JPH05124037A - Composite sheet for stamping molding and manufacture thereof and stamping molded product and manufacture thereof - Google Patents

Abstract

PURPOSE:To manufacture a composite sheet for stamping mold by using an aqueous bonding agent which can form a stamping molded product hard to generate the release of a skin material off a resin foamed body. CONSTITUTION:A composite sheet 1 for stamping mold is composed of a crosslinking polyolefin resin foamed body 2 of average gel content of 30-75% and a skin material 3 laminated thereon having its stress of 150kg/cm<2> or less at the time of 100% elongation at 25 deg.C. The resin foamed body 2 is bonded with the skin material 3 by a bonding agent layer 4. The bonding agent layer 4 is composed of an aqueous bonding agent cured by an epoxy curing agent and baked preliminarily on the resin foamed body 2 and/or the skin material 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite sheet, a method for producing a composite sheet, a molded article and a method for producing a molded article, particularly a composite sheet for stamping mold, a method for producing a composite sheet for stamping mold, and a stamping mold molded article. And a method for manufacturing a stamping molded product.

[0002]

2. Description of the Related Art For example, interior materials such as automobile door trims and ceilings are made of a composite sheet made of a laminate of a resin foam pad and a skin material, and a thermoplastic resin arranged on the pad side of the composite sheet. It is mainly composed of the aggregate layer.
In this type of vehicle interior material, a composite sheet and an aggregate layer are integrated by a stamping molding method, and a desired shape such as a door trim or a ceiling is formed.

In the composite sheet used in the vehicle interior material described above, the pad and the skin material are adhered by an adhesive. As the adhesive, an organic solvent type adhesive containing an isocyanate cross-linking agent is used (for example, Japanese Patent Publication Nos. 57-55067 and 63-228). However, when an organic solvent type adhesive is used, there is a risk of environmental pollution due to the volatile solvent, and safety equipment such as explosion proof equipment is required for the interior material manufacturing device. Therefore, in the above-mentioned composite sheet, a water-soluble adhesive has begun to be used in place of the organic solvent type adhesive. For example, Japanese Patent Publication No. 63-3351
No. 8 shows an aqueous adhesive containing an aziridine compound as a crosslinking agent.

[0004]

In the above-mentioned conventional composite sheet using the water-based adhesive, the adhesive strength between the resin foam pad and the skin material is not sufficient, and the pad and the skin material are easily peeled off from each other. .. In particular, when the composite sheet is deep-drawn by a stamping molding method into a complicated shape or placed at a high temperature, the pad and the skin material are easily separated from each other.

A first object of the present invention is to provide a stamping mold composite sheet using a water-based adhesive capable of forming a stamping mold molded product in which peeling between a resin foam and a skin material does not easily occur. An object of the second invention is to provide a method for manufacturing a composite sheet according to the first invention.

A third object of the present invention is to provide a stamping molded product using a water-based adhesive, in which the resin foam and the skin material are unlikely to come off from each other. An object of the fourth invention is to provide a method for manufacturing a stamping mold product according to the third invention.

[0007]

The composite sheet for stamping molds according to the first invention has an average gel fraction of 30-.
75% crosslinked polyolefin resin foam, a skin material laminated on the crosslinked polyolefin resin foam and having a stress of 100 kg elongation at 25 ° C. of 150 kg / cm ² or less, and crosslinked polyolefin resin foam An adhesive layer for adhering the body and the skin material is provided. The adhesive layer is
It is composed of a water-based adhesive that is cured with an epoxy-based curing agent, and is previously baked on the crosslinked polyolefin resin foam and / or the skin material.

A method of manufacturing a composite sheet for stamping mold according to the second invention includes the following steps. ◎ Crosslinkable polyolefin resin foam having an average gel fraction of 30 to 75% and / or a water-based adhesive containing an epoxy-based curing agent in a skin material having a stress of 150 kg / cm ² or less at 100% elongation at 25 ° C. Step of applying and drying. ◎ A step of heating the water-based adhesive and baking it on the crosslinked polyolefin resin foam and / or the surface material to form an adhesive layer. ◎ A step of laminating a cross-linked polyolefin resin foam and a skin material with an adhesive layer interposed therebetween, and thermocompression bonding.

