JPH06126906A - Laminate for automobile door interior material and its manufacture - Google Patents

Abstract

PURPOSE:To provide a laminate for automobile door interiors which is the laminate by laminating a skin material layer and a substrate material layer by using a specific bonding material layer, which can be bonded at a comparatively low temperature, is high in bonding workability, excellent in both bonding strength and heat creeping resistance, and can be efficiently manufactured by thermally bonding in vacuum molding. CONSTITUTION:In a laminate wherein a substrate material layer and a skin material layer which are selected from resin felt or resin wood are laminated via a bonding material layer, the bonding material layer is a thermoplastic resin composition composed of (A) an ethylene much component copolymer consisting of a radical polymerizable anhydride of ethylene, maleic anhydride, etc., and the other radical polymerizable comonomer (for example, methyl methacrylate), (B) an ethylene dimensional polymer consisting of radical polymerizable acid anhydride of ethylene, maleic anhydride, etc., and (C) a thermoplastic resin composition consisting of group I A or group II A metallic salt of organic carboxylic acid. Further, respective layers of the laminate are thermally bonded by vacuum molding to manufacture a laminate for automatic door interiors.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate for an automobile door interior material and a method for manufacturing the same, and more particularly to an automobile door interior material in which a skin material layer and a certain substrate layer are laminated via a specific adhesive layer. A laminated body for automobile door materials, which can be heat-bonded by vacuum forming at a relatively low temperature, has high adhesive workability, and has excellent adhesive strength and heat-resistant creep in a wide temperature range, and an efficient manufacturing method thereof Regarding

[0002]

2. Description of the Related Art Generally, as an automobile door interior material,
A laminated body is used in which a skin material and a substrate material are adhesively bonded to each other with an emphasis on aesthetics of the room. When laminating such a laminate, the method of using a solvent-based adhesive has low workability, and there are problems of occupational hygiene and danger (fire etc.) due to organic solvents, while environmental issues are being emphasized in recent years. , Not the proper way.

Therefore, there has been proposed a laminate for an automobile door interior material, which uses a heat-sensitive adhesive resin to bond the skin material and the substrate material. As such a heat-sensitive adhesive resin, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, low melting point copolymer nylon, etc. are used.

The laminate using the heat-sensitive adhesive resin is formed by a method of heat-pressing with a heat press by sandwiching a heat-sensitive adhesive resin film between the skin material and the substrate material, and extruding the heat-sensitive adhesive resin on the skin material. The laminated material or the laminated material in which the heat-sensitive adhesive resin film is heat-roll laminated on the surface material is manufactured by a method such as heat-pressing the substrate material with a hot press.

In these methods, automobile door interior materials are particularly required to have a texture, feel, and aesthetics of the skin material. Therefore, in the molding method using the hot press as described above, the surface of the skin material has a strong pressure. A vacuum forming method capable of forming at a low pressure is mainly used so that there is no influence such as crushing. For the same reason, the molding temperature should be kept as low as possible.

A laminate for an automobile door interior material using such a heat-sensitive adhesive resin has good laminating workability.
The laminate obtained by vacuum forming at a relatively low heating temperature and a low pressure has insufficient adhesive strength at room temperature. Also, automobiles are exported to countries all over the world, and because of wide range of usage conditions and usage conditions, they are exposed to extremely cold to extremely hot climates. Especially under direct sunlight, the surface of the door interior material becomes a high temperature exceeding 80 ° C. However, in such a case, there is a problem that the laminated body using the heat-sensitive adhesive resin has low adhesive strength and deformation such as sagging, peeling, cracking and warping.

Therefore, in order to improve the adhesive strength, it is necessary to raise the heating temperature of the adhesive, but there is a problem that the production efficiency is lowered and the appearance is deteriorated as described above.

[0008]

As described above, a laminate for an automobile door interior material, in which a skin material layer and a substrate material layer are laminated via an adhesive material layer, which is laminated at a relatively low processing temperature and processing pressure. A laminated body suitable for an automobile door interior material having a high adhesive strength, a high temperature creep resistance and the like in a wide temperature range while maintaining the aesthetic property and high-grade feeling of the skin material layer has not been proposed yet.

[0009]

Therefore, the present inventors have
As a result of intensive research to develop a laminate for automobile door interior materials, which has excellent adhesive strength and heat resistance and creep resistance without damaging the texture of the skin material that has solved the conventional problems, the adhesion between the skin material layer and the substrate material layer It has been found that by using a specific thermoplastic resin composition as the material layer, the intended laminate can be obtained and this laminate can be efficiently produced by thermocompression bonding in vacuum forming. The present invention has been completed based on such findings.

