JP3167136B2 - Foam composite - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foam composite article,
The polyurethane foam and the polyurethane foam
Including halogen such as vinyl chloride resin
It relates to become more foam composite article a chromatic resin member.

[0002]

2. Description of the Related Art Halogen-containing resin such as vinyl chloride resin
Polyurethane foam covered with skin or box
The foamed composite articles are widely used as cushioning materials for automobile interior parts such as seats and instrument panels or furniture such as mattresses, or as heat insulating materials.

However, foam composite products are made of polyurethane.
Contact the foam with a halogen-containing resin member, or for use in close proximity, there is likely a problem discolored halogen-containing resin member during use. Although the cause or mechanism of the discoloration has not yet been determined, one of the causes is presumed as follows. The polyurethane foam is obtained by reacting a polyol and a polyisocyanate in the presence of an amine catalyst and an auxiliary. For this reason, the amine catalyst remaining in the polyurethane foam after foam molding reacts with hydrogen halide generated by the deterioration of the halogen-containing resin to form a halogenated amine, which is used as a decomposition catalyst for the halogen-containing resin. It acts to promote the discoloration of the halogen-containing resin member. The amine catalyst is indispensable because it is excellent for improving the foaming state. As auxiliary agents, foaming agents, foam stabilizers, flame retardants,
Pigments, crosslinking agents and the like are used as needed.

Conventionally, as a method for reducing the discoloration of the halogen-containing resin member , a polyurethane foam is subjected to foam molding in the presence of an amine catalyst, and then heated for a certain period of time to release residual amine from the polyurethane foam. (Japanese Patent Publication No. 2-42374) or a method in which a polyurethane foam after foam molding is held under reduced pressure for a certain time to release residual amine from the polyurethane foam has been proposed (Japanese Patent Publication No. 2-42851). I have.

[0005]

However, in the above method, an additional heating operation or decompression operation is required to separate the residual amine from the polyurethane foam after foaming, which makes the operation complicated. There's a problem.

Accordingly, the present invention provides a halogen-containing resin member.
Foam composite that is less likely to cause discoloration and is easy to manufacture
Products .

[0007]

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides a polyurethane foam,
Made of halogen-containing resin placed in contact with or in close proximity to body
In a foam composite article comprising a member, the polyurethane
Foam with a polyol in the presence of an amine catalyst and an auxiliary.
Foam molded by reaction with polyisocyanate
Wherein one of said auxiliaries is 100% by weight of said polyol
Anion exchange capacity of 0.05 parts by weight or more per part
It is made of a metal compound having the same.

[0008]

The polyurethane foam after reaction molding contains a metal-containing substance having an anion exchange ability. Therefore, even if the halogen-containing resin member that is in contact with or close to the polyurethane foam deteriorates and generates hydrogen halide, the hydrogen halide is converted into a metal-containing material having an anion exchange ability in the polyurethane foam. It is absorbed and does not react with amines. Therefore, according to the present invention, the halogenated amine which has conventionally been generated by the reaction between the hydrogen halide and the amine is no longer generated, and the discoloration of the halogen-containing resin member which proceeds using the halogenated amine as a catalyst can be suppressed. .

[0099] Polyurethane foam produced in the present invention
The body may be soft, semi-rigid or rigid.

The polyol used in the present invention is the same polyether polyol, polyester polyol or polymer polyol used in the production of ordinary polyurethane foams .

The polyisocyanate used in the present invention is the same aromatic polyisocyanate, alicyclic polyisocyanate or aliphatic polyisocyanate used in the production of ordinary polyurethane foams , or a mixture of two or more thereof. It is. 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.

The catalyst used in the present invention uses a tertiary amine or a combination of a tertiary amine and a metal catalyst. Examples of the tertiary amine include triethylamine (TEA), triethylenediamine (TEDA), tributylamine, N-
Methylmorpholine, N-methylmorpholine, dimethylethanolamine (DEA) can be mentioned. Examples of the metal catalyst include dimethyltin malate and dibutyltin dilaurate as tin catalysts.

The metal-containing material having an anion exchange ability used in the present invention includes, for example, natural or artificial minerals such as zeolite group and hydrotalcite group, or all or a part of the anion exchange portion is formed with an organic acid. Examples include artificial minerals such as a substituted zeolite group and a hydrotalcite group, or two or more of them. If the compounding amount of the metal-containing substance having an anion exchange ability is 0.05 parts by weight or more with respect to 100 parts by weight of the polyol, the effect of preventing discoloration of the halogen-containing resin is exhibited. To achieve this, 0.1 parts by weight or more is preferred. In addition, the metal-containing material having an anion exchange ability,
In order to facilitate dispersion in the polyurethane resin raw material, those having an average particle size of 0.1 to 1000 microns are preferable.

