JP2015224310A - Agglutination inhibitor and resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agglutination inhibitor which is excellent in agglutination prevention, water repellency and tensile strength and extensibility and a resin composition containing the agglutination inhibitor.SOLUTION: An agglutination inhibitor (X) contains a polyurethane resin (C) obtained by reacting an active hydrogen constituent (A) with an organic polyisocyanate constituent (B), and (A) contains 0.1-20 wt.%, relative to the weight of (A), of a monovalent active hydrogen compound (a1) having a 8-40C aliphatic hydrocarbon group. A resin composition containing the agglutination inhibitor is also provided.

Description

  The present invention relates to an anti-sticking agent and a resin composition containing the anti-sticking agent and a resin.

  Conventionally, polyurethane resins are excellent in tensile strength and elongation properties, and thus have been used in a wide range of applications such as molding materials, paints, adhesives, synthetic leather, artificial leather, and elastic fibers. However, when a polyurethane resin is used as a film or sheet, there is a problem that a sticking phenomenon easily occurs due to the adhesiveness of the polyurethane resin. As a method for solving this problem, it is known to suppress stickiness by blending a lubricant such as an amide compound or metal soap or an inorganic fine powder (see, for example, Patent Document 1).

  However, when a film or sheet made of a resin composition containing the above additives for the purpose of imparting anti-sticking properties is used, the additive may decrease transparency or There is a problem of bleeding out.

  Further, in paint applications, a water-repellent paint is used to impart antifouling properties, and a method of adding fluororesin powder is disclosed as a method for imparting this water repellency (for example, Patent Document 2). reference). However, the fluororesin powder has a problem that it is expensive and lowers the tensile strength and elongation of the coating film of the resin composition.

JP-A-6-32917 JP 2002-121489 A

  An object of the present invention is to provide an anti-sticking agent excellent in anti-sticking property, water repellency and tensile strength and elongation, and a resin composition containing the anti-sticking agent.

  As a result of intensive studies to solve the problems, the present inventors have reached the present invention. That is, the present invention provides an anti-sticking agent (X) containing a polyurethane resin (C) obtained by reacting an active hydrogen component (A) with an organic polyisocyanate component (B), wherein (A) is a carbon Anti-sticking agent containing 0.1 to 20 wt% of monovalent active hydrogen compound (a1) having an aliphatic hydrocarbon group of several 8 to 40 based on the weight of (A); and the anti-sticking agent It is the resin composition formed by containing.

  The resin composition comprising the anti-sticking agent of the present invention can achieve both anti-sticking properties and recovery characteristics, and has the effect of being excellent in water repellency and tensile strength and elongation.

  The anti-sticking agent containing the polyurethane resin (C) of the present invention comprises an active hydrogen component (A) containing a monovalent active hydrogen compound (a1) having an aliphatic hydrocarbon group having 8 to 40 carbon atoms and an organic poly Obtained by reacting with the isocyanate component (B).

When the active hydrogen component (A) contains the monovalent active hydrogen compound (a1) having an aliphatic hydrocarbon group having 8 to 40 carbon atoms, a fatty acid having 8 to 40 carbon atoms at the end of the polyurethane resin (C) When an aliphatic hydrocarbon group is introduced and the aliphatic hydrocarbon group having 8 to 40 carbon atoms is oriented on the surface of the film or the like of (C), it is excellent in all of anti-sticking properties, water repellency and tensile strength and elongation. A film of an anti-sticking agent can be obtained.
In the case of (a1) an aliphatic hydrocarbon group having less than 8 carbon atoms, the anti-sticking property of the polyurethane resin (C) deteriorates, and when (a1) has 40 or more carbon atoms, the production of (C) From this point of view, the reactivity between the aliphatic hydrocarbon group and the urethane prepolymer is deteriorated.

The monovalent active hydrogen compound (a1) having an aliphatic hydrocarbon group having 8 to 40 carbon atoms is at least one selected from the group consisting of monools and monoamines described in (1) to (9) below. Examples thereof include active hydrogen compounds.
(1) C8-40 alkane monool (a11);
(2) Glycerin dialkyl ether (a12) in which the carbon number of at least one alkyl group is 8 to 40;
(3) At least one monovalent fatty acid diester (a13) of glycerin having 9 to 41 carbon atoms;
(4) A group consisting of an alkanediol having 8 to 40 carbon atoms, a glycerol monoalkyl ether having 8 to 40 carbon atoms in an alkyl group, and a monovalent fatty acid monoester of glycerol in which the monovalent fatty acid has 9 to 41 carbon atoms. A monool (a14) obtained by reacting at least one diol selected from the group consisting of monocarboxylic acids having 8 or less carbon atoms;
(5) Selected from the group consisting of an alkanediol having 7 or less carbon atoms, a glycerin monoalkyl ether having an alkyl group having 7 or less carbon atoms and a monovalent fatty acid monoester of glycerin having a monovalent fatty acid having 8 or less carbon atoms. A monool (a15) obtained by reacting at least one diol with a monovalent fatty acid having 9 to 41 carbon atoms;
(6) C8-C40 alkane monoamine (a16);
(7) A monoamine (a17) obtained by reacting an alkanediamine having 8 to 40 carbon atoms with a monocarboxylic acid having 8 or less carbon atoms;
(8) Monoamine (a18) obtained by reacting an alkanediamine having 7 or less carbon atoms with a monovalent fatty acid having 9 to 41 carbon atoms;
(9) Mono products obtained by adding an alkylene oxide having 2 to 12 carbon atoms and / or a lactone monomer having 3 to 12 carbon atoms to the monools (a11) to (a15) and / or the monoamines (a16) to (a18). All (a19).

  Examples of the alkane monool (a11) having 8 to 40 carbon atoms include linear or branched octanol, decanol, dodecanol, octadecanol, eicosanol and docosanol.

  The alkyl group in the glycerin dialkyl ether (a12) in which at least one alkyl group has 8 to 40 carbon atoms is at least one alkyl group having 8 to 40 carbon atoms (straight or branched octyl group, decyl group, dodecyl group). Group, octadecyl group, eicosyl group and behenyl group, etc., the other is an alkyl group having 1 to 7 carbon atoms (methyl group, ethyl group, linear or branched propyl group, butyl group, pentyl group, hexyl). Group or heptyl group) or an alkyl group having 8 to 40 carbon atoms. Specific examples of (a12) include glycerin dihexyl ether, glycerin dioctyl ether, glycerin di-2-ethylhexyl ether, glycerin didecyl ether, glycerin didodecyl ether, and glycerin dioctadecyl ether.

  The monovalent fatty acid diester (a13) of glycerin having 9 to 41 carbon atoms of at least one monovalent fatty acid is an ester monool obtained by reacting 1 mol of glycerin with 2 mol of monovalent fatty acid. At least 1 mole of 2 moles of fatty acid is a monovalent fatty acid having 9 to 41 carbon atoms. The monovalent fatty acid having 9 to 41 carbon atoms introduces an aliphatic hydrocarbon group having 8 to 40 carbon atoms excluding carbon of the carboxyl group.

