JP2699497B2 - Laminate - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a laminate comprising a polyurethane layer and a vinyl chloride resin composition layer used for footwear, automobile interior materials, furniture, exterior materials and the like. is there.

"Conventional technology" In general, vinyl chloride resin compositions are inferior in stability to heat and light, and are liable to undergo thermal deterioration mainly due to a dehydrochlorination reaction or the like at the time of heat molding processing. It has disadvantages such as thermal discoloration or reduced mechanical properties.

Conventionally, in order to improve such disadvantages, as a stabilizer, lead of fatty acids such as stearic acid, cadmium, barium, fatty acid metal salt compounds such as zinc salts, inorganic lead compounds such as basic lead sulfate, or dialkyl A method of adding a tin compound or the like has been adopted. Among these stabilizers, lead-based and dialkyltin-based stabilizers are widely used because of their high heat discoloration prevention effect.

Such a vinyl chloride resin composition is used in footwear such as boots, a steering wheel of a car, an interior agent, furniture, and a surface covering material.In order to increase abrasion resistance, flexibility, feel, and the like, urethane foam is used. In many cases, it is used by being laminated on a polyurethane base material such as. In the state where the polyurethane base material is laminated and formed on the molded article made of the vinyl chloride resin composition, coloring due to thermal deterioration of the vinyl chloride resin is larger than in the state where the polyurethane base material is not laminated. Therefore, especially in the injection molding process at a high temperature during the molding process, a dialkyltin-based stabilizer having an excellent effect of preventing heat-resistant discoloration is frequently used.

"Problems to be Solved by the Invention" However, this dialkyltin-based stabilizer has a problem that it has a strong effect of promoting hydrolysis of a polyurethane base material, particularly a polyurethane resin having an ester group.

For this reason, the laminate of the polyurethane base material and the molded article made of the vinyl chloride resin composition, the adhesive force decreases over time, and eventually the polyurethane base material and the vinyl chloride resin composition are used. This causes a problem of peeling off from the molded product.

For example, in the case of footwear, an adhesive interface between a sole made of a vinyl chloride resin composition and a polyurethane synthetic leather, or an adhesive interface between a sole made of a polyurethane resin composition and a torso made of a vinyl chloride resin composition, etc. There is a problem that is peeled off.

As means for remedying this problem, attempts have been made to use a metal soap-based stabilizer such as barium / zinc or a monoalkyltin-based stabilizer as a stabilizer. There is a problem that yellow boots are formed when white boots are formed by the method. Further, as a stabilizer, an epoxy compound, an organic phosphite,
Attempts have been made to use a monoalkyltin mercapto compound and a dialkyltin mercapto compound in combination, but the anti-heat coloring effect and the peel strength after deterioration such as wet heat deterioration are not sufficient.

“Means for Solving the Problems” The present invention provides an epoxy compound as a stabilizer, an organic phosphite, a layer made of a vinyl chloride resin composition to which a monoalkyltin mercapto compound is added, and a polyurethane layer. The use of a laminate obtained by laminating is a means for solving the problem.

[Action] By using an epoxy compound, an organic phosphite, and a monoalkyltin mercapto compound in combination as a stabilizer, the molded article made of the vinyl chloride resin composition does not discolor even when heated. Further, the peel strength of the molded article made of the vinyl chloride resin composition and the polyurethane substrate after deterioration such as wet heat deterioration does not decrease.

 Hereinafter, the laminate of the present invention will be described in detail.

As the vinyl chloride resin used in the vinyl chloride resin composition of the present invention, vinyl chloride and vinylidene chloride, or a mixture of vinyl chloride and a monomer polymerizable with vinylidene chloride, a bulk polymerization method, a suspension polymerization method, legal,
It is produced by a usual method such as an emulsion polymerization method. Examples of monomers copolymerizable with vinyl chloride and vinylidene chloride include vinyl esters such as vinyl acetate, acrylates such as methyl acrylate and butyl acrylate, and methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate. , Acrylonitrile, vinyl cyanides such as methacrylonitrile, α, such as ethylene and propylene
-Olefins and the like.

As the monoalkyltin compound to be added as a stabilizer of the vinyl chloride resin composition, a compound represented by the following general formula (1) is preferable.

