JPH0919978A - Laminated sheet for interior decoration and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet for interior decoration which is less expensive and excellent in appearance, texture, touch, heat resistance, extensibility, and strength and the method for manufacturing the sheet. SOLUTION: In a laminated sheet for interior decoration, a surface layer 1a made from a thermoplastic elastomer of a mixture between polyolefin and partially crosslinked α-olefin copolymer rubber, a base material layer 1b made from polypropylene, a foamed layer 1c made from a thermoplastic resin, and a thermosensible adhesive layer 1d are laminated in this order.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interior laminate which can be attached to a synthetic resin molding (core material) such as an automobile interior material, and can be formed even after being attached to an unformed core material. The present invention relates to a sheet and a manufacturing method thereof.

[0002]

2. Description of the Related Art Conventionally, an interior laminated sheet to be attached to the surface of an automobile interior material or the like is made of, for example, a soft vinyl chloride resin (hereinafter referred to as PVC) sheet having an embossed surface, and if necessary. A laminated sheet having a foamed sheet laminated on its back surface has been used. But,
Such a PVC sheet lacks flexibility and requires multiple manufacturing steps in its manufacturing stage. On the other hand, for example, Japanese Patent Publication No. 1-104023 and Japanese Patent Publication No. 3-14023
As described in Japanese Patent No. 25346, a blend of a polyurethane-based resin and a partially cross-linked ethylene / α-olefin-based rubber is formed on the back surface side of a polyolefin-based thermoplastic elastomer layer whose surface is embossed. ,
An interior sheet has been proposed in which a foam layer made of polyolefin such as polyethylene or polypropylene is laminated.

In addition, when sticking to a core material or the like, after the corona discharge treatment is applied to the surface of the foamed sheet, a solvent type adhesive is coated on this surface, or a solvent type adhesive is applied to the surface of the core material. There is a method of pasting.

[0004]

However, such a thermoplastic polyolefin-based elastomer has low dispersibility,
There is a problem that it is difficult to form a film on a sheet unless blended with another resin. Further, since such a thermoplastic polyolefin-based elastomer is more expensive than a general-purpose resin, a thin film and a blending ratio with a general-purpose resin have been studied. However, there is a problem in that the strength is reduced due to the thinning, and the transfer becomes insufficient when an embossed pattern is formed, resulting in a poor appearance.

In addition, a blend of a thermoplastic polyolefin-based elastomer and a general-purpose resin is used as the elastomer 1 in view of film formation.
It is generally carried out in the range of 10 to 40 parts by weight with respect to 00 parts by weight of polyethylene or polypropylene or a combination thereof. There is a problem in that the softness, flexibility, and texture are reduced.

Even if the surface of a foamed sheet or the like is subjected to corona discharge treatment, the effect of the corona discharge treatment deteriorates with time and the required adhesiveness cannot be obtained. Therefore, it is necessary to control the expiration date of the treatment. Subject to time constraints. Further, there is a problem in environmental hygiene since the solvent type adhesive is used.

The present invention solves the above-mentioned problems of the prior art and provides an interior laminated sheet excellent in appearance, feel, contact feeling, heat resistance, extensibility and strength and a method for producing the same, at low cost. To aim.

[0008]

A laminated sheet for interior according to the present invention according to claim 1 comprises a surface layer comprising a thermoplastic elastomer which is a mixture of a polyolefin resin and a partially crosslinked α-olefin copolymer rubber. A base material layer made of a polypropylene resin, and a foam layer made of a thermoplastic resin,
And a heat-sensitive adhesive layer are laminated in this order.

In the method for producing a laminated sheet for interior according to the present invention as defined in claim 2, the polyolefin resin is partially cross-linked with α.
A thermoplastic elastomer that is a mixture of an olefin copolymer rubber and a polypropylene resin are coextruded in a sheet shape, and the polypropylene resin layer surface in a molten state,
It is characterized in that a thermoplastic resin foam having a heat-sensitive adhesive layer provided on at least one surface is laminated and laminated so that the heat-sensitive adhesive layer is on the outside.