  Examples of the monovalent fatty acid having 9 to 41 carbon atoms include linear or branched nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, octadecanoic acid, and behenic acid. Even if the other monovalent fatty acid in (a13) is a monovalent fatty acid having 9 to 41 carbon atoms, a monovalent fatty acid having 8 or less carbon atoms (acetic acid, propionic acid, linear or branched butanoic acid) , Pentanoic acid, hexanoic acid, heptanoic acid and octanoic acid).

  Specific examples of (a13) include glycerin decanoic acid diester, glycerin dodecanoic acid diester, and glycerin octadecanoic acid diester.

  Examples of the alkanediol having 8 to 40 carbon atoms used for the monool (a14) include linear or branched octanediol, decanediol, dodecanediol, and octadecanediol.

  The glycerol monoalkyl ether having 8 to 40 carbon atoms of the alkyl group used in the monool (a14) is a linear or branched octyl group, decyl group, dodecyl group, octadecyl group, eicosyl group or behenyl as the alkyl group. Examples thereof include glycerin monoalkyl ether having a group, specifically glycerin monohexyl ether, glycerin monooctyl ether, glycerin mono-2-ethylhexyl ether, glycerin monodecyl ether, glycerin monododecyl ether, and glycerin monooctadecyl ether.

  As monovalent fatty acid monoester of glycerol having 9 to 41 carbon atoms of monovalent fatty acid used for monool (a14), 1 mol of glycerol and 1 mol of monovalent fatty acid having 9 to 41 carbon atoms are used. Examples of the esterified product include glycerin decanoic acid monoester, glycerin dodecanoic acid monoester, and glycerin octadecanoic acid monoester.

  As monocarboxylic acid having 8 or less carbon atoms used for monool (a14), acetic acid, propionic acid, linear or branched aliphatic carboxylic acid such as butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid and octanoic acid Aromatic carboxylic acids such as benzoic acid and methylbenzoic acid; araliphatic carboxylic acids such as phenylacetic acid;

  Examples of the alkanediol having 7 or less carbon atoms used for the monool (a15) include ethylene glycol, linear or branched propylene glycol, butanediol, pentanediol, hexanediol and heptanediol.

  The glycerol monoalkyl ether having 7 or less carbon atoms in the alkyl group used for the monool (a15) is an alkyl group having 1 to 7 carbon atoms (methyl group, ethyl group, linear or branched propyl group). Glycerol monoalkyl ethers such as butyl group, pentyl group, hexyl group and heptyl group), specifically, glycerol monomethyl ether, glycerol monoethyl ether, glycerol monobutyl ether and glycerol monohexyl ether.

  As monovalent fatty acid monoester of glycerin in which monovalent fatty acid used in monool (a15) has 8 or less carbon atoms, esterified product of 1 mol of glycerin and 1 mol of monovalent fatty acid having 8 or less carbon atoms. Specific examples include glycerin acetic acid monoester, glycerin propionic acid monoester, glycerin butanoic acid monoester, and glycerin hexanoic acid monoester.

  Examples of the monovalent fatty acid having 9 to 41 carbon atoms used for the monool (a15) include the same monovalent fatty acids having 9 to 41 carbon atoms used for (a13).

  Examples of the alkane monoamine (a16) having 8 to 40 carbon atoms include linear or branched octylamine, dodecylamine, stearylamine, eicosylamine and docosylamine.

  The monoamine (a17) is an amidated product of 1 mol of an alkanediamine having 8 to 40 carbon atoms and 1 mol of a monocarboxylic acid having 8 or less carbon atoms. The alkanediamine having 8 to 40 carbon atoms to be used is linear or branched. And octane diamine, decane diamine, dodecane diamine, octadecane diamine and eicosane diamine.

  The monoamine (a18) is an amidation product of an alkanediamine having 7 or less carbon atoms and a monovalent fatty acid having 9 to 41 carbon atoms. Examples of the alkanediamine having 7 or less carbon atoms include ethane-1,2-diamine, Examples include chain or branched propanediamine, butanediamine, pentanediamine, hexanediamine, and heptanediamine.

  Examples of the alkylene oxide having 2 to 12 carbon atoms (hereinafter abbreviated as AO) used for the monool (a19) include ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 1,3- Alternatively, 2,3-butylene oxide, tetrahydrofuran (hereinafter abbreviated as THF), 3-methyltetrahydrofuran, styrene oxide, α-olefin oxide, epichlorohydrin, and the like can be given.

  Examples of the lactone monomer having 3 to 12 carbon atoms used for the monool (a19) include β-propiolactone, γ-butyrolactone, γ-valerolactone, ε-caprolactone, η-caprolactone, 11-undecanolactone, and Examples thereof include 12-tridecanoid.

  The AO and lactone monomers used for the monool (a19) may be used alone or in combination of two or more. When two or more types of AO and lactone monomers are used in combination, the order of bonding to monools (a11) to (a15) and / or monoamines (a16) to (a18) is arbitrary, and the bonding type is random or blocked. The format or a combination of these may be used.

  The number of moles of AO and lactone monomers added in the monool (a19) (when both are added, the total number of moles added) is preferably 1 to 7 moles, more preferably from the viewpoint of anti-sticking and water repellency. Is 1 to 5 moles.

  The aliphatic hydrocarbon group having 8 to 40 carbon atoms which the active hydrogen compound (a1) has may be substituted with a hydrocarbylcarbonyloxy group having 8 or less carbon atoms or a hydrocarbylcarbonylamino group having 8 or less carbon atoms. Well, for example, monool (a14) has an aliphatic hydrocarbon group having 8 to 40 carbon atoms substituted with a hydrocarbylcarbonyloxy group having 8 or less carbon atoms, and monoamine (a17) is a hydrocarbon having 8 or less carbon atoms. It has a C8-C40 aliphatic hydrocarbon group substituted with a carbylcarbonylamino group.

  Among monools (a11) to (a15) and (a16) and monoamines (a16) to (a18), from the viewpoints of anti-sticking and water repellency, alkane monool (a11) having 8 to 40 carbon atoms and carbon number 8-40 alkane monoamines (a16) are preferred.

  The carbon number of the aliphatic hydrocarbon group contained in the active hydrogen compound (a1) is preferably 8 to 40, more preferably 12 to 30, from the viewpoints of anti-sticking property, water repellency and tensile strength and elongation. Especially preferably, it is 12-20.

The content of the monovalent active hydrogen compound (a1) having an aliphatic hydrocarbon group having 8 to 40 carbon atoms in the active hydrogen component (A) is selected from the viewpoints of anti-sticking property, water repellency and tensile strength and elongation ( Based on the weight of A), it is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight.
Further, when the content of (a1) is less than 0.1% by weight based on the weight of (A), the anti-sticking property of the polyurethane resin (C) deteriorates, and the content of (a1) In the case of 20% by weight or more based on the weight of (A), the reactivity between the aliphatic hydrocarbon group and the urethane prepolymer deteriorates from the viewpoint of the production of (C).

