JP2001316653A - Hot-melt adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester polyol composition and an urethane prepolymer composition which are suitably used as a hot-melt adhesive showing an excellent initial adhesion and heat-resistant adhesion strength, and also provide a reactive hot-melt adhesive. SOLUTION: The polyester polyol composition for a hot-melt adhesive essentially comprises (A) 12-hydroxystrearic acid and (B) a 2-40C polyol having a functionality of from 2 to 6 to which (C) a polycarboxylic acid is optionally added and allowed to undergo reaction. The urethane prepolymer composition used in a reactive hot-melt adhesive is obtained by allowing a polyisocyanate compound to react with the polyester polyol composition so that there are excessive isocyanate groups of the polyisocyanate compound against the hydroxyl groups of the polyester polyol. The reactive hot-melt adhesive comprises the urethane prepolymer composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyester polyol for a hot melt type adhesive, a urethane prepolymer composition using the polyester polyol and a reactive hot melt type adhesive, and more particularly to 12-hydroxystearic acid. And a reactive hot-melt adhesive containing the urethane prepolymer composition obtained by reacting the polyester polyol with a polyisocyanate.

[0002]

2. Description of the Related Art A hot-melt adhesive is instantaneously cured by cooling after hot-melt coating, exhibits strong adhesive performance, is solvent-free, and is environmentally friendly. It is widely used because of its excellent surface. On the other hand, hot melt adhesives
A decrease in adhesion performance when reheated is inevitable. Therefore, as a solution to the drawbacks of such a hot-melt adhesive, a reactive hot-melt adhesive has been developed in which the adhesive is crosslinked by a chemical reaction after bonding to improve the heat-resistant adhesive performance. As a reactive hot-melt adhesive, for example, a urethane prepolymer containing an isocyanate group at a terminal obtained by reacting a polyester polyol with an excess amount of a polyisocyanate compound is known, and the urethane polymer is subjected to moisture crosslinking. Develop adhesive strength.

However, in the conventional methods, a thermoplastic polymer or a tackifying resin is blended,
Although some satisfactory initial adhesive properties were obtained, none of the adhesive strength after curing and heat-resistant adhesive properties were satisfactory. For example, JP-A-11-60
No. 673 proposes a urethane prepolymer using a polyester polyol blended with an organophosphorus compound, but the urethane prepolymer has an improved storage stability but an insufficient adhesive strength. Did not. Also, in JP-A-10-338834,
A polyurethane resin obtained from an alcohol component containing a castor oil fatty acid derivative and a diisocyanate compound has been proposed. The obtained polyurethane resin has excellent adhesiveness to various plastics, but its use is limited to a resin for printing ink. are doing. Further, there is no description about the use of a hot melt type adhesive.

Accordingly, an object of the present invention is to provide a polyester polyol composition, a urethane prepolymer composition and a reactive hot melt adhesive which can be suitably used especially as a hot melt adhesive. .

[0005]

As a result of various studies, the present inventors have found that the above object can be achieved by using a polyester polyol composition containing 12-hydroxystearic acid as an essential component. did.

That is, the present invention has been made on the basis of the above findings, and has the following “polyester polyol composition”,
"A urethane prepolymer composition" and "reactive hot melt adhesive" are provided. (A) 12-hydroxystearic acid and (B) 2
Polyester polyol composition for hot-melt adhesives, comprising a polyol having from 6 to 6 functional groups having 2 to 40 carbon atoms as an essential component, and optionally adding (C) a polycarboxylic acid to react. "" A urethane used in a reactive hot-melt adhesive obtained by reacting the polyester polyol composition and a polyisocyanate compound such that the isocyanate groups of the polyisocyanate compound are excessive with respect to the hydroxyl groups of the polyester polyol. "Prepolymer composition.""Reactive hot-melt adhesive comprising the urethane prepolymer composition."

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester polyol composition, urethane prepolymer composition and reactive hot melt adhesive of the present invention will be described in detail below.

The polyester polyol composition of the present invention comprises (A) 12-hydroxystearic acid and (B)
It is obtained by subjecting a polyol having 2 to 6 functionalities having 2 to 40 carbon atoms as an essential component, adding a polycarboxylic acid (C) as needed, and subjecting it to a normal esterification reaction.