A stamping mold molded article according to the third invention comprises a crosslinked polyolefin resin foam having an average gel fraction of 30 to 75%; 100 laminated at 25 ° C. on the crosslinked polyolefin resin foam. A composite sheet layer having a skin material having a stress at the time of elongation of 150 kg / cm ² or less; an adhesive layer for adhering the cross-linked polyolefin resin foam and the skin material, and a cross-linked polyolefin of the composite sheet layer And an aggregate layer disposed on the surface of the resin foam. The adhesive layer is a water-based adhesive that has been cured with an epoxy-based curing agent, and has been previously baked on the cross-linked polyolefin resin foam and / or the skin material. Also,
The aggregate layer is made of a thermoplastic resin and is thermally fused to the crosslinked polyolefin resin foam.

A method of manufacturing a stamping mold molded product according to a fourth aspect of the present invention is a method of manufacturing by a stamping mold method using a mold having an upper mold and a lower mold. This manufacturing method includes the following steps. ◎ A step of disposing the molten thermoplastic resin in the lower mold. ◎ The crosslinked polyolefin resin foam having an average gel fraction of 30 to 75%, and the stress at 100% elongation at 25 ° C. when laminated on the crosslinked polyolefin resin foam is 150.
It has a skin material of not more than kg / cm ² and an adhesive layer for adhering the cross-linked polyolefin resin foam and the skin material, and the adhesive layer is made of an aqueous adhesive cured with an epoxy curing agent. And a cross-linked polyolefin resin foam and / or a composite sheet previously baked on the skin material is placed on the thermoplastic resin in a heated state so that the skin material faces the upper mold. ◎ A step of integrating the composite sheet and the thermoplastic resin by closing the molding die.

*** Composite Sheet for Stamping Mold FIG. 1 is a longitudinal sectional view of an example of a composite sheet for stamping mold according to the first invention. In the figure, a stamping mold composite sheet 1 includes a sheet-shaped resin foam 2, a skin material 3 laminated on the resin foam 2, and an adhesive layer for bonding the resin foam 2 and the skin material 3 together. 4 and mainly. In this stamping mold composite sheet 1, the adhesive layer 4 is baked on the resin foam 2 and / or the skin material 3. Crosslinked polyolefin resin foam The polyolefin resin constituting the crosslinked polyolefin resin foam used in the present invention is, for example, a polymer of olefin such as polyethylene resin, polypropylene resin and polyvinyl chloride resin. Examples of the polyethylene resin include ethylene homopolymers and polyethylene resins obtained by copolymerizing olefins other than ethylene, vinyl acetate, acrylic acid, acrylic acid ester, and the like. The ethylene homopolymer has a density of 0.8.
It is preferably 97 to 0.955 g / cm ³ and has a melt index of 0.5 to 55. Examples of the polypropylene resin include a homopolymer of propylene and a copolymer of propylene and vinyl acetate.

The most preferable polyolefin resin is a polypropylene resin in which ethylene or butene is copolymerized in an amount of 0.5 to 35 mol%. The polypropylene resin may be any copolymer of random, block and random blocks. The above-mentioned various polyolefin resins may be used alone or in combination of two or more kinds.

The cross-linkable polyolefin resin foam used in the present invention is obtained by crosslinking the above-mentioned polyolefin resin by irradiation with electron beams, α rays, β rays, γ rays and the like, dicumyl peroxide and the like. It is the one that is chemically crosslinked with a peroxide, or the one that is crosslinked by ultraviolet irradiation is foamed. This foam has an average gel fraction of 30 to 75%, preferably 40 to 65%. When the average gel fraction is less than 30%, the foam is damaged by the temperature of the base resin and the molding pressure during molding, resulting in unevenness on the surface of the molded product. On the other hand, when it exceeds 75%, the expansion rate of the foam becomes low, so that the foam tends to be damaged during the molding process, and it is difficult to obtain a desired molded article. The average gel fraction referred to in the present invention is expressed as a percentage of the weight of the original foam by immersing 0.1 g of the foam sample in tetralin at 130 ° C. for 3 hours and the weight of the insoluble matter remaining after that. Say the value.

The foam used in the present invention has an apparent density of 0.5 to 0.020 g / cm ³ , more preferably 0.0.
It is preferably 60 to 0.040 g / cm ³ . When the apparent density is less than 0.5 g / cm ³ , the touch feeling is poor,
The function as a pad material cannot be expected. Conversely, 0.02
If it exceeds g / cm ³ , the material hardness of the foam becomes small, so the foam is easily damaged during molding. The apparent density is a value according to JIS-K6767.