  The active hydrogen component (A) is a polyol having a number average molecular weight (hereinafter abbreviated as Mn) of 500 or more, in addition to the monovalent active hydrogen compound (a1) having an aliphatic hydrocarbon group having 8 to 40 carbon atoms. a2), a chain extender (a3) and a reaction terminator (a4) can be contained.

  Examples of the polyol (a2) having Mn of 500 or more include polyester polyol, polyether polyol, polyether ester polyol, polyolefin polyol, acrylic polyol, castor oil-based polyol, and polymer polyol.

  Examples of the polyester polyol having Mn of 500 or more include condensed polyester polyol, polylactone polyol, and polycarbonate polyol.

  Examples of the condensed polyester polyol having Mn of 500 or more include polyhydric alcohols having 2 to 20 carbon atoms and polyvalent carboxylic acids having 2 to 10 carbon atoms or ester-forming derivatives thereof [acid anhydrides, lower (1 to 4 carbon atoms)]. ) Alkyl esters and acid halides, etc.].

  Examples of the polyhydric alcohol having 2 to 20 carbon atoms include linear or branched aliphatic dihydric alcohols having 2 to 12 carbon atoms [ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentane. Linear chain such as diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, triethylene glycol and tetraethylene glycol 1,2-, 1,3- or 2,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-methyl -1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,6-hexane All, 3-methyl-1,6-hexanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7-heptanediol, 4-methyl-1,7-heptanediol, 2-methyl- Branched alcohols such as 1,8-octanediol, 3-methyl-1,8-octanediol and 4-methyloctanediol]; alicyclic dihydric alcohols having 6 to 20 carbon atoms [1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7 -Norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, 1,4- Sus (hydroxymethyl) cyclohexane and 2,2-bis (4-hydroxycyclohexyl) propane, etc.]; divalent alcohols having 8-20 carbon atoms [m- or p-xylylene glycol, bis (hydroxyethyl) benzene AO adducts of bis (hydroxyethoxy) benzene, bisphenol (such as bisphenol A, bisphenol S and bisphenol F) (Mn less than 500), AO adducts of dihydroxynaphthalene (Mn less than 500) and bis (2-hydroxyethyl) terephthalate, etc.] A trihydric alcohol having 3 to 20 carbon atoms [aliphatic triol (such as glycerin and trimethylolpropane)]; a tetrahydric to tetrahydric alcohol having 5 to 20 carbon atoms [aliphatic polyol (pentaerythritol, sorbitol, mannitol, sorbitan, Diglycerin and dipentaerythritol, etc.); saccharides (sucrose, glucose, mannose, fructose, methyl glucoside and derivatives thereof)] and the like.

  Of these polyhydric alcohols, dihydric alcohols are preferable from the viewpoint of tensile strength and elongation, and aliphatic dihydric alcohols having 2 to 8 carbon atoms are more preferable. A polyhydric alcohol may be used individually by 1 type, or may use 2 or more types together.

  Examples of the polyvalent carboxylic acid having 2 to 10 carbon atoms or ester-forming derivatives thereof include aliphatic dicarboxylic acids (such as succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid and maleic acid), and alicyclic dicarboxylic acids ( Dimer acids, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), trivalent or higher polycarboxylic acids (trimellitic acid, pyromellitic acid, etc.), and their anhydrides (succinic anhydride, Maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), their acid halides (such as adipic acid dichloride), their low molecular weight alkyl esters (such as dimethyl succinate and dimethyl phthalate), and combinations thereof. . Of these, preferred are aliphatic dicarboxylic acids and ester-forming derivatives thereof. A polyvalent carboxylic acid may be used individually by 1 type, or may use 2 or more types together.

  Examples of the polylactone polyol include those obtained by ring-opening polymerization of a lactone monomer having 3 to 12 carbon atoms using the above polyhydric alcohol having 2 to 20 carbon atoms as an initiator. A lactone monomer may be used individually by 1 type, or may use 2 or more types together.

  As a polycarbonate polyol, it is 1 type (s) or 2 or more types (preferably 2 ~ 2) of C2-C20 polyhydric alcohol (preferably C3-C9, more preferably C4-C6 aliphatic dihydric alcohol). 4 types) and a low-molecular carbonate compound (for example, an alkyl group having 1 to 6 carbon atoms, an alkylene carbonate having 2 to 6 carbon atoms, and a diaryl carbonate having 6 to 9 carbon atoms) From the above, polycarbonate polyol produced by condensation while causing dealcoholization reaction is mentioned.

  Examples of the polyether polyol include compounds obtained by adding AO to a polyhydric alcohol having 2 to 20 carbon atoms. AO may be used alone or in combination of two or more. In the latter case, block addition (chip type, balance type, active secondary type, etc.), random addition, or a combination of these may be used.

  The addition of AO to the polyhydric alcohol can be carried out by a usual method, without catalyst or in the presence of a catalyst (such as an alkali catalyst, an amine catalyst and an acidic catalyst) (particularly at the latter stage of AO addition). The reaction is carried out in one stage or multiple stages under normal pressure or under pressure.

  Specific examples of the polyether polyol include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol (hereinafter abbreviated as PTMG), polyoxy-3-methyltetramethylene glycol, THF / EO copolymerized diol, and THF / 3. -Methyltetrahydrofuran copolymer diol and the like. Of these, PTMG is preferred from the viewpoint of tensile strength and elongation.

  The polyether ester polyol is a polycondensation of one or more of the above polyether polyols and one or more of the polyvalent carboxylic acids having 2 to 10 carbon atoms or the ester-forming derivatives thereof exemplified as the raw material of the condensed polyester polyol. Can be obtained.

  Examples of the polyolefin polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol.

  As the acrylic polyol, a hydroxyl group-containing ethylenically unsaturated monomer [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc.] and other examples, for example, described in JP-A-4-292683 And a copolymer with an ethylenically unsaturated monomer. Specific examples of the acrylic polyol include a copolymer of hydroxyethyl acrylate and ethyl acrylate, a copolymer of hydroxyethyl acrylate, ethyl acrylate and styrene, and the like.

  Castor oil-based polyols include castor oil, castor oil fatty acids and polyester polyols from polyhydric alcohols having 2 to 20 carbon atoms and polyoxyalkylene polyols (mono- or diglycerides of castor oil fatty acids, castor oil fatty acids and trimethylolpropane). Mono-, di- or triester from castor, mono- or diester from castor oil fatty acid and polyoxypropylene glycol, etc.), castor oil added with AO, and mixtures of two or more thereof. .

  As the polymer polyol, for example, one or more ethylenically unsaturated monomers (styrene, acrylonitrile, etc.) described in JP-A-4-292683 are (co) polymerized in one or more polyols (a2). Examples of the dispersion stabilized (polymer content is usually 5 to 40% by weight).

  A polyol (a2) may be used individually by 1 type, or may use 2 or more types together.

  Mn of the polyol (a2) is preferably 500 or more, more preferably 1,000 to 5,000, and particularly preferably 1,500 to 3,000, from the viewpoint of tensile strength and elongation.