The average molecular weight of the polyester polyol composition of the present invention is preferably at least 300, more preferably from 500 to 10,000, particularly preferably from 1,000 to 1,000.
5000. If the average molecular weight is less than 300, flexibility may be poor and adhesion to plastic may be reduced. If it exceeds 10,000, the viscosity becomes high, handling becomes difficult, and strength and solvent resistance are increased. Tends to decrease.

In the polyester polyol composition of the present invention, the content of (A) 12-hydroxystearic acid is preferably from 10 to 90% by weight, more preferably from 20 to 90% by weight.
(B) 2 to 6 functional carbon number of 2 to 4
The content of the polyol of 0 is preferably from 10 to 90% by weight, and more preferably from 20 to 80% by weight. If necessary, one or more (C) polycarboxylic acids can be used in a range of less than 90% by weight. As described above, the polyester polyol composition of the present invention comprises (A) 12-
It can be produced by a usual esterification reaction using hydroxystearic acid, (B) polyol and, if necessary, (C) polycarboxylic acid, but (B) polyol is excessive in order to reduce the acid value of the polyester polyol composition. Since the amount is used and is distilled off after the esterification, the above content is the ratio of each component involved in the esterification reaction, not the ratio used when producing the polyester polyol composition. Here, the content of (A) 12-hydroxystearic acid is 1% of the polyester polyol component.
If the amount is less than 0% by weight, the physical properties of the obtained urethane prepolymer composition are undesirably reduced.

The polyol of the component (B) used for producing the polyester polyol composition of the present invention includes, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl 1,
3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol,
1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9
Aliphatic diols such as nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, 12-hydroxystearyl alcohol, alicyclic diols such as cyclohexanedimethanol and cyclohexanediol, trimethylolethane, and trimethylolpropane Hexitols, pentitols, glycerin, pentaerythritol, sorbitol, mannitol, dulcitol, sucrose, trihydric or higher alcohols such as tetramethylolpropane, hexamethylene glycol, hydrogenated bisphenol A, bisphenol A and the like.

The polycarboxylic acid (C) optionally used for producing the polyester polyol composition of the present invention includes, for example, oxalic acid, malonic acid, succinic acid (succinic acid), glutaric acid, adipine Acid, pimelic acid, suberic acid, trimetic acid, azelaic acid, sebacic acid, dodecane diacid, 2-methyl succinic acid, 2-methyl adipic acid, 3-methyl adipic acid, 3-methyl pentanedioic acid, 2-methyl octane di Acid, 3,8-dimethyldecandioic acid, 3,7-dimethyldecandioic acid, hydrogenated dimer acid, dimer acid, phthalic acid, terephthalic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid, isophthalic acid Acid, orthophthalic acid,
And polyvalent carboxylic acids such as naphthalenedicarboxylic acid and cyclohexanedicarboxylic acid.

A catalyst can be used to produce the polyester polyol composition of the present invention. Examples of the catalyst include, but are not particularly limited to, titanium esterification catalysts; tetraalkoxytitanium compounds such as tetraisopropyl titanate, tetra-n-butyl titanate, tetra-2-ethylhexyl titanate, and tetrastearyl titanate; Titanium acylate compounds such as polyhydroxytitanium stearate and polyisopropoxytitanium stearate; titanium acetyl acetate;
Examples include titanium chelate compounds such as triethanolamine titanate, titanium ammonium lactate, titanium ethyl lactate, and titanium octylene glycolate; and organotin catalysts such as dibutyltin oxide. The use amount of these catalysts is preferably in the range of 0.1 to 100 ppm, more preferably in the range of 1 to 50 ppm, based on the total amount of the raw materials for producing the polyester polyol.

