JP2002121251A - Skin-forming agent for urethane foam with skin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a two-part type skin-forming agent for a urethane foam with a skin by a solventless mold coating method having excellent light resistance and skin strength. SOLUTION: This skin-forming agent for the urethane foam with the skin by the solventless mold coating method comprises (A) an isocyanate component comprising (A1) an isocyanate group-terminated urethane prepolymer having 300-5,000 isocyanate group equivalents and derived from (a1) an excess polyisocyanate, (a2) a high polymeric polyol having at least 250 OH equivalents and, as necessary, (a3) a low-molecular polyol and (B) an active hydrogen component containing at least 50 equivalent % of (B1) a polyamine having at least two primary or secondary amino groups in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a skin forming agent for urethane foam with skin (hereinafter abbreviated as skin foam). More specifically, the present invention relates to a skin-forming agent for a skin foam of a mold coating method used for interior materials of automobiles and the like.

[0002]

2. Description of the Related Art As a method for forming a skin of a skin foam, a method has been proposed in which a polyisocyanate or a modified product thereof and an active hydrogen-containing compound such as a polyamine or a polyol are directly mixed and sprayed on a mold surface to form a skin ( For example, JP-A-2-283711.

[0003]

However, the above method has a problem that the mechanical strength of the obtained skin varies greatly.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to obtain a skin forming agent for skin foam which solves the above problems, and as a result, have reached the present invention.

That is, the present invention provides an isocyanate group equivalent derived from an excess of an organic polyisocyanate (a1), a high molecular weight polyol (a2) having an OH equivalent of at least 250 and, if necessary, a low molecular weight polyol (a3), having an isocyanate group equivalent of 300 to 300. Isocyanate component (A) comprising 5,000 isocyanate group-terminated urethane prepolymer (A1)
And at least two primary or secondary amino groups in the molecule.
A non-solvent type skin-forming agent for a mold foaming method skin foam (first invention), comprising an active hydrogen-containing component (B) containing at least 50 equivalent% of a polyamine (B1) having at least one polyamine (B1); ) And first grade or 2
A non-solvent type mold coating method for forming a skin foam, comprising an active hydrogen-containing component (B) comprising a polyamine (B1) having at least two secondary amino groups in the molecule and a plasticizer (C). Agent (second invention);
A method for forming a skin for a mold foaming method using a mixture coating method, wherein the skin forming agent is mixed and sprayed on the surface of the mold cavity to react and cure the mixture; A method for producing a polyurethane foam with a skin, comprising introducing a polyurethane foam stock solution and foaming the core material before, simultaneously with or after the curing of the skin forming agent; It is intended to provide a polyurethane foam with a skin having a cured skin layer; and an automotive interior material comprising the foam.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the organic polyisocyanate (a1) constituting the above prepolymer (A1), those conventionally used for producing polyurethane can be used. (A1) is an aliphatic polyolefin having 2 to 18 or more (preferably 2) isocyanate groups (NCO groups) and having 2 to 18 carbon atoms (excluding carbon in the NCO groups; the same applies hereinafter). Isocyanates, alicyclic polyisocyanates having 4 to 15 carbon atoms, araliphatic polyisocyanates having 8 to 15 carbon atoms and aromatic polyisocyanates having 6 to 20 carbon atoms, and modified products of these polyisocyanates (modified carbodiimide, urethane Modified products, uretdione-modified products, isocyanurate-modified products, etc.) and mixtures of two or more of these.

Examples of the aliphatic polyisocyanate include diisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate and 2,6-diisocyanate. Natomethyl caproate, bis (2-isocyanatoethyl)
Fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate; triisocyanates, such as 1,6-11-undecane triisocyanate.

The alicyclic polyisocyanate includes isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MD)
I), cyclohexylene diisocyanate, methyl cyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate. Examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate, diethylbenzene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

As aromatic polyisocyanates, diisocyanates such as 1,3- and / or 1,4-
Phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 4,
4'- and / or 2,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl -4,4'-diisocyanatodiphenylmethane and 1,5-naphthylene diisocyanate; and tri- or higher functional polyisocyanates (such as triisocyanate) such as polyphenylmethane polyisocyanate (crude MDI).

Among (a1), preferred are organic diisocyanates. Preferred from the viewpoint of light resistance are non-aromatic (aliphatic, alicyclic and araliphatic) polyisocyanates, particularly aliphatic diisocyanates, alicyclic diisocyanates and combinations thereof.

The high molecular polyol (a2) is at least 250, preferably 250 to 2,500, more preferably 350 to 2,250, particularly preferably 450 to 250.
It has an OH equivalent of 2,000 (56,100 / the amount indicated by the hydroxyl value; the hydroxyl value is determined by a titration method), and is usually 500 to 5,000 or more, preferably 70.
0 to 4,500, more preferably 900 to 4,000
(By GPC method; hereinafter abbreviated as Mn). (A2) includes a polyether polyol (a2
1), polyester polyol (a22), polybutadiene-based polyol (a23), acrylic polyol (a
24), a polymer polyol (a25), and a mixture of two or more thereof.

As (a21), an active hydrogen atom-containing polyfunctional compound may be an alkylene oxide (hereinafter abbreviated as AO).
And compounds having a structure to which one or more of these are added, and a mixture of two or more of these. In the above and below, AO refers to unsubstituted AO having 2 to 12 or more (preferably 2 to 4) carbon atoms, such as ethylene oxide (EO), 1,2- and 1,3-propylene oxide (PO ), 1,2-, 2,3- and 1,
3-butylene oxide, tetrahydrofuran (TH
F), isobutylene oxide, 3-methyltetrahydrofuran (3M-THF) and α-olefin oxide; and substituted AO such as styrene oxide, epihalohydrin (epichlorohydrin, epibromohydrin, etc.); and a combination of two or more of these. It is.
When two or more kinds are used in combination, either a block addition (chip type, balance type, active secondary type, etc.) or a random addition may be used as a mixed system of both (tips after random addition: EO chains arbitrarily distributed in the molecule are reduced to 0). EO chain of 0 to 30% by weight (preferably 5 to 25% by weight) at the molecular end].