Examples of the mixture of the polyolefin resin constituting the surface layer and the partially crosslinked α-olefin copolymer rubber in the present invention include the following. Various polyolefin resins represented by homopolymers of ethylene or propylene, or copolymers of these with a small amount of other polymerizable monomers, and binary of ethylene and α-olefin having 3 to 14 carbon atoms A thermoplastic resin composition comprising a copolymer rubber or a mixture of partially cross-linked ethylene-α-olefin copolymer rubber, which is a terpolymer rubber in which various polyene compounds are further copolymerized.

Polyolefin resin, ethylene-
A thermoplastic resin composition obtained by heat-treating a mixture with an α-olefin copolymer rubber. A thermoplastic resin composition which is obtained by dynamically heat-treating a mixture of a polyolefin-based resin and an ethylene-α-olefin-based copolymer rubber, and further mixed with a polyolefin-based resin.

Peroxide-crosslinking polyolefin resin represented by ethylene homopolymer or a copolymer of ethylene and a small amount of other polymerizable monomer, propylene homopolymer, or a small amount of other polymerization thereof A thermoplastic resin composition obtained by dynamically heat-treating a mixture of a peroxide non-crosslinking polyolefin polymer rubber represented by a copolymer with a hydrophilic monomer.

In the above-mentioned various thermoplastic elastomers, the polyolefin resin and the partially cross-linked ethylene-α-olefin copolymer rubber are 80/20 to 20 /
The mixture is used in a weight ratio of 80, preferably 70/30 to 30/70.

As the polyolefin resin, polyethylene, particularly low-density polyethylene and polypropylene are mixed at a weight ratio of 10/90 to 70/30 from the viewpoints of ease of molding at the time of molding a sheet, scratch resistance of the sheet, and the like. It is preferable to use it.

As the ethylene-α-olefin copolymer rubber to be partially crosslinked, 50/50 to 9 of ethylene and α-olefin are mainly used for the reason of strength.
It is desirable that the molar ratio is 0/10, preferably 70/30 to 85/15, and the Mooney viscosity (121 ° C.) is about 20 or more, preferably about 40 to 80.

The partial cross-linking of these ethylene-α-olefin copolymer rubbers is carried out by subjecting a material to be treated which is generally used in forming a thermoplastic elastomer (in the above case, ethylene-α-olefin copolymer rubbers, to Is expressed as a mixture) about 0.1 to 100 parts by weight
˜2 parts by weight of organic peroxide and dynamically heat treated.

The polyolefin resin constituting the surface layer preferably has a weight average molecular weight of 80,000 to 500,000. When the weight average molecular weight is small, the heat resistance, extensibility and strength of the obtained laminated sheet for interior are lowered, and when it is large, the flexibility is lowered.

The polypropylene resin (hereinafter referred to as PP resin) used as the base material layer in the present invention is capable of elastically expanding. Therefore, the PP resin has an elution amount of 25 to 75% by weight at 0 ° C or less by the cross fractionation method.
And 5 to 45% by weight at 0 ° C or higher and 80 ° C or lower, 80
It is preferable to have 2 to 45% by weight above 100 ° C and below 100 ° C, and 2 to 40% by weight above 100 ° C and below 125 ° C.

When the elution amount of the above PP resin by the cross fractionation method is 0 ° C. or less or more than 0 ° C. and less than 80 ° C. and less than the above range, the flexibility and extensibility of the obtained laminated sheet for interior are deteriorated. However, if it is more than the above range, the heat resistance and the strength are lowered. Further, when the elution amount is more than 80 ° C. and 100 ° C. or less and less than the above range, the heat resistance and strength of the obtained interior laminated sheet are lowered, and when it is more than the above range, the flexibility of the obtained interior laminated sheet. And the extensibility decreases. Furthermore,
When the elution amount is more than 100 ° C. and 125 ° C. or less and less than the above range, the heat resistance and strength of the obtained interior laminated sheet decrease, and when the elution amount exceeds the above range, the flexibility of the obtained interior laminated sheet. And the extensibility decreases.