In addition, the measurement of Mn of the polyol in this invention can be measured by the gel permeation chromatography, for example on the following conditions.
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation)”
Sample solution: 0.25 wt% tetrahydrofuran solution solution injection amount: 10 μl
Flow rate: 0.6 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene

  Examples of the chain extender (a3) include water, polyhydric alcohols having 2 to 20 carbon atoms, and polyamine compounds having a chemical formula amount of less than 500.

  Among the polyhydric alcohols having 2 to 20 carbon atoms as chain extenders, aliphatic dihydric alcohols having 2 to 8 carbon atoms and trihydric alcohols having 3 to 20 carbon atoms are preferable from the viewpoint of tensile strength and elongation. Ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, glycerin and trimethylolpropane are more preferable, and ethylene glycol, 1,3-propanediol and 1,4-butanediol are particularly preferable.

  Examples of polyamine compounds having a chemical formula amount of less than 500 include aliphatic polyamines having 2 to 36 carbon atoms [alkylene diamines such as ethylenediamine and hexamethylenediamine; diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepentamine, Poly (n = 2-6) alkylene (carbon number 2-6) poly (n = 3-7) amine, etc.] such as pentaethylenehexamine and hexaethyleneheptamine], alicyclic polyamines having 6-20 carbon atoms ( 1,3- or 1,4-diaminocyclohexane, 4,4′- or 2,4′-dicyclohexylmethanediamine, isophoronediamine, etc.), aromatic polyamines having 6 to 20 carbon atoms (1,3- or 1,4 -Phenylenediamine, 2,4- or 2,6-tolylene diamine And 4,4'- or 2,4'-methylenebisaniline), C3-C20 heterocyclic polyamines (2,4-diamino-1,3,5-triazine, piperazine and N-aminoethyl) Piperazine, etc.), hydrazine or derivatives thereof (dibasic acid dihydrazide, adipic acid dihydrazide, etc.) and amino alcohols having 2 to 20 carbon atoms (for example, ethanolamine, diethanolamine, 2-amino-2-methylpropanol and triethanolamine), etc. Is mentioned. Of these, aromatic diamines having 6 to 20 carbon atoms are preferred, and 4,4'-diaminodiphenylmethane is more preferred from the viewpoint of the strength and elongation of the resulting polyurethane resin.

Of (a2) and (a3), the active hydrogen component (A) is preferably a polyester polyol, polyether polyol, polyether ester polyol, or polyamine from the viewpoint of tensile strength and elongation. More preferred are ether esters and polyamines.
For example, PTMG, ethylene glycol, ethylenediamine and the like.

  The content of the total active hydrogen component (A) as a constituent unit of the polyurethane resin (C) is preferably 15 to 35% by weight or less based on the total weight of (C) from the viewpoint of anti-sticking property, More preferably, it is 18-30 weight%, Most preferably, it is 20-28 weight%.

  As the reaction terminator (a4), monoalcohols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.), monoamines having 1 to 20 carbon atoms (Mono- or dialkylamines such as monomethylamine, monoethylamine, monobutylamine, dibutylamine and monooctylamine and mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine). In addition, the monovalent active hydrogen compound (a1) having an aliphatic hydrocarbon group having 8 to 40 carbon atoms also has a function as a reaction terminator.

  As the organic polyisocyanate component (B), those conventionally used for polyurethane production can be used. Specifically, the aromatic polyisocyanate having 8 to 26 carbon atoms having 2 to 3 or more isocyanate groups ( b1), C4-C22 aliphatic polyisocyanate (b2), C8-C18 alicyclic polyisocyanate (b3), C10-C18 araliphatic polyisocyanate (b4) and their poly Examples thereof include a modified product of isocyanate (b5).

  Examples of the aromatic polyisocyanate (b1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), and crude product. TDI, 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), crude MDI, polyaryl polyisocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4, 4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate and m-or p-isocyanatophenylsulfonyl isocyanate is mentioned.

  Examples of the aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl- 2,6-diisocyanatohexanoate is mentioned.

  Examples of the alicyclic polyisocyanate (b3) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, and methyl. Examples include cyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the araliphatic polyisocyanate (b4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

  As the modified polyisocyanate (b5) of (b1) to (b4), the urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group or oxazolidone group of the polyisocyanate. And modified products [for example, modified MDI (such as urethane-modified MDI, carbodiimide-modified MDI, and trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI).

  Among these, from the viewpoint of tensile strength and elongation of the polyurethane resin (C), an aromatic polyisocyanate (b1) having 8 to 26 carbon atoms is preferable, and among them, an aromatic diisocyanate having 8 to 26 carbon atoms is more preferable. Of these, MDI is particularly preferred. An organic polyisocyanate component (B) may be used individually by 1 type, or may use 2 or more types together.

  The content of the organic polyisocyanate (B) as a constituent unit of the polyurethane resin (C) is preferably 2 to 10% by weight or less based on the total weight of (C), more preferably from the viewpoint of the strength of the resin. Is from 3 to 9% by weight, particularly preferably from 4 to 8% by weight.

  From the viewpoint of the strength of the polyurethane resin (C), when the total weight of the active hydrogen component (A) and the organic polyisocyanate (B) is 100, the weight ratio [(A) / (B)] is preferably [ (65 to 95) / (5 to 35)], more preferably [(68 to 90) / (10 to 32)], particularly preferably [(72 to 85) / (15 to 28)]. It is.

The molar ratio [(urethane group) / (urea group)] of urethane group / urea group introduced into the polyurethane resin (C) is preferably [(0.80-2.00) / (0 to 0.75)], more preferably [(0.84 to 1.96) / (0.01 to 0.50)].
From the weight of the water which reacts with the organic polyisocyanate (B) and the active hydrogenated compounds (a1) and (B) used in the production of the polyurethane resin (C), the molar ratio is as follows. The ratio of the number of moles of the urethane group (—NHCOO—) contained and the number of moles of the urea group (—NHCONH—) was determined by calculation.

From the viewpoint of anti-sticking property, the solubility parameter of the functional group in the polyurethane resin (C) contained in the anti-sticking agent of the present invention is preferably 7.0 to 10 (cal / cm ² ) ^1/2 . more preferably from ^{7.1~9 (cal / cm 2) 1/2} , particularly preferably ^{7.2~8.5 (cal / cm 2) 1/2} .
The SP value in the present invention is calculated by the method described in the following document proposed by Fedors et al.
It is a value calculated by the following formula (1) in “POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147 to 154)”.
General formula δ = (ΔH / V) ^1/2 (1)
{Wherein δ is the solubility parameter (cal / cm ² ) ^1/2 , ΔH is the heat of molar evaporation (cal), and V is the molar volume (cm ³ ). }

The production method of the anti-sticking agent comprising the polyurethane resin (C) of the present invention is not particularly limited, but the urethane prepolymer and preferably the organic solvent are continuously line-mixed with a static mixer, and further an instantaneous mixer. And a method of instantaneously mixing and reacting this urethane prepolymer and a chain extender, a method of batch-reacting (A), (B) and, if necessary, adding a solvent and reacting with heating.
Although it does not specifically limit as a manufacturing method of a urethane prepolymer, For example, in the absence of a solvent, (A) and (B) are mixed and heated in a kneader, or in the presence of a solvent in a batch-type reaction tank with a stirrer or not. In the presence, a method in which (A) and (B) are mixed and reacted by heating can be mentioned.

