JP2003260766A - Laminated sheet and molded article using the laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low-density laminated sheet for stamping molding excellent in heat resistance and high-temperature extensibility, and also to provide a molding using the laminated sheet. <P>SOLUTION: An olefin resin sheet having such two or more melting endothermic peak temperatures by a differential thermal analysis that at least one of the two or more is 110 to 130°C, and the other is 140 to 170°C is laminated on at least one surface of an olefin resin crosslinked foam consisting of an olefin resin in which at least one of melting endothermic peak temperatures by the differential thermal analysis is 148°C or higher. The molding uses the thus laminated resin sheet. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flexible, low-cost, hot product obtained by laminating a low-density olefin resin crosslinked foam foam and an olefin resin sheet having excellent heat resistance. The present invention relates to a laminated sheet having excellent stamping moldability, and a molded product using the laminated sheet.

[0002]

2. Description of the Related Art Generally, an olefin resin foam is lightweight and has excellent high temperature characteristics, flexibility and moldability, and thus has been widely used as a vehicle interior material by stamping molding such as doors and instrument panels. There is. As such an interior material, Japanese Patent Laid-Open No. 2-102034 discloses that a skin material is attached to a polypropylene resin foam having a gel fraction of 35% or more and an average cell diameter from the surface layer to 1 mm of 200 μm or less. There is disclosed an interior molded article for a vehicle in which a melted thermoplastic resin is integrally molded as an aggregate in a skin portion of the composite. However, by reducing the average cell diameter of the surface layer of the polypropylene resin foam, the heat resistance is improved, but the flexibility is insufficient and the interior material deteriorates the flexibility of the resin foam.

Further, JP-A-10-127658 discloses a stamping composite sheet in which a foamed sheet having an apparent density of 0.33 to 0.91 g / cm ³ is attached to at least one surface of a polyolefin resin foam. It is disclosed. However, sufficient heat resistance cannot be obtained with this foamed sheet, and with a high density foamed sheet, buckling wrinkles, etc., occur when the skin material is attached, and surface irregularities and wrinkles are formed after stamping molding. The surface property of the interior material was insufficient.

[0004]

DISCLOSURE OF THE INVENTION In view of the above problems, the present invention laminates an olefin resin foam having a low density and heat resistance with a thin, heat-resistant and flexible soft resin sheet By doing so, it has excellent flexibility and high temperature characteristics,
It is to provide a laminated sheet that can be used for stamping molding.

[0005]

The laminated sheet of the present invention comprises:
At least one of melting endothermic peak temperatures by differential thermal analysis is made of an olefin resin having a temperature of 148 ° C. or higher, a density of 0.025 to 0.040 g / cm ³ , and a gel fraction of 20.
Olefin having a melting endothermic peak temperature by differential thermal analysis of 2 or more, at least one of which is 110 to 130 ° C., and the other of which is 140 to 170 ° C. In the laminated sheet in which the resin sheets are laminated, the ratio A / B of the expansion ratio of the olefin resin crosslinked foam and the thickness of the olefin resin sheet is in the range of 125 to 500. In the formula, A represents the expansion ratio (cm ³ / g) of the crosslinked olefin resin foam, and B represents the thickness (mm) of the olefin resin sheet.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION (Olefin-based resin crosslinked foam)
The olefin-based resin crosslinked foam can be heat-sealed with an olefin-based resin sheet or bonded via an adhesive, and further heat-sealed with a skin material or bonded via an adhesive. It is possible to match, the surface of the molded product does not suffer from the impact of the heat and injection of the base material that accompanies the thinning of the olefin resin sheet during molding, and high foaming to further improve flexibility Magnification required.

In order to meet the above requirements, when the melting endothermic peak of the olefin-based crosslinked foam by differential thermal analysis is lowered, the heat resistance and mechanical strength of the olefin-based resin crosslinked foam are lowered, so that it is used as a laminated sheet. In order to obtain sufficient moldability, one of them is limited to 148 ° C or higher.

