JPH06198825A - Composite structure of halogen-containing resin and polyurethane resin - Google Patents

Abstract

PURPOSE:To provide a composite structure having excellent discoloration preventing action. CONSTITUTION:In a composite structure consisting of a halogen-containing resin molded object (part) and the polyurethane resin molded object (part) coming into contact with or coming close to the halogen-containing molded object (part), 0.01-20 pts.wt. of an oxidation inhibitor is contained in the polyurethane resin compsn. at the time of the molding of the polyurethane resin molded object with respect to 100 pts.wt. of polyol contained in the polyurethane resin compsn. This oxidation inhibitor is composed of at least one of a phenolic oxidation inhibitor (BHT, BHA), a phosphorous oxidation inhibitor and a sulfur oxidation inhibitor.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-containing resin / polyurethane resin composite structure, and more specifically, a halogen-containing resin molded body (part) and a polyurethane resin molded body (part) are arranged in close contact with each other. The present invention relates to a structure of a halogen-containing resin / polyurethane resin which is arranged in close proximity or is integrally laminated and formed. INDUSTRIAL APPLICABILITY The present invention is widely used for instrument panels, crash pads, armrests, headrests, consoles, meter covers, door trims, automobile interior materials such as vehicle seats, furniture cushioning materials such as mattresses, and heat insulating materials.

[0002]

2. Description of the Related Art A structure of a halogen-containing resin / polyurethane resin has a polyurethane resin molding (including both foam and non-foam) covered with a skin or box-shaped body made of a halogen-containing resin. It is configured and widely used for automobile interior parts and the like. However, when the polyurethane resin molded body is used in contact with or close to the halogen-containing resin molded body, there is a problem that the halogen-containing resin molded body is likely to be discolored during use. Conventionally, to reduce this discoloration, 1.
Disclosed is an integrated structure comprising a chlorine-containing resin layer formed from a chlorine-containing resin powder composition containing 0 part by weight or more of a perchlorate, and a polyurethane resin foam integrally formed with the resin layer. (JP-A-62-270645)
No. 1).

[0003]

However, even with the above-mentioned integrated structure, although discoloration is improved to some extent,
Although it cannot be said that discoloration can be completely prevented, there is a demand for a structure having a further excellent discoloration preventing action.

The present invention has been made in view of the above point of view, and is a halogen-containing resin having an excellent discoloration preventing action.
It is an object of the present invention to provide a composite structure of polyurethane resin (hereinafter, simply referred to as “present composite structure”).

[0005]

Means for Solving the Problems The present inventor has conducted various studies on the cause of discoloration in the present composite structure, and has found that the cause is deterioration of the polyurethane resin, and completed the present invention. The present composite structure of the first invention is
In a composite structure comprising a halogen-containing resin molded body and a polyurethane resin molded body that is in contact with or close to the halogen-containing resin molded body, the polyurethane resin composition in molding the polyurethane resin molded body contains the polyurethane. It is characterized in that 0.01 to 20 parts by weight of the antioxidant is contained with respect to 100 parts by weight of the polyol contained in the resin composition. The present composite structure of the second invention is an integral composite structure comprising a halogen-containing resin molded part and a polyurethane resin molded part formed on at least one surface of the halogen-containing resin molded part. In the polyurethane resin composition at the time of molding the resin molding part, 0.01 to 20 antioxidant is added to 100 parts by weight of the polyol contained in the polyurethane resin composition.
It is characterized by including parts by weight.

The "halogen-containing resin molded product" and the "halogen-containing resin molded part" are made of a halogen-containing resin. Examples of the contained resin include vinyl chloride resins, copolymers of vinyl chloride and other monomers, chlorinated polyolefins, polyvinylidene chloride, and halogen-containing rubbers. The shape, size, and thickness of these resin molded body and resin molded portion are not particularly limited. The resin may contain various additives or pigments.

The "polyurethane resin molding" and the "polyurethane resin molding" are made of polyurethane resin. These may be either non-foam or foam,
It may be soft, semi-hard, or hard. The shape, size, and thickness of these resin moldings (parts) are not particularly limited. Furthermore, an insert made of a reinforcing body or the like may be embedded in the polyurethane resin molded body (part). This polyurethane resin is obtained by reacting a polyol and a polyisocyanate in the presence of an amine catalyst, an anion exchange resin and other auxiliary agents used as necessary.

Examples of the above-mentioned polyols include polyether polyols, polyester polyols and polymer polyols for ordinary polyurethane resins. As the above-mentioned polyisocyanate, it is possible to use an aromatic polyisocyanate for ordinary polyurethane resin, an alicyclic polyisocyanate, an aliphatic polyisocyanate, or a mixture of two or more thereof.
Typical examples of this polyisocyanate include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), xylylene diisocyanate (XDI), isophorone diisocyanate, hexamethylene diisocyanate, etc. Can be mentioned.