  In the production method of the present invention, an organic solvent can be used in any production process. The organic solvent is not particularly limited, and examples thereof include ketone solvents having 3 to 10 carbon atoms (for example, acetone, methyl ethyl ketone and methyl isobutyl ketone), and ester solvents having 2 to 10 carbon atoms (for example, ethyl acetate, butyl acetate and γ-butyrolactone). ), C 4-10 ether solvents (for example, dioxane, THF, ethyl cellosolve, and diethylene glycol dimethyl ether), C 3-10 amide solvents [for example, N, N-dimethylformamide, N, N-dimethylacetamide ( Hereinafter, abbreviated as DMAC), N-methyl-2-pyrrolidone and N-methylcaprolactam], sulfoxide solvent having 2 to 10 carbon atoms (for example, dimethyl sulfoxide), alcohol solvent having 1 to 8 carbon atoms (for example, methanol, ethanol) ,Isopropyl alcohol Fine octanol) and 4-10 hydrocarbon solvents carbon atoms (e.g. n- butane, cyclohexane, toluene and xylene) and the like.

  Among these, from the viewpoint of tensile strength and elongation of the anti-sticking agent containing the polyurethane resin (C), an amide solvent having 3 to 10 carbon atoms and a sulfoxide solvent having 2 to 10 carbon atoms are preferable, and 3 to 3 carbon atoms are preferable. Ten amide solvents are more preferred, and DMAC is particularly preferred.

  When an organic solvent is used, the amount of the resin used is preferably 10 to 90% by weight, more preferably 30 to 80% by weight.

  Further, in the production of the anti-sticking agent containing the polyurethane resin (C), a catalyst usually used for polyurethane can be contained as necessary for promoting the reaction. Specific examples of the catalyst include, for example, organometallic compounds [dibutyltin dilaurate, dioctyltin dilaurate, bismuth carboxylate, bismuth alkoxide, a chelate compound of bismuth with a compound having a dicarbonyl group, etc.], inorganic metal compounds [bismuth oxide, hydroxide Bismuth, bismuth halide, etc.]; amines [triethylamine, triethylenediamine, diazabicycloundecene, etc.] and combinations of two or more of these.

Pigments, stabilizers and other additives can be added to the anti-sticking agent containing the polyurethane resin (C) of the present invention.
The pigment is not particularly limited, and known organic pigments and / or inorganic pigments can be used. Examples of the organic pigment include insoluble azo pigments, soluble azo pigments, copper phthalocyanine pigments, and quinacridone pigments. Examples of inorganic pigments include chromates, ferrocyan compounds, metal oxides, selenium sulfide compounds, metal salts (sulfates, silicates, carbonates, phosphates, etc.), metal powders, and carbon black. The amount of the pigment used is preferably 0 to 5% by weight, more preferably 0.1 to 3% by weight, based on the weight of the polyurethane resin (C).

A stabilizer is not specifically limited, A well-known antioxidant and / or a ultraviolet absorber can be used.
Antioxidants include phenolic [2,6-di-t-butyl-p-cresol and butylated hydroxyanisole, etc.]; bisphenol [2,2′-methylenebis (4-methyl-6-t-butylphenol) Etc.]; phosphorus-based [triphenyl phosphite and diphenylisodecyl phosphite etc.] and the like. Examples of the ultraviolet absorber include benzophenone [2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone and the like]; benzotriazole [2- (2′-hydroxy-5′-methylphenyl) benzotriazole and the like]; Salicylic acid type [phenyl salicylate and the like]; hindered amine type [bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like] and the like. The addition amount of the stabilizer is preferably 0 to 5% by weight, more preferably 0.1 to 3% by weight, based on the weight of the polyurethane resin (C).

Other additives include anti-fusing agents and flame retardants.
As the anti-fusing agent, it is better to have high heat resistance because it is not volatilized by high-temperature heat treatment in solid phase polymerization, and inorganic materials such as salt, talc and smectite, fluorine compounds, siloxane compounds (dimethylpolysiloxane, diphenylpolysiloxane) Siloxane, methylphenylpolysiloxane, etc.) and mixtures thereof.
Examples of the flame retardant include phosphorus-containing cyclic compounds, phosphorus-containing bromine compounds, chlorinated alkyl phosphates, methylol phosphonates, condensed phosphate esters, and condensed phosphates.

  The pigment, stabilizer and other additives can be added at any stage during the production of the anti-sticking agent containing the polyurethane resin (C), and may be added after the production.

The anti-sticking agent containing the polyurethane resin (C) of the present invention is formed into a molded article such as a block-like article, a plate-like article, a sheet, a film and a thread by a molding machine (such as a heating molding machine and an injection molding machine). Used for various purposes.
Applications include excellent anti-sticking properties, water repellency and tensile properties, and therefore include automotive parts, electrical products, OA equipment, architecture, paints, artificial leather, synthetic leather, elastic fibers, and the like.

  The anti-sticking agent containing the polyurethane resin (C) of the present invention may be used by adding to the resin (R) or may be used alone.

Examples of the resin (R) mixed with the anti-sticking agent containing the polyurethane resin (C) of the present invention include polyurethane resin (R1), polyurethane urea resin (R2), polyester resin (R3), epoxy resin (R4), acrylic Examples include resin (R5), polyolefin (R6), polyimide (R7), polystyrene (R8), and polyamide (R9).
(R) may be used alone or in combination of two or more.

Examples of the polyurethane resin (R1) include those having the polyol (1) and the isocyanate (2) as structural units.
Examples of the polyol (1) include polyether polyol, polyester polyol, polycarbonate polyol, silicone polyol, and alkyl polyol.
Among the polyether polyols, examples of the aliphatic polyether polyol include polyoxyethylene polyol (polyethylene glycol, etc.), polyoxypropylene polyol (polypropylene glycol, etc.), polyoxyethylene / propylene polyol, and polytetramethylene ether glycol. It is done.
As the aromatic polyether polyol, a polyol having a bisphenol skeleton (for example, an ethylene oxide of bisphenol A (hereinafter abbreviated as EO) and / or a propylene oxide (hereinafter abbreviated as PO) 2 to 20 mol adduct), and An EO and / or PO adduct of resorcin, and the like can be mentioned.