As the active hydrogen atom-containing polyfunctional compound,
Compounds having from 2 to 8 or more active hydrogen atoms, such as polyhydric alcohols, polyphenols and polycarboxylic acids. As polyhydric alcohol,
Diols, for example, aliphatic diols having 2 to 12 carbon atoms [ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol (hereinafter BD)
, 1,6-hexanediol, diethylene glycol, neopentyl glycol, dodecanediol, etc.], an alicyclic diol having 6 to 10 carbon atoms [1,4-cyclohexanediol, bis (hydroxymethyl) cyclohexane, etc.], carbon Aromatic ring-containing diols of number 8 to 20 [xylylene glycol, bis (hydroxyethyl) benzene, etc.]; and tri- or higher-valent or higher polyols such as alkane polyols (glycerin, trimethylolpropane, 1,2,6- Hexanetriol, pentaerythritol, sorbitol, etc., their intramolecular or intermolecular dehydrates (sorbitan, diglycerin and other polyglycerins, dipentaerythritol, etc.), saccharides and their derivatives (sucrose, methylglucoside, etc.) And the like.

Examples of the polyhydric phenol include monocyclic dihydric phenols (hydroquinone, catechol, resorcin, etc.) and bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.). Examples of the polycarboxylic acid include those mentioned as a raw material of (a22) described later.

The addition of AO to the active hydrogen atom-containing polyfunctional compound can be carried out by a usual method, without a catalyst or in the presence of a catalyst (alkali catalyst, amine catalyst, acidic catalyst, etc.) (particularly, AO addition). In the latter half of the process) under normal pressure or under pressure in one or more stages. (A21)
Specific examples of polyether diols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol (hereinafter referred to as PE, respectively)
G, PPG, PTMG), poly-3-methyltetramethylene ether glycol, polyoxyethylene bisphenol A, and the like, and a copolymerized polyalkylene ether diol [THF / EO copolymerized diol, THF / 3
M-THF copolymerized diol (copolymerization weight ratio, for example, 1/9 to 9/1)]. Preferred among (a21) are polyether diols, especially PTM
G, THF / EO copolymerized diol and THF / 3M-
It is a THF copolymerized diol.

(A22) includes condensed polyester polyols, polylactone polyols, polycarbonate polyols and castor oil-based polyols. The condensed polyester polyol is composed of a polyol (a diol and, if necessary, a trivalent or higher valent polyol), a polycarboxylic acid (a dicarboxylic acid and, if necessary, a trivalent or higher polycarboxylic acid) or an ester-forming derivative thereof, or a polycarboxylic anhydride and It can be produced by reacting with AO.

As the polyol, a low molecular weight polyol and / or a polyether polyol can be used; examples of the low molecular weight polyol include the polyhydric alcohols mentioned as the starting material (a21) [for example, diols (ethylene glycol, 1,4-butane). Diol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, etc.) and a combination of these diols with a small proportion (for example, 10 equivalent% or less) of a tri- or higher valent polyol (glycerin, trimethylolpropane, pentaerythritol, etc.) System]; as a polyether polyol, a ring-opened polymer of AO having a hydroxyl equivalent of 500 or less and (a
AO adducts of the active hydrogen atom-containing polyfunctional compound mentioned in 21), for example, PEG, PPG and PTMG.

As the polycarboxylic acid, dicarboxylic acid,
And a tri- or higher polycarboxylic acid in a small proportion (for example, 10 equivalent% or less) with dicarboxylic acid can be used. Examples thereof include saturated and unsaturated aliphatic polycarboxylic acids having 2 to 12 carbon atoms, such as saturated dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc.), unsaturated dicarboxylic acids (Maleic acid, fumaric acid, itaconic acid, etc.), tricarboxylic acids (hexanetricarboxylic acid, etc.); aromatic polycarboxylic acids having 8 to 15 carbon atoms, such as dicarboxylic acids (terephthalic acid,
Isophthalic acid, phthalic acid, etc.), tri- and tetra-
Carboxylic acids (trimellitic acid, pyromellitic acid, etc.);
And an alicyclic polycarboxylic acid having 6 to 40 carbon atoms (such as dimer acid). Ester-forming derivatives include acid anhydrides, lower alkyl (1-4 carbon atoms) esters, and acid halides (such as acid chlorides).

The polylactone polyol is a lactone (having 4 to 12 carbon atoms, for example ε
-Caprolactone, γ-butyrolactone, and γ-valerolactone). The polycarbonate polyol is obtained by reacting a polyol with a di-lower alkyl carbonate (1-4 carbon atoms) ester (such as dimethyl carbonate). As the polyols used in these productions, low molecular weight polyols and / or polyether polyols can be used; examples thereof include the above-mentioned diols and / or polyols having a valency of 3 or more, and polyethers having a hydroxyl equivalent of 500 or less, respectively. Polyols. The castor oil-based polyol includes castor oil (ricinoleic acid triglyceride) and its transesterified product. The latter is obtained by transesterification of castor oil with a polyol, and the polyol includes the low-molecular polyol and / or the polyether polyol described above.

Specific examples of (a22) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, Polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol, polycaprolactone diol, polyhexamethylene carbonate diol, and the like. .

As (a23), polybutadiene diols, for example, those having a 1,2-vinyl structure, 1,4
Those having a trans structure, those having a 1,4-cis structure and those having two or more of these structures (1,
The molar ratio of 2-vinyl / 1,4-trans / 1,4-cis is 100 to 0/100 to 0/100 to 0, preferably 10.
To 30/50 to 70/10 to 30) can be used. Further, (a23) includes homopolymers and copolymers (such as styrene-butadiene copolymer and acrylonitrile-butadiene copolymer), and hydrogenated products thereof (hydrogenation ratio: for example, 20 to 100%). (A24) is a copolymer obtained by introducing a hydroxyl group into an acrylic copolymer [alkyl (C 1-20) (meth) acrylate or a copolymer of these and another monomer (such as styrene)]. Mainly uses hydroxyethyl (meth) acrylate.

As (a25), a vinyl monomer [acrylic monomer such as (meth) acrylonitrile, alkyl (1 to carbon atoms)] in a polyol [for example, the above (a21) and / or (a22) or these and the above low molecular weight polyol] 20) (meth) acrylates (eg, methyl methacrylate), aromatic vinyl monomers (eg, styrene), aliphatic hydrocarbon monomers (α-olefins,
Butadiene) and a combination thereof (such as a combination of acrylonitrile and styrene)] and polymerized in situ (polymer content, for example, 5 to 70% by weight). Among (a2), a polymer diol is preferred. Among the high molecular diols, preferred are polyether diols and particularly polyester diols (further, condensed polyester diols)
It is.