In the material for forming the base layer and the surface layer, if necessary, a coloring agent such as a pigment or a dye, an antioxidant,
An ultraviolet absorber, an antistatic agent, a flame retardant, a filler and the like can be added. The thickness of the base material layer is preferably 10 to 1000 μm, and the thickness of the surface layer is also 10 to 1000 μm.
It is preferred that

In order to form a laminated sheet by laminating the surface layer made of the thermoplastic elastomer and the base material layer made of a polypropylene resin, the resins constituting the both layers are extruded and laminated in a molten state. Extrusion is preferred. Co-extrusion molding is, for example, an inflation method using a plurality of extruders, or a feed block method, a combined use method of a field block and a multi-manifold die,
T such as multi-manifold method and multi-throttle die method
It can be manufactured by coextrusion by die molding or extrusion lamination. The temperature at the time of extrusion varies depending on the resin used, but in general, both the base material layer and the surface layer are 190-90.
250 ° C.

The laminated sheet for interior according to claim 1 is one in which a foam layer is laminated on the base material layer of the laminated sheet. By stacking the foam layers, the cushioning properties can be improved.

The foam layer made of a thermoplastic resin used here is a polyolefin resin such as polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polystyrene, styrene-maleic anhydride copolymer. A foamable thermoplastic resin such as a polystyrene resin, a polyurethane resin, a polyvinyl chloride resin, or various thermoplastic elastomers is used. The expansion ratio of these foam layers is preferably about 5 to 50 times, particularly preferably about 10 to 40 times, in order to exhibit good cushioning properties and soft touch feeling. The thickness of the foam layer is preferably 1 to 3 mm.

As the material constituting the heat-sensitive adhesive, ethylene-vinyl acetate copolymer, polyamide, styrene-
A known heat-sensitive adhesive containing a binder resin such as isoprene-styrene copolymer as a main component and a tackifying resin such as a rosin resin or a petroleum resin mixed therein is used.
The melting temperature of these compositions is usually 150 to 200 ° C.

As a method for laminating the foamed layer on the surface of the polypropylene resin layer which is the base layer of the laminated sheet, the polypropylene resin of the coextruded laminated sheet is laminated or pressed in a molten or semi-molten state. There are a method of passing through a roll and fusing and unifying, or a method of adhering with an adhesive. Of these, the method of laminating the coextrusion-molded polypropylene resin in a molten or semi-molten state is the most suitable.

The heat-sensitive adhesive layer provided on the surface of the foam layer is
The adhesive layer may be provided on both sides of the foam layer, although the adhesive layer is to be attached to the core material of the interior material of an automobile or the like. When the heat-sensitive adhesive layer is provided on both sides of the foam layer,
Only the heat-sensitive adhesive layer on the surface to be attached to the laminated sheet may be melted and pressure-bonded to be adhered to the laminated sheet.

When passing through the pressing roll, if a roughened embossing roll is used as the roll on the surface layer side, the surface layer is embossed and the designability of the surface layer can be improved. If the surface layer is printed and embossed, the design can be further enhanced.

[0028]

In the laminated sheet for interior according to claim 1, the surface layer is made of a thermoplastic elastomer which is a mixture of a polyolefin resin and a partially crosslinked α-olefin copolymer rubber, and the base material layer is a polypropylene resin. Because it consists of
It has excellent appearance, feeling, contact feeling, heat resistance, extensibility and strength. Further, since the foam layer made of a thermoplastic resin is laminated on the base material layer, it has excellent cushioning properties. Further, since the heat-sensitive adhesive layer is laminated on the surface of the foam layer, the adhesive can be easily adhered to the core material only by heat-melting the adhesive, so that the core material can be bonded efficiently.

According to the method for producing a laminated sheet for interiors according to claim 2, it has excellent appearance, feel, contact feeling, heat resistance, extensibility and strength, and has good cushioning properties, and has good workability in bonding with a core material. A good laminated sheet for interior can be manufactured.

[0030]

Embodiments of the present invention will be described below. In the following examples and comparative examples, the following materials were used as each material. (1a) Surface Layer Forming Material Surface Layer Forming Material 1a: Olefin-based thermoplastic elastomer resin (Mitsui Petrochemical Co., Ltd., trade name "MILASTOMA 9
020N ") and 40 parts by weight of an olefinic thermoplastic elastomer resin (Mitsui Petrochemical Co., Ltd., trade name" Milastoma 8030N 40 parts by weight ", and 20 parts by weight of polypropylene (Cisso Co., trade name" F3122 ") in a pellet blend. Surface layer forming material 1a: olefin-based thermoplastic elastomer resin (Mitsui Petrochemical Co., Ltd., trade name "MILASTOMA 8"
030N ") 30 parts by weight and 70 parts by weight of polyethylene (trade name" NF90 "manufactured by Mitsubishi Chemical Corporation) are pellet-blended.