Polyether polyols open an alkylene oxide (hereinafter abbreviated as AO) to an aliphatic or aromatic active hydrogen atom-containing compound in the presence of an addition catalyst (a known catalyst such as an alkali metal hydroxide and a Lewis acid). Obtained by cycloaddition reaction.
Examples of the polyester polyol include condensed polyester and polylactone polyol.
Examples of the condensed polyester include polyesters of a low molecular weight (Mn 300 or less) polyhydric alcohol and a polyvalent carboxylic acid or an ester-forming derivative thereof.
Examples of the low molecular weight polyhydric alcohol include 2 to 8 or more aliphatic polyhydric alcohols having a hydroxyl group equivalent of 30 or more and less than 150, and 2 to 8 or more phenols AO having a hydroxyl group equivalent of 30 or more and less than 150. Examples include low molar adducts.
Among the low molecular weight polyhydric alcohols constituting the condensed polyester, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexane glycol, bisphenol A EO and / or PO low molar addition Are preferable, and it is preferable to use these in combination.
Examples of the polyvalent carboxylic acid constituting the condensed polyester or its ester-forming derivative include aliphatic dicarboxylic acids (such as succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid and maleic acid), alicyclic dicarboxylic acids ( Dimer acids, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), trivalent or higher polycarboxylic acids (1,2,4-benzenetricarboxylic acid and 1,2,4,5-benzene) Tetracarboxylic acid, etc.), anhydrides thereof (succinic anhydride, maleic anhydride, phthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, etc.), acid halides thereof (adipic acid dichloride, etc.), these Low molecular weight alkyl esters (such as dimethyl succinate and dimethyl phthalate) and combinations thereof may be mentioned.

The polylactone polyol is a polyaddition product of a low molecular weight polyhydric alcohol and a lactone. As the lactone, a lactone having 4 to 12 carbon atoms can be used, specifically, 4-butanolide, 5-pentanolide, and 6-hexanolide. Etc.
Specific examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

The polycarbonate polyol is a polyaddition product of a low molecular weight polyhydric alcohol and an alkylene carbonate. Examples of the alkylene carbonate include alkylene carbonates having 2 to 8 carbon atoms, and specific examples include ethylene carbonate and propylene carbonate. Two or more of these may be used in combination.
Examples of the polycarbonate polyol include polyhexamethylene carbonate diol.

  Examples of the silicone polyol include a diol having a hydroxyl group at the terminal of the silicone resin.

Examples of the alkyl polyol include the low molecular weight aliphatic polyhydric alcohols described above.
Mn of the THF soluble content of the polyol (1) is preferably 100 to 20,000, more preferably 200 to 10,000, and particularly preferably 400 to 9,000 from the viewpoint of resin strength.

  As the diisocyanate (2), an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), an aliphatic diisocyanate having 2 to 18 carbon atoms, a modified product of these diisocyanates (urethane group, Carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group-containing modified product) and mixtures of two or more thereof.

  Aromatic diisocyanates include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, m- or p-xylylene diisocyanate (XDI), α , Α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI {crude diaminophenylmethane [formaldehyde and aromatic amine (aniline) ) Or a mixture thereof and a mixture thereof.

  Examples of the aliphatic diisocyanate include a chain aliphatic diisocyanate and a cyclic aliphatic diisocyanate.

  Examples of chain aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethylcaproate. Bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and mixtures thereof.

  Cycloaliphatic diisocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanatoethyl). -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, and mixtures thereof.

  As the modified product of diisocyanate, a modified product containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a burette group, a uretdione group, a uretoimine group, an isocyanurate group and / or an oxazolidone group is used. Urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and mixtures thereof (for example, a mixture of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)).

  Examples of the polyurethane urea resin (R2) include those having a polyol (1), an isocyanate (2), and a diamine (3) as structural units.

  Examples of the diamine (3) include aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms.

  Examples of the aliphatic diamine having 2 to 18 carbon atoms include a chain aliphatic diamine and a cyclic aliphatic diamine.

  Examples of chain aliphatic diamines include alkylene diamines having 2 to 12 carbon atoms (ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and polyalkylene (2 to 6 carbon atoms) polyamines [diethylene triamine, imino. Bispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.].

  Cycloaliphatic polyamines include alicyclic diamines having 4 to 15 carbon atoms {1,3-diaminocyclohexane, isophorone diamine, mensen diamine, 4,4'-methylene dicyclohexane diamine (hydrogenated methylene dianiline) and 3 , 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like} and a heterocyclic diamine having 4 to 15 carbon atoms [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, etc.] and the like.

  The aromatic diamine having 6 to 20 carbon atoms is an aromatic having an unsubstituted aromatic diamine or an alkyl group (an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n- or isopropyl group, and a butyl group). Examples include diamines.

  Examples of the unsubstituted aromatic diamine include 1,2-, 1,3- or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, diaminodiphenylsulfone, benzidine, thiodianiline, bis (3 , 4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, naphthylenediamine and mixtures thereof.

  The aromatic diamine having an alkyl group (alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n- or isopropyl group and butyl group) includes 2,4- or 2,6-tolylenediamine, crude Tolylenediamine, diethyltolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2 , 4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl -2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl -2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl -2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6 -Dibutyl-1,5-diaminonaphthalene, 3,3 ', 5,5'-tetramethylbenzidine, 3,3', 5,5'-tetraisopropylbenzidine, 3,3 ', 5,5'-tetramethyl -4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraisopropyl-4, '-Diaminodiphenylmethane, 3,3', 5,5'-tetrabutyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,5-diisopropyl- 3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3', 5 5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4 ′ -Diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone and mixtures thereof Can be mentioned.

As polyester resin (R3), what has a polyol (1) and dicarboxylic acid (4) as a structural unit is mentioned.
Examples of the dicarboxylic acid (4) include alkanedicarboxylic acids having 4 to 36 carbon atoms (such as succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, and decylsuccinic acid); Cyclic dicarboxylic acid [dimer acid (dimerized linoleic acid), etc.], alkene dicarboxylic acid having 4 to 36 carbon atoms [alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.), malee Acid, fumaric acid, citraconic acid, etc.]; aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-biphenyl Dicarboxylic acids, etc.); and their anhydrides or lower alkyls (1 to 4 carbon atoms) or hydroxy Cialkyl (C1-C4) ester [(anhydrous) phthalic acid, dimethyl terephthalate, terephthalic acid 1,2-propylene glycol diester, etc.] etc. are mentioned.

  Examples of the epoxy resin (R4) include ring-opening polymer of polyepoxide (5), polyepoxide (6) and active hydrogen-containing compound [water, polyol (1), dicarboxylic acid (4), diamine (3), etc.] Examples include adducts.

  Examples of the epoxy resin (R4) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds.

  Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols.

  Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyldi Glycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -T-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, phenol Or cresol novolak resin glycidyl ether, limonene phenol novolak resin glycidyl ether, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, condensation of phenol and glyoxal, glutaraldehyde or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by the reaction and polyglycidyl ethers of polyphenols obtained by the condensation reaction of resorcin and acetone.

  Examples of the glycidyl ester of polyhydric phenol include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester.

  Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine. Furthermore, as the aromatic system, triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, glycidyl group obtained by reacting polyol with the two reactants Also included is a diglycidyl ether of an AO adduct of bisphenol A and a containing polyurethane (pre) polymer.