The thickness of the crosslinked polyolefin resin foam is usually set to 0.5 to 10 mm. This thickness is
It can be appropriately set according to the usage of the stamping mold composite sheet. Skin material Examples of the skin material used in the present invention include a cloth-like material using natural fibers or synthetic fibers, a synthetic resin sheet containing a polyvinyl chloride resin as a main component, a thermoplastic elastomer sheet, leather, and the like. These skin materials can be appropriately selected according to the method of using the composite sheet for stamping mold or the stamping mold molded product of the present invention.

The skin material used in the present invention has a stress at 100% elongation at 25 ° C. of 150 kg / cm ² or less, preferably 120 kg / cm ² or less, 25 kg / cm ² or more. When the stress exceeds 150 kg / cm ² , the skin material is likely to be damaged during molding, and the foam side is likely to be damaged at the bonding interface between the skin material and the foam. The stress is a value measured according to JIS-K6767.

The skin material usually has a thickness of 0.2 to 2.0 mm.
It is set to a degree. Adhesive Layer The adhesive layer for adhering the cross-linked polyolefin resin foam and the skin material is made of a water-based adhesive containing an epoxy curing agent. Examples of the water-based adhesive include emulsions of acrylic resin or urethane resin having a polar group.

The polar group contained in the acrylic resin or urethane resin is a polar functional group generally contained in the acrylic resin or urethane resin, and examples thereof include those represented by the following formula.

[0019]

[Chemical 1]

Examples of the acrylic resin having a polar group include acrylic copolymers consisting of 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid, styrene, 2-hydroxyethyl methacrylate, butyl acrylate, ethyl acrylate and acrylamide. it can. Emulsions of these acrylic resins can be obtained, for example, by emulsion polymerization of the above acrylic resins by a conventional method.

The urethane resin having a polar group is a urethane resin composed of a compound having a polar group such as polyester, polyether or polyether ester, and polyisocyanate. Examples of the polyester include polyvalent saturated or unsaturated carboxylic acids such as adipic acid, succinic acid, maleic anhydride, and sebacic acid, or acid anhydrides thereof, and ethylene glycol, propylene glycol, tetramethylene glycol, trimethylol. Polyhydric saturated alcohols such as propane, 1,6-hexanediol and 1,4-butanediol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol having a relatively low molecular weight, or these An example is a condensation product obtained from the mixture. Examples of the polyether include alkylene oxides such as ethylene oxide and propylene oxide, polymerization products such as styrene oxide and epichlorohydrin, and random or block copolymers of these and addition polymerization products of polyhydric alcohols. Examples of the polyether ester include those obtained by adding an epoxy compound such as ethylene oxide or propylene oxide to the polyesters.

Examples of the polyisocyanate include tolylene diisocyanate and its foreign substances, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, araliphatic diisocyanates such as xylylene diisocyanate, hexamethylene diisocyanate, 2, and the like.
Examples thereof include aliphatic diisocyanates such as 2,4-trimethylhexamethylene diisocyanate, and polyisocyanates obtained by previously adding trimethylolpropane to the above diisocyanates. These polyisocyanates may be used alone or in combination of two or more.

The urethane resin emulsion can be obtained by dispersing the urethane resin in water using an emulsifier. In the case of urethane resin, an aqueous urethane resin may be used instead of an emulsion. The aqueous urethane resin has a hydroxyl group or a carboxyl group at the molecular end. In addition, an aqueous solution may be used in which the raw material distribution is adjusted so that the molecular terminal ends with an isocyanate group, and the isocyanate group is blocked with a salt such as bisulfite group.

The above-mentioned acrylic adhesive or urethane adhesive may be used alone, respectively.
A mixture of two or more species may be used. When an acrylic adhesive and a urethane adhesive are mixed and used, the drying property and adhesiveness of the adhesive can be adjusted appropriately. The epoxy curing agent contained in the above water-based adhesive is a water-soluble epoxy compound or a water-dispersed epoxy compound. Examples of such an epoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl-tris (2-hydroxyethyl) isocyanurate, glycerol polyglycidyl ether. , Trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,8-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ',
Examples thereof include compounds having two or more glycidyl groups such as N ″ -tetraglycidyl-m-xylenediamine and acrylic polymers obtained by copolymerizing glycidyl methacrylate. Of these compounds, those insoluble in water can be used by emulsifying and dispersing them in water using an emulsifier.

The epoxy-based curing agent can form the following cross-linked structures with the above-mentioned acrylic resin or urethane-based resin. In the following crosslinked structure, Poly. Represents a polymer chain. When the resin has hydroxyl groups.

[0026]

[Chemical 2]

When the resin has a carboxyl group.

[0028]

[Chemical 3]

When the resin has an amino group.

[0030]

[Chemical 4]

The mixing ratio (A: B) of the above-mentioned water-based adhesive (A) and the above-mentioned epoxy-based curing agent (B) is 100: 1 to 100: 20, and further 100: 8 in terms of solid content. ~
100: 15 is preferred. Method for Manufacturing Composite Sheet for Stamping Mold First, the above-mentioned crosslinked polyolefin resin foam and skin material are prepared. Then, the above-mentioned water-based adhesive containing the above-mentioned curing agent is applied to the joint surface of the foam and / or the skin material. The application of the water-based adhesive is performed using a wire coater, a doctor knife, a roll coater, a reverse coater, or the like. The coating amount is usually 5 to 200 g / c
set to m ² . When applying the water-based adhesive, the viscosity should be 6000 to 12000 cp to improve workability.
It is preferable to adjust To adjust the viscosity like this,
For example, a thickener such as polycarboxylic acid polymer or carboxymethyl cellulose is used.

Next, after drying the applied water-based adhesive, the adhesive is baked on the application surface. As a result, an adhesive layer is formed on the foam and / or the skin material. If the water-based adhesive is not baked, or if the water-based adhesive is simply dried using a warm air fan or the like, sufficient adhesive strength between the foam and the skin material cannot be obtained. The baking process is preferably performed with an infrared heater. In this case, the average wavelength of infrared rays is preferably 0.75 to 1000 μm,
2 to 14 μm is more preferable.

When the water-based adhesive is applied to the foam, the baking temperature is preferably set so that the surface temperature is 70 to 150 ° C. Surface temperature during baking is 70 ℃
If it is less than the above range, sufficient adhesive strength between the foam and the skin material cannot be obtained. On the other hand, when the temperature exceeds 150 ° C., the surface of the foam tends to be roughened, which may lower the product value. Next, the foam and the skin material are laminated via an adhesive layer. Then, both are heated to 50 to 100 ° C. and pressure-bonded to obtain the composite sheet for stamping mold according to the first invention. Stamping Molded Product FIG. 2 is a partial vertical cross-sectional view of a stamping molded product according to the third invention. In the figure, a stamping molded product 5 is mainly composed of a composite sheet 1 and an aggregate layer 6 for maintaining the composite sheet 1 in a predetermined molding shape.

The composite sheet 1 is a composite sheet for stamping mold according to the first invention, and has a sheet-shaped resin foam 2, a skin material 3 laminated on the resin foam 2, a resin foam 2 and a skin. It is mainly composed of an adhesive layer 4 for adhering the material 3. The aggregate layer 6 is made of a thermoplastic resin and is arranged on the resin foam 2 side of the composite sheet 1. The aggregate layer 6 is heat-sealed to the resin foam 2 and maintains the molded shape of the composite sheet 1. As the thermoplastic resin constituting the aggregate layer aggregate layer, a polymer resin of α-olefin such as polyethylene resin, ethylene and α-
Copolymer resin of olefin, especially low density, medium density and high density linear polyethylene resin obtained by copolymerizing ethylene and α-olefin, and vinyl acetate, acrylic acid, acrylic acid ester and other monomers The polyethylene resin etc. which were made can be illustrated. These thermoplastic resins may be used alone or as a mixture of two or more kinds. Preferred as the thermoplastic resin used in the present invention are homopolymers of ethylene, propyne or butene, and resins obtained by copolymerizing them in random, block or random-block form.

If necessary, a filler, a thickener, a dye, an antioxidant and a stabilizer may be added to the above-mentioned thermoplastic resin. Method for Manufacturing Stamping Molded Product A stamping mold product can be manufactured by a stamping mold method. This manufacturing method will be described.

