JPH0224352A - Resin composite material - Google Patents

Abstract

PURPOSE:To obtain the title material deceased in loss of an interfeacial peeling strength and improved in an effect of preventing thermal discoloration by melt laminating a specified vinyl chloride resin composition on a polyurethane. CONSTITUTION:A vinyl chloride resin composition is obtained by mixing 100 pts.wt. vinyl chloride resin obtained by polymerizing vinyl chloride with, optionally, a comonomer mixture polymerizable therewith with 0.5-5 pts.wt. monoalkyltin compound of the formula (wherein R1 is a 1-12C alkyl; R2-4 are each an 8-14C alkyl, benzyl or cyclohexyl; and m1-3 are each 1-2), e.g., monobutyltin tris(octylthioglycolate) and, optionally, an epoxy plasticizer, an epoxy resin, a monomeric epoxy plasticizer or a polymeric epoxy plasticizer. This composition is melt laminated on a polyurethane obtained from a hydroxyl- terminated polyether polyol and/or a hydroxyl-terminated polyester polyol, a polyisocyanate and, optionally, a chain extender, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin composite material formed by melt-laminating a vinyl chloride resin composition on polyurethane.

More specifically, the present invention relates to a resin composite material suitable for footwear such as boots, automobile interior materials such as automobile steering wheels, tarascenes, armrests, and headrests, furniture covering materials, and the like.

[Conventional technology]

In general, vinyl chloride-based resins have poor stability against heat and light9, and are prone to thermal deterioration mainly due to dehydrochlorination reactions during thermoforming.As a result, products processed from such resins may suffer from thermal discoloration or a decline in mechanical properties. There are drawbacks.

Conventionally, in order to improve these defects, fatty acid metal salt compounds such as lead, cadmium, barium, and zinc salts of fatty acids such as stearic acid, inorganic lead compounds such as basic lead sulfate, or dialkyl tin compounds have been added. A method is being taken to do so. Among these stabilizers, lead-based and dialkyltin-based stabilizers are widely used because they have a large heat-resistant discoloration prevention effect.

A composite product of polyurethane and vinyl chloride resin with foamed urethane inside to increase wear resistance, flexibility, and texture for footwear such as boots, automobile steering wheels, interior materials, furniture surface materials, etc. is becoming more widely used.

When polyurethane is laminated onto vinyl chloride resin, thermal deterioration of the vinyl chloride resin is greater than when polyurethane is not laminated. Particularly in injection molding processes where the temperature during the molding process is high, dialkyltin stabilizers are often used because of their excellent heat-resistant discoloration prevention effects.

[Problem to be solved by the invention]

Dialkyltin-based stabilizers and lead-based stabilizers are highly effective in preventing heat-resistant discoloration of vinyl chloride-based resins, but they promote hydrolysis of ester groups for polyurethanes, especially polyurethanes with ester groups that have excellent foaming properties. The disadvantage is that the polyurethane and the vinyl chloride resin tend to separate, causing a bleed phenomenon (sweating) at the contact interface of the /IJ polyurethane vinyl resin. For example, in the case of footwear, the vinyl chloride resin The problem is that the adhesive interface between the sole of the resin composition and the urethane synthetic leather or the adhesive interface between the sole of the urethane resin composition and the torso of the vinyl chloride resin composition peels off, making it unusable for practical use. .

[Means to solve the problem]

As a result of various studies to solve the above problems, the present inventors found that the general formula (1) was used as a stabilizer for vinyl chloride resin.
The inventors have discovered that by adding a monoalkyltin compound represented by the following formula, the heat-resistant discoloration prevention effect of vinyl chloride resin is increased, and even when laminated with polyurethane, there is less deterioration in peel strength at the interface, leading to the present invention.

That is, the present invention Fi (A) polyurethane, (B) 100 parts by weight of vinyl chloride resin and the general formula (wherein R1 is an alkyl group having 1 to 12 carbon atoms, R2
#R6J R4 is an alkyl group having 8 to 14 carbon atoms, a benyl group, or a 7-chlorohekifur group, and may be the same or different from each other. Furthermore, the town 9m2 and m are integers of 1 or 2. 0.5 to 5 parts by weight of a monoalkyltin compound represented by ) or further comprising an epoxy plasticizer or an epoxy resin is provided. do.