(Wherein R ₁ is an alkyl group having 1 to 12 carbon atoms, and R ₂ , R ₃ ,
R ₄ is an alkyl group having 4 to 16 carbon atoms, an alkoxyalkyl group, a benzyl group, or a cyclohexyl group, which may be the same or different. Further, m ₁ , m ₂ and m ₃ are integers of 1 or 2. Examples of the compound represented by the formula (1) include monomethyltin tris (octylthioglycolate), monomethyltin tris (3-methoxybutylthioglycolate), monomethyltin tris (benzylthioglycolate), and monomethyltin tris (octyl). Thiopropionate), monomethyltin tris (3-methoxythiopropionate), monobutyltin tris (octylthioglycolate), monobutyltin tris (tridisylthioglycolate), monobutyltin tris (stearylthioglycolate), Monobutyltin tris (cyclohexylthioglycolate), monobutyltin tris (benzylthioglycolate), monobutyltin tris (octylthiopropionate), monobutyltin tris (tridecylthiopropionate) ), Monobutyltin tris (stearylthiopropionate), monobutyltin tris (benzylthiopropionate), monobutyltin tris (cyclohexylthiopropionate), monobutyltin tris (cyclohexylthiopropionate), monooctyltin tris (Octylthioglycolate), monooctyltin tris (decylthioglycolate), monooctyltin tris (tridecylthioglycolate), monooctyltin tris (cyclohexylthioglycolate), monooctyltin tris (benzylthioglycolate) ), Monooctyltin tris (methoxybutyl thioglycolate), monooctyltin tris (octylthiopropionate), monooctyltin tris (decylthioglycolate), monooctyltin Lis (nonylthiopropionate), monooctyltin tris (tridecylthiopropionate), monooctyltin tris (stearylthiopropionate), monooctyltin tris (methoxybutylthiopropionate), monooctyltin Tris (benzylthiopropionate), monooctyltin tris (cyclohexylthiopropionate) and the like can be mentioned.

The amount of the monoalkyltin mercapto compound added is
0.3 to 3 parts by weight is suitable for 100 parts by weight of the vinyl chloride resin. Here, if the amount is less than 0.3 part by weight, the molded article may become yellow, and if it exceeds 3 parts by weight, the peel strength may decrease.

Organic phosphites added as stabilizers include diphenyldecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite,
Tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, tris (dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis (neopentyl glycol) -1,4-cyclohexane Dimethyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, tris (lauryl-2-thioethyl)
Phosphite, tetra-tridecyl-1,1,3-tris (2'-methyl-5'-tert-butyl-4'-oxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) 4, 4'-isopropylidenediphenyl diphosphite, tris (4-oxy-2,5-di-tert-butylphenyl) phosphite, tris (4-oxy-3,5
-Di-tert-butylphenyl) phosphite, 2-ethylhexyldiphenylphosphite, tris (mono, dimixed nonylphenyl) phosphite, hydrogenated-4,4'-
Isopropylidene diphenol polyphosphite, diphenylbis [4,4'-n-butylidenebis (2-tert-
Butyl-5-methylphenol)] thiodiethanol diphosphite, bis (octylphenyl (bis [4,4 '
-N-butylidenebis (2-t-butyl-5-methylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4'-isopropylidene diphenol, pentaerythritol diphosphite, phenyldiisodecyl phosphite , Tetratridecyl-4,4'-
n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, tris (2,4-di-tert-
Butylphenyl) phosphite, tristearylphosphite, octyldiphenylphosphite, diphenyltridecylphosphite, phenyldi (tridecyl) phosphite, tris (2-cyclohexylphenyl) phosphite, ditridecyldi (2-cyclohexylphenyl) hydrogenated bisphenyl Nord A diphosphite, di (2,
4-di-tert-butylphenyl) cyclohexyl phosphite, 2,4-di-tert-butylphenyl, diisodecyl phosphite, tris (butoxyethoxyethyl) phosphite, diphenyl acid phosphite, bis (2
-Cyclohexylphenyl) acid phosphite, bis (2,4-di-tert-butylphenyl) acid phosphite and the like are used.

The addition amount of the organic phosphite is preferably 0.05 to 1 part by weight based on 100 parts by weight of the vinyl chloride resin. Here, if it is less than 0.05 part by weight, the initial heat-resistant coloring property is poor, and if it exceeds 1 part by weight, the long-term heat-resistant coloring property is unfavorably deteriorated.