First, a thermoplastic resin for forming an aggregate layer is placed in a lower die of a molding die having an upper die and a lower die.
The thermoplastic resin is arranged in a molten dumpling or sheet form. The temperature of the thermoplastic resin varies depending on the material, but is usually set to about 180 to 220 ° C. next,
The composite sheet for stamping mold is placed on the thermoplastic resin placed in the lower mold. Here, the composite sheet is arranged so that the skin material faces the upper mold. The composite sheet is usually placed at room temperature, but may be placed by heating depending on the shape of the molded product.

Next, the molding die is closed. That is, the upper die is pressed against the lower die. As a result, the composite sheet is pressed against the thermoplastic resin and molded into a predetermined shape. At the same time, the molten thermoplastic resin is fused to the resin foam of the composite sheet, and both are integrated. As a result, a stamping molded product is obtained. The pressure when the mold is closed is usually set to about 30 to 120 kg / cm ² .

The obtained stamping molded product is
For example, it may be provided in the form of interior materials for vehicles such as door trims, ceilings and floor materials. With this stamping molded product,
Since the composite sheet according to the first aspect is provided, the adhesiveness between the resin foam 2 and the skin material 3 is high. Therefore, the resin foam 2 and the skin material 3 are stably bonded even when the stamping molded product is deep-drawn into a complicated shape. Further, since the average gel fraction of the resin foam constituting the composite sheet and the stress of the elongation value of the skin material are set within the above ranges, the stamping molded product has wrinkles and whitening phenomena on the skin material. Difficult and good appearance.

[0039]

EXAMPLES Examples 1 to 3 Acrylic emulsion having hydroxyl groups and carboxyl groups and having a solid content of 45% (BW-210-1: Toray Industries, Inc.)
100 parts by weight and epoxy curing agent (BW-00)
1: mixed with 10 parts by weight of Toray Co., Ltd. to prepare a thickener (B
W001: Viscosity of 8000 cP using Toray Industries, Inc.
To obtain an emulsion type adhesive. This emulsion type adhesive has gel fractions of 34% and 53%, respectively.
% And 70% and an apparent density of 0.067 g / c
50 g / m ^{2 was} applied to one surface of the three types of the plate-shaped polypropylene resin foam of m ^{3 by} the gravure roll method.

The applied adhesive was dried and then baked using an infrared heater (main wavelength range is 2 to 15 μm) to form an adhesive layer. The surface temperature is 8 on this adhesive layer.
Polyvinyl chloride resin sheet heated to 0 ° C (stress at 100% elongation at 25 ° C: 100 kg / cm ² , thickness: 0.
5 mm) was pressed to obtain a composite sheet for stamping mold.

Next, in a 350 mm × 350 mm square, the slopes of one side are 90 °, 60 °, and 45 °, respectively.
A stamping mold molded product was manufactured from the obtained composite sheet for stamping mold using a molding die including the box-shaped male mold and the female mold set in the above. Here, an aggregate resin composed of 80% by weight of polypropylene resin and 20% by weight of an extender was placed on the lower mold, and the mold was closed under a pressure of 50 t. Example 4 As a skin material, the stress at 100% elongation at 25 ° C. was 145
A composite sheet for stamping mold was manufactured in the same manner as in Example 2 except that a soft polyvinyl chloride resin sheet of kg / cm ² was used. Further, a stamping mold molded product was manufactured in the same manner as in Example 2 using the stamping mold composite sheet. Comparative Example 1 As a skin material, the stress at 100% elongation at 25 ° C. was 159.
A composite sheet for stamping mold was manufactured in the same manner as in Example 2 except that a soft polyvinyl chloride resin sheet of kg / cm ² was used. Further, a stamping mold molded product was manufactured in the same manner as in Example 2 using the stamping mold composite sheet. Comparative Example 2 As a skin material, the stress at 100% elongation at 25 ° C. was 170
A composite sheet for stamping mold was manufactured in the same manner as in Comparative Example 1 except that a soft polyvinyl chloride resin sheet of kg / cm ² was used. Further, a stamping mold molded product was manufactured in the same manner as in Example 2 using the stamping mold composite sheet. Comparative Example 3 Gel fraction was 27% and apparent density was 0.067 g.
/ Cm ³ polypropylene resin foam, mixed sheet of polyvinyl chloride resin and ABS resin (acrylonitrile-butadiene-styrene resin) (100% at 25 ° C
A stress-extending stress of 180 kg / cm ² ) was used to manufacture a composite sheet for stamping mold by the same method as in Examples 1 to 3, and the composite sheet was used in Examples 1 to 1.
A stamping molded product was manufactured in the same manner as in 3. Comparative Examples 4 and 5 Examples 1 to 3 except that the foam was replaced by a plate-shaped polypropylene foam having a gel fraction of 27% or 77% and an apparent density of 0.067 g / cm ^3. A stamping mold composite sheet was manufactured by the same method, and a stamping mold molded product was manufactured from this composite sheet by the same method as in Examples 1 to 3.

