JP2002249545A - Resin composition and laminated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which excels in the balance of the melt flowability to be required on fabrication and the adhesion to a polyurethane foam, and can give a laminated product firmly bonded to a polyurethane without using a primer (an adhesive), and a laminated product to be obtained by using the resin composition. SOLUTION: The resin composition comprises (A) 100 pts.wt. copolymer of an epoxy group-containing monomer with an α-olefin and (B) 3-150 pts.wt. polyhydric phenol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition and a laminate. More specifically, the present invention provides an excellent balance between the melt fluidity required at the time of molding and the adhesiveness to the polyurethane foam, and it is possible to obtain a laminate which is firmly adhered to polyurethane without using a primer (adhesive). The present invention relates to a resin composition which can be obtained and a laminate obtained using the resin composition.

[0002]

2. Description of the Related Art For example, resin laminates are frequently used for interior parts of automobiles. Usually, the laminate is formed by laminating a skin layer for improving appearance on a polyurethane foam layer for expressing cushioning property, and a vinyl chloride resin has been widely used as the skin layer. However, from the viewpoint of environmental protection in recent years, the tendency of vinyl chloride resin to be avoided has increased, and a material replacing vinyl chloride resin has been desired. Researches using olefin-based or styrene-based thermoplastic elastomers as the material have been conducted. However, according to the prior art, the adhesion between the olefin-based and styrene-based thermoplastic elastomers and the polyurethane is insufficient, and it is necessary to use a primer (adhesive) to obtain a strong laminate. . However, the technique using a primer has a problem that the working environment is deteriorated due to an organic solvent contained in the primer, in addition to an increase in cost for the primer, a complicated process involved in the primer application step.

[0003]

Under such circumstances,
The problem to be solved by the present invention is to obtain a laminate which has an excellent balance between the melt fluidity required at the time of molding and the adhesiveness with a polyurethane foam, and which is firmly adhered to polyurethane without using a primer (adhesive). The present invention relates to a resin composition which can be used and a laminate obtained using the resin composition.

[0004]

That is, one aspect of the present invention relates to a resin composition containing the following component (A) 100 parts by weight and component (B) 3 to 150 parts by weight. . (A): a copolymer comprising an epoxy group-containing monomer and an α-olefin (B): a polyhydric phenol In another aspect of the present invention, the above-mentioned resin composition layer (1) and polyurethane It relates to a laminate (I) formed by laminating a layer (2).

[0005]

DETAILED DESCRIPTION OF THE INVENTION Component (A) of the present invention is a copolymer comprising an epoxy group-containing monomer and an α-olefin. The copolymer comprising an epoxy group-containing monomer and an α-olefin is a copolymer of a monomer having an epoxy ring and an α-olefin, and examples of the monomer having an epoxy ring include glycidyl. Examples include acrylate, glycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether, methacryl glycidyl ether, glycidyl itaconate, and the like. Examples of the α-olefin include ethylene, propylene, 1-butene and the like.

A copolymer comprising an epoxy group-containing monomer and an α-olefin is a copolymer of a monomer having an epoxy ring and an α-olefin. Also includes those in which monomers other than olefins are copolymerized.

As monomers other than the monomer having an epoxy ring and the α-olefin, carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone, styrene, α-methylstyrene, vinyl aromatic compounds such as vinyltoluene, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate,
Examples include acrylates such as n-octyl acrylate, methoxymethyl acrylate, and methoxyethyl acrylate.

[0008] Component (B) of the present invention is a polyhydric phenol. A polyhydric phenol is an aromatic hydroxy compound in which a hydrogen atom of an aromatic hydrocarbon nucleus is substituted with a hydroxyl group, and a phenol, and an aromatic hydroxy compound in which two or more hydrogen atoms are substituted with a hydroxyl group is collectively called a polyhydric phenol. .
For example, an aromatic hydroxy compound in which two hydrogen atoms have been substituted with hydroxyl groups is called a dihydric phenol, which includes catechol, resorcin, hydroquinone, orcin, urushiol, bisphenol A, binaphthol,
And anthrahydroquinone. Hydrogen atom is converted to 3 by hydroxyl group
The substituted aromatic hydroxy compound is called trihydric phenol, and examples of trihydric phenol include pyrogallol, phloroglucin, and hydroxyhydroquinone. The component (B) of the present invention comprises, in a laminate with a thermoplastic elastomer,
From the viewpoint of the adhesiveness between the layer composed of the resin composition of the present invention and the layer composed of the thermoplastic elastomer, a dihydric polyhydric phenol is preferred, and it is preferably solid at room temperature for convenience in handling.