Epoxy compounds also used as stabilizers include epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil fatty acid butyl ester, epoxidized butyl stearate, epoxy Methyl stearate, epoxidized octyl stearate, epoxidized butadiene, epoxy resin (this epoxy resin is obtained by the reaction of polyhydric phenols with epichlorohydrin or methyl epichlorohydrin, and is a bisphenol-type or novolak-type epoxy resin ).

The addition amount of this epoxy compound is 100 vinyl chloride resin.
0.5 parts by weight to 5 parts by weight with respect to parts by weight is preferred. 0.5
When the amount is less than 5 parts by weight, the heat-resistant coloring property is not sufficient, and the molded article may be colored. When the amount exceeds 5 parts by weight, mold may be easily generated.

The vinyl chloride resin composition can be used in combination with other stabilizers, antioxidants, and the like, if necessary. In addition,
Dialkyltin mercapto compounds are not usually used, but may be added in amounts that do not impair the effects of the present invention.

For example, monobutyltin trioctoate, monobutyltin trilaurate, monobutyltin trineodecanate, monobutyltin tristearate, monooctyltin trioctoate, monooctyltin trineodecanate, monooctyltin trinedecanoate, etc. Monoalkyltin fatty acid salt stabilizers, metal soap stabilizers such as barium / zinc fatty acid salts and calcium / zinc fatty acid salts, β-diketone compounds such as dibenzoylmethane and stearoylbenzoylmethane, 2,6-di- 1-ter
t-butyl-4-methylphenol, 4,4'-thiobis (6-tert-butyl-3-methylphenol), 2,2 '
-Methylenebis- (6-tert-butyl-4-methylphenol), tert-butylhumanoxyoxyanisoleoctadecyl 3- (3 ', 5'-di-tert-butyl4'hydroxyphenyl) propionate, pentaerythrityl-tetrakis And antioxidants such as [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

Generally, the vinyl chloride-based resin composition layer laminated on the polyurethane layer has many soft products containing a plasticizer.

Examples of the plasticizer that can be used in the composition include phthalate plasticizers such as dibutyl phthalate, dioctyl phthalate, didecyl phthalate, and butylbenzyl phthalate; dibasic acids such as adipic acid and sebacic acid;
Polyester plasticizers obtained by reacting with dihydric alcohols such as 3butylene glycol and ethylene glycol; ester plasticizers such as dioctyl adipate and dinonyl adipate; phosphorus plasticizers such as tricresyl phosphate; chlorinated paraffin And the like.

If necessary, for example, a pigment, an ultraviolet absorber, a filler, a lubricant, a processing aid, a reinforcing agent, and the like can be included.

As the polyurethane which is a component of the polyurethane layer in the present invention, a polyol such as a polyether polyol, a polyester polyol, or a polycarbonate diol having a hydroxyl group at both terminals and a polyisocyanate, if necessary, together with a chain extender or the like are usually used. And those produced using a prepolymer method, a pseudo prepolymer method, a one-shot method, or the like.

As the polyether polyol, for example, water,
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3 (or
Alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and 1,4) -butylene glycol, 1,6-hexamethylene glycol, etc.
It is obtained by adding one or more kinds of tetrahydrofuran, styrene oxide and the like.

Examples of the polyester polyol include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3 (or 1,4)
-Butylene glycol, neopentyl glycol, 1,6
One or more of hexamethylene glycol, decamethylene glycol and the like, and malonic acid, maleic acid, succinic acid, adipic acid, glutaric acid, pimelic acid, sebacic acid, oxalic acid, phthalic acid, isophthalic acid, terephthalic acid A polyester diol comprising one or two or more kinds of hexahydrophthalic acid or the like, or a diol obtained by ring-opening polymerization of a cyclic ester such as propiolactone, butyrolactone, or caprolactone; further, the above glycol and the cyclic ester or the glycol, It is a polyester polyol composed of three types of dibasic acids and cyclic esters.