Further, when the density of the olefin resin crosslinked foam becomes small, the heat resistance and mechanical strength of the olefin resin crosslinked foam are deteriorated, and in combination with a thin olefin resin sheet, it can withstand impact during molding. I can't.
On the other hand, when the density is high, the flexibility of the laminated sheet is lowered and the performance as a laminated sheet which is very important in the present invention cannot be obtained. Therefore, 0.025 to 0.040 g / c is required.
Limited to m ³ .

Further, the gel fraction can be mentioned as a measure of the crosslinked state of the olefin resin crosslinked foam, but when the gel fraction of the obtained olefin resin crosslinked foam becomes smaller, the heat resistance of the olefin resin crosslinked foam becomes smaller. However, the mechanical strength is reduced, sufficient moldability cannot be imparted to the laminated sheet, and when the laminated sheet becomes large, flexibility, elongation and high magnification are impaired, so the content is limited to 20 to 50%.

The gel fraction in the present invention means that ₁ g of the olefin-based crosslinked foam is weighed, immersed in xylene at 120 ° C. for 24 hours, and the residue is filtered through a wire mesh of 200 mesh to obtain a wire mesh. The insoluble matter was dried under vacuum, the weight (W ₂ g) at that time was measured, and the value was calculated by the following formula. Gel fraction (%) = (W ₂ / W ₁ ) × 100

The resin used in the crosslinked foamed olefin resin satisfying the above-mentioned performance is not particularly limited as long as it is an olefin resin satisfying the above range. Examples of the polypropylene resin include homopolypropylene and propylene. In addition to copolymers with other monomers containing as a main component, olefin-based thermoplastic elastomers containing propylene-based resins such as ethylene-propylene-butene three-dimensional copolymers.

Examples of the above-mentioned copolymer containing polypropylene as a main component and another monomer include propylene-α.
-Olefin copolymer, and the propylene-α-olefin copolymer may be any of a block copolymer, a random copolymer or a random block copolymer, which are used alone. May also be used in combination.

Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene. Among these, a mixture of a resin obtained by further adding homopolypropylene to a mixture of an ethylene-propylene copolymer and a polyethylene resin, which are generally used as a conventional foam structure, is preferable.

As the polyethylene resin,
In addition to ethylene homopolymer, it refers to a copolymer of ethylene as a main component and ethylene and an α-olefin copolymerizable with ethylene, for example, low density polyethylene, ultra low density polyethylene, linear low density polyethylene, medium Examples include density polyethylene and high density polyethylene. Note that α-
As olefins, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1
-Heptene, 1-octene and the like.

Regarding the mixing ratio of each of the above resin mixtures, when the homopolypropylene is increased, the strength is improved, but the flexibility is lowered and the foamability is impaired, and when the homopolypropylene is decreased, the heat resistance and the elongation at high temperature are obtained. Therefore, 7 to 20% by weight is preferable. Further, in the ethylene-propylene copolymer, when the amount is increased, the flexibility is reduced, and when the amount is reduced, the mechanical strength is impaired.
Is preferred. Further, polyethylene is preferably contained in 10 to 40% by weight because the heat resistance is impaired when it is increased and the flexibility is lowered when it is decreased.

Next, a method for producing an olefin resin crosslinked foam will be described. As a method for producing the olefin resin crosslinked foam, any known method for producing a foam can be used, but the following method can be used for production. A foaming resin composition composed of the olefin resin and a thermal decomposition type foaming agent, after optionally adding a crosslinking aid, extruding the foaming resin composition, the resulting foaming resin composition An object is irradiated with a predetermined amount of ionizing radiation to impart a crosslinked structure to the foamable resin molded body, and the crosslinked foamable resin molded body is heated to a temperature not lower than the decomposition temperature of the thermal decomposition type foaming agent to produce an olefin-based resin. Method for producing a resin crosslinked foam, the foamable resin composition comprising the above olefin resin and a thermal decomposition type foaming agent, after adding a crosslinking agent and, if necessary, a crosslinking auxiliary agent to the foamable resin composition Is supplied to an extruder and melt-kneaded to extrude a foamable resin molded body, and the resulting foamable resin molded body is heated at the same time as extrusion by a heating roll or the like to a temperature not lower than the decomposition temperature of the thermal decomposition type foaming agent. Manufacture olefin crosslinked foam And the like.