In the resin composition of the present invention, (A) 1
00 parts by weight and 3 to 150 parts by weight of (B) are used, and preferably 5 to 100 parts by weight of (B) are used. (B)
Is too small ((A) is too large), the adhesion to the polyurethane becomes insufficient, while (B) is too large ((A) is too small).
It is. In a laminate with a thermoplastic elastomer,
Adhesion between the layer composed of the resin composition of the present invention and the layer composed of the thermoplastic elastomer may be insufficient.

In the present invention, the essential component (A) is
In addition to (B) and (B), (C) an olefin polymer may be used. As the olefin polymer, polypropylene, low-density polyethylene, linear low-density polyethylene,
Copolymers composed of ethylene and α-olefins other than ethylene, copolymers composed of monomers copolymerizable with ethylene other than ethylene and α-olefins, and the like can be given. As monomers copolymerizable with ethylene other than α-olefin, vinyl acetate, carboxylic acid vinyl esters such as vinyl propionate, methyl ketone, vinyl ketone such as ethyl vinyl ketone, styrene, α-methyl styrene, vinyl Vinyl aromatic compounds such as toluene,
Examples include acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate, methoxymethyl acrylate, and methoxyethyl acrylate.

The amount of (C) used is preferably from 10 to 1,000 parts by weight, more preferably from 50 to 800 parts by weight, per 100 parts by weight of (A). If the amount of (C) is too small, the obtained composition may have poor adhesion to the thermoplastic elastomer layer, while if the amount of (C) is too large, the adhesion to polyurethane may be insufficient. .

In order to obtain the resin composition of the present invention, (A) and (B) and, if necessary, (C) may be melt-kneaded.

The laminate (I) of the present invention is a laminate obtained by laminating the layer (1) of the resin composition of the present invention and the layer (2) of polyurethane. To obtain the laminate (I), for example,
The resin composition layer (1) is molded by a known method such as a powder molding method, an extrusion molding method, a compression molding method, a calendar molding method, an injection molding method, a vacuum molding method, etc., and then a pair of male and female gold for molding a polyurethane layer. The layer (1) of the resin composition is set on one side of the mold, and a polyurethane raw material may be formed by injecting, clamping, foaming and curing a polyurethane raw material.

The laminate (II) of the present invention is a laminate obtained by laminating a layer (1) of the resin composition of the present invention and a layer (3) of a thermoplastic elastomer. Examples of the thermoplastic elastomer include olefin-based, styrene-based, ester-based, and urethane-based thermoplastic elastomers. Among them, olefin-based and styrene-based materials having excellent physical property balance including durability properties such as heat resistance and light resistance are preferable. The olefin-based thermoplastic elastomer is a thermoplastic elastomer comprising an olefin-based resin and an olefin-based rubber, and is classified into a blend type, a cross-linked type in which a rubber portion is cross-linked by dynamic cross-linking, and a polymerization type. Styrene-based thermoplastic elastomers include block copolymers such as styrene-butadiene-styrene and styrene-isoprene-styrene, hydrogenated products thereof, and compounds obtained by compounding these block copolymers with polyolefin resins.

In order to obtain the laminate (II), it may be formed by a known method such as a powder molding method, an extrusion molding method, a compression molding method, a calender molding method, an injection molding method, and a vacuum molding method.

For example, a laminate (II) is formed by a powder molding method.
Can be obtained by, for example, a powder slush molding method, a fluid immersion method, an electrostatic coating method, a powder spraying method, a powder rotational molding method, or the like.

In order to obtain the laminate (II) by the powder molding method, the resin composition of the present invention must have an average particle size of 30 to 1000 μm.
m of the resin composition powder. The average particle size is preferably between 50 and 700 μm. If the average particle size is too small, the blocking resistance of the resin composition powder will be reduced. On the other hand, if the average particle size is too large, the meltability of the resin composition will be reduced during powder molding.

As an example of a method for obtaining a resin composition powder, pellets of the resin composition are obtained by melt-kneading using an extruder. Next, the pellets of the obtained resin composition are cooled (preferably cooled to a glass transition temperature or lower of the resin composition).
Then, a resin composition powder can be obtained using an impact-type pulverizer.

In order to further improve the blocking resistance of the obtained resin composition powder, a fine powder having an average particle size of 10 μm or less is added to 100 parts by weight of the resin composition.
It is preferable to add 1 to 10 parts by weight.

As the fine powder having an average particle diameter of 10 μm or less, powder pigments, alumina, silica, alumina silica, calcium carbonate and the like can be used.