The urethane prepolymer composition of the present invention comprises:
To the above-mentioned polyester polyol composition of the present invention, a polyisocyanate compound containing an excess amount of isocyanate groups with respect to the hydroxyl groups of the polyester polyol and, if necessary, a chain extender and the like are added. And the like. In the production of the urethane prepolymer composition of the present invention, polyether polyols such as polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol and polytetramethylene glycol, low molecular weight polyols and succinic acid, glutaric acid, adipic acid, sebacin Acids, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, endmethylenetetrahydrophthalic acid, polybasic acids such as hexatetrophthalic acid, or polyols such as polyester polyols, polycarbonate polyols and polycaprolactone, which are condensation products with carbonic acid They can be used together if necessary.

The polyisocyanate compound used for producing the urethane prepolymer composition of the present invention includes the following aliphatic, alicyclic and aromatic polyisocyanates.

Aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate (HDI), 2,2,4 (2,2,4) -trimethylhexamethylene diisocyanate and lysine diisocyanate.

Isophorone diisocyanate (IPD
I), alicyclic diisocyanates such as dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), trans-1,4-cyclohexyl diisocyanate, norbornene diisocyanate and the like.

Tolylene diisocyanate (TDI), diphenylmethane-4,4'-diisocyanate (MD
I), p-phenylene diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthylene diisocyanate (NDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate And aromatic diisocyanates.

Triphenylmethane triisocyanate,
Trifunctional or higher isocyanates such as 1-methylbenzol-2,4,6-triisocyanate and dimethyltriphenylmethanetetraisocyanate. Further, the polyisocyanate compound may be used in the form of a modified product such as carbodiimide-modified, isocyanurate-modified, biuret-modified, or the like, or may be used in the form of a blocked isocyanate blocked by various blocking agents.

The above-mentioned polyisocyanate compound is preferably 1.1 to the total of the active hydrogen of the polyester polyol composition of the present invention, the above-mentioned polyol optionally used in combination, and the following chain extender optionally used. ~
It is used so as to be 3.0 equivalents, more preferably 1.5 to 2.5 equivalents. When the amount of the polyisocyanate compound used is less than 1.0 equivalent, a prepolymer having no terminal isocyanate group is obtained, and the effect of the present invention cannot be obtained. If it is more than 3.0 equivalents, the isocyanate may remain unreacted and deteriorate the properties.

In order to produce the urethane prepolymer composition of the present invention, a chain extender may be used if necessary. As the chain extender, a commonly used chain extender is used, and examples thereof include a low molecular weight polyol compound having an average molecular weight of less than 200 and a low molecular weight polyamine compound.

As the low molecular weight polyol compound,
Low-molecular-weight polyol and other polyols used in the production of the polyester polyol composition of the present invention,
Examples include amines and amino alcohols. As other polyols, 1,4-dichlorohexanedimethanol, trimethylolpropane, hexanetriol,
1,4-bis (β-hydroxyethoxy) benzene,
N, N′-bis (β-hydroxyethyl) aniline is exemplified. Further, as the low molecular weight polyamine compound, hydrazine, ethylenediamine, propylenediamine, menthanediamine, isophoronediamine, 4,4 ′
-Diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, p-
Phenylenediamine, m-phenylenediamine, tolylenediamine, naphthylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylether, 4,4′-diaminodiphenylthioether,
2,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3.
Examples include amines such as 3'-dichloro-4,4'-diaminodiphenylmethane and 1,6-hexamethylenediamine, and amino alcohols such as monoethanolamine, diethanolamine, monopropanolamine and dipropanolamine.

The amount of the chain extender used is 0.5 to 10% by weight based on all components constituting the target urethane resin.
Is used.

Further, an organic solvent may be used as needed for producing the urethane prepolymer composition of the present invention. Examples of the organic solvent include solvents such as benzene, toluene, methyl ethyl ketone, chlorobenzene, tetrahydrofuran, and dimethylformamino. The reaction temperature is appropriately selected from the range of 20 to 150 ° C.

As described above, the urethane prepolymer composition of the present invention can be produced from these raw materials by a conventional method, and the order of charging these raw materials can be appropriately changed.
Or it is also possible to divide and prepare.