Stan using a foam having a gel fraction of 27%
The whitening phenomenon is observed in the corners of the ping mold formed products.
It was not done, but the surface of the skin material has irregularities, so it is practical
Not a good product. On the other hand, a foam with a gel fraction of 77%
The stamping mold products using
The foam broke at the corner. Also, 60 ° and 4
At the 5 ° corner, the expansion rate of the foam is small, so
It is not possible to form sharp corners corresponding to the angle.
It wasExample 5 Having a hydroxyl group and a carboxyl group and having a solid content of 55%
Urethane emulsion (BW-210: Toray Industries, Inc.)
40 parts by weight and acrylic emulsion (BW-20
1-1: 60 parts by weight of Toray Industries, Inc. and epoxy curing agent
(BW-001: manufactured by Toray Industries, Inc.) mixed with 10 parts by weight
Then, an emulsion type adhesive was manufactured. This emalgio
The gel type adhesive has a gel fraction of 54% and an apparent density of 0.0
50 g / cm ³Of plate-shaped polypropylene resin foam
60 g / cm on one side by the doctor knife method²Applied
It was

The applied adhesive was dried and then baked using an infrared heater (wavelength range 1 to 15 μm) to form an adhesive layer. The surface temperature is 8 on this adhesive layer.
A skin material heated to 0 ° C. (a mixed soft sheet of polyvinyl chloride resin and ABS resin having a stress of 142 kg / cm ² at 100% elongation at 25 ° C. and a thickness of 0.4 mm) is arranged and pressure-bonded. A composite sheet for stamping mold was obtained.

Using the obtained composite sheet for stamping mold, stamping mold molded products similar to those in Examples 1 to 3 were manufactured. Comparative Example 6 A composite sheet for stamping mold was produced in the same manner as in Example 5, except that a general solvent-type polyester adhesive was mixed with isocyanate at a ratio of 100: 10. .. Further, a stamping mold molded article was manufactured from the composite sheet for stamping mold in the same manner as in Example 3. Evaluation (1) The following tests were carried out on the stamping molded products obtained in Examples 1 to 4 and Comparative Examples 1 to 3. The results are shown in Table 1. Destruction status of pad material (resin foam) and interfacial peeling status The pad material destruction status and the interfacial peeling status between the pad material and the skin material were investigated. The evaluation criteria are as follows. ◯: No breakage or interfacial peeling. Δ: The destruction rate of the pad material is 70% or more, but there is no problem in practical use. X: Destruction or interfacial peeling occurred. Wrinkles at corners The presence or absence of wrinkles was examined at the corners of the molded product. The evaluation criteria are as follows. ○: No wrinkles occurred. Δ: There are some wrinkles. X: There are wrinkles. Whitening phenomenon in R part The presence or absence of whitening phenomenon in the R part of the molded product was examined for each case where the mold gradient was 90 °, 60 ° and 45 °. The evaluation criteria are as follows. ◯: No whitening phenomenon. Δ: There is some whitening phenomenon. ×: There is a whitening phenomenon.

[0045]

[Table 1]

(2) The following tests were carried out on Example 5 and Comparative Example 6. The results are shown in Table 2. The elongation of the adhesive layer. An intermediate material of a composite sheet for stamping mold, that is, a material obtained by applying an adhesive to a polyolefin resin foam and baking it, is cut into a strip having a width of 30 mm,
Stretching was performed by applying stress in one direction using an autograph.
At that time, the point at which the adhesive layer breaks was taken as the limit point of the elongation of the adhesive layer, and the elongation rate of the adhesive layer at that time was expressed in%. Since the stamping mold method does not need to follow the temperature, it was measured at room temperature (25 ° C). The state of the adhesive layer in the R part of the molded product.