For example, the powder slush molding method is performed by a method comprising the following first to ninth steps. First step: a step of applying a fluorine and / or silicon release agent on the molding surface of the mold Second step: on the molding surface of the mold heated to a melting temperature of the thermoplastic elastomer composition powder or higher Supplying the thermoplastic elastomer composition powder to the third step: heating the thermoplastic elastomer composition powder on the molding surface of the second step for a predetermined time, and fusing the powders having at least their surfaces fused to each other. The fourth step: a step of collecting the unfused thermoplastic elastomer composition powder after a lapse of a predetermined time in the third step. Fifth step: The mold of the mold to which the thermoplastic elastomer composition powder has been fused. The step of supplying the powder of the resin composition of the present invention onto the molding surface. The sixth step: the powder of the resin composition of the present invention is heated on the molding surface of the fifth step for a predetermined time, and at least the powder whose surface is melted. Process of fusing with each other. Seventh step: a step of collecting the unfused resin composition powder of the present invention after a lapse of a predetermined time in the sixth step. Eighth step: If necessary, a powder of the molten thermoplastic elastomer composition. And a step of further heating the mold on which the powder of the resin composition of the present invention is placed. Ninth step: After the eighth step, the mold is cooled, and the molded body formed thereon is removed from the mold. Removal process

As the thermoplastic elastomer composition used in the present powder slush molding, those proposed in JP-A-5-5050 and JP-A-10-30036 are preferably used.

The laminate (III) of the present invention is a laminate obtained by sequentially laminating a layer (3) of a thermoplastic elastomer, a layer (1) of a resin composition of the present invention, and a layer (2) of polyurethane. . Here, "sequential lamination" does not indicate the time sequence of the lamination process, but indicates the structure of the laminated body (the same applies hereinafter). In order to obtain the laminate (III), for example, the laminate (II) is molded by a known method such as a powder molding method, an extrusion molding method, a compression molding method, a calendar molding method, an injection molding method, and a vacuum molding method. The laminate (II) may be set in one of a pair of male and female molds for forming a polyurethane layer, and a polyurethane foam layer may be formed by injecting, clamping, foaming and curing a polyurethane raw material.

The laminate (IV) of the present invention comprises a thermoplastic elastomer layer (3), a resin composition layer (1) of the present invention, a polyurethane layer (2), and a thermoplastic resin core layer (4). Are sequentially laminated. In order to obtain the laminate (IV), for example, the laminate (II) and a thermoplastic resin core material layer formed by injection molding or the like are set on each of a pair of male and female molds for forming a polyurethane layer, and polyurethane is formed. The raw material may be injected, clamped, foamed, and cured to form a polyurethane foam layer.

The laminate of the present invention can be optimally used, for example, for automobile interior parts such as instrument panels, door trims, console boxes, and pillars.

[0026]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Example 1 An ethylene-glycidyl methacrylate-vinyl acetate copolymer (MFR 340 g / 10 m) having a glycidyl methacrylate content of 18% by weight and a vinyl acetate content of 1% by weight.
in, 190 ° C), 10 parts by weight of resorcinol (manufactured by Sumitomo Chemical Co., Ltd.), ethylene-vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Sumitate HC-1)
0) 80 parts by weight and 0.1 part by weight of an antioxidant (IRGANOX 1076, manufactured by Ciba Specialty Chemicals Co., Ltd.) were added to Labo Plastomill (Toyo Seiki Co., Ltd., Model 65).
C150) at 110 ° C. and 100 rpm.
After kneading for 5 minutes, the mixture was heated and compressed by a press molding machine heated to 200 ° C. for 5 minutes to obtain a molded sheet having a thickness of 1 mm. The obtained molded sheet is set in a polyurethane foaming mold, and a raw material liquid of polyurethane (a mixture composed of propylene oxide of glycerin, a polyol mainly composed of an ethylene oxide adduct, water, triethanolamine, triethylenediamine and the like, and polymeric MDI). 10
After mixing with a high-speed stirrer for 2 seconds, the mixture was supplied to the above-mentioned mold for polyurethane foaming, clamped, foamed and cured to obtain a laminate. After being left overnight, the laminate was cut to a width of 25 mm, and the adhesive strength between the molded sheet and the polyurethane foam layer was measured. Table 1 shows the results. In addition, as an evaluation of the melt fluidity of the resin composition, a melt flow rate (hereinafter referred to as MFR) of the resin composition obtained by kneading with Labo Plastomill is used.
Measurement). The measurement of MFR was performed at a measurement temperature of 13
The test was conducted at 0 ° C and a load of 2.16 kg.
Implemented in accordance with K 7210. Table 1 shows the results.