  Examples of the heterocyclic polyepoxy compound include trisglycidylmelamine. ; As the alicyclic polyepoxy compound, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy -6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6-methyl (Cyclohexylmethyl) butylamine and dimer acid diglycidyl ester. The alicyclic group also includes a nuclear hydrogenated product of the aromatic polyepoxide compound. Examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether Can be mentioned. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate and diglycidyl pimelate. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. As the aliphatic group, a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate is also included.

  Of these polyepoxides, aliphatic polyepoxy compounds and aromatic polyepoxy compounds are preferred. Two or more polyepoxides may be used in combination.

As an acrylic resin (R5), the polymer which homopolymerized or copolymerized the monomer which has a polymerizable double bond is mentioned.
As a monomer having a polymerizable double bond, an unsaturated monocarboxylic acid having 3 to 30 carbon atoms [for example, (meth) acrylic acid (representing acrylic acid and / or methacrylic acid; the same shall apply hereinafter), crotonic acid isocrotonic acid. And cinnamic acid, etc.]; an unsaturated dicarboxylic acid (anhydride) having 3 to 30 carbon atoms [for example, (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid, mesaconic acid, etc.]; 30 monoalkyl (1 to 24 carbon atoms) esters of unsaturated dicarboxylic acids (eg maleic acid monomethyl ester, maleic acid monooctadecyl ester, fumaric acid monoethyl ester, itaconic acid monobutyl ester, itaconic acid glycol monoether and citraconic acid) Monoeicosyl ester, etc.).

  Examples of the polyolefin (R6) include those having an α-olefin as a structural unit.

  Examples of the polyimide resin (R7) include aliphatic polyimide resins (polymers obtained from aliphatic carboxylic dianhydrides and aliphatic diamines) and aromatic polyimide resins (aromatic carboxylic dianhydrides and aliphatic diamines) And polymers obtained from aromatic diamines).

  Examples of polystyrene (R8) include those having styrene as a structural unit.

  Examples of the polyamide resin (R9) include lactam ring-opening polymers, aminocarboxylic acid polycondensates, polycarboxylic acids and polyamine polycondensates, and the like.

In addition, the phenomenon that the solution viscosity of the mixed solution becomes higher than expected compared to the solution viscosity of the polyurethane (C) before the addition occurs by mixing the polyurethane resin (C) solution of the anti-sticking agent and the resin (R). There is a case.
From the viewpoint of preventing this phenomenon, dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine, diethyleneamine Mixing one or more end capping agents such as monoamines such as diamine triamine, triamines such as diethylenetriamine, ethanol, propanol, butanol, isopropanol, monools such as allyl alcohol, cyclopentanol, and monoisocyanates such as phenyl isocyanate It is also preferably used.

In the resin composition containing the anti-sticking agent containing the polyurethane resin (C) of the present invention and the resin (R), the contact angle with respect to water of the resin composition is preferably 97 ° or more from the viewpoint of anti-sticking property, More preferably, it is 98 ° or more, and particularly preferably 99.0 ° or more.
<Measurement method of contact angle to water of resin composition containing anti-sticking agent containing polyurethane resin (C) and resin (R)>
The contact angle with respect to water of the resin composition containing the anti-sticking agent containing the polyurethane resin (C) of the present invention and the resin (R) can be measured by the following method.
[1] Film production method A resin composition solution is applied to a release-treated glass plate with a thickness of 1.0 mm, dried in a circulating dryer at 70 ° C. for 3 hours, and then peeled off from the glass plate. A film having a thickness of about 0.2 mm was produced.
[2] Method of measuring contact angle with water The contact angle of the film of [1] with respect to water was measured using a fully automatic interfacial tension meter PD-W [manufactured by Kyowa Interface Science Co., Ltd.].

  The content of the anti-sticking agent in the resin composition containing the anti-sticking agent containing the polyurethane resin (C) of the present invention and the resin (R) other than the anti-sticking agent is compatible with anti-sticking properties and recovery characteristics. In view of the above, based on the weight of the resin composition, it is preferably 0.01 to 50% by weight, more preferably 0.02 to 35% by weight, and particularly preferably 0.03 to 20% by weight. .

In the present invention, the mixing method of the anti-sticking agent (X) and the resin (R) is not particularly limited, and may be a known method that is usually performed, and examples thereof include melt mixing.
Examples of the mixing device in the case of melt mixing include a batch type mixing device such as a reaction tank and a continuous mixing device. In order to uniformly mix at an appropriate temperature in a short time, a continuous mixing device is preferable.

The resin composition of the anti-sticking agent and the resin (R) containing the polyurethane resin (C) of the present invention is produced by using a molding machine (such as a heating molding machine and an injection molding machine) with a block-like product, a plate-like product, a sheet, It is a molded product such as a film and a thread, and is used for various applications.
Applications include excellent anti-sticking properties, recovery properties, water repellency and tensile properties, and thus include automotive parts, electrical products, OA equipment, architecture, paints, artificial leather, synthetic leather, elastic fibers, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this.

Examples 1 to 6 and Comparative Example 1
Based on the formulation described in Table 1, in a reaction vessel equipped with a stirrer and a temperature controller, the polyol (a2), chain extender (a3), organic polyisocyanate component (B) of the active hydrogen component (A), and After adding an organic solvent and reacting at 70 ° C. for 10 hours in a dry nitrogen atmosphere, a monovalent active hydrogen compound (a1) having an aliphatic hydrocarbon group having 8 to 40 carbon atoms or a monovalent activity for comparison The hydrogen compound (a′1) was added and reacted for 1 hour. After completion of the reaction, a solution viscosity stabilizer was added to the reaction solution. Anti-sticking agents (X-1) to (X-6) containing the polyurethane resins (C-1) to (C-6) of Examples 1 to 6 and the sticking containing the polyurethane resin (R) of Comparative Example 1 An inhibitor (X′-1) was produced.

  In addition, PTMG2000 as polyol (a2) in Table 1 represents polyoxytetramethylene glycol (trade name: “PTMG2000”) having a Mn of 2,000 manufactured by Mitsubishi Chemical Corporation, and represents an organic polyisocyanate component (B). MDI represents 4,4′-diphenylmethane diisocyanate (trade name: “Millionate MT”) manufactured by Nippon Polyurethane Co., Ltd.

  Table 1 shows the content (% by weight) of the monovalent active hydrogen compound (a1) having an aliphatic hydrocarbon group having 8 to 40 carbon atoms in the active hydrogen component (A).

Anti-sticking agents (X-1) to (X-6) containing the polyurethane resins (C-1) to (C-6) obtained in Examples 1 to 6 and the polyurethane resin obtained in Comparative Example 1 ( R) are blended in the proportions shown in Tables 2 and 3, and the resin compositions (Y-1) to (Y-12) of Examples 11 to 22 and the resin compositions (Y′- of Comparative Examples 2 and 3). 2) and (Y′-3) were obtained.
Resin composition (Y) containing anti-sticking agent (X) of Examples 1, 3, 4 and 6, anti-sticking agents of Examples 1 to 6 and polyurethane resin (R) of Comparative Example 1, (Y Table 2 and Table 3 show the measurement results of the contact angle, peel adhesion strength, recovery characteristics, and tensile strength / elongation of the film.