The thermal decomposition type foaming agent is not particularly limited as long as it is one that has been conventionally used for producing foams.
For example, azodicarbonamide, dinitropentamethylenetetramine, hydrazodicarbonamide, azodicarboxylic acid barium salt, nitrosoguanidine, p, p'-oxybisbenzenesulfonyl semicarbazide, benzenesulfonylhydrazide, N, N'-dinitrosopentamethylenetetramine. , Toluenesulfonyl hydrazide,
4,4-oxybis (benzenesulfonyl hydrazide), azobisisobutyronitrile and the like can be mentioned. Among these thermal decomposition type foaming agents, azodicarbonamide is preferable.

The amount of the thermal decomposition type foaming agent added is appropriately adjusted, but if it increases, it may break, and if it decreases, it may not foam. Therefore, it may be added to 100 parts by weight of the olefin resin. 1 to 50 parts by weight is preferable,
1 to 30 parts by weight is more preferable.

The cross-linking aid is not particularly limited as long as it is used in the production of foams, and for example, trimeryl trimellitate, triallyl melitate, diallyl melitate, diallyl phthalate, divinylbenzene,
Trimethylolpropane trimethacrylate, 1, 9-
Nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, trimellitic acid triallyl ester, triallyl isocyanurate, ethyl vinylbenzene, neopentyl glycol dimethacrylate,
1,2,4-benzenetricarboxylic acid triallyl ester, 1,6-hexanediol dimethacrylate and the like can be mentioned, and they may be used alone or in combination.

The addition amount of the above-mentioned cross-linking auxiliary agent is appropriately adjusted, but if it is too large, the cross-linking of the foamable resin molded product may proceed too much to hinder foaming, and if it is too small, the added effect cannot be obtained. 0.5 to 20 parts by weight is preferable with respect to 100 parts by weight of the olefin resin, and 2 to 10 parts by weight.
More preferably parts by weight.

The cross-linking agent is not particularly limited as long as it can be used in the production of foams, and examples thereof include isobutyl peroxide, dicumyl peroxide and 2,5-.
Dimethyl-2,5-di (t-butylperoxy) hexane-3,1,3-bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-butylperoxide, t- Butyl peroxybenzoate, cyclohexane peroxide, 1,1-
Bis (t-butylperoxy) cyclohexane, 1,1
-Bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) vellate, Benzoyl peroxide,
Cumyl peroxide, cumyl peroxy neodecanoate, 2,5-dimethyl-2,5-di (benzoyl opoxy) hexane, t-butyl peroxy isopropyl carbonate, t-butyl peroxy allyl carbonate, t-butyl peroxy Examples thereof include acetate, 2,2-bis (t-butylperoxy) butane, di-t-butylperoxyisophthalate, and t-butylperoxymaleic acid.

If the amount of the above-mentioned cross-linking agent added is too large, the cross-linking density may be too high to cause foaming, and if it is too small, the cross-linking density may be insufficient and the shear viscosity required for foaming may not be obtained. Therefore, the above olefin resin 100
0.1 to 10 parts by weight is preferable with respect to parts by weight.

The ionizing radiation is not particularly limited as long as it has been conventionally used for crosslinking a foamable resin composition, and examples thereof include α-ray, β-ray, γ-ray and electron beam. .

In addition to the above-mentioned crosslinking aid, the expandable resin composition contains phenol-based, phosphorus-based, such as 2,6-di-butyl-p-cresol, etc.
Antioxidants such as amine-based and dilaurylthiodipropionate; metal-harmful inhibitors such as methylbenzotriazole, phosphorus-based, nitrogen-based, halogen-based, antimony-based, and flame retardants, fillers, electrified mixtures of these Inhibitors, pigments and the like may be added.

(Olefin-Based Resin Sheet) The above-mentioned olefin-based resin sheet can be heat-sealed with the olefin-based resin cross-linked foam, or can be attached via an adhesive, and can also be melt-bonded with a thermoplastic resin substrate. In addition, the base material does not break due to heat of the base material during molding and shear stress during flow, and it is possible to reduce the thickness to improve flexibility. It is required that no problems occur.