Example 2 An ethylene-glycidyl methacrylate-vinyl acetate copolymer (MFR 340 g / 10 m2) having a glycidyl methacrylate content of 18% by weight and a vinyl acetate content of 1% by weight.
in, 190 ° C) 47.5 parts by weight, resorcinol (Sumitomo Chemical Co., Ltd.) 5 parts by weight, ethylene-vinyl acetate copolymer (Sumitomo Chemical Co., Ltd., Sumitate HC-1)
0) 47.5 parts by weight, antioxidant (IRGANOX 1076, manufactured by Ciba Specialty Chemicals Co., Ltd.)
One part by weight was kneaded using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd., Model 65C150) at 110 ° C. and 100 rpm for 3 minutes, and then heated and compressed by a press molding machine heated to 200 ° C. for 5 minutes. To obtain a molded sheet having a thickness of 1 mm. Hereinafter, a laminate was obtained in the same manner as in Example 1, and the adhesive strength between the molded sheet and the polyurethane foam layer was measured. Table 1 shows the results. Also, as an evaluation of the melt fluidity of the resin composition, the MFR was measured in the same manner as in Example 1.
Table 1 shows the results.

Example 3 An ethylene-glycidyl methacrylate-vinyl acetate copolymer (MFR 340 g / 10 m2) having a glycidyl methacrylate content of 18% by weight and a vinyl acetate content of 1% by weight.
in, 190 ° C) 47.5 parts by weight, catechol (Kanto Chemical Co., Ltd., special grade) 5 parts by weight, ethylene-vinyl acetate copolymer (Sumitomo Chemical Co., Ltd., Sumitate HC-
10) 47.5 parts by weight, antioxidant (IRGANOX 1076, manufactured by Ciba Specialty Chemicals Co., Ltd.)
0.1 parts by weight of Labo Plastomill (Toyo Seiki Co., Ltd.
After kneading at 110 ° C. and 100 rpm for 3 minutes using a model 65C150), the mixture was heated and compressed by a press molding machine heated to 200 ° C. for 5 minutes to obtain a molded sheet having a thickness of 1 mm. Hereinafter, a laminate was obtained in the same manner as in Example 1,
The adhesive strength between the molded sheet and the polyurethane foam layer was measured. Table 1 shows the results. Also, as an evaluation of the melt fluidity of the resin composition, the MFR was measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 90 parts by weight of ethylene-vinyl acetate copolymer (Sumito Chemical Co., Ltd., Sumitate HC-10), 10 parts by weight of resorcinol (Sumitomo Chemical Co., Ltd.), antioxidant (IRGA manufactured by Ciba Specialty Chemicals Co., Ltd.)
NOX1076) 0.1 part by weight using a Labo Plastomill (Model 65C150, manufactured by Toyo Seiki Co., Ltd.)
After kneading for 3 minutes at 100 ° C. and 100 rpm, 200 ° C.
Was heated and compressed for 5 minutes by a press molding machine heated to obtain a molded sheet having a thickness of 1 mm. Hereinafter, a laminate was obtained in the same manner as in Example 1, and the adhesive strength between the molded sheet and the polyurethane foam layer was measured. Table 1 shows the results. Also, as an evaluation of the melt fluidity of the resin composition, the MFR was measured in the same manner as in Example 1. Table 1 shows the results.

[0030]

[Table 1]

[0031]

As described above, according to the present invention, the balance between the melt fluidity required at the time of molding and the adhesion to the polyurethane foam is excellent, and the polyurethane adheres firmly to the polyurethane without using a primer (adhesive). A resin composition capable of obtaining a laminate and a laminate obtained by using the resin composition could be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F100 AK01D AK03A AK04 AK22 AK25 AK25A AK34 AK34A AK51B AK68 AL01 AL01A AL09C BA02 BA03 BA10A BA10B BA10C GB32 JB16C JB16D JL11 YY00A 4J036 AK03 DC02 DB02

Claims (6)

[Claims] 1. A resin composition containing the following component (A) 100 parts by weight and component (B) 3 to 150 parts by weight. (A): Copolymer of epoxy group-containing monomer and α-olefin (B): Polyhydric phenol 2. A laminate (I) obtained by laminating a layer (1) of the resin composition according to claim 1 and a layer (2) of polyurethane. 3. A laminate (II) comprising a layer (1) of the resin composition according to claim 1 and a layer (3) of a thermoplastic elastomer. 4. A method for producing a laminate, wherein the laminate (II) according to claim 3 is produced by a powder molding method. 5. A laminate (III) obtained by sequentially laminating a layer (3) of a thermoplastic elastomer, a layer (1) of the resin composition according to claim 1, and a layer (2) of polyurethane. 6. A layer obtained by sequentially laminating a layer (3) of a thermoplastic elastomer, a layer (1) of a resin composition according to claim 1, a layer (2) of a polyurethane, and a layer (4) of a thermoplastic resin core material. Laminate (IV).