[1] Method for producing film The resin composition (Y) is applied to a release-treated glass plate with a thickness of 1.0 mm, dried in a circulating dryer at 70 ° C. for 3 hours, and then peeled off from the glass plate. Thus, a film having a thickness of about 0.2 mm was produced.

[2] Method of measuring contact angle of film with water The contact angle of the film with water was measured using a fully automatic interfacial tension meter PD-W [manufactured by Kyowa Interface Science Co., Ltd.].
If the contact angle of the film with respect to water is 97 ° or more, the anti-sticking property is excellent.

[3] Measuring method of peel adhesion strength between films Two films with a size of 100 mm x 225 mm are overlapped and sandwiched between glass plates of 100 mm x 225 mm x thickness 3 mm, and a 5 kg weight is not offset on the glass plate And then left to stand in a 70 ° C. environment for 3 hours, the overlap film was cut into a size of 25 mm × 225 mm and used as a test piece. The thickness of the parallel part of the test piece is about 200 μm, the width of the parallel part is 25 mm, and the length of the vertical part is 225 mm. After leaving the test piece in a room adjusted to a temperature of 25 ° C. and a humidity of 65% RH for 1 day, the peel adhesion strength was measured according to JIS K 6854-3. The smaller this value, the better the blocking resistance.

[4] Measuring method of recovery characteristics of film A strip-shaped test piece having a length of 100 mm and a width of 5 mm was cut out from the film obtained above and marked so that the distance between the marked lines was 50 mm. This test piece is set on the chuck of an Instron type tensile tester (manufactured by Shimadzu Corporation) and stretched at a constant speed of 500 mm / min in an atmosphere of 25 ° C. until the distance between the marked lines reaches 300%. Immediately, the same speed was returned to the distance between the chucks before stretching.
The distance (L ₁ ) between the marked lines after the operation was measured, and the residual strain rate (%) was determined from the following equation using this value and the distance between the marked lines before the test (L ₀ = 50 mm).
Residual strain (%) = {(L ₁ −L ₀ ) / L ₀ } × 100
If the residual strain is in the range of 20 to 30%, the recovery characteristics are excellent.

[5] Method for measuring tensile strength and elongation of film After leaving the film obtained above in a room adjusted to a temperature of 25 ° C. and a humidity of 65% RH for 1 day, the tensile strength at break according to JIS K 6251 The elongation and the elongation at break were measured. In addition, the thickness of the parallel part of the dumbbell-shaped test piece is 200 μm, the width of the parallel part is 5 mm, and the initial distance between the marked lines is 20 mm.
As a tensile strength at the time of cutting, a range of 54 to 67 MPa is excellent from the viewpoint of durability, and as a tensile elongation at the time of cutting, a range of 630 to 750% is excellent from the viewpoint of stretchability.

The anti-sticking agent of the present invention can be added to a resin that requires anti-sticking properties and water repellency, thereby making it possible to achieve both anti-sticking properties and recovery properties, and excellent water repellency and tensile strength and elongation. Therefore, it is useful as an additive used in applications such as automobile parts, electrical products, office automation equipment, architecture, paints, artificial leather, synthetic leather and elastic fibers.

Claims (11)

  An anti-sticking agent (X) containing a polyurethane resin (C) obtained by reacting an active hydrogen component (A) with an organic polyisocyanate component (B), wherein (A) has 8 to 40 carbon atoms An anti-sticking agent containing 0.1 to 20% by weight of a monovalent active hydrogen compound (a1) having an aliphatic hydrocarbon group, based on the weight of (A). The monovalent active hydrogen compound (a1) having an aliphatic hydrocarbon group having 8 to 40 carbon atoms is at least one activity selected from the group consisting of monools and monoamines described in (1) to (9) below. The anti-sticking agent according to claim 1, which is a hydrogen compound;
(1) C8-40 alkane monool (a11);
(2) Glycerin dialkyl ether (a12) in which the carbon number of at least one alkyl group is 8 to 40;
(3) Glycerin monovalent fatty acid diester (a13) in which the carbon number of at least one monovalent fatty acid is 9 to 41;
(4) Alkanediol having 8 to 40 carbon atoms, glycerol monoalkyl ether having 8 to 40 carbon atoms in the alkyl group, and glycerol monovalent fatty acid monoester having 9 to 41 carbon atoms in the monovalent fatty acid. Monool (a14) obtained by reacting at least one diol selected with a monocarboxylic acid having 8 or less carbon atoms;
(5) at least selected from the group consisting of an alkanediol having 7 or less carbon atoms, a glycerol monoalkyl ether having an alkyl group having 7 or less carbon atoms, and a glycerin monovalent fatty acid monoester having a monovalent fatty acid having 8 or less carbon atoms. Monool (a15) obtained by reacting one kind of diol with a monovalent fatty acid having 9 to 41 carbon atoms;
(6) C8-40 alkane monoamine (a16);
(7) A monoamine (a17) obtained by reacting an alkanediamine having 8 to 40 carbon atoms with a monocarboxylic acid having 8 or less carbon atoms;
(8) Monoamine (a18) obtained by reacting an alkanediamine having 7 or less carbon atoms with a monovalent fatty acid having 9 to 41 carbon atoms;
(9) Monools in which monools (a11) to (a15) and / or monoamines (a16) to (a18) are added with alkylene oxides having 2 to 12 carbon atoms and / or lactone monomers having 3 to 12 carbon atoms. (A19).   The anti-sticking agent according to claim 1 or 2, wherein the active hydrogen component (A) further contains a polyol (a2) having a number average molecular weight of 500 or more and a chain extender (a3).   The anti-sticking agent according to claim 3, wherein the polyol (a2) having a number average molecular weight of 500 or more is polyoxytetramethylene glycol.   The anti-sticking agent according to any one of claims 1 to 4, wherein the organic polyisocyanate component (B) is an aromatic polyisocyanate (b1) having 8 to 26 carbon atoms. The anti-sticking agent according to any one of claims 1 to 5, wherein the polyurethane resin (C) has a functional group having a solubility parameter of 7 to 10 (cal / cm ³ ) ^1/2 .   The anti-sticking agent according to any one of claims 1 to 6, which is used for artificial leather, synthetic leather or elastic fibers.   The resin composition (Y) containing the anti-sticking agent (X) in any one of Claims 1-7, and resin (R).   The resin composition according to claim 8, wherein the resin (R) is at least one selected from the group consisting of polyurethane resin, polyurethane urea resin, polyester resin, epoxy resin, acrylic resin, polyolefin, polyimide, polystyrene, and polyamide.   The resin composition according to claim 8 or 9, wherein a contact angle of the resin composition (Y) with respect to water is 97 ° or more. The resin composition according to any one of claims 8 to 10, wherein the content of the anti-sticking agent (X) in the resin composition (Y) is 0.01 to 50% by weight based on the weight of (Y). object.