To meet the above requirements, even if the sheet is thinned in combination with the foam, it must have heat resistance to withstand the heat at the time of molding, and flow while being cooled from the molten state. Since it is necessary that the base resin does not break due to shear stress, the olefin resin sheet has two or more melting endothermic peaks by differential thermal analysis, at least one of which is 110 to 130 ° C., and the other is 140 to 130 ° C. 17
Limited to 0 ° C.

The resin used for the olefin resin sheet satisfying the above-mentioned performance is not particularly limited as long as it is an olefin resin and has a melting endothermic peak within the above range. For example, as polypropylene resin, homopolypropylene can be used. In addition to copolymers with other monomers containing propylene as a main component, homopolypropylene, copolymers with other monomers containing propylene as a main component, propylene-based ethylene-propylene-butene three-dimensional copolymers, etc. Examples include olefin-based thermoplastic elastomers containing a resin.

Examples of the above-mentioned copolymer containing polypropylene as a main component and another monomer include, for example, propylene-α.
-Olefin copolymer, and the propylene-α-olefin copolymer may be any of a block copolymer, a random copolymer or a random block copolymer, which are used alone. May also be used in combination. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-
Methyl-1-pentene, 1-heptene, 1-octene and the like can be mentioned.

The polyethylene resin includes ethylene homopolymers and copolymers of ethylene as a main component with ethylene and an α-olefin copolymerizable with ethylene, such as low density polyethylene and ultra low density. Polyethylene, linear low density polyethylene, medium density polyethylene,
Examples include high-density polyethylene. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like. Among these resins, a mixture of a reactor type olefin-based thermoplastic elastomer and a linear low-density polyethylene is particularly preferable for the reason that the above performance is exhibited.

As for the mixing ratio of the above resin mixture, if the reactor type olefinic thermoplastic elastomer is too much, the strength is lowered, and if it is too small, sufficient flexibility, heat resistance and elongation at high temperature cannot be obtained. , 30-70
Weight percent is preferred. Further, when the linear low density polyethylene is large, the heat resistance is impaired, and when the linear low density polyethylene is small, the strength is lowered, so 70 to 30 wt% is preferable.

(Laminated sheet) In the laminated sheet of the present invention, the heat resistance decreases as the ratio of the olefin resin crosslinked foam increases, so it is necessary to increase the thickness of the olefin resin sheet to compensate for this. is there. However, if the thickness of the olefin resin sheet is increased, the flexibility is reduced and buckling and wrinkling occur. On the contrary, when the ratio of the crosslinked olefin resin foam is reduced, the heat resistance is improved and the thickness of the olefin resin sheet can be reduced, but the original purpose of the laminate is impaired.

Therefore, the ratio A / B between the magnification of the olefin resin crosslinked foam and the thickness of the olefin resin sheet is
It is limited to the range of 125 to 500. In the formula, A represents the expansion ratio (cm ³ / g) of the crosslinked olefin resin foam, and B represents the thickness (mm) of the olefin resin sheet. Furthermore, since elongation at high temperature is required during molding, the elongation at 140 ° C. is preferably 320% or more.

(Surface material) The skin material to be laminated on the laminated sheet of the present invention is not particularly limited as long as it is used as a skin material. For example, polyvinyl chloride sheet, polyvinyl chloride / ABS. Examples thereof include a mixed sheet, a thermoplastic elastomer sheet, a fiber knitted fabric, and a nonwoven fabric.

(Thermoplastic Resin Base Material) The thermoplastic resin used as the base material of the molded article using the laminated sheet of the present invention is not particularly limited as long as it is used as the base material. For example, as a polypropylene resin,
Polypropylene resin, polypropylene resin in which polypropylene and α-olefin are copolymerized, polyethylene resin, or copolymer resin of ethylene and α-olefin, and monomers such as vinyl acetate, acrylic acid, and acrylic ester are copolymerized. A polyethylene resin and a resin in which these are arbitrarily mixed can be applied.