The vinyl chloride resin composition used in the present invention is vinyl chloride resin 100! ! By having 0.5 to 5 weight of a monoalkyltin compound represented by general formula (1) in the f part, and further using an epoxy group-containing 5T epoxy plastic or epoxy M resin, heat resistance can be improved. The discoloration prevention effect can be improved. Also, as the polyurethane and the vinyl chloride resin composition, a soft or semi-hard one containing a plasticizer is usually used. In this case, the object of the present invention is not impaired even if the plasticizer used is not only a monomeric plasticizer but also a polymeric plasticizer. Polymeric plasticizers are increasingly used to improve the oil resistance, heat aging resistance, and non-volatility (fogging properties) of vinyl chloride resin molded products, but dialkyltin stabilizers use polymeric plasticizers. Although the monoalkyltin stabilizer represented by the general formula (1) used in the present invention acts on the ester group of the plasticizer to promote hydrolysis and tends to cause a bleed phenomenon, it is difficult to use it in combination with a polymeric plasticizer. There are no such drawbacks.

The vinyl chloride resin used in the present invention is any resin produced by conventional methods such as suspension polymerization, bulk polymerization, and emulsion polymerization using vinyl chloride or a mixture of vinyl chloride and a comonomer polymerizable thereto. Examples of comonomers that can be copolymerized with vinyl chloride include vinyl esters such as vinyl acetate, acrylic acid esters such as methyl acrylate and butyl acrylate, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, acrylonitrile, methacrylonitrile, etc. Examples include vinyl cyanides, α-olefins such as ethylene and propylene, vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, and vinyl halides.

The monoalkyltin compounds represented by the general formula [■] used in the present invention include monobutyltin tris(octylthioglycolate), monobutyltintris(nonylthioglycolate), monobutyltintris(indecylthioglycolate), and monobutyltintris(indecylthioglycolate). ), Monobutyltin Tris (Laurylthioglycolate), Monobutyltin Tris (Tridecylthioglycolate), Monobutyltin Tris (Cyclohexylthioglycolate), Monobutyltin Tris (Benzylthioglycolate), Monooctyltin Tris (Octylthioglycolate) glycolate), monooctyltin tris (nonylthioglycolate), monooctyltin tris (isodecyl glycolate), monooctyltin tris (lauryl thioglycolate), monooctyltin tris (tridecylthioglycolate), monooctyltin tris (tridecylthioglycolate), Octyltin Tris (Cyclohexylthioglycolate), Monooctyltin Tris (Benzylthioglycolate), Monobutyltin Tris (Octylthiopropionate), Monobutyltin Tris (Nonylthiopropionate), Monobutyltin Tris (Isodecylthio tin tris (cyclohexylthiozolopione)), monobutyltin tris (benzylthiopropionate), monooctyltin tris (octylthiopropionate), monooctyltin tris(indecylthiopropionate) 760 bionate), monooctyltin tris (nonylthiopropionate), monooctyltin tris (cyclohexylthiopropionate)
, monooctyltin tris (benzylthiozolopione)
), monomethyltin tris (octyl thioglyflate)
, monomethyltin tris(octylthiopropionate)
etc. can be mentioned.

The amount of the monoalkyltin compound added is 0.5 to 5.0 parts by weight per 100 parts by weight of the vinyl chloride resin.
If it is less than the heavy part, the heat resistance and discoloration prevention effect will be low, and
If the amount is more than 0 parts by weight, the compatibility with the vinyl chloride resin decreases, which is not preferable.

The effects of the present invention are not impaired even when the above-mentioned monoalkyltin compound is used in combination with fatty acid metal salts, organic layer phosphate esters, and antioxidants, which are generally used as stabilizers.

It can also be used in combination with other monoalkyltin compounds, such as monoalkyltin tris(furkyl maleate) yamonoalkyltin trilaurate.

Epoxy plasticizers that can be used in the present invention include epoxidized soybean oil, epoxidized soybean oil, epoxidized castor oil, epoxidized flower oil, epoxidized linseed oil fatty acid butyl ester, oxidized butyl stearate,
Examples include epoxidized octyl stearate and epoxidized polybutadiene. Examples of epoxy resins include bisphenol A type and No. The rack type one is made of epoxy.
A liquid type of about 100 to 700% is preferable.

Monomeric plasticizers that can be used in the present invention include dibutyl phthalate, 7-tar acid esters such as dioctyl phthalate, trimellitic acid esters such as tributyl trimellitate and trioctyl trimellitate, and dioctyl esters. These include adipate esters such as adipate and diisononylaziide, and citric acid esters such as tributyl acetyl citrate. The polymeric plasticizer is a polyester compound having a molecular weight of 500 to 10,000, which is obtained by reacting a dibasic acid, a glycol, and usually a terminator (medium or higher alcohol or fatty acid). Examples of dibasic acids include glutaric acid, succinic acid, adipic acid, azelaic acid, sepacic acid, phthalic acid, terephthalic acid, and maleic acid, and examples of glycols include ethylene glycol, 1.2-f robylene glycol, and 1° 3-butylene glycol, 1.4
-ftanediol, neopentyl glycol, l, 5-
Examples include -<ntanediol, 2,2.6-)limethylpentanediol, 1,6-hexanediol, and the like.

The vinyl chloride resin composition of the present invention may contain other additives, such as ultraviolet absorbers, fillers, pigments, antistatic agents, lubricants, processing aids, etc., as necessary.

The polyurethane of the present invention can be produced by a conventional prepolymer method, pseudo-prepolymer method, one-shot method, etc., using a polyether biliol and/or polyester polyol having a hydroxyl group at the end and a polyisocyanate together with a chain extender, etc., if necessary. It is manufactured using Such polyurethane may be in the form of foam, elastomer, or resin.

For example, what is the ether polyol? Examples include lyoxypropylene glycol and polyoxybutylene glycol.

The ether polyol is produced from a polybasic acid and a polyhydric alcohol, and examples of the polybasic acid include succinic acid, adipic acid, sepacic acid, maleic acid, and trimellitic acid.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, intanediol, hexanediol, trimethylolzolonokune, glycerin, hexanetriol, and pentaerythritol.

Examples of chain extenders include glycols such as ethylene glycol, propylene glycol, 1.4-f tanediol, and diethylene glycol, amines such as 1,6-hexanediamine, and amino alcohols such as jetanolamine and jetanolamine. can give.

Examples of the polyincyanate include 2.4-) lylene diisocyanate, 2.6-) lylene diisocyanate,) lylene diisocyanate, triphenylmethane diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, diphenyl ether diisocyanate, etc. It will be done.

Melt lamination methods for polyurethane and vinyl chloride resin compositions include injection molded vinyl chloride resin compositions, such as methods for heat-sealing urethane, i.e. urethane synthetic leather, on shoe soles, injection molding or sol molding. How to inject polyurethane into armrests and headrests,
There is a method in which a paste vinyl chloride resin composition is injected into a shoe sole obtained by injection molding polyurethane using a sludge molding method, and then heated and molded.

〔Effect of the invention〕

The present invention aims to improve the adhesion strength between the vinyl chloride resin composition and the urethane resin in a composite obtained by melt-laminating a vinyl chloride resin composition containing a monoalkyltin compound represented by the general formula (1) onto a urethane resin. This improved product is useful for footwear such as boots and boots, automobile parts such as steering wheels, headrests, and armrests, and furniture covered with urethane leather.

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. Note that parts in the examples are parts by weight.