The state of the adhesive layer in the R part of the molded product is
The cases where the mold gradient was 90 °, 60 ° and 45 ° were examined. The evaluation criteria are as follows. ◯: No peeling of the adhesive layer. Δ: The adhesive layer was slightly peeled off. X: There is peeling of the adhesive layer. Adhesive strength A composite sheet for stamping molds is cut into strips with a width of 25 mm, and a 180 ° peel test is performed using an autograph at room temperature (23 ° C) and high temperature (120 ° C) to obtain adhesive strength and adhesion. The sex was evaluated. The evaluation criteria are as follows. ◯: No breakage in the adhesive layer. X: There is breakage in the adhesive layer.

[0048]

[Table 2]

[0049]

In the composite sheet for stamping mold according to the first aspect of the present invention, the adhesive layer is a cross-linked polyolefin resin foam and / or a skin material even though the adhesive layer is made of a water-based adhesive. Since it is baked, it is possible to form a stamping molded product in which peeling between the foam and the skin material does not easily occur.

According to the method of manufacturing the stamping mold composite sheet of the second invention, the stamping mold composite sheet of the first invention can be efficiently manufactured.
In the stamping molded article according to the third aspect of the present invention, the adhesive layer of the composite sheet layer is baked on the cross-linked polyolefin resin foam and / or the skin material, even though the adhesive layer is made of the water-based adhesive. Therefore, peeling between the foam and the skin material is unlikely to occur.

According to the method for producing a stamping mold product according to the fourth invention, the stamping mold product according to the third invention can be efficiently produced.

[Brief description of drawings]

FIG. 1 is a vertical sectional partial view of an example of a first invention.

FIG. 2 is a partial vertical cross-sectional view of an example of the second invention.

[Explanation of symbols]

 1 Composite Sheet for Stamping Mold 2 Resin Foam 3 Skin Material 4 Adhesive Layer 5 Stamping Molded Product 6 Aggregate Layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area B29L 7:00 4F

Claims (4)

[Claims] 1. A crosslinked polyolefin resin foam having an average gel fraction of 30 to 75%; and a laminate laminated on the crosslinked polyolefin resin foam.
The stress at 100% elongation at 25 ° C is 150 kg / cm ²
The following skin material, and an adhesive layer for adhering the cross-linked polyolefin-based foam and the skin material, the adhesive layer is composed of an aqueous adhesive cured by an epoxy curing agent, Pre-baked on the cross-linked polyolefin resin foam and / or the skin material,
Composite sheet for stamping mold. 2. A crosslinked polyolefin resin foam having an average gel fraction of 30 to 75% and / or 100% at 25 ° C.
A step of applying a water-based adhesive containing an epoxy-based curing agent to a skin material having a stress of not more than 150 kg / cm ² at the time of elongation and drying, and heating the water-based adhesive to produce the crosslinked polyolefin resin foam and / Alternatively, a step of baking on the surface material to form an adhesive layer, a step of laminating the crosslinked polyolefin resin foam and the surface material via the adhesive layer, and thermocompression bonding,
A method for manufacturing a composite sheet for stamping mold, comprising: 3. A crosslinked polyolefin resin foam having an average gel fraction of 30 to 75%, and a stress of 150 kg / cm when laminated on the crosslinked polyolefin resin foam and 100% elongation at 25 ° C. ² or less skin material, a composite sheet layer having an adhesive layer for adhering the cross-linkable polyolefin resin foam and the skin material, on the cross-linkable polyolefin resin foam surface of the composite sheet layer And an aggregate layer arranged, the adhesive layer is made of a water-based adhesive cured by an epoxy-based curing agent and is pre-baked on the cross-linked polyolefin resin foam and / or the skin material. The stamping molded article, wherein the aggregate layer is made of a thermoplastic resin and is heat-sealed to the crosslinked polyolefin resin foam. 4. A method for manufacturing a stamping mold product using a molding die having an upper die and a lower die, wherein a step of disposing a molten thermoplastic resin in the lower die, and an average gel fraction of 30. Up to 75% of the crosslinked polyolefin resin foam, and the stress at 100% elongation at 25 ° C. of 15 when laminated on the crosslinked polyolefin resin foam.
A water-based material having a skin material of 0 kg / cm ² or less, an adhesive layer for adhering the crosslinked polyolefin resin foam and the skin material, and the adhesive layer being cured by an epoxy curing material. A composite sheet made of an adhesive and pre-baked on the cross-linked polyolefin resin foam and / or the skin material is placed on the thermoplastic resin in a heated state so that the skin material faces the upper mold. And a step of integrating the composite sheet and the thermoplastic resin by closing the molding die.