Further, an inorganic compound such as talc, silicic acid or calcium carbonate may be mixed with these resins as a filler as long as the characteristics of the resin substrate are not impaired. Also,
Known heat stabilizers, antioxidants, nucleating agents, colorants and the like may be added to the base resin as required. In addition, an ABS resin, polystyrene resin, petroleum resin, or other non-olefin resin may be added as long as the moldability is not impaired. Further, the resin may be foamed or crosslinked.

(Hot Stamping Molding Method) The hot stamping molding method used in the present invention is not particularly limited as long as it is a known method, but it will be described in detail below. First, a thermoplastic resin for forming a base material layer is placed in a lower mold of a molding die including an upper mold and a lower mold. 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 170 ° C to 230 ° C. Next, the laminated sheet having the outer skin laminated on the thermoplastic resin arranged in the lower mold is arranged. Here, the laminated sheet is arranged so that the skin material faces the upper mold. The laminated sheet is usually placed at room temperature, but may be placed by heating depending on the shape of the molded body.

Next, by pressing the upper mold to the lower mold,
Close the mold. As a result, the laminated 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 olefin resin sheet of the laminated sheet, and both are integrated. As a result, any molded product can be obtained. The pressure when the mold is closed is usually set to about 0.5 to 13 MPa.

Examples will be described below. (Example 1) As an olefin-based resin crosslinked foam, a melting endothermic peak by differential thermal analysis was 160 ° C, a bending elastic modulus was 2 x 10 ⁶ kPa, MI was 14.0 g / 10 min, and density was 0.90 g / cm. 10 parts by weight of homopolypropylene which is ³ , ethylene having a melting endothermic peak by differential thermal analysis of 150 ° C., a bending elastic modulus of 1 × 10 ⁶ kPa, an MI of 3.0 g / 10 min and a density of 0.90 g / cm ^3. -Propylene copolymer 70 parts by weight, linear chain having a melting endothermic peak by differential calorimetric analysis of 120 ° C, a bending elastic modulus of 3 x 10 ⁵ , an MI of 2.5 g / 10 min and a density of 0.92 g / cm ^3. Low-density polyethylene 20 parts by weight, trimethylolpropane trimethacrylate as a cross-linking aid 3.0 parts by weight, azodicarbonamide 10 parts by weight as a thermal decomposition type foaming agent, and antioxidant Then, 0.3 part by weight of 2,6-di-t-butyl-p-cresol and 0.3 part by weight of dilaurylthiodipropiolate were supplied to a twin-screw extruder and extrusion-molded at a resin temperature of 190 ° C. Thus, a foamable resin composition sheet having a thickness of 1.50 mm was obtained. The obtained sheet is irradiated with an electron beam of 1.5 Mrad at an accelerating voltage of 800 kV to be crosslinked, and the obtained crosslinked foamable resin composition sheet is foamed at 250 ° C. for 5 minutes to give an olefin resin crosslinked foam having a thickness of 3 mm. Got the body

The melting endothermic peak, density and gel fraction of the obtained olefin resin crosslinked foamed product were measured, and the obtained results are shown in Table 1.

(Melting endothermic peak) The melting endothermic peak of the foam was measured using a differential thermal analyzer manufactured by Seiko Instruments. (Density) The density of the foam was measured using an electronic hydrometer “ED20T” manufactured by Mirage. (Gel fraction) W ₁ g of the olefin-based crosslinked foam was weighed,
This was immersed in xylene at 120 ° C. for 24 hours, the residue was filtered through a 200-mesh wire net, the insoluble matter on the wire net was vacuum dried, and the weight (W ₂ g) at that time was measured. It was calculated. Gel fraction (%) = (W ₂ / W ₁ ) × 100

The olefinic resin sheet has a melting endothermic peak by differential thermal analysis of 160 ° C. and a flexural modulus of 1.
50 parts by weight of olefin-based thermoplastic elastomer having 5 × 10 ⁵ kPa, MI of 1.0 g / 10 min and density of 0.90 g / cm ³ , and melting endothermic peak by differential calorimetric analysis of 125 ° C., flexural modulus Is 3 × 10 ⁵ kPa, M
A resin mixture of 50 parts by weight of linear low-density polyethylene having an I of 1.0 g / 10 min and a density of 0.92 g / cm ³ was supplied to a single-screw extruder and thickened by a T-die method at a resin temperature of 190 ° C. It was extruded at 0.150 mm and heat-bonded to the foam to obtain a laminated sheet of an olefin resin sheet and a foam.