That is, the present invention comprises a substrate material layer and a skin material layer selected from resin felt or resin wood,
In the laminate obtained by laminating via an adhesive layer, the adhesive layer is (A) an ethylene-based multi-component copolymer comprising ethylene, a radical-polymerizable acid anhydride and other radical-polymerizable comonomer, The ratio of units derived from the radical-polymerizable acid anhydride in the ethylene-based multi-component copolymer is 0.1 to
5% by weight, the proportion of units derived from other radically polymerizable comonomers is 3 to 50% by weight, an ethylene-based multi-component copolymer (hereinafter referred to as component (A)), (B) ethylene and radically polymerizable acid. An ethylene-based binary copolymer comprising an anhydride, wherein the proportion of units derived from the radical-polymerizable acid anhydride in the ethylene-based binary copolymer is 0.1 to 5% by weight. Original copolymer (hereinafter referred to as component (B))
And (C) Group IA or IIA of the periodic table of organic carboxylic acids
Provided is a laminate for an automobile door interior material, which is a thermoplastic resin composition comprising a group metal salt (hereinafter referred to as a component (C)), and thermally bonding such a laminate by vacuum forming. The present invention also provides a method for producing a laminate for an automobile door interior material.

In the laminate of the present invention, the material for the skin material layer is not particularly limited, and is usually used for interior materials of automobile doors, and various materials can be used depending on the purpose of the interior. Specific examples thereof include polyester non-woven fabric, brushed knit, vinyl chloride leather, polyurethane leather, polypropylene thermoplastic elastomer, and those obtained by laminating a cushion material such as urethane foam, polyethylene foam or polypropylene foam on these materials. .

In the present invention, the material of the substrate material layer is selected from resin felt or resin wood. These substrate materials are excellent in lightness, workability, and cost, and have extremely good adhesiveness with the adhesive layer of the present invention, and have high adhesiveness even under low pressure adhesive conditions such as vacuum forming. Strength can be obtained.

The laminate for an automobile door interior material of the present invention comprises the above-mentioned skin material layer and substrate material layer laminated with a thermoplastic resin composition layer as an adhesive layer. Here, the adhesive layer is a layer of a thermoplastic resin composition comprising the above-mentioned component (A), component (B) and component (C). By using such a resin composition, strong adhesion can be achieved at a relatively low temperature,
Adhesive strength in a wide temperature range without damaging the texture of the skin material,
That is, a laminate having excellent heat resistance and creep resistance can be obtained.

In this thermoplastic resin composition, (A)
The component is an ethylene-based multi-component copolymer composed of ethylene, a radical-polymerizable acid anhydride and other radical-polymerizable comonomers. Here, the radical-polymerizable acid anhydride is a compound having one or more radical-polymerizable unsaturated bond and one or more acid anhydride group in the molecule and capable of introducing an acid anhydride group into the molecule by polymerization. Is.

Specific examples of such compounds include:
Maleic anhydride, itaconic anhydride, endic acid anhydride, citraconic anhydride, 1-butene-3,4-dicarboxylic acid anhydride, alkenyl succinic anhydride having a double bond at the end having at most 18 carbon atoms, Examples thereof include alkadienyl succinic anhydride having a double bond at the terminal, which has at most 18 carbon atoms. These may be used in combination of two or more kinds at the same time. Of these, maleic anhydride and itaconic anhydride are particularly preferable.

As the radical-polymerizable comonomer other than the radical-polymerizable acid anhydride, many compounds can be used. Specifically, an ethylenically unsaturated ester compound,
Examples thereof include ethylenically unsaturated amide compounds, ethylenically unsaturated acid compounds, ethylenically unsaturated ether compounds, and ethylenically unsaturated hydrocarbon compounds.

More specifically, as ethylenically unsaturated ester compounds, vinyl acetate, methyl (meth) acrylate [(meth) acrylic acid means acrylic acid and methacrylic acid. The same applies below. ] Ethyl (meth) acrylate, Propyl (meth) acrylate,
Examples thereof include butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, and benzyl (meth) acrylate.

As the ethylenically unsaturated amide compound,
(Meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N
-Octyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide; N, N-diethyl (meth) acrylamide and the like.

Examples of the ethylenically unsaturated acid compound include (meth) acrylic acid. Examples of the ethylenically unsaturated ether compound include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octadecyl vinyl ether, and phenyl vinyl ether. Further, as the ethylenically unsaturated hydrocarbon compound and other compounds, styrene,
Examples thereof include α-methylstyrene, acrylonitrile, methacrylonitrile, acrolein, trimethoxyvinylsilane, triethoxyvinylsilane, vinyl chloride and vinylidene chloride.