The low molecular polyol (a3) has an OH equivalent of less than 250. Examples thereof include the polyhydric alcohols exemplified as the starting materials in the above (a21); and ring-opened polymers of AO and AO adducts of active hydrogen atom-containing polyfunctional compounds having an OH equivalent of less than 250. . (A3) and (a) when (a3) is used
The ratio (equivalent ratio) of 2) can be appropriately changed depending on the use of the skin foam and required performance, but is generally 0 to 0.5: 1, preferably 0.01 to 0.2, and more preferably 0.01 to 0.2. Is 0.02 to 0.1 mol.

(A1) has an NCO group equivalent of usually 300 to 5,000, preferably 350 to 3,000. 3
If it is less than 00, good skin strength cannot be obtained, and 5,000
If it exceeds, the spraying property is reduced. In the production of (A1), the equivalent ratio of the NCO group of (a1) to the hydroxyl group of (a2) and, if necessary, (a3) is the above-mentioned NCO group.
Although it can be variously changed within a range for giving the group equivalent, it is usually 1.1 to 10, preferably 1.4 to 4, and more preferably 1.4 to 2. For example, based on 1 mol of (a1), 0.1 to 0.5 mol, preferably 0.2 to 0.4 mol of (a2) and 0 or 0.01 to 0.2 mol, preferably 0.05 to 0.5 mol. 0.15 mol of (a3) can be used. (A1) can be produced by a method similar to the usual urethanization reaction (single-stage method or multi-stage method).

Examples of the polyamine (B1) constituting the active hydrogen-containing component (B) include aliphatic polyamines such as alkylene diamines having 2 to 12 or more carbon atoms [ethylene diamine (hereinafter abbreviated as EDA), propylene diamine, hexamethylene Diamine, octamethylene diamine, 2,2,4-trimethylhexamethylene diamine (hereinafter abbreviated as TMHDA), etc.), polyalkylene polyamine (alkylene group having 2 to 6 carbon atoms, polymerization degree of 2 to 6 or more) (diethylene triamine , Triethylenetetramine, etc.); an alicyclic polyamine having 6 to 15 carbon atoms, for example, 4,4'-diaminodicyclohexylmethane, 4,
4′-diamino-3,3′-dimethyldicyclohexylmethane, isophoronediamine (hereinafter abbreviated as IPDA),
Diaminocyclohexane or the like; an araliphatic polyamine having 8 to 15 carbon atoms, for example, xylylenediamine, α, α,
α ′, α′-tetramethylxylenediamine and the like; aromatic polyamines having 6 to 15 carbon atoms, for example, diaminobenzene, toluenediamine, diethyltoluenediamine,
4,4′-diaminophenylmethane, polyphenylmethanepolyamine and the like; polyoxyalkylene polyamine (oxyalkylene group having 2 to 4 carbon atoms, degree of polymerization of 2 to 100 or more) [listed in the above (a21) and (a3)] Polyether polyols, ring-opening polymers of AO, AO adducts of active hydrogen atom-containing polyfunctional compounds (PEG, PP
G, PTMG, etc.) obtained by cyanoalkylation (cyanoethylation, etc.) and hydrogenation (polyoxypropylenediamine, polyoxypropylenetriamine, etc.)]; and mixtures of two or more thereof.

Of these, preferred are diamines,
In particular, it is a non-aromatic diamine (aliphatic diamine, alicyclic diamine, araliphatic diamine and a combination thereof). Part or all of the amino group of (B1) is a ketone [C 3-8; acetone, methyl ethyl ketone (hereinafter ME)
K) or an aldehyde (2-8 carbon atoms; acetaldehyde, etc.) (ketimine or aldiminate).

(B) may contain, if necessary, a polyol (B2) and / or an amino alcohol (B3) together with (B1). As (B2), a low molecular polyol (OH equivalent less than 250) and / or a high molecular polyol (OH equivalent of 250 or more) can be used. The low molecular polyol includes the polyhydric alcohol [diol (ethylene glycol,
1,4-butanediol, etc.) and / or polyols having 3 to 8 or more valences (glycerin, trimethylolpropane, etc.)] and amine-based polyols (tertiary amino group-containing polyols), and their AOs
Includes low molar adducts.

As the amine-based polyol, an oxyalkylated product of an amine having 2 to 8 or more active hydrogen atoms (a compound having a structure obtained by adding AO to an amine) can be used. Examples of the amine include primary monoamines such as aliphatic, alicyclic, araliphatic and aromatic monoamines having 1 to 20 carbon atoms (such as alkylamine, cyclohexylamine, benzylamine, aniline, toluidine, and naphthylamine); and alkanolamine ( Hydroxyalkyl groups having 2 to 4 carbon atoms, such as mono-, di- and tri-ethanolamine; polyamines, such as aliphatic polyamines having 2 to 18 carbon atoms, 4 to 15 carbon atoms
Alicyclic polyamines, araliphatic polyamines having 8 to 15 carbon atoms and aromatic polyamines having 6 to 20 carbon atoms [polyamines corresponding to the above-mentioned polyisocyanates (NCO groups are replaced by amino groups)], poly Alkylene polyamine (alkylene group having 2 to 6 carbon atoms, degree of polymerization of 2 to 6 or more) such as diethylenetriamine, heterocyclic polyamine such as piperazine and aminoalkyl (2 to 6 carbon atoms) piperazine (such as aminoethylpiperazine)
Is mentioned. The number of oxyalkylene units (the number of moles of AO added) per active hydrogen atom of the amine is usually 1 to 5. When 1 is used, an N-hydroxyalkyl-substituted product is formed, and when 2 or more, amine polyether polyol is used. Is generated. Specific examples of the amine-based polyol include trialkanolamine (having 2 to 2 carbon atoms in a hydroxyalkyl group)
4, triethanolamine, etc.), N-alkyl (C1-20) dialkanolamine (C2-C4 hydroxyalkyl group, N-methyldiethanolamine, etc.) and tris (hydroxypropyl) ethylenediamine, and furthermore AO (EO and / or P
O).

The high molecular polyol includes polyether polyol, polyester polyol, polybutadiene-based polyol, acrylic polyol and polymer polyol. The above-mentioned (a21), (a22),
The same as (a23), (a24) and (a25) can be mentioned. Another example of the polyether polyol is a tertiary amino group-containing polyether polyol obtained by adding AO to the amine polyol.

Further, these high molecular polyols may be urethane-modified (hydroxyl-terminated urethane prepolymer) or a mixture of this and an unmodified high-molecular polyol. These include a polyisocyanate [the above-mentioned (a1), preferably a non-aromatic polyisocyanate], and an excess (OH / NCO equivalent ratio is greater than 1, for example, 1.01-2 or more, preferably, 1.03 to 2) [(a21), (a
22), (a23), (a24) and / or (a2)
5)], and
For example, those described in US Pat. No. 4,576,855 can be mentioned.

(B3) includes mono- and di-alkanolamines (having a hydroxyalkyl group having 2 to 2 carbon atoms).
4), for example, ethanolamine, diethanolamine and the like; partially oxyalkylated products of the above-mentioned polyamines (containing primary and / or secondary amino groups), for example, N, N- or N, N'-dihydroxypropylethylenediamine.

In the skin-forming agent of the present invention (first invention), the content of (B1) in (B) is usually at least 50 equivalent%, preferably at least 67 equivalent%, more preferably at least 80 equivalent%.
It is equivalent% or more. The amount of the polyol is preferably equal to or less than 50 equivalent% of (B1). In the skin-forming agent of the present invention (second invention), the content of (B1) in (B) can be changed over a wide range (for example, 10 equivalent% or more, especially 30 equivalent% or more). preferable. When the content is in the above range, excellent physical properties, rapid curability, and releasability can be obtained. As (B), those containing substantially no water [those containing a small amount (for example, 1% by weight or less) of water are acceptable, but those to which water is not actively added] are preferable.

The plasticizer (C) used in the skin forming agent of the present invention (second invention) and optionally used in the skin forming agent of the present invention (first invention) usually contains 15
Room temperature liquid carboxylic esters and phosphoric esters having a boiling point of 0 ° C. or higher; and mixtures of two or more thereof.

Examples of the carboxylic acid esters include: 1) monocarboxylic acids having 1 to 30 carbon atoms [aliphatic monocarboxylic acids (formic acid, acetic acid, oleic acid, acetoacetic acid, etc.), alicyclic monocarboxylic acids (cyclohexanecarboxylic acid, Abietic acid) and / or aromatic monocarboxylic acid: an alkyl group having 1 to 10 carbon atoms and / or a halogen (Cl,
Benzoic acid (benzoic acid, toluic acid, xylenecarboxylic acid, 4-butylbenzoic acid, 2,4-dibutylbenzoic acid)
2-methyl-4-chlorobenzoic acid, nonylbenzoic acid, etc.)] and polyhydric alcohols [the ones mentioned as the raw material of (a21)] or polyether polyols [the ones mentioned in the (a21), the (a21)]. With an active hydrogen atom-containing polyfunctional compound, such as polyalkylene glycol (oxyalkylene group having 2 to 4 carbon atoms,
P 2 to 25, preferably 3 to 15, especially 3 to 10;
EG, PPG, etc.) and a diester of the above aromatic monocarboxylic acid (such as benzoic acid) [JP 2000-10395
7, a diester of the above-mentioned monocarboxylic acid with an AO (8 to 20 mol) adduct of an alkanediol having 4 or more carbon atoms or a diol having a cyclic group. A compound represented by formula (2) described in Japanese Patent Publication No. 3-56590]; and 2) a monohydric alcohol having 1 to 30 carbon atoms [aliphatic alcohol (methyl, ethyl, propyl, butyl, hexyl,
Octyl, 2-ethylhexyl, decyl, isodecyl,
Dodecyl, eicosyl and oleyl alcohol, etc.), alicyclic alcohols (cyclohexyl alcohol, etc.), aromatic alcohols (benzyl alcohol, etc.)]
Or polyether monool [AO (1 to 30 mol) adduct of the above monohydric alcohol, monohydric phenol having 6 to 30 carbon atoms (phenol, cresol, xylenol, alkylphenol, benzylated and / or styrenated phenol, etc.) AO (1 to 30 mol) adduct or the like] and an ester of a polycarboxylic acid [listed as a raw material of (a22)] or a monocarboxylic acid (described above): for example, phthalic acid esters (dibutyl phthalate, dioctyl phthalate) , Diisodecyl phthalate, dibenzyl phthalate, etc.), aliphatic dicarboxylic acid esters (di-2 adipate)
-Ethylhexyl, di-2-ethylhexyl sebacate, etc.), trimellitate (trimellitic acid tri-
AO of 2-ethylhexyl, trioctyl trimellitate, etc.), fatty acid ester (butyl oleate, etc.), monohydric alcohol or monohydric phenol (phenol, alkylphenol, styrenated phenol, etc.)
(1 to 30 mol) adduct monocarboxylic acid monoester and dicarboxylic acid diester [Japanese Patent Publication No. 3-59590]
And the compounds represented by the general formulas (1) and (3) described in Japanese Patent Application Laid-Open Publication No. H11-157, respectively.

Examples of the phosphoric acid ester include a phosphoric acid ester of the above-mentioned monohydric alcohol, its halogen-substituted product, the above-mentioned monohydric phenol and / or the above-mentioned polyether monool, for example, an aliphatic phosphoric acid ester (trimethyl phosphate, triethyl phosphate, tributyl Phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, etc.); aromatic phosphates [triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate,
2-ethylhexyl diphenyl phosphate, tris (2,6-dimethylphenyl) phosphate, etc.]; halogen aliphatic phosphate [tris (chloroethyl)
Phosphate, tris (β-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromoneopentyl) phosphate and the like].

Among (C), preferred are aromatic monocarboxylic acid diesters of polyalkylene glycol (C1) [the compounds represented by the general formula (1) described in JP-A-2000-103957, Benzoate and PPG dibenzoate], and the combination of (C1) with one or more other plasticizers ([C1) is determined from the viewpoint of good low-temperature physical properties and fogging resistance of the skin.
Based on the weight of (C), preferably 50% by weight or more, especially 70% by weight or more].

The ratio of (C) is the sum of (A) and (B) of 1
The amount is usually 80 parts or less, preferably 1 to 50 parts, more preferably 2 to 40 parts, and particularly preferably 5 to 30 parts, from the viewpoint of bleed-out resistance to the surface of the skin. Above and below, parts refer to parts by weight. By containing (C), excellent sprayability and rapid curability can be obtained. (C) may be contained on either side of (A) or (B), but is preferably contained in (A) from the viewpoint of improving sprayability.