As other auxiliaries, foaming agents, foam stabilizers,
There are pigments, flame retardants, crosslinking agents and the like. The foaming agent and the foam stabilizer are necessary for forming a polyurethane 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. Pigments are used when the polyurethane foam is colored to a desired color, and include carbon plaque.The flame retardant is used for imparting flame retardancy to the polyurethane foam . Phosphates and the like can be mentioned. The crosslinking agent adjusts the hardness of the polyurethane foam , and examples thereof include polyhydroxy compounds having 3 to 6 hydroxyl groups, amino alcohols, and unsaturated polyesters.

In contact with the polyurethane foam or
Used as the material of the halogen-containing resin member placed close to
In addition to the above-mentioned vinyl chloride resin, copolymers of vinyl chloride and other monomers, chlorinated polyolefins, polyvinylidene chloride, halogen-containing rubbers, and the like can be given. These resins include various additives or pigments. May be included. In addition, the proximity means that both (polyurethane foam and halogen-containing resin member) are located in a space of several tens of mm or less, or that both are in contact via a gas-permeable substance such as a fibrous substance. The case is also included. Furthermore, in the foam composite article of the present invention, an insert made of a reinforcing member or the like may be embedded in the polyurethane foam during or after the foam molding.

[OO16]

Embodiments of the present invention will be described below. 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, trifunctional polymer polyol (FA-728R, manufactured by Sanyo Chemical Industries), dimethylethanolamine (D
EA), a 33% dipropylene glycol solution of triethylamine (TEA) and triethylenediamine (Dapco 33LV), water as a foaming agent, hydrotalcite having an average particle diameter of 0.7 micron as a metal-containing substance having an anion exchange capacity ( ALCAMIZER-4, manufactured by Kyowa Chemical)
Polymeric MDI with 30.5% NCO as polyisocyanate (MR-200, manufactured by Nippon Polyurethane)
Were mixed in accordance with the formulations shown in Examples 1 to 5 in Table 1 to prepare a polyurethane foam raw material, and 300 × 300 × 20 m
polyurethane foam in a mold with a cavity of m
The body material was injected and reacted to produce a semi-rigid polyurethane foam. For comparison, semi-rigid polyurethane foams of Comparative Examples 1 and 2 were prepared using the same mold as those in the above Examples, and were composed of a composition containing no metal-containing substance having anion exchange ability.

[O017]

[Table 1]

The polyurethane foams of the above Examples and Comparative Examples were cut into test pieces having a size of 40.times.40.times.10 mm, and each test piece was formed of a polyvinyl chloride having a thickness of 0.2 mm and having the following composition. The discoloration test of the vinyl chloride resin sheet was performed by overlapping the 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 (Nippon Synthetic Chemistry) 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

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 was discolored (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.

[0021]

[Table 2]

[0022]

As described above, the present invention relates to an amine catalyst.
Polyol and polyisocyanate in the presence of a solvent and an auxiliary
Polyurethane foam foamed by the reaction of
C that is placed in contact with or in close proximity to the polyurethane foam
Smell of foam composite product consisting of a resin-containing resin member
One of the polyurethane foam auxiliaries is the polyol
Negative ion that becomes 0.05 or more superposition parts per 100 superposition parts
It is a metal-containing material having heat exchange ability . That
According to the product of the present invention,
The discoloration of the halogen-containing resin member could be suppressed by the action of the metal-containing substance having an anion-exchanging ability contained in or near the polyurethane foam . Further, since a heating or depressurizing operation for removing the residual amine in the polyol is not required as a post-process after the polyurethane foam molding , the halogen-containing resin is used .
There is also an effect that it is possible to extremely easily manufacture a foam composite product in which a member is not easily discolored.

──────────────────────────────────────────────────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 Works (56) References JP-A-3-292364 (JP, A) JP-A-59-133248 (JP, A) (58) Fields investigated (Int. . ^7, DB name) C08G 18/00 - 18/87 B32B 27/40 C08L 75/04 - 75/12

Claims (1)

(57) [Claims] 1. A polyurethane foam and the polyurethane
Halogen-containing tree placed in contact with or in close proximity to the foam
In a foam composite product comprising a fat member, the polyurethane foam may include an amine catalyst and an auxiliary agent.
Foam by reaction between lower polyol and polyisocyanate
Molded, wherein one of the auxiliaries is the polio.
Is 0.05 parts by weight or more with respect to 100 parts by weight of
It is characterized by being composed of a metal compound having ion exchange capacity
Foam composite products .