(1b) Substrate layer forming material Substrate layer forming material 1b: weight average molecular weight of 170,000, elution amount of 38.5% by weight below 0 ° C. with respect to the total amount of PP resin measured by the cross fractionation method. Yes, above 0 ° C 8
2.1.8% by weight below 0 ° C, 36.4% by weight above 80 ° C and below 100 ° C, and 3.400% above 100 ° C and below 125 ° C.
3 wt% PP resin (manufactured by Highmont, trade name "Cataloy NKS-052P").

Substrate layer forming material 1b: weight average molecular weight of 365,000, elution amount of 39.2% by weight at 0 ° C or below, relative to the total amount of PP resin measured by the cross fractionation method, exceeding 0 ° C. 20.1% by weight below 80 ° C, 8.4% by weight above 80 ° C and below 100 ° C, 12 above 100 ° C
PP-based resin (manufactured by Highmont, trade name “Cataloy NKS-025P”) which is 32.3% by weight at 5 ° C. or lower.

Substrate layer forming material 1b: weight average molecular weight 240,000, elution amount with respect to the total amount of PP resin measured by the cross fractionation method is 39.1% by weight at 0 ° C. or lower,
26.7% by weight above 0 ° C and below 80 ° C, 31.6% by weight above 80 ° C and below 100 ° C, 125 above 100 ° C
A PP-based resin (product name "Cataloy FX7083" manufactured by Highmont Co., Ltd.) which is 2.6% by weight at a temperature of not higher than 0 ° C.

(1c) Foaming layer material Foaming layer material 1c: 30-fold foamed crosslinked foamed polyethylene sheet having a thickness of 2 mm (Sekisui Chemical Co., Ltd., trade name "Softlon"). Foam layer material 1c: A crosslinked foamed polypropylene sheet having a thickness of 30 mm and a thickness of 2 mm (manufactured by Sekisui Chemical Co., Ltd., trade name "Softlon").

Examples 1 to 4 Using the surface layer forming material 1a and the base layer forming material 1b in the combinations shown in Table 1, each was supplied to two extruders (not shown) and kneaded to obtain a molten state, These molten resins are combined in a laminated state in a feed block 2 of a coextrusion molding machine 4 shown in FIG. 1, spread in the width direction in a coextrusion die 3 and coextrusion molded from a slit of the die 3, The two-layer laminated sheet 10 in which the surface layer 1a is laminated on the material layer 1b is molded to form the base material layer 1b.
Was supplied to a pair of pressing rolls 5, 51, one of which was an embossing roll 51.

As the extruder for forming the surface layer, those having a diameter of 50 mm manufactured by GM Engineering Co., Ltd. were used, and an extruder having a diameter of 90 mm manufactured by Mitsubishi Heavy Industries, Ltd. was used as an extruder for forming the base material layer. I used one. The resin temperature was 230 ° C. and the coextrusion die temperature was 230 ° C.

Ethylene-vinyl acetate resin (MI = 11
g / 10 minutes, softening temperature 160 ℃) thickness 50μm
The film of 1 is used as a heat-sensitive adhesive 1d, which is heated and attached to one surface of the foam 1c to prepare in advance,
The base layer 1 with the heat-sensitive adhesive 1d on the outside
The laminated sheet for interior 1 which is supplied from the b side to the pressing rolls 5 and 51 and pressed to be fused and laminated on the base material layer 1b in a molten state.
I got

FIG. 2 is a cross-sectional view showing the laminated sheet 1 for interior according to the present invention obtained in the above embodiment. The surface layer 1a is laminated on one side of the base material layer 1b, and the surface layer 1a is an embossed surface. 1e, the foam layer 1c is laminated on the other surface of the base material layer 1b, and the heat-sensitive adhesive layer 1d is provided on the surface of the foam layer 1c.