In order to accelerate the reaction between (A) and (B), the skin-forming agent of the present invention may optionally contain a catalyst (D).
Can be contained. (D) includes a metal catalyst, an amine catalyst and those described in JP-A-2-283711. Examples of the metal catalyst include tin catalysts (eg, trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannas octoate, dibutyltin maleate), and lead catalysts (eg, oleic acid). Lead, lead 2-ethylhexanoate, lead naphthenate, lead octenoate), bismuth-based catalysts (eg, bismuth 2-ethylhexanoate, bismuth naphthenate) and other metal catalysts (eg, cobalt naphthenate,
Phenylmercury propionate) and the like.

Examples of the amine catalyst include tertiary amines such as triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diazabicycloalkene [1,8-diazabicyclo [5,4,0] undecene-7 (trade name) DBU: manufactured by Sun Apro) etc.),
N-methylmorpholine, N-ethylmorpholine, triethylamine and the like; amine salts such as amines [the above tertiary amines; dialkyl (C1-4) aminoalkyl (C2-8) amines such as dimethylaminoethylamine, dimethylamino Propylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropylaminopropylamine and the like; heterocyclic aminoalkylamine such as 2-
(1-aziridinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine, etc.] and organic acid salts (such as formate); and combinations of two or more of these.

The amount of (D) to be added is generally (A) and (B)
Is usually 3% or less, preferably 0.1% based on the total weight of
01 to 2%. It is generally desirable that (D) be contained in the component (B).

The skin-forming agent of the present invention may further comprise, if necessary, an internal release agent (E) and / or other additives (F).
Can be contained. (E) includes, for example, polydimethylsiloxane, a functional group (carboxyl group, hydroxyl group,
Modified organopolysiloxanes having an epoxy group, an amino group, a mercapto group, an oxyalkylene group, etc., zinc stearate, stearamide and wax. (F) includes an antioxidant such as a phenol [2,6-di-t-butyl-4-methylphenol (B
HT) and the like; sulfur-containing compounds (such as dilaurylthiodipropionate) and phosphorus-containing compounds (such as triphenylphosphite); UV absorbers such as benzoate (such as salicylate) and benzophenone (2-
Hydroxy-4-methoxybenzophenone), benzotriazole [2 (2′-hydroxy-5′-methylphenyl) benzotriazole etc.] and cyanoacrylate [ethyl-2-cyano-3- (3,4-methylenedi Oxyphenyl) acrylates and the like]; flame retardants, for example, bromine-containing (such as hexabromobenzene), phosphate ester (such as triphenyl phosphate), and halogen-containing phosphorus (such as tris (2-chloroethyl) phosphate); For example, calcium carbonate, talc,
Clay, barium sulfate and glass fiber; coloring agents, such as pigments (lead white, titanium white, iron oxide, ultramarine, carbon black, etc.) and dyes; physical blowing agents (such as Freon gas); thixotropic thickeners, such as fine powder Silica; a foam stabilizer such as a silicone surfactant (such as a polysiloxane-polyoxyalkylene block copolymer); and an antifoaming agent such as silicone oil.

The amount of (E) to be added is generally 20% or less, preferably 1 to 2, based on the total weight of the skin-forming agent.
10%. Further, (E) may be contained in any of (A) and (B), and is appropriately adopted according to the purpose.
The amount of (F) added can vary over a wide range depending on the required performance and the like, but is generally 40% or less, preferably 0.2%, based on the total weight of the skin-forming agent.
~ 20%. The amount of each additive can be appropriately selected according to the purpose of the addition. For example, the antioxidant and the ultraviolet absorber are usually 5% or less, preferably 0.2 to 2%; the filler and the colorant are usually 40% or less. Preferably 1-20%; flame retardants, physical blowing agents, thixotropic thickeners usually 20%
Below, preferably 1 to 10%, the amount of foam stabilizer and defoamer is usually 5
% Or less, preferably 1% or less. Further, (F) may be contained in any of (A) and (B), and is appropriately adopted depending on the type and purpose of the additive.

The mixing ratio of the isocyanate component (A) and the active hydrogen-containing component (B) in the skin-forming agent of the present invention can be changed according to the required performance and the like.
From the viewpoint of the mechanical properties of the formed skin, the NC of (A)
O group and the active hydrogen-containing group of (B) (NH , NH, OH
Is equivalent to 1: (0.9 to 1.1), especially 1:
(0.95 to 1.05) is preferred. The application viscosity of each of (A) and (B) is preferably from 100 to 2,000 mPa · s from the viewpoint of good sprayability.
Particularly, it is 200 to 1,200 mPa · s.

The skin-forming agent of the present invention is applied to the surface of the mold cavity (the inner surface of the mold) and is used for forming a skin for a mold-foaming skin foam. The application method is not particularly limited, and a conventionally known method can be used. Preferably, (A) and (B) are sprayed (spray gun)
Is mixed and sprayed onto the surface of the mold cavity.

The spray gun used for the mixed spraying is a single-head gun (a two-liquid high-pressure mixing spray gun, a two-liquid concentric gun, etc., and a plurality of single-head guns may be used) and a double-head gun. Is included. Examples of the two-liquid high-pressure mixing type spray gun include a dynamic mixer type in which stirring and mixing are performed by rotating a rotor, a static in-pipe mixing (static mixer) type, and a collision mixing type spray gun. Specifically, Gasmer's GY-7 gun, AR
-A gun; Glasscraft's prober gun; Binks' model 43P gun; Anest Iwata's RG
-II (diameter 0.8 mm), SG-569; Toray High Mixer; Spray gun described in JP-A-3-65315 by Recticel and JP-A-63-63 of Showa Corporation
A spray gun described in JP-A-235379. An example of the two-liquid concentric gun is TCG-G100 manufactured by Anest Iwata Co., Ltd. Examples of a spray gun using a plurality of single-head guns include 206T-660 (spray tip G-527) of Japan Gray Co., Ltd., SA-71 automatic gun (nozzle diameter 0.8 mm) of Anest Iwata Co., Ltd., and W-88. -08C2P.
As a double-headed gun, for example, S-
16D.

As a mold to which the skin forming agent is applied, a mold usually used for producing a skin foam by a mold coating method can be used. Examples of the material of the mold include metal, plastic, and rubber. Preferred are metals. In mixing and spraying, the mold surface and the components (A) and (B) may be preliminarily heated, and the temperature is preferably 30 to 100 ° C. from the viewpoint of curability of the spray-formed coating film. , More preferably 40-80 ° C
It is.

The amount of skin former applied to the surface of the mold cavity can vary widely depending on the use of the skin foam and the required performance. From the viewpoint of demoldability,
The thickness of the skin to be formed is usually 0.05 mm or more, preferably 0.1 to 6 mm, more preferably 0.2 to 3 m.
m, especially 0.3 to 2 mm.