The polycarbonate diol is a compound represented by HO—R—OCO—nROH (n ≧ 1), and R is a residue of a glycol or a dihydric phenol. Methylene glycol, diethylene glycol, 1,3 (or 1,4) -butylene glycol, 1,6-hexamethylene glycol, decamethylene glycol, p-xylylene glycol, bisphenol A [2,2-bis (4'-hydroxyphenyl) ) Propane], bisphenol F (4,4'-dihydroxydiphenylmethane) and the like.

As other high molecular polyols, 1,2-polybutadiene glycol, 1,4-polybutadiene glycol, polychloroblendiol, butadiene-acrylonitrile copolymer diol and the like are also used.

These various polymer polyols are used alone or in combination of two or more.

Examples of the polyisocyanate include tolylene diisocyanate (having various isomer ratios), diphenylmethane-4,4'-diisocyanate (hereinafter referred to as MDI), naphthylene-1,5-diisocyanate, and 3,3'-dimethyl-4. ,
4'-biphenylene diisocyanate, xylylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and the like.

These various organic diisocyanates may be used alone or in combination of two or more.

As a method of laminating the polyurethane layer and the vinyl chloride-based resin composition layer, the two layers are laminated without an adhesive therebetween, and specifically, a molded article made of an injection-molded vinyl chloride-based resin composition, For example, a method of thermally fusing polyurethane synthetic leather to the sole of a shoe, a method of injecting and foaming a polyurethane resin into an injection-molded or sol-molded armrest or a headrest, and a method of injecting and molding a polyurethane resin by a slash molding method. For example, there is a method in which a paste vinyl chloride resin composition is injected and then heated and molded.

Examples Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples.

(Example 1) A sheet comprising a polyvinyl chloride resin composition obtained by adding a dioctyl phthalate part by weight as a plasticizer, a stabilizer and other additives to 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 1300 on a polyurethane leatherette. Were melt-laminated to form a laminate. In this laminate, the blend of the stabilizer was salified to form laminates of Examples 1 to 8 and Comparative Examples 1 to 8, and heat resistance coloring property and peel strength were evaluated. In Table 1,
The formulation of each stabilizer and the evaluation results in Examples 1 to 8 and Comparative Examples 1 to 8 are shown.

As is clear from Table 1, the laminates of the examples had good heat-resistant coloring in both oven heat resistance and press heat resistance. In addition, good results were also obtained with respect to the peel strength after wet heat deterioration.

The materials, manufacturing methods, and evaluation methods of the laminates used in Examples 1 to 8 and Comparative Examples 1 to 8 shown in Table 1 are described below.

[Production Method of Polyurethane Synthetic Leather] Polyester diol composed of adipic acid and ethylene glycol and diphenylmethane diisocyanate were synthesized to obtain a polyurethane resin. This polyurethane resin was dissolved in a mixed solvent of dimethylformamide and methyl ethyl ketone so that the solid component content became 20% by weight to obtain a polyurethane resin liquid. This resin liquid is first applied to release paper to a thickness of 150 g / m ² and then at 100 ° C.
Dry for minutes to form a film. Then this film, further 150 g / m ² coated with the polyurethane resin solution,
After laminating the woven fabric, it was dried at 120 ° C. for 3 minutes, and then released to obtain a polyurethane synthetic leather.

[Production method of vinyl chloride resin composition sheet] For 100 parts by weight of vinyl chloride resin having an average degree of polymerization of 1300,
80 parts by weight of dioctyl phthalate as a plasticizer, a stabilizer having the composition shown in Table 1 and other additives are added, and the mixture is kneaded with a double roll at 150 ° C. for 5 minutes to form a vinyl chloride resin composition.
A 0.5 mm thick sheet was taken out.

Three sheets were stacked, placed in a 1 mm thick mold, preheated at 200 ° C. for 5 minutes, and then pressed by a cooling press to obtain a 1 mm thick sheet made of the vinyl chloride resin composition.

[Lamination Method of Polyurethane Resin Leather and Vinyl Chloride Resin Composition Sheet] The vinyl chloride resin composition sheet and the above polyurethane resin synthetic leather are laid on a mold having a thickness of 2 mm.
After pressing under pressure at 50 kg / cm ² for 5 minutes, the mixture was cooled and taken out as a laminate.

[Laminate evaluation method] Peel strength test The above laminate was cut into a predetermined size, left at 70 ° C x 95% relative humidity for a predetermined number of days, left in a constant temperature room at 23 ° C overnight, and then pulled at a speed of 100 mm / min. , 180 degree peel strength was measured.

Oven heat resistance The laminate was placed in a 200 ° C oven and taken out every 10 minutes, and the heat resistance coloring was evaluated according to the following criteria.

1.Colorless 2.Light yellow 3.Yellow 4.Red-brown 5.Black Press heat resistance The above laminate is put in a mold at 200 ° C, put under no pressure for a predetermined time, taken out, and the heat resistance coloring is based on the above oven heat resistance standard. evaluated.

(Example 2) Polyurethane leather leather, 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 1300, 30 parts by weight of dioctyl phthalate as a plasticizer and 50 parts by weight of adipic acid / 1.3 butylene glycol-based polyester-based plasticizer, Sheets comprising a vinyl chloride resin composition to which a stabilizer and other additives were added were laminated to form a laminate. In this laminate, Examples 9 to 14 and Comparative Examples 9 to
Seventeen laminates were evaluated for heat resistance coloring property, peel strength and sweating property. Table 2 shows Examples 9 to 14 and Comparative Examples 9 to 17.
Shows the formulation of each stabilizer and the evaluation results.

As is evident from Table 2, the laminate of the example had good heat resistance coloring property in both oven heat resistance and press heat resistance. The laminates of the examples also showed good results in peel strength and sweat resistance.

Examples 9 to 14 and Comparative Examples 9 to 17 shown in Table 2 above
The material of the laminate, the manufacturing method, and the evaluation method used in the above are described below.

[Production Method of Polyurethane Synthetic Leather] As a urethane material, a propylene glycol, a polyesterdiol composed of propiolactone and hexamethylene diisocyanate are used as a urethane resin.
A urethane synthetic leather was obtained in the same manner as in Experimental Example 1.

[Production method of vinyl chloride resin composition sheet] For 100 parts by weight of vinyl chloride resin having an average degree of polymerization of 1300,
Using a vinyl chloride resin composition containing 30 parts by weight of dioctyl phthalate, 50 parts by weight of adipic acid / 1.3 butylene glycol-based polyester-based plasticizer, and a stabilizer and other additives as plasticizers, in the same manner as in Experimental Example 1. Thus, a vinyl chloride resin composition sheet was obtained.

[Lamination Method of Polyurethane Resin Leather and Vinyl Chloride Resin Composition Sheet] The same method as in Experimental Example 1 was used.

[Evaluation Method of Laminate] Peel strength test, oven heat resistance test and press heat resistance were performed in the same manner as in Experimental Example 1.

For evaluation of sweating properties, the laminate was cut into a predetermined size and 70 ° C x
After standing for a predetermined number of days under a relative humidity of 95%, the sweating property was observed and evaluated based on the following evaluation criteria.

 ○ No sweating is observed.

 × Sweating is observed.

"Effects of the Invention" The present invention provides that a layer made of a vinyl chloride resin composition to which an epoxy compound, an organic phosphite, and a monoalkyltin mercapto compound are added as a stabilizer, and a polyurethane layer are laminated. Since it is a laminate characterized by the above, the effect of preventing the heat-resistant discoloration of the vinyl chloride resin composition is extremely excellent, and the peel strength of the layer composed of the vinyl chloride resin composition and the polyurethane layer after deterioration such as wet heat deterioration is improved. It has the effect of not lowering. Therefore, when used in footwear such as boots and boots, automobile parts such as steering wheels, headrests and armrests, urethane leather surface covering materials, furniture, etc., problems such as discoloration and peeling at the interface may occur even after long-term use. There is an effect that there is no.

Claims (2)

(57) [Claims] 1. A laminate comprising a vinyl chloride resin composition layer to which an epoxy compound, an organic phosphite, and a monoalkyltin mercapto compound are added as a stabilizer, and a polyurethane layer. 2. 0.5 to 5 parts by weight of an epoxy compound as a stabilizer, 0.05 to 1 part by weight of an organic phosphite, and 0.3 to 3 parts by weight of a monoalkyltin mercapto compound with respect to 100 parts by weight of a vinyl chloride resin. A laminate comprising a vinyl chloride-based resin composition layer to which is added and a polyurethane layer.