In producing the urethane prepolymer composition of the present invention, the following tin-based urethanization catalyst and amine-based urethanization catalyst can be used. Examples of the tin-based urethanization catalyst include tin octylate, monomethyltin mercaptoacetate, monobutyltin triacetate, monobutyltin monooctylate, monobutyltin monoacetate, monobutyltin maleate, monobutyltin maleate benzyl ester, and monooctyl. Tin thiodipropionate, monooctyltin tris (isooctylthioglycolate), monophenyltin triacetate, dimethyltin maleate, dimethyltin bis (ethylene glycol monothioglycolate), dimethyltin bis (mercaptoacetic acid) ) Salt, dimethyltin bis (3-mercaptopropionic acid) salt, dimethyltinbis (isooctylmercaptoacetate), dibutyltin acetate, dibutyltin dioctoate Dibutyltin distearate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin maleate ester salt, dibutyltin bis (mercaptoacetic acid),
Dibutyltin bis (alkyl mercaptoacetate)
Salt, dibutyltin bis (3-mercaptopropionate alkoxybutyl ester) salt, dibutyltin bisoctylthioglycol ester salt, dibutyltin (3-mercaptopropionate) salt, dioctyltin maleate, dioctyltin maleate, dioctyltin maleate Acid polymers such as acid salt polymer, dioctyltin dilaurate, dioctyltin bis (isooctylmercaptoacetate), dioctyltinbis (isooctylthioglycolate), dioctyltin bis (3-mercaptopropionate) salt, and mercaptocarboxylic acid And dialkyltin diasylate such as dibutyltin diacetate and dibutyltin dilaurate; and dibutyltin bis (3-
Dialkyltin dimercaptocarboxylates such as ethoxybutyl mercaptopropionate) are preferred. These tin-based urethanization catalysts are preferably used in an amount of 0.05 to 100 ppm, more preferably 0.1 to 20 ppm, in terms of tin atom, based on the total amount of the reactive raw materials of the urethane prepolymer composition.

Examples of the amine urethanization catalyst include monoamines such as triethylamine and N, N-dimethylcyclohexylamine; N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-. Tetramethylpropane-1,3-diamine, N, N, N ', N'-
Diamines such as tetramethylhexane-1,6-diamine; N, N, N ', N ", N" -pentamethyldiethylenetriamine, N, N, N', N ", N"-pentamethyldipropylenetriamine; Triamines such as tetramethylguanidine; triethylenediamine, N, N'-dimethylpiperazine N-methyl-N '-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N
-(N ', N'-dimethylaminoethylmorpholine,
Cyclic amines such as 1,2-dimethylimidazole; dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethylethanolamine, N-methyl-N '-(2-hydroxyethyl) piperazine, N Alcohol amines such as-(2-hydroxyethyl) morpholine; ether amines such as bis (2-dimethylaminoethyl) ether and ethylene glycol bis (3-dimethyl) -aminopropyl ether; , Reactivity, shape and performance of the target polyurethane.

The urethane prepolymer composition of the present invention comprises:
For example, the urethane prepolymer composition of the present invention can be used as it is, for example, as a reactive hot-melt adhesive, or it can be used alone or mixed with the urethane prepolymer composition of the present invention. And plasticizers (dioctyl phthalate, butyl benzyl phthalate, dinonyl phthalate, diethylene glycol dibenzoate, alkyl polycyclic aromatic hydrocarbons, chlorinated paraffins, etc.) used in ordinary reactive hot-melt adhesives. , Thermoplastic polymers (polyurethane, ethylene-based copolymer, propylene-based copolymer,
Vinyl chloride copolymer, acrylic copolymer, styrene
Various rubbers such as conjugated diene block copolymers), tackifiers (EVA, polyamide, wax, atactic polypropylene, rosin resin, rosin ester resin, hydrogenated rosin ester resin, terpene resin, terpene phenol resin, hydrogenated terpene Resin, petroleum resin, hydrogenated petroleum resin, coumarone resin, ketone resin, styrene resin, modified styrene resin, xylene resin, epoxy resin, etc., filler (silicic acid derivative, talc, metal powder, calcium carbonate, clay, carbon black) ), A catalyst (dibutyltin dilaurate, dibutyltin dioctate, dimethylcyclohexylamine, dimethylbenzylamine, etc.),
It is optional to add an acid (inorganic acid or organic acid), a pigment, a surfactant, a flame retardant or an additive.