Of these, preferred compounds include
Examples thereof include (meth) acrylic acid esters and (meth) acrylic acid. Among them, methyl methacrylate, methyl acrylate, and -n-butyl acrylate are preferable. If necessary, two or more of these comonomers may be used in combination at the same time.

In the component (A), the proportion of units derived from the radical-polymerizable acid anhydride is 0.1 to 5% by weight, preferably
0.5 to 4% by weight, the proportion of units derived from other radically polymerizable comonomers is 3 to 50% by weight, preferably 5
-40% by weight. If the proportion of the units derived from the radical-polymerizable acid anhydride is less than 0.1% by weight, the adhesive strength will be low, and if it exceeds 5% by weight, the flexibility of the resulting copolymer will be significantly reduced and the production The cost is high, which is not preferable. Further, if the proportion of units derived from other radically polymerizable comonomers is less than 3% by weight, the crystal melting point of the obtained copolymer does not become sufficiently low and adhesion at low temperature becomes difficult. Is difficult to handle,
It is not practical because the heat resistance of the obtained laminate decreases.

The component (A) is not particularly limited as long as it satisfies the above conditions, but the MFR value (JIS-K72).
(10, the same below) is preferably 0.1 to 50 for film formation.

Next, the component (B) of the thermoplastic resin composition of the present invention comprises ethylene and a radical-polymerizable acid anhydride. Here, the radical-polymerizable acid anhydride is the same as the above-mentioned radical-polymerizable acid anhydride of the component (A).

In the component (B), the proportion of units derived from the radical-polymerizable acid anhydride is 0.1 to 5% by weight, preferably 0.5 to 4% by weight. If the ratio of the units derived from the radical-polymerizable acid anhydride is less than 0.1% by weight, high heat-resistant creep property cannot be obtained, and if it exceeds 5% by weight, the flexibility of the obtained copolymer is significantly lowered. However, the production cost becomes high, which is not preferable.

The component (B) is not particularly limited as long as it satisfies the above conditions, but an MFR value of 0.1 to 50 is preferable for film forming.

In producing the components (A) and (B) as described above, generally, ordinary low-density polyethylene production equipment and techniques can be used. Generally, it is a bulk polymerization, and is produced by radical polymerization under a pressure of 700 to 3000 atm in a temperature range of 100 to 300 ° C. The preferred range of polymerization pressure and temperature is 100.
0 to 2500 atm, average temperature in reactor 150 to 270
It can be ° C.

When the pressure is less than 700 atm, the molecular weight of the polymer becomes low, and the moldability and the resin physical properties of the composition deteriorate. Also, 3
Pressures above 000 atm are virtually meaningless and only increase manufacturing costs. When the average polymerization temperature is 100 ° C. or lower, the polymerization reaction is not stable and the conversion rate to the copolymer is lowered, which is economically problematic. If it exceeds 300 ° C., the molecular weight of the copolymer decreases, and at the same time, there is a risk of a runaway reaction.

As the manufacturing apparatus, it is preferable to use a vessel type reactor. Particularly, the radical-polymerizable acid anhydride is poor in polymerization stability, and therefore requires a high degree of homogenization in the reactor. If necessary, a plurality of reactors may be connected in series or in parallel to carry out multistage polymerization. Further, by partitioning the inside of the reactor into a plurality of zones, more precise temperature control can be performed.

The components (A) and (B) used in the present invention are produced under the above reaction conditions in the presence of at least one free radical initiator. Examples of the free radical initiator include oxygen; dialkyl peroxides such as di-t-butyl peroxide, t-butyl cumyl peroxide and dicumyl peroxide; acetyl peroxide, i-butyryl peroxide, octanoyl peroxide. Diacyl peroxides such as oxides; Peroxycarbonates such as di-i-propylperoxycarbonate and di-2-ethylhexylperoxycarbonate; Peroxyesters such as t-butylperoxypivalate and t-butylperoxylaurate Ketone peroxides such as methylethylketone peroxide and cyclohexanone peroxide; Peroxyketals such as 1,1-bis-t-butylperoxycyclohexane and 2,2-bis-t-butylperoxyoctane; t-butylhydropa Oxide, hydroperoxide such as cumene hydroperoxide; and 2,2 azo -i- azo compounds such as butyronitrile and the like.

In the polymerization, various chain transfer agents can be used as a molecular weight modifