic material according to any one of claims 1 to 4 , wherein the cosmetic material is at least one selected from the group consisting of a polyesteramide polyol, a polyurethane polyol, an epoxy polyol, an epoxy-modified polyol, a polyhydroxyalkane, an oil-modified polyol, and a castor oil-based polyol. 6. (U) in the (B) decorative material according to any one of claims 1 to 5 content of 1-70% by weight of. 7. (U) a polyol (A) in a water-absorbent resin dispersion (D) and optionally another polyol and an organic polyisocyanate compound (P), a foaming agent and, if necessary, a catalyst and a foam stabilizer; The cosmetic material according to any one of claims 1 to 6, wherein the cosmetic material is a urethane foam which is reacted in the presence of other additives. 8. A decorative material comprising a humidity control material layer for a cosmetic material and a decorative material base material, wherein a moisture-proof and waterproof layer is provided on one side or both sides of the decorative material base material opposite to the cosmetic material humidity control material layer. Be provided
The cosmetic material according to claim 1 .