Examples of the additives include phenolic antioxidants, organic phosphorus antioxidants such as organic phosphite, thioether antioxidants, ultraviolet absorbers, and light stabilizers such as hindered amine compounds. .

Examples of the phenolic antioxidants include stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and stearyl-β-
(3-tert-butyl-4hydroxy-5-methylphenyl) propionate, 1,6-hexamethylenebis [β
-(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate], triethylene glycol bis [β-
(3-tert-butyl-4hydroxy-5-methylphenyl)
Propionate], 3,9-bis [1,1-dimethyl-
2- (β-3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxyethyl] -2,4
8,10-tetraoxaspio [5,5] undecane,
1,3,5-tris [β- (3,5-di-tert-butyl-4
(Hydroxyphenyl) propionyloxyethyl] isocinurate, tetrakis [methylene-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,6-di-tert-butyl-p-cresol,
2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-
6-tert-butylphenol), 2,2′-ethylidenebis (4,6-ditertbutylphenol), 2,2′-ethylidenebis (4-secbutyl-6-tertbutylphenol), bis [3 3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, 4,4'-butylidenebis (6-tert-butyl-m
-Cresol), 4,4′-thiobis (6-tert-butyl-m-cresol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,
1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene,
1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate,
3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate and the like.

The amount of these phenolic antioxidants added is based on 100 parts by weight of the urethane prepolymer composition.
Preferably 0.001 to 5 parts by weight, more preferably 0.1 to 5 parts by weight.
05 to 3 parts by weight.

Examples of the organophosphorus antioxidants include tris (nonylphenyl) phosphite, tris (mono- and di-mixed nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, Tetra (C ₁₂ ` ₁₅ mixed alkyl) bisphenol A diphosphite, tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, hexa (tridecyl) -1,1,3- Tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanetriphosphite, distearylpentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis ( 2,6-ditert-butyl-4-methylphenyl) pentaerythritol di Phosphite, bis (2,
4-di-α-cumylphenyl) pentaerythritol phosphite, 2,2′-ethylidenebis (4,6-ditertbutylphenyl) fluorophosphite, 2,2′-
Methylene bis (4,6-di-tert-butylphenyl) octyl phosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite and the like can be mentioned.

The addition amount of these organic phosphorus antioxidants is
0.001 to 5 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the urethane prepolymer composition.
３3 parts by weight.

Examples of the thioether antioxidants include dialkylthiodipropionates such as dilauryl-, dimyristyl- and distearyl-thiodipropionate;
Esters of alkyl (C = 8-18) thiopropionic acid such as pentaerythritol tetra (dodecylthiopropionate).

The amount of the thioether-based antioxidant added is 100 parts by weight of the urethane prepolymer composition.
Preferably it is 0.001-10 weight part, More preferably, it is 0.005-5 weight part.

As the above-mentioned ultraviolet absorber, for example,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2-hydroxybenzophenones such as (hydroxy-4-methoxybenzophenone); (2′2-hydroxy-
5′-methylphenyl) benzotriazole, (2′2
-Hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5-ditert-butylphenyl) benzotriazole, 2- (2'-
Hydroxy-3'5'-di-tert-butylphenyl) -5
Chlorobenzotriazole, 2- (2'-hydroxy-
3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
3 ′, 5′-dicumylphenyl) benzotriazole,
2- (2'hydroxyphenyl) benzotriazoles such as 2,2'-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butyl Benzoates such as phenyl-3 ', 5'-di-tert-butyl-4'-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2,4-diphenyl-6- (2- Hydroxy-4-
Methoxyphenyl) 1,3,5-triazine, 2,4-
Bis- (2,4-dimethylphenyl) -6- (2-hydroxy-4-octoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-
4-hexyloxy) triazines such as 1,3,5-triazine; 2-ethyl-2'-ethoxyoxanilide, 2
Substituted oxanilides such as -ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3-
And cyanoacrylates such as (p-methoxyphenyl) acrylate.

The amount of these ultraviolet absorbers added is preferably 0.05 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the urethane prepolymer composition.

