JP2949450B2 - 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 provides a structure comprising a halogen-containing resin and a polyurethane resin in contact with or adjacent to the halogen-containing resin. It was formed from a composition containing 0.01 parts by weight or more of the ion exchange resin.

[0008]

[Function] The anion exchange resin is contained in the polyurethane resin.
Caused by the deterioration of the halogen-containing resin
Hydrogen hydrogen is adsorbed and fixed on the anion exchange resin.
You. Therefore, the amine remaining in the polyurethane resin is
Halogen content by-product of the reaction of hydrogenogenogen
Reduce the amount of halogenated amines that act as catalysts for promoting discoloration of resins
Reduce. And thereby, the transformation of the halogen-containing resin
Color is prevented

Examples of the halogen-containing resin in the present invention include vinyl chloride resins, copolymers of vinyl chloride and other monomers, chlorinated polyolefins, polyvinylidene chloride, and halogen-containing rubbers. May be included.

On the other hand, the polyurethane resin in the present invention comprises
It is obtained by reacting a polyol and a polyisocyanate in the presence of an amine catalyst, an anion exchange resin, and other auxiliaries used as necessary.They may be non-foamed or foamed, and may be soft or soft. It may be either semi-rigid or rigid.

Examples of the polyol used in the present invention include ordinary polyether polyols for polyester resins, polyester polyols and polymer polyols. As the polyisocyanate, a general aromatic polyisocyanate, an alicyclic polyisocyanate, an aliphatic polyisocyanate for polyurethane resin, or a mixture of two or more thereof can be used. Representative examples of the polyisocyanate include tolylene diisocyanate (TDI), 4,4'-
Diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate (Crude MD
I), xylylene diisocyanate (XDI), isophorone diisocyanate, and hexamethylene diisocyanate. As the catalyst, a tertiary amine,
Alternatively, a tertiary amine and a metal catalyst are used in combination. Examples of the tertiary amine include triethylamine (TEA), triethylenediamine (TEDA), tributylamine, N-methylmorpholine, and dimethylethanolamine (DEA). Examples of the metal catalyst include tin catalysts such as dimethyltin malate and dibutyltin dilaurate.

As the anion exchange resin, a strongly basic anion exchange resin or a weakly basic anion exchange resin or a combination of two or more thereof can be used. As the strong basic anion exchange resin, those having a quaternary ammonium group, for example, styrene strong basic anion exchange resins DIAION SA 10A, DIAION SA
12A and DIAION SA 20A (all manufactured by Mitsubishi Kasei). Examples of the weakly basic anion exchange resin include those having a primary amine group, those having a secondary amine group, and those having a tertiary amine group. Having, for example, styrene-based weakly basic anion exchange resin DIAI
ON WA 21A, DIAION WA 30A (all manufactured by Mitsubishi Kasei) and acrylic weak basic anion exchange resin DIAION WA 12A (made by Mitsubishi Chemical) can be exemplified. The compounding amount of the anion exchange resin is
The amount is 0.01 part by weight or more based on 100 parts by weight of the polyol, but 0.05 part by weight or more is suitable for obtaining a practical discoloration prevention effect.

Other auxiliary agents used as needed include foaming agents, foam stabilizers, pigments, flame retardants 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, without contact. 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.

[0015]

Embodiments of the present invention will be described below. A vinyl chloride resin sheet having the following composition as a halogen-containing resin was formed in a size of 40 × 40 × 0.2 mm.

・ Blending of vinyl chloride resin sheet (parts by weight) Vinyl chloride resin straight resin (manufactured by Tosoh) 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 (manufactured by Sakai Chemical) 0.1

On the other hand, a polyurethane resin was formed as follows. As polyol, OH value 28, number of functional groups 2
DIAION PA 312LOH as an anion exchange resin using a polymer polyol (Polyol 33, manufactured by Sanyo Kasei) and a polymer polyol having an OH value of 27.5 and a number of functional groups of 3 (FA-728R, manufactured by Sanyo Chemical).
(Manufactured by Mitsubishi Kasei), dimethylethanolamine (DEA), triethylamine (TEA), and a 33% dipropylene glycol solution of triethylenediamine (Dapco 33LV) were used as a catalyst, water was used as a foaming agent, and NCO was used as a polyisocyanate. Using 5% of polymeric MDI (MR-200, manufactured by Nippon Polyurethane), they were mixed according to the composition shown in Table 1 to prepare a polyurethane resin raw material. Then, the polyurethane resin raw material was poured into a mold having a cavity of 300 × 300 × 20 mm and reacted to form semi-rigid polyurethane foams of Examples and Comparative Examples.

[0018]

[Table 1]

Next, a polyurethane foam having the composition of the examples and comparative examples shown in Table 1 was used in an amount of 40 × 40 × 10
The test pieces were cut into mm-sized test pieces, and the test pieces were superimposed on the above-mentioned vinyl chloride resin sheet, and a discoloration test of the vinyl chloride resin sheet was performed.

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 2 shows the test results. As is clear from Table 2, the examples of the present invention have a longer time to discoloration than the comparative examples, and have a very high discoloration prevention effect.

[0021]

[Table 2]

[0022]

As described above, the structure of the halogen-containing resin and the polyurethane resin of the present invention is such that the polyurethane resin in contact with or in proximity to the halogen-containing resin has an anion exchange resin of 0 parts by weight with respect to 100 parts by weight of the polyol. .01
Since the composition contains more than one part by weight, the action of the anion exchange resin is extremely high in preventing discoloration of the halogen-containing resin.

──────────────────────────────────────────────────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 Office (58) Field surveyed (Int. Cl. ⁶ , DB name) B32B 1/00-35/00 C08J 5/12

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 polyurethane resin has a composition containing at least 0.01 part by weight of an anion exchange resin with respect to 100 parts by weight of polyol. A structure comprising a halogen-containing resin and a polyurethane resin.