Further, as the above catalyst, a tertiary amine can be used, or a tertiary amine and a metal catalyst can be used in combination. As the tertiary amine, triethylamine (T
EA), triethylenediamine (TEDA), tributylamine, N-methylmorpholine, dimethylethanolamine (DEA) and the like. Examples of this metal catalyst include tin catalysts such as dimethyltin maleate and dibutyltin dilaurate.

As the "antioxidant", one or more of phenolic antioxidants, phosphorus antioxidants and sulfur antioxidants can be used. In this phenolic antioxidant, examples of monophenolic compounds include 2,6-di-t-p-cresol (BHT) and butylated hydroxyanisole (BHA), and examples of bisphenolic compounds include: 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol), 2,2'-methylene-bis- (4-methyl-6-
t-butylphenol) and the like, and as the polymer type phenol-based compound, 1,1,3-tris- (2-
Examples include methyl-4-hydroxy-5-t-butylphenyl) butane, and examples of tocophenols include vitamin E. Examples of the sulfur-based antioxidant include dilauryl thiopropionate and dimytyl thiodipropionate, and examples of the phosphorus-based antioxidant include triphenyl phosphite and diphenyl isodecyl phosphite. be able to. The blending amount of the above antioxidant is 0.01 to 20 parts (preferably 0.03 parts or more) with respect to 100 parts by weight of the polyol. If it is less than 0.01 part, the effect of addition is not sufficient, and if it exceeds 20 parts, the moldability of the urethane decreases and the cost increases, which is not preferable.

Other addition aids used as required include foaming agents, foam stabilizers, pigments, flame retardants, crosslinking agents 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 above-mentioned pigment is used when coloring the polyurethane resin in a desired color, and examples thereof include carbon black. The flame retardant is used for imparting flame retardancy to the polyurethane resin. A phosphate etc. can be mentioned. The cross-linking agent is
It controls the hardness of the polyurethane resin, and examples thereof include polyhydroxy compounds having 3 to 6 hydroxyl groups, amino alcohols, unsaturated polyesters, and the like.

As for the positional relationship between the halogen-containing resin molding (part) and the polyurethane resin molding (part) in the present invention, as shown in the first invention, the halogen-containing resin molding and the polyurethane resin molding are Touch (contact)
In the case, it does not matter if they are in direct contact with each other or they are in close proximity,
As shown in the invention, there may be mentioned a case where both parts are integrally molded so that they cannot be separated. The term "proximity" means that the two are located apart from each other by several tens of millimeters or less (for example, 50 mm or less) (for example, when they are arranged with a space without any intervening, and between them is like a fibrous substance). Such as when they are opposed to each other through a breathable substance, etc.).

[0013]

[Function] The relationship between the antioxidant and the discoloration, that is, the cause and mechanism of deterioration when both resin moldings (parts) are laminated is not yet determined, but as one of the causes In consideration of the results shown in the following examples, the following is estimated. That is, when a conventional polyurethane resin that does not positively contain an antioxidant is deteriorated and crosslinks are cleaved (an ester portion or a urethane portion is decomposed), an acid, an alcohol, an amine compound or the like is generated. Therefore, the polarity of the resin is increased, so that the plasticizer contained in the halogen-containing resin easily migrates to the deteriorated polyurethane resin side. This plasticizer contained in the halogen-containing resin has the purpose of imparting flexibility to the halogen-containing resin and at the same time reducing the discoloration of the halogen-containing resin. Therefore, it is considered that the deterioration of the polyurethane resin promotes the migration of the plasticizer in the halogen-containing resin to the polyurethane resin, which impairs the flexibility of the halogen-containing resin and at the same time promotes the discoloration of the halogen-containing resin. To be

On the other hand, in the present invention, the polyurethane resin contains a predetermined antioxidant. Therefore, in the phenolic antioxidant, the radical chain that promotes the deterioration reaction is suppressed. Further, in the sulfur-based or phosphorus-based antioxidant, the deterioration reaction-promoting peroxide is decomposed to suppress the deterioration reaction. As described above, in the present invention, the crosslinking of the polyurethane resin is less likely to be cut. Therefore, the transfer of the plasticizer in the halogen-containing resin to the polyurethane resin is delayed. Therefore, it is considered that the discoloration of the halogen-containing resin is prevented and the flexibility is maintained.