Examples of the above hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-
Tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2 , 2,
6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrakis (1,2,2,6,6,
-Pentamethyl-4-piperidyl) -1,2,3,4-
Butanetetracarboxylate, bis (2,2,6,6
-Tetramethyl-4-piperidyl) di (tridecyl)
-1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate , Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2-
(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,
6,6-tetramethyl-4piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6 -Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-
Dichloro-6-tert-octylamino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino- and s-triazine polycondensates.

These light stabilizers are preferably used in an amount of 0.001 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the urethane prepolymer composition, depending on the type of the resin to be added. Used in a range of parts.

The urethane prepolymer composition of the present invention comprises:
Excellent adhesion to various materials. The urethane prepolymer composition of the present invention is used as a hot melt adhesive by applying it to various synthetic resins as well as paper. As synthetic resins, for example, low density polyethylene, linear low density polyethylene, high density polyethylene,
Α-olefin homopolymers and copolymers such as polypropylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, ethylene-vinyl acetate copolymer, ethylene-propylene random and block copolymers; Polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber chloride, vinyl chloride-vinyl acetate copolymer,
Halogen-containing resins such as vinyl chloride-ethylene copolymer, vinyl chloride-acrylate copolymer, vinyl chloride-cyclohexylmaleimide copolymer; amorphous or syndiotactic polystyrene, styrene and / or syndiotactic polystyrene; Styrene and / or α-
Copolymer of methylstyrene and other monomers (eg, maleic anhydride, acrylonitrile, methyl methacrylate, butadiene, phenylmaleimide, etc.) (eg, Hi
PS resin, AS resin, ABS resin, MBS resin, heat resistant A
Styrene resins such as BS resin and super heat-resistant ABS resin); linear polyesters such as polyethylene terephthalate, polybutylene terephthalate and polycaprolactone; polyamides such as polycaprolactam and polyhexamethylene adipamide; linear or branched Aromatic polycarbonate; polyvinyl acetal such as polyvinyl formal and polyvinyl butyral; polyoxymethylene; polymethyl methacrylate; acrylic resin; polyphenylene oxide; polyphenylene sulfide, polyether ether ketone; petroleum resin; Examples include thermoplastic resins such as resins and mixtures thereof. Also, a mixture of an elastomer such as an ethylene-propylene copolymer elastomer, an ethylene-propylene-ethylidene norbornene copolymer elastomer, and the above-mentioned thermoplastic resin may be used. Among them, particularly, polyolefins such as polypropylene and polyethylene are used in the urethane polymer composition of the present invention.
Low value, strong adhesion.

The urethane prepolymer composition of the present invention comprises:
As a hot-melt adhesive, bonding of automotive parts (bonding of seat cushion, side molding, windshield, door trim, front hood hemming, molded roof, silencer, reinforced plastic outer panel, etc.), bonding of building materials ( It is suitable for bookbinding, packaging, textiles, etc. As an application method,
There is a usual method, for example, a method of applying to an adherend with a spray (spiral, curtain coat), a roll coater, dipping, a hot gun or the like, and curing after application.

[0042]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[Production of Polyester Polyol Composition] Production Example 1 (Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1--1)
2) excess polyol component, polycarboxylic acid component, 1
2-Hydroxystearic acid was subjected to dehydration condensation at 200 ° C. to 220 ° C. by a conventional method, and then an excess polyol component was distilled off under reduced pressure to produce a polyester polyol having a hydroxyl group at a terminal. However, tetraisopropoxy titanate is added as a catalyst in an amount of 20 ppm based on all components of the raw material. The following Table 1 and Table 2 show the polyol component and polycarboxylic acid component as raw materials, and the number average molecular weight (MW), acid value (AV) and hydroxyl value (O) of the obtained polyester polyol composition.
HV). Further, polyester polyol composition A
ＫK are used to make the urethane prepolymer compositions of the present invention, and the polyester polyol compositions LM are used to make comparative urethane prepolymer compositions.