The skin for the mold foam method skin foam is formed by mixing and spraying the skin forming agent onto the surface of the mold cavity, and reacting and curing the mixture. The time from mixing and spraying the skin-forming agent onto the surface of the mold cavity until the formed skin becomes demoldable (demolding time) is the amount of (D), mold temperature, (A) and (B). It can be adjusted depending on the temperature and the like, but from the viewpoint of work efficiency, preferably 8 minutes or less, more preferably 5 minutes or less, and especially 3 minutes or less.
Minutes or less.

The skin to be formed can be obtained by removing only the skin from the mold. However, without removing the skin, a polyurethane foam stock solution (hereinafter abbreviated as foam stock solution) is further introduced into the mold cavity to form the skin foam. It is preferably manufactured. As the foam stock solution used for the production of skin foam, a commonly used polyurethane foam-forming reaction mixture can be used. Foam stock solutions include those for forming flexible polyurethane foam,
It includes those for forming a semi-rigid polyurethane foam and those for forming a rigid polyurethane foam, and can be appropriately selected according to the use of the skin foam. The foam stock solution generally comprises a polyisocyanate component, a polyol component, a foaming agent and, if necessary, a catalyst, a foam stabilizer and other auxiliaries.

The polyisocyanate component includes an organic polyisocyanate, an isocyanate group-terminated urethane prepolymer, and a mixture thereof. Examples of these include those described in the above (a1) and (A1). Preferred are aromatic polyisocyanates, especially TDI, MDI and crude MDI. The polyol component includes a high molecular polyol (OH equivalent: 250 or more), a low molecular polyol (OH equivalent: less than 250), and a combination thereof, and examples thereof include those described in the above (B2). Among these, high molecular polyols (particularly polyether polyols, polyester polyols and polymer polyols) and combinations of these with low molecular polyols are preferred for forming flexible polyurethane foams and for forming semi-rigid polyurethane foams. Preferred for forming rigid polyurethane foams are low molecular polyols (polyhydric alcohols, low-molecule AO adducts, amine polyols) and combinations of these with small proportions of high molecular polyols (such as polyether polyols).

The polyol component may contain other active hydrogen atom-containing compounds (polyamine, amino alcohol, etc.) in addition to the polyol. As the polyamine, those described in (B1) can be used, and as the amino alcohol, those described in (B3) can be used. The amount of the low molecular polyol (and other compounds containing active hydrogen atoms as necessary) is preferably 0 to 3 per 100 parts of the high molecular polyol.
00 parts, more preferably 0.5 to 100 parts, especially 1
~ 20 parts. The equivalent weight (Mn per active hydrogen atom-containing group) of the polyol (and optionally another active hydrogen atom-containing compound) is usually 70 to 5,000, preferably 300
~ 3,000, more preferably 1,000 ~ 2,000
0.

Examples of the foaming agent include water and / or volatile foaming agents [eg, CFC substitutes (CFC 123, CFC 14).
1b) and hydrocarbons such as butane]. The amount of blowing agent can be varied over a wide range, for example 0.01~0.4g / cm ³
Or more, preferably 0.02 to 0.2 g / cm
³ , more preferably an amount that gives a free rise density in the range of 0.03 to 0.15 g / cm ³ .

As the catalyst, those mentioned in the above (D) can be used. In addition, an isocyanurate ring-containing foam can be produced using a catalyst for trimerizing isocyanate groups [for example, those described in US Pat. No. 4,299,924 (eg, strong organic bases)]. The foam stabilizer includes a silicone surfactant, and the other auxiliaries include a colorant, a filler, and a flame retardant.
Described in (1).

The mixing ratio of the isocyanate component and the active hydrogen-containing component (polyol component and water) in the foam stock solution can be changed according to the required performance and the like, but the isocyanate index [[NCO group / active hydrogen-containing group] (NH , NH, OH, etc.)] = 9]
A ratio of 0 to 110, particularly 0.95 to 1.05 is preferable. In addition, higher than the above range (for example, 120 or more,
(200-5000) An isocyanurate ring-containing foam can be produced using an isocyanate index and a trimerization catalyst.

For the skin foam, a skin forming agent is mixed and sprayed on the surface of the mold cavity, and before the skin forming agent is cured,
Simultaneous with or after the curing, the foam can be manufactured by introducing a foam solution and foaming to form a core material. The introduction of the foam stock solution can be performed using a commonly used foaming machine (mixing and discharging machine), and may be either a low-pressure foaming machine or a high-pressure foaming machine.

The amount of the stock solution to be introduced into the mold cavity can be varied over a wide range, and usually the overpack ratio (excess filling ratio) is 100 to 800% (compression ratio 1 to 8),
Preferably 110-500%, more preferably 150%
It can be used in an amount of up to 300%. The total density of the skin foam formed can vary widely, for example from 0.05 to 0.8 g / cm < ³ > or more, preferably from 0.1 to 0.5 g / cm < ³ >, more preferably 0.12 g / cm < ³ >. ０．３0.35 g / cm ³ .

Since the skin formed from the skin forming agent of the present invention has particularly excellent mechanical strength, it is extremely useful as a skin forming agent for skin foam used in automobile interior parts. The skin foam obtained by the present invention can be used for various purposes, for example, interior and exterior members of vehicles (automobiles, other vehicles (railroads, etc.), aircraft, ships (motor boats, etc.)), interior and exterior materials of buildings, furniture, decorative articles. Useful for

[0058]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In the following, “parts” indicates parts by weight.

The abbreviations of the raw materials used below are as follows. (A2-1): Polyhexamethylene isophthalate diol (Mn900); (a2-2): Polycarbonate diol (Mn100)
0, trade name: Nipporan 981, manufactured by Nippon Polyurethane Industry); (a2-3): polybutylene adipate diol (Mn)
1000); (a2-4): EO / PO block adduct of glycerin (hydroxyl value 35, primary hydroxyl group content 80%, Mn 480)
0) (a2-5): EO / PO block adduct of glycerin (hydroxyl value 28, primary hydroxyl group content 85%, Mn 600)
0) (C1): PEG dibenzoate (plasticizer, Mn60)
(D1): lead 2-ethylhexanoate; (D2) lead naphthenate; (D3): 1,8-diazabicyclo [5,4,0] undecene-7 (trade name DBU: manufactured by San Apro Co.); (E1): Carboxyl-modified silicone (release agent, trade name: X-22-3710, Shin-Etsu Chemical Co., Ltd.).