[0015]

[Halogen-containing resin composition]

Vinyl chloride resin Straight resin (manufactured by Tosoh Corporation) 100 Plasticizer dioctyl phthalate 60 Epoxidized soybean oil 10 Stabilizer Dialkyl tin maleate polymer (manufactured by Nitto Kasei Co.) 0.2 Barium stearate (manufactured by Sakai Chemical Co., Ltd.) 1.0 Zinc stearate (manufactured by Sakai Chemical Industry) 0.2 Stearoylbenzoylmethane (manufactured by Showa Denko KK) 0.1 Stabilizing agent 2,6-di-t-butyl-p-cresol (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) 0.1 Tri Phenylphosphite (manufactured by Sakai Chemical Industry) 0.2 Pentaerythritol (manufactured by Nippon Synthetic Chemical Industry) 0.2 Lubricants Synthetic paraffin (manufactured by Hoechst) 0.3 NN ′ Methylenebisstearylamide (manufactured by Nippon Synthetic Chemical Company) 3 Stearic acid (manufactured by NOF CORPORATION) 0.5 Pigment quinacridone red (manufactured by Dainichiseika) 0.2 Titanium oxide (Sakai Chemical Co., Ltd.) ) 0.2 red iron oxide (manufactured by Sakai Chemical Industry) 0.1

On the other hand, a polyurethane resin molded body was manufactured as follows. First, a polyurethane resin raw material composition having a compounding ratio (unit: parts by weight) shown in Table 1 is prepared. Table 1
Among them, "Polyol 33" as a polyol (trade name,
Sanyo Chemical Co., Ltd.) is a polymer polyol having an OH value of 28 and a functional number of 2, and “FA-728R” (trade name, manufactured by Sanyo Chemical Co., Ltd.) is a polymer polyol having an OH value of 27.5 and a functional group number of 3. "BHT" (2,6-di-t-p-cresol) is a phenol antioxidant, "phosphorus antioxidant" is trinonylphenyl phosphite, and "sulfur antioxidant" is dicarboxylic acid. Lauryl thiodipropionate, "DEA" is dimethylethanolamine as a catalyst, "TEA" is triethylamine, and "TEDA" is triethylenediamine. Water was used as the foaming agent. Then, the above polyurethane resin raw material composition is added to 300
It was poured into a mold having a cavity of mm × 300 mm × 20 mm and reacted at 40 ° C. for 1 hour to form semi-rigid polyurethane foam sheets of Examples and Comparative Examples.

[0017]

[Table 1]

Next, 40 mm × 40 mm of each polyurethane foam sheet having the composition of Examples and Comparative Examples in Table 1 was prepared.
A polyurethane foam test piece having a size of × 10 mm was cut, each test piece was placed on the vinyl chloride resin sheet, and a discoloration test of the vinyl chloride resin sheet was performed. In the discoloration test, the laminate of the polyurethane foam test piece and the vinyl chloride resin sheet was placed on the glass surface at 180 ° C. with the polyurethane foam test piece facing the glass surface, The measurement was performed by measuring the time until the vinyl resin sheet discolored (by visual observation).
The discoloring time is divided into four stages, the discolored state of the vinyl chloride resin sheet, that is, discolored start, slight discolored (yellowish), marked discolored (black discolored partly), and black discolored all over, and start heating. The time from when to each step was measured. The test results are shown in Table 2.

[0019]

[Table 2]

As is clear from Table 2, in the examples of the present invention, the time until discoloration is longer than that in the corresponding comparative examples, and discoloration of the vinyl chloride resin sheet is prevented by addition of any antioxidant. Was done. The present invention is not limited to the specific examples described above, and various modifications may be made within the scope of the present invention depending on the purpose and application.

[0021]

As described above, in the halogen-containing resin / polyurethane resin structure of the present invention, discoloration / deterioration of the halogen-containing resin molding (part) is prevented.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C08L 27/04 LFM 9166-4J 75/04 NGG 8620-4J (72) Inventor Hideo Suzuki Aichi Prefectural Anth 3-1, 36 Imaike-cho, Shiro-shi Inoac Corporation Anjo Works

Claims (3)

[Claims] 1. A composite structure comprising a halogen-containing resin molded body and a polyurethane resin molded body in contact with or close to the halogen-containing resin molded body, wherein the polyurethane resin composition is used when molding the polyurethane resin molded body. Contains a halogen-containing resin / polyurethane resin composite in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polyol contained in the polyurethane resin composition. 2. A composite structure comprising a halogen-containing resin molded part and a polyurethane resin molded part formed on at least one surface of the halogen-containing resin molded part, wherein the polyurethane resin molded part is molded. Halogen-containing resin / polyurethane resin composite, wherein the polyurethane resin composition contains 0.01 to 20 parts by weight of an antioxidant with respect to 100 parts by weight of the polyol contained in the polyurethane resin composition. Structure. 3. The halogen-containing resin / polyurethane resin composite according to claim 1, wherein the antioxidant comprises at least one of a phenol-based antioxidant, a phosphorus-based antioxidant and a sulfur-based antioxidant. Structure.