[0044]

[Table 1]

[0045]

[Table 2]

[Production of Urethane Prepolymer Composition] Production Example 2 (Examples 2-1 to 2-16 and Comparative Examples 2-1 to 2-
2) The polyester polyol compositions A to M and the polyisocyanate compounds obtained in Production Example 1 are shown in Table 3 below.
And reacted at 100 ° C. under nitrogen reflux to obtain a urethane prepolymer composition.

[0047]

[Table 3]

<Test Example 1> (Examples 3-1 to 3-11 and Comparative Examples 3-1 to 3-
2) Polypropylene (P) obtained by subjecting the urethane prepolymer composition obtained in Production Example 2 to a corona discharge treatment at 120 ° C.
P) film and polyethylene terephthalate (PE)
T) Apply to film. After 24 hours in a constant temperature chamber of 20 ° C. and 65% RH, and curing for 7 days, the adhesion was evaluated. Adhesion test: The peel strength was evaluated by rapidly peeling the cellophane tape onto the urethane prepolymer composition at an application angle of 60 ° C. 1: The area ratio exceeded 70% and 100% or less peeled off. 2: Exceeding 50% or more of area ratio exceeding 50%. 3: More than 20% of the area ratio peeled off. 4: More than 0% and 20% or less of the area ratio peeled off. 5: did not peel. The results are shown in Table 4 below.

[0049]

[Table 4]

From the results in each of the above tables, the urethane prepolymer composition of Comparative Example, which does not contain 12-hydroxystearic acid as an essential component, is extremely poor in adhesion to a film and is not practically satisfactory. On the other hand, the urethane prepolymer composition of the present invention in which the polyester polyol having 12-hydroxystearic acid as an essential component and the polyisocyanate as the essential components is PET or P
It was confirmed that it had excellent adhesion to P.

<Test Example 2> 1 to No. Eleven Examples of Urethane Prepolymer Compositions of the Invention and N
o. 17-No. The urethane prepolymer composition of Comparative Example No. 18 was heated at 120 ° C., and 0.1 mm thick polypropylene sheet / polypropylene sheet was 0.1 mm thick.
After applying, thermocompression bonding at 90 ° C and curing at room temperature for 1 week,
Peeling adhesive strength was measured under normal conditions and after immersion in hot water at 60 ° C. for 48 hours. The results are shown in Table 5 below.

[0052]

[Table 5]

The peel adhesive strength of PP / PP is inferior in the peel adhesive strength of the urethane prepolymer composition of the comparative example, which is not practically satisfactory. In contrast,
It was confirmed that the urethane prepolymer compositions of the present invention of Examples have excellent peel adhesion strength.

Test Example 3 [Examples of Formulation of Reactive Hot Melt Adhesive] << Examples of Formulation >> 80 parts by weight of urethane prepolymer composition of the present invention 10 parts by weight of thermoplastic polyurethane 10 parts by weight of xylene resin

When the above “Compounding Example” was used as a hot-melt type adhesive, excellent initial adhesion and long-term adhesion were also observed.

[0056]

The urethane prepolymer composition of the present invention using the polyester polyol composition of the present invention is effective as a hot melt adhesive having excellent initial adhesion and heat-resistant adhesive strength.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kenji Miyauchi F-term (reference) 4J040 ED011 ED031 ED081 EF111 MA07 MA10 NA10 NA11 NA12 NA13 NA16 PA30 in Asahi Denka Kogyo Co., Ltd.

Claims (4)

[Claims] 1. An essential component comprising (A) 12-hydroxystearic acid and (B) a polyol having 2 to 6 functional carbon atoms having 2 to 40 carbon atoms and, if necessary, adding (C) a polycarboxylic acid to cause a reaction. And polyester polyol compositions for hot melt adhesives. 2. (A) 12 in the polyester polyol
The content of hydroxystearic acid is 10 to 90% by weight
The polyester polyol composition according to claim 1, which is: 3. A reactive hot water obtained by reacting the polyester polyol composition according to claim 1 or 2 with a polyisocyanate compound such that the number of isocyanate groups of the polyisocyanate compound is excessive relative to the number of hydroxyl groups of the polyester polyol. A urethane prepolymer composition used for a melt-type adhesive. 4. A reactive hot melt adhesive comprising the urethane prepolymer composition according to claim 3.