JP2958540B2 - Structure of halogen-containing resin and polyurethane resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a structure of a halogen-containing resin and a polyurethane resin combined in contact with or in close proximity to each other.

[0002]

2. Description of the Related Art The structure of a halogen-containing resin and a polyurethane resin has a structure in which a polyurethane resin (including both a foamed body and a non-foamed body) is covered with, for example, a skin-containing or box-shaped halogen-containing resin. Being seated,
It is widely used as an automobile interior part such as an instrument panel, a cushion material for furniture such as a mattress, or a heat insulating material.

However, when a polyurethane resin is used in contact with or in close proximity to a halogen-containing resin, there has been a problem that the halogen-containing resin tends to be discolored during use. Although the cause or mechanism of the discoloration has not yet been determined, one of the causes is presumed as follows. A polyurethane resin is obtained by reacting a polyol with a polyisocyanate in the presence of an amine catalyst and an auxiliary. Therefore, the amine remaining in the polyurethane resin after molding reacts with hydrogen halide generated by the deterioration of the halogen-containing resin to form a halogenated amine, and the halogenated amine acts as a decomposition catalyst for the halogen-containing resin, It is to promote the discoloration of the halogen-containing resin. The amine catalyst is indispensable because it is excellent for improving the molding state. Further, as an auxiliary agent, a foaming agent, a foam stabilizer, a flame retardant, a pigment, a crosslinking agent, and the like are used as needed.

Conventionally, as a method for reducing the discoloration,
A structure comprising a chlorine-containing resin in which 1.0 part by weight or more of an organic acid zinc is blended with respect to 100 parts by weight of the chlorine-containing resin, and a polyurethane resin foam has been proposed (Japanese Patent Publication No. Sho 6 (1988)).
No. 2-24269).

[0005]

However, even in the above-mentioned structure having improved discoloration, it is difficult to completely prevent discoloration, and a structure having a higher discoloration prevention action has been demanded. .

Accordingly, an object of the present invention is to provide a structure of a halogen-containing resin and a polyurethane resin having an excellent discoloration preventing action.

[0007]

In order to achieve the above object, the present invention relates to a structure comprising a halogen-containing resin and a polyurethane resin in contact with or adjacent to the halogen-containing resin, wherein the halogen-containing resin is contained in 100 parts by weight of the resin. The content of the metal-containing material having a cation exchange capacity is 0.05 parts by weight or more.

[0008]

The amine remaining in the polyurethane resin is adsorbed and fixed on a metal material having a cation exchange ability in the halogen-containing resin in contact with or close to the polyurethane resin. Therefore, since the amine does not exist in a free state,
Even if hydrogen halide is generated due to the deterioration of the halogen-containing resin, it cannot react with the amine, and the formation of a halogenated amine that promotes the discoloration of the halogen-containing resin is prevented, thereby discoloring the halogen-containing resin. Prevention is made.

The resin constituting the halogen-containing resin in the present invention includes a vinyl chloride resin, a copolymer of vinyl chloride and another monomer, a chlorinated polyolefin, polyvinylidene chloride, a halogen-containing rubber, and the like. Examples of the metal-containing material having a cation exchange ability to be mixed with the resin include natural minerals such as montmorinite and metal phosphate (eg, aluminum phosphate, sepionite, and palygoskite), or artificially synthesized compounds (eg, zirconium phosphate) , Fajasite, cobalt ferrocyanide) and the like, or a mixture of two or more thereof. The amount of the metal-containing substance having cation exchange capacity is 0.0
When the content is 5 parts by weight or more, the effect of preventing discoloration of the halogen-containing resin is exhibited.
1 part by weight or more is preferable. The metal-containing substance having a cation exchange ability preferably has an average particle diameter of 0.1 to 1000 microns in order to facilitate dispersion in the resin.

In addition, various additives such as a plasticizer, a stabilizer, a stabilizing aid, a lubricant, and a pigment are added to the halogen-containing resin according to the use of the product.