<Production of Urethane Prepolymer> Production Example 1 (a2-1) was placed in a reaction vessel equipped with a stirrer and a thermometer.
2000 parts were charged and heated at 110 ° C. under a reduced pressure of 3 mmHg to perform dehydration for 1 hour. Next, hydrogenated MDI 20
The reaction was carried out at 90 ° C. for 3 hours to obtain a prepolymer (A1-1) having an isocyanate group equivalent of 360.

Production Example 2 Into the same reaction vessel as in Production Example 1, 3500 parts of (a2-1) was charged, and heated at 110 ° C. under a reduced pressure of 3 mmHg to obtain 1
After dewatering for 100 hours, 100 parts of BD was charged and uniformly mixed. Next, 2000 parts of hydrogenated MDI was charged and reacted at 90 ° C. for 3 hours to obtain a prepolymer (A1-2) having an isocyanate group equivalent of 1020.

Production Example 3 4000 parts of (a2-1) and 9000 parts of (a2-2) were charged into a reaction vessel similar to that of Production Example 1, heated at 110 ° C. under a reduced pressure of 3 mmHg, and dehydrated for 1 hour. Was done. Next, 7000 parts of hydrogenated MDI were charged and reacted at 90 ° C. for 3 hours to obtain a prepolymer (A1-3) having an isocyanate group equivalent of 730.

Production Example 4 4000 parts of (a2-1) and 7000 parts of (a2-2) were charged into the same reaction vessel as in Production Example 1, and heated at 110 ° C. under a reduced pressure of 3 mmHg to dehydrate for 1 hour. And then 10
0 parts of BD was charged and uniformly mixed. Next, hydrogenated MDI
7000 parts were charged and reacted at 90 ° C. for 3 hours, and a prepolymer having an isocyanate group equivalent of 620 (A1-4)
I got

Production Example 5 In a reaction vessel similar to that of Production Example 1, 4500 parts of (a2-3) were charged, and heated at 110 ° C. under a reduced pressure of 3 mmHg to obtain 1
After dewatering for 100 hours, 100 parts of BD was charged and uniformly mixed. Next, 7000 parts of hydrogenated MDI were added, and the reaction was carried out at 90 ° C. for 3 hours to obtain a prepolymer (A1-5) having an isocyanate group equivalent of 2710.

<Production of Ketimine> Production Example 6 50 parts of IPDA and MEK were placed in the same reaction vessel as in Production Example 1.
After charging 50 parts and reacting at 70 ° C. for 10 hours (ketiminization ratio 85%), excess MEK was removed to obtain a partially ketiminated product (B1-1). Production Example 7 In a reaction vessel similar to that of Production Example 1, 50 parts of IPDA and MEK were added.
After charging 50 parts and reacting at 70 ° C. for 10 hours (ketiminization rate: 85%), 5 parts of diethanolamine was added to remove excess MEK to obtain a mixture of partially ketiminated products (B1-2). .

Production Example 8 50 parts of EDA and MEK5 were placed in the same reaction vessel as in Production Example 1.
0 parts, and the mixture was reacted at 70 ° C. for 10 hours (ketiminization rate: 85%) to remove excess MEK to obtain a partially ketiminated product (B1-3).

Example 1 (A1-1) 1000 parts of (E1) was mixed with 1.2 parts of (E1), and the temperature of the mixture was adjusted to 70 ° C.
The skin forming agent comprising the component (B) whose temperature was adjusted to 50 ° C. and the temperature of the component (A) component heat exchanger at 70 ° C. and the component (B) component side Temperature 5
At 0 ° C., a stainless steel mold (flat plate having a thickness of 2 mm) was sprayed to produce a skin having a thickness of about 1 mm. Spraying device: Model H-2000 of Gasmer Co., Ltd. Static pressure: 110 kg / cm ² ; Discharge pressure: 80 to 1
10 Kg / cm ² ; Liquid sending pump to spraying device: Supply pump OP-2328 from Gasmer; Spray gun: Probler gun from Glasscraft (using round chamber No. 1)

Example 2 1000 parts of prepolymer (A1-2) and 200 parts of (C1)
And a component (B) in which 76 parts of TMHDA was adjusted to a temperature of 50 ° C., and a skin-forming agent composed of component (A) mixed with 1.2 parts of (E1) and (E1) and adjusted to a temperature of 50 ° C. Using a similar spraying device, the mixture was sprayed onto a stainless steel mold (flat plate having a thickness of 2 mm) at a temperature of the component (A) heat exchanger of 50 ° C and a temperature of the component (B) heat exchanger of 50 ° C. A skin having a thickness of about 1 mm was produced. The release agent was applied and the skin forming agent comprising the components (A) and (B) was sprayed on the surface of the electroformed mold cavity having a grain pattern maintained at 50 ° C. in the same manner as described above to obtain a thickness. A skin layer of about 1 mm was formed. Next, before the skin layer was completely cured, a foam stock solution having the following formulation was introduced into the cavity, and the mold was closed to foam. After leaving it for about 5 minutes, it was demolded to produce a skin foam having a uniform and fine surface.

Form stock solution formulation part Polyoxypropylene polyoxyethylenetetraol (hydroxyl value 37) 93 Triethanolamine 2 Ethylene glycol 5 Water 0.5 Freon 123 10 Triethylenediamine 0.2 Crude MDI 38

Example 3 1000 parts of prepolymer (A1-3) and 100 parts of (C1)
Part (E1) and 1.2 parts of (E1) were mixed and the temperature was adjusted to 50 ° C., the component (A), (B1-1) 199 parts and (D1) 0.3.
A skin and a skin foam were produced in the same manner as in Example 2 except that a skin-forming agent comprising the component (B), which was mixed with 8 parts and temperature-controlled to 50 ° C., was used.

Example 4 1000 parts of prepolymer (A1-4) and 100 parts of (C1)
Part (E1) and 1.2 parts of (E1) were mixed and the temperature was adjusted to 50 ° C., component (A), (B1-2) 175 parts by weight, and (D1)
Skin and skin foam were prepared in the same manner as in Example 2, except that 0.88 parts and 2.6 parts of (D3) were mixed and the temperature was adjusted to 50 ° C., and a skin-forming agent comprising the component (B) was used. Was manufactured. (A) Temperature of component-side heat exchanger 50
At a temperature of 50 ° C. in the heat exchanger on the component (B) side, sprayed on a stainless steel mold (flat plate having a thickness of 2 mm) to a thickness of about 1 m.
m of skin were produced.