The ratio A / B value was measured from the melting endothermic peak, density and thickness of the olefin resin sheet extruded from the T-die, and the elongation at 140 ° C. was measured. Shown in 1. The elongation at 140 ° C is JIS
It was measured based on K 6767. A soft vinyl chloride sheet having a thickness of 0.50 mm was attached to the foam side of the obtained laminated sheet using a polyester adhesive to obtain a laminated body.

(Evaluation by Stamping Molding) The above laminated material was molded into a planar square shape of 150 mm × 150 mm, and was placed horizontally between the upper mold and the lower mold so that the skin material was placed on the upper mold side. Placed on the lower mold, MI of 30g / 10
10 minutes each of propylene-based resin having a temperature of 200 ° C. is supplied from two gates, and immediately the upper die is pressed toward the lower die at a pressure of 5000 kPa for 5 seconds using a hydraulic press kept at 20 ° C. 5 at a pressure of 1000 kPa
The upper die and the lower die were pressed against each other for 0 seconds and water was passed through the hydraulic press to cool the laminated material, and then the upper die was moved upward to release the pressure on the laminated material. The unevenness of the skin material of the obtained molded product was visually observed, and the breakage at the corner is shown in Table 2.
In addition, a sensory evaluation of flexibility was performed on the obtained molded product, and the results are shown in Table 2. Surface irregularity ○: No irregularities or wrinkles were found on the surface, and the appearance was good. X: The surface had irregularities and wrinkles, and the appearance was poor. Corner breakage ○: No breakage was observed in the corner, and the appearance of the corner was good. X: The corner portion was torn, and the appearance of the corner portion was poor. Flexibility: Good flexibility. X: The flexibility was insufficient.

(Example 2) In the blending of the olefin resin crosslinked foam in Example 1, extruding / irradiating / foaming was carried out in the same manner as in Example 1 except that only 13 parts by weight of the thermal decomposition type foaming agent was used to obtain a thick coating. A 3 mm olefin resin crosslinked foam was obtained. The obtained foam was evaluated in the same manner as in Example 1, and the results are shown in Table 1. An olefin resin sheet having a thickness of 0.2 mm was fused to the obtained olefin resin crosslinked foamed product in the same manner as in Example 1 to obtain a laminated sheet of the olefin resin sheet and the foamed product. The obtained olefin resin sheet was evaluated in the same manner as in Example 1, and the results are shown in Table 1. Further, the same skin as in Example 1 was attached to the above-mentioned laminated sheet, the stamping molding evaluation was performed, and the obtained results are shown in Table 2.

(Comparative Examples 1 to 5) In the composition of the expandable resin composition sheet of the olefin resin crosslinked foam in Example 1, the same resin, crosslinking aid and thermal decomposition type foaming agent as in Example 1 were used. The respective ratios are shown in Table 3 to obtain an olefin resin crosslinked foam. Extrusion, irradiation and foaming were carried out in the same manner as in Example 1 to obtain an olefin resin crosslinked foam having a thickness of 3 mm. The obtained foam was evaluated in the same manner as in Example 1, and the results are shown in Table 1. An olefin resin sheet similar to that of Example 1 was fused to the obtained olefin resin crosslinked foam to obtain a laminated sheet of the olefin resin sheet and the foam. The obtained olefin resin sheet was evaluated in the same manner as in Example 1, and the results are shown in Table 1. Further, the same skin as in Example 1 was attached to the above-mentioned laminated sheet, the stamping molding evaluation was performed, and the obtained results are shown in Table 2.