On the other hand, a polyurethane resin in contact with or in proximity to a halogen-containing resin is formed by reacting a polyol and a polyisocyanate in the presence of a catalyst and other necessary auxiliaries. Any of them may be used, and any of soft, semi-hard or hard may be used.

Examples of the polyol used as a raw material of the polyurethane resin include the same polyether polyol, polyester polyol or polymer polyol as used in the production of ordinary polyurethane resins.

Examples of the polyisocyanate include the same aromatic polyisocyanate, alicyclic polyisocyanate or aliphatic polyisocyanate used in the production of ordinary polyurethane resins, or a mixture of two or more thereof. . Representative examples of the polyisocyanate include tolylene diisocyanate (TDI),
4,4'-diphenylmethane diisocyanate (MD
I), polymethylene polyphenyl isocyanate (crude MDI), xylylene diisocyanate (XD
I), isophorone diisocyanate and hexamethylene diisocyanate.

A tertiary amine or a combination of a tertiary amine and a metal catalyst is used as a catalyst for the raw material of the polyurethane resin. Examples of the tertiary amine include triethylamine (TEA), triethylenediamine (TEDA), tributylamine, N-methylmorpholine, N-methylmorpholine, and dimethylethanolamine (DEA). On the other hand, examples of the metal catalyst include dimethyltin malate and dibutyltin dilaurate as tin catalysts.

Other auxiliaries of the polyurethane resin raw material include a foaming agent, a foam stabilizer, a pigment, a flame retardant, a crosslinking agent and the like. The foaming agent and the foam stabilizer are necessary when the polyurethane resin is a foam, and those used for ordinary polyurethane foams can be used. For example, examples of the foaming agent include water, freon, and methylene chloride, and examples of the foam stabilizer include a silicon compound. The pigment is used to color the polyurethane resin to a desired color, and examples thereof include carbon black.The flame retardant is used to impart flame retardancy to the polyurethane resin. Salts and the like can be mentioned. The crosslinking agent adjusts the hardness of the polyurethane resin, and examples thereof include a polyhydroxy compound having 3 to 6 hydroxyl groups, an amino alcohol, and an unsaturated polyester.

The contact between the halogen-containing resin and the polyurethane resin in the present invention includes the case where the two (the halogen-containing resin and the polyurethane resin) come into contact with each other when the product is used, even if they do not normally come into contact with each other. This includes the case where both are located in a space of several tens of mm or less, or the case where both are in contact via a gas-permeable substance such as a fibrous substance. Further, an insert made of a reinforcing body or the like may be embedded in the polyurethane resin.

[0017]

Embodiments of the present invention will be described below.

Zirconium phosphate IX-100 having an average particle size of 1.0 μm as a metal-containing material having a cation exchange ability
(Toa Gosei Co., Ltd.) in the range of 0 to 0.8 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. It was formed in a size of × 40 × 0.2 mm. Table 1 shows the amount of zirconium phosphate relative to 100 parts by weight of the resin in the vinyl chloride resin sheet.

・ Blending of vinyl chloride resin sheet parts by weight Vinyl chloride resin straight resin (manufactured by Tosoh Corporation) 100 plasticizer dioctyl phthalate 60 epoxidized soybean oil 10 stabilizer dialkyltin maleate polymer (manufactured by Nitto Kasei) 0.2 stearic acid Barium (manufactured by Sakai Chemical) 1.0 Zinc stearate (manufactured by Sakai Chemical) 0.2 Stearoylbenzoylmethane (manufactured by Showa Denko) 0.1 Stabilizing aid 2,6-di-t-butyl-p-cresol (Yoshitomi) 0.1 Triphenylphosphite (manufactured by Sakai Chemical) 0.2 Pentaerythritol (manufactured by Nippon Synthetic Chemical) 0.2 Lubricant Synthetic paraffin (manufactured by Hoechst) 0.3 NN'methylenebisstearylamide (manufactured by Nippon Gosei) Chemical) 0.3 Stearic acid (Nippon Yushi) 0.5 Pigment quinacridone red (Dainichisei Ltd.) 0.2 titanium oxide (manufactured by Sakai Chemical) 0.2 iron oxide (Sakai Chemical Co., Ltd.) 0.1 metal inclusions zirconium phosphate having a cation exchange capacity (Toagosei) 0-0.8