Example 5 1000 parts of prepolymer (A1-5) and 100 parts of (C1)
Part (E1) and 1.2 parts of (E1) were mixed and the temperature was adjusted to 50 ° C., component (A), 23 parts of (B1-3) and 0.12 of (D2)
Part (D3) and 0.18 part of (D3), and a skin forming agent consisting of the component (B) adjusted to 50 ° C. was used.
A skin and a skin foam were produced in the same manner as in Example 2.

Comparative Example 1 1000 parts of a prepolymer having an isocyanate group equivalent of 150, prepared from hydrogenated MDI and PPG (Mn400), 100 parts of (C1) and 1.2 parts of (E1) were mixed and heated at 50 ° C.
The component (A) whose temperature has been adjusted to 2,000 parts, (a2-4) 2000 parts, (D1) 10 parts, sodium phenolate 16 parts, diethylene glycol 160 parts and 2-amino-2-methyl-1-propanol 100 parts are mixed. A skin and a skin foam were produced in the same manner as in Example 2 except that a skin-forming agent comprising the component (B) whose temperature was adjusted to 50 ° C. was used.

Comparative Example 2 Trimer containing isocyanurate ring based on hydrogenated MDI (containing hydrogenated MDI monomer, isocyanate group equivalent of 1
40) 1000 parts, (C1) 100 parts and (E1) 1.2
Part (A), and the mixture was adjusted to 50 ° C., and (a)
2-5) 2200 parts, (D2) 9 parts, (D3) 22 parts, tetrabutyltin distanoxane dilaurate 11 parts, ethylene glycol 110 parts and 2-amino-2-methyl-1-propanol 110 parts are mixed. A skin and a skin foam were produced in the same manner as in Example 2 except that a skin-forming agent comprising the component (B) whose temperature was adjusted to 50 ° C. was used.

<Evaluation of Physical Properties> Examples 1 to 5 and Comparative Examples 1 and 2
The tensile strength, elongation, and tear strength of each of the skins manufactured in 2 were measured in accordance with JIS K6301-1995. Also, for each skin, the black panel temperature 83
After treating in a carbon arc fade meter at 400 ° C. for 400 hours, elongation was measured according to JIS K6301-1995 to evaluate light resistance. Table 1 shows the results.

[0076]

[Table 1]

[0077]

The skin-forming agent of the present invention can form a skin having excellent mechanical strength such as tensile strength, elongation and tear strength, and this skin is also excellent in light resistance. Because of the above-mentioned effects, the skin foam produced using the skin forming agent of the present invention is useful for various uses, and particularly useful as an automobile interior member. It is also useful for interior furniture such as sofas with skins.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B29K 75:00 B29K 75:00 105: 04 105: 04 B29L 31:58 B29L 31:58 F-term (Reference) 3D023 BA01 BB01 BC00 BD00 BE02 BE31 4F204 AA31 AA42 AB02 AG03 AG20 AH26 AJ02 EA01 EB01 EB22 EB30 EE02 EF25 EF27 EL04 4J034 BA08 CA04 CA05 CA14 CB03 CB04 CB05 CB07 CB08 CC03 DC02 CC02 CC02 CC02 CC02 DF20 DF22 DG03 DG04 DG05 DG06 DG08 DG09 DG14 DG16 DG20 DQ04 DQ09 DQ15 EA12 HA01 HA06 HA07 HA08 HB11 HB12 HC03 HC12 HC17 HC22 HC46 HC52 HC54 HC61 HC64 HC67 HC71 HC73 JA24 JA42 KA01 KC08 K02 K02 K18 K02 K18 K03 K02 K18 K18 K18 K12 K18 RA12

Claims (14)

[Claims] 1. An excess of polyisocyanate (a1) and O
Polymer polyol (a2) having an H equivalent of at least 250
And an isocyanate component (A) comprising an isocyanate group-terminated urethane prepolymer (A1) having an isocyanate group equivalent of 300 to 5,000 derived from a low molecular weight polyol (a3), if necessary, and a primary or secondary amino group. Polyamine having at least two in the molecule (B
A non-solvent type skin-forming agent for urethane foam with a mold-coating method, comprising an active hydrogen-containing component (B) containing at least 50 equivalent% of 1). 2. An excess of polyisocyanate (a1) and O
Polymer polyol (a2) having an H equivalent of at least 250
And an isocyanate component (A) comprising an isocyanate group-terminated urethane prepolymer (A1) having an isocyanate group equivalent of 300 to 5,000 derived from a low molecular weight polyol (a3), if necessary, and a primary or secondary amino group. Polyamine having at least two in the molecule (B
A non-solvent type skin-forming agent for urethane foam with a mold-coating method, comprising an active hydrogen-containing component (B) comprising 1) and a plasticizer (C). 3. The skin-forming agent according to claim 1, wherein (a1) is an aliphatic and / or alicyclic diisocyanate. 4. The skin-forming agent according to claim 1, wherein (a2) is a polyester diol and / or a polyether diol. 5. The skin-forming agent according to claim 1, wherein (B1) is at least one selected from the group consisting of aliphatic polyamines, alicyclic polyamines and araliphatic polyamines. 6. The skin-forming agent according to claim 1, wherein at least a part of the amino group of (B1) is ketiminated. 7. The method according to claim 1, wherein the plasticizer (C) is contained in an amount of 1 to 80% by weight based on the total weight of (A) and (B).
7. The skin forming agent according to any one of 6. 8. The skin-forming agent according to claim 1, further comprising a catalyst (D) and / or an internal release agent (E) and / or another additive (F). 9. An equivalent ratio of an isocyanate group in (A) to an active hydrogen-containing group in (B) is 1: (0.9 to 1.1).
The skin-forming agent according to any one of claims 1 to 8, wherein 10. The applied viscosity of each of (A) and (B) is 100 to 2,000 mPa · s.
The skin forming agent according to any one of the above. 11. A skin for a urethane foam with a mold coat method skin, wherein the skin forming agent according to any one of claims 1 to 10 is mixed and sprayed on the surface of a mold cavity, reacted and cured. Forming method. 12. A mixture of the skin forming agent according to any one of claims 1 to 10 and sprayed on the surface of a mold cavity. A method for producing a polyurethane foam with a skin, comprising forming a core material by foaming. 13. A polyurethane foam with a skin having a skin layer obtained by curing the skin forming agent according to claim 1. Description: 14. An automotive interior material comprising the polyurethane foam with a skin according to claim 13.