Comparative Examples 6 to 9 The same resin as in Example 1 was used in the crosslinked olefin resin foam obtained in Example 1, and the respective proportions are shown in Table 5. The sheets were fused to obtain a laminated sheet. The obtained olefin resin sheet was evaluated in the same manner as in Example 1, and the results are shown in Table 5. Further, the same skin as in Example 1 was attached to the above laminated sheet, and stamping molding evaluation was performed. The results are shown in Table 3.

(Comparative Example 10) As a foam, ethylene-
Propylene copolymer (melting endothermic peak: 150 ° C., flexural modulus: 7.2 × 10 ⁵ kPa, MI: 1.0 g / 10
Min, density: 0.90 g / cm ³ ) and linear low-density polyethylene (melting endothermic peak: 120 ° C., flexural modulus: 3 ×)
10 ⁵ kPa, MI: 2.5 g / 10 minutes, density: 0.9
2 g / cm ³ ) 4 parts by weight of the same cross-linking agent as in Example 1, 6 parts by weight of a thermal decomposition type foaming agent, and the same amount of an antioxidant were added, and only irradiation was performed by irradiating an electron beam of 4.0 Mrad with an acceleration voltage of 800 kV. Except for the above, the same extrusion, irradiation and foaming as in Example 1 were carried out,
An olefin resin crosslinked foam having a thickness of 3 mm, a gel fraction of 62%, and an average cell diameter from the surface of 180 μm was obtained.
The obtained olefin-based resin crosslinked foam was laminated with the same skin as in Example 1 and subjected to stamping evaluation. The results are shown in Table 3.

Comparative Example 11 An olefin resin crosslinked foam obtained in the same manner as in Example 1 was added with 100 parts by weight of the same olefin thermoplastic elastomer as in Example 1,
1 part by weight of the thermal decomposition type foaming agent used in the olefin resin crosslinked foam of Example 1 and 1 part by weight of a crosslinking aid were mixed and extruded,
Irradiation and foaming were performed, and the obtained olefin resin foam sheet having a thickness of 0.200 mm and an apparent density of 0.50 g / cm ³ was laminated by heat fusion to obtain a laminated sheet. Further, the same skin as in Example 1 was attached to the above laminated sheet, and stamping molding evaluation was performed. The results are shown in Table 1.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 5]

[0054]

EFFECTS OF THE INVENTION Since the present invention has the above-mentioned constitution, it can be molded into a complicated shape at high temperature, and a beautiful molded product having a complicated shape such as an automobile interior material can be obtained in a desired shape. In addition, the molded product obtained has excellent surface properties. In addition, since the flexibility at room temperature is excellent, the flexibility and feel of the molded product are also excellent.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4F100 AK01E AK03A AK03B AK03C                       AK07 AK63 AK64 AT00D                       BA02 BA03 BA04 BA05 BA07                       BA10B BA10C BA10D BA10E                       DJ01A EJ05A EJ20 EJ42                       GB33 JA04A JA04B JA04C                       JA13A JB16E JK08 JM10A                       YY00A YY00B YY00C

Claims (4)

[Claims] 1. An olefin resin having at least one melting endothermic peak temperature of 148 ° C. or higher by differential thermal analysis and having a density of 0.025 to 0.040 g / cm ³ ,
At least one surface of the olefin resin crosslinked foam having a gel fraction of 20 to 50% has two or more melting endothermic peak temperatures by differential thermal analysis, at least one of which is 110
In a laminated sheet in which olefin resin sheets having a temperature of 130 ° C to 140 ° C and the other temperature of 140 ° C to 170 ° C are laminated,
A laminated sheet, wherein the ratio A / B of the expansion ratio of the crosslinked olefin resin foam and the thickness of the olefin resin sheet is in the range of 125 to 500. [In the formula, A is the expansion ratio (cm ³ / g) of the olefin resin crosslinked foam,
B indicates the thickness (mm) of the olefin resin sheet, respectively] 2. The laminated sheet according to claim 1, which has an elongation at 140 ° C. of 320% or more. 3. The laminated sheet according to claim 1, wherein a skin material is attached to the non-laminated surface of the olefin resin sheet. 4. A molded product produced by hot stamping a laminate in which a thermoplastic resin substrate is further laminated on the olefin resin sheet laminated surface of the laminated sheet according to claim 1.