[0020]

[Table 1]

On the other hand, a polyurethane resin was formed from the following raw materials. As the polyol, an OH value of 28, a bifunctional polymer polyol (Polyol 33, manufactured by Sanyo Chemical), and an OH value of 27.5, a trifunctional polymer polyol (FA-
728R, manufactured by Sanyo Chemical Industries), 33% dipropylene glycol solution of dimethylethanolamine (DEA), triethylamine (TEA), and triethylenediamine (Dapco 33LV) as a catalyst, water as a blowing agent, and 30.5% NCO as a polyisocyanate Polymeric M
DI (MR-200, manufactured by Nippon Polyurethane) was mixed according to the formulation shown in Table 2 to prepare a polyurethane resin raw material, and the polyurethane resin raw material was injected into a mold having a cavity of 300 × 300 × 20 mm and reacted. Thus, semi-rigid polyurethane foams of Examples and Comparative Examples were produced.

[0022]

[Table 2]

Then, the polyurethane foams of Examples and Comparative Examples in Table 2 were cut into test pieces having a size of 40 × 40 × 10 mm, and each test piece was used as an example of the vinyl chloride resin sheet in Table 1. Further, a discoloration test of the vinyl chloride resin sheet was performed over the comparative example. At that time, the vinyl chloride resin sheet and the polyurethane foam were combined with the same example number and comparative example number.

In the discoloration test, a laminate of the polyurethane foam test piece and the vinyl chloride resin sheet was subjected to a 180-degree test so that the polyurethane foam was on the glass surface side.
The test was carried out by placing the sample on a glass surface at a temperature of 0 ° C. and measuring the time until the vinyl chloride resin sheet changed its color (by visual observation). The discoloration time indicates the discoloration state of the vinyl chloride resin sheet, starting discoloration, slight discoloration (to take on a yellow tint),
It was divided into four stages of significant discoloration (partial black discoloration occurred) and black discoloration on the entire surface, and the time from the start of heating to each stage was measured. Table 3 shows the test results. As is clear from Table 3, the examples of the present invention have a longer time until discoloration than the comparative examples, and have an extremely high discoloration prevention effect.

[0025]

[Table 3]

[0026]

As described above, the structure of the halogen-containing resin and the polyurethane resin of the present invention is characterized in that the halogen-containing resin in contact with or in proximity to the polyurethane resin is a resin 1
Since the metal-containing material having a cation exchange ability is contained in an amount of 0.05 part by weight or more with respect to 00 parts by weight, the action of the metal-containing material having the cation exchange ability prevents the halogen-containing resin from discoloring. Is extremely high.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroshi Goto 3-36 Imaikecho, Anjo-shi, Aichi Prefecture Inoac Corporation Anjo Works (72) Inventor Koji Asaoka 3-chome, Imaikecho, Anjo-shi, Aichi Prefecture No. 1-36 Inoac Corporation Anjo Plant (56) References JP-A-58-71152 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B32B 1/00- 35/00

Claims (1)

(57) [Claims] 1. A structure comprising a halogen-containing resin and a polyurethane resin in contact with or adjacent to the halogen-containing resin, wherein the halogen-containing resin is 0.05 parts by weight of a metal-containing substance having a cation exchange ability with respect to 100 parts by weight of the resin. A structure comprising a halogen-containing resin and a polyurethane resin, characterized by containing at least one part by weight.