Examples 1 to 6, Comparative Examples 1 to 3 (Urethane resin synthetic leather) Dimethyl formamide and methyl ethyl ketone 1 = 1 solvent were used so that the solid component content of urethane resin consisting of adipic acid, ethylene glycol, and diphenylmethane diisocyanate was 20%. 150% of the adjusted resin on release paper
After coating to a thickness of Jil/m2, it was dried at 100°C for 1 minute. The urethane resin liquid was applied on top of this film-formed resin at 1501! /m2, and then the fabric was laminated, dried at 120°C for 3 minutes, and then released from the mold.

(Vinyl chloride resin composition sheet) Vinyl chloride resin composition consisting of vinyl chloride resin (average degree of polymerization 1100) 100 parts phthalic acid diester (DOP) 60% 4-oxygenated soybean oil 3 Test stabilizer (Table 1) 2.5 The material was mixed with two rolls at 160° C. for 5 minutes and then taken out at a thickness of 0.5 m.

(Lamination of urethane resin synthetic leather and vinyl chloride resin composition sheet) Lamination of urethane resin synthetic leather and vinyl chloride resin composition sheet in a 2 m thick mold, 150℃, 3 minutes, 5
After pressure bonding at 01, 7.2, it was cooled and taken out.

(Peel strength test) Cut the above laminated sheet into a predetermined size and test at 70°C, 95%
After being left under relative humidity (3 days, 7 days), tensile speed 100W
Iy/min, 180e peel strength was measured.

(Oven Heat Resistance) The above laminated sheet was cut into a predetermined size, placed in a gear oven at 185°C, and peeled off every 10 minutes to measure the coloring property (initial heat resistance) and the time until blackening.

Table 1 shows the results of the peel strength test and open heat resistance.

/ Examples 7 to 11, Comparative Examples 4 to 6 A vinyl chloride resin composition sheet consisting of 100 parts of vinyl chloride resin (average degree of polymerization 1300) OP epoxidized soybean oil test stabilizer (Table 2) 2.0 was prepared as an example. It was produced in the same manner as in Examples 1 to 6, and the peel strength and open heat resistance with respect to the urethane resin synthetic leather of Examples 1 to 6 were measured. The results are shown in Table 2.

Examples 12 to 15, Comparative Examples 7 to 8 Vinyl chloride resin (average degree of polymerization 1450) 1
00 part DOP
60 polymeric plasticizer (molecular weight 2
600) (Adipic acid/1,3-butylene glycol type) 40 Calcium carbonate 20 Test stabilizer (Table 3) A vinyl chloride resin composition consisting of 1.5 was mixed with two rolls at 140°C for 5 minutes. , a sheet with a thickness of 0.5 m was taken out.

(Lamination of foamed urethane resin and vinyl chloride resin composition sheet) Place the above vinyl chloride resin composition sheet in a mold, and place Delideq pyrene glycol (molecular weight 3000) 1 on top of it.
A stirred mixture consisting of 00 parts and 50 parts of diphenylmethane diisocyanate was introduced, and the mold was closed and fixed.
Heated at 0°C for 10 minutes. After cooling, the laminated sheets were demolded.

Demolding and cutting the nine sheets into predetermined sizes, Example 1~
The aging deterioration of peel strength and open heat resistance were measured under the same conditions as in Example 6. The results are shown in Table 3.

Claims (1)

[Claims] 1. (A) polyurethane and (B) vinyl chloride resin 10
0 parts by weight and general formula ▲ Numerical formula, chemical formula, table, etc. ▼... (I) (In the formula, R_1 is an alkyl group having 1 to 12 carbon atoms, and R
_2, R_3, R_4 are alkyl groups having 8 to 14 carbon atoms,
They are a benzyl group or a cyclohexyl group, and may be the same or different from each other. m_1, m_2, and m_3
is an integer of 1 or 2. ) A resin composite material obtained by melt-laminating a vinyl chloride resin composition containing 0.5 to 5 parts by weight of a monoalkyltin compound represented by: 2. The resin composite material according to claim 1, wherein the vinyl chloride resin composition contains an epoxy plasticizer or an epoxy resin. 3. The vinyl chloride resin composition has a molecular weight of 500 to 10,0
2. The resin composite material according to claim 1, which contains a polymeric plasticizer of 0.00.