Comparative Examples 1 and 2 As shown in FIG. 3, the surface layer forming material 1a was calibrated to a diameter of 110 m.
The resin temperature is set to 230 by the extruder (not shown) of m and the mold 3.
The same foam layer 1c as that used in the example is pressed on one surface of the surface layer 1a extruded and molded at the temperature shown in FIG. It laminated | stacked and the laminated sheet 11 for interiors was obtained.

Performance Evaluation With respect to the interior laminated sheets 1 and 11 obtained in Examples 1 to 4 and Comparative Examples 1 and 2, the appearance, feel, contact feeling, heat resistance, extensibility, strength and material cost ratio were measured by the following methods. Was evaluated. Table 1 shows the results. Appearance: The embossed state was observed. Feeling: The matte state of the surface layer was observed. Feeling of contact: Feeling of flexibility when the surface layer is touched by hand. Heat resistance: The sheet excluding the foam layer was heated in an oven heated to 100 ° C. for 1 hour, and the shrinkage ratio was measured. Extensibility: 200mm in normal condition by Tensilon with constant temperature bath
It was observed whether or not there was elongation at the pole when 100% was stretched at a pulling speed of 1 / min. Strength: Measured in the same manner as the extensibility, and the laminated sheet excluding the foamed layer was rated as good when the stress range at 100% elongation was 0.9 kg / cm or more. Adhesiveness: Kraft paper was laminated as a core material on the surface of the heat-sensitive adhesive layer of the laminated sheet for interior, sandwiched in a press at a temperature of 110 ° C., adhered at a pressure of 0.5 kg / cm ² , and cooled to room temperature. After that, the adhesive portion was peeled off, and when the material of the foam layer was destroyed, it was marked with ◯, and when it was not broken, it was marked with x.

[0041]

[Table 1]

As is clear from Table 1, all of the evaluation items of Examples 1 to 4 are excellent, but Comparative Example 1
The product has poor appearance, low strength and high material cost. Further, in Comparative Example 2, the texture is insufficient, the contact feeling is hard, and the extensibility is poor.

[0043]

EFFECT OF THE INVENTION Since the present invention has the above-mentioned constitution, the laminated sheet for interior of the present invention according to claim 1 is inexpensive and has an excellent appearance,
It has excellent feeling, contact feeling, heat resistance, extensibility, and strength, and also has excellent cushioning properties because the foam layer is laminated on the base material layer. Further, since the heat-sensitive adhesive layer is laminated on the surface of the foam layer, the adhesive can be easily adhered to the core material only by heat-melting the adhesive, so that the core material can be bonded efficiently.

According to the method for producing a laminated sheet for interiors according to claim 2, the appearance, feel, contact feeling, heat resistance, extensibility and strength are excellent, the cushioning property is good, and the workability of laminating with the core material is improved. A good interior laminated sheet can be manufactured efficiently and inexpensively without using a solvent.

[0045]

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment of a laminated sheet for interior according to the present invention.

FIG. 2 is an explanatory view showing an example of a method for producing a laminated sheet for interior according to the present invention.

FIG. 3 is an explanatory view showing a method for manufacturing an interior laminated sheet of a comparative example.

[Explanation of Codes] 1, 11: Laminated sheet for interior 1a: Surface layer forming material 1b: Base layer forming material 1c: Foam layer 1d: Heat-sensitive adhesive layer 1e: Embossed surface 2: Feed block 3: Coextrusion Mold 4: Coextrusion molding machine 5: Pressing roll 51: Embossing roll

Claims (2)

[Claims] 1. A surface layer made of a thermoplastic elastomer, which is a mixture of a polyolefin resin and a partially crosslinked α-olefin copolymer rubber, a base material layer made of a polypropylene resin, and a foam made of a thermoplastic resin. A laminated sheet for interior, wherein the layer and the heat-sensitive adhesive layer are laminated in this order. 2. A thermoplastic elastomer, which is a mixture of a polyolefin resin and a partially cross-linked α-olefin copolymer rubber, and a polypropylene resin are coextruded in a sheet form to obtain a polypropylene resin layer surface in a molten state. A method for producing a laminated sheet for interior, comprising laminating thermoplastic resin foams having a heat-sensitive adhesive layer on at least one surface so that the heat-sensitive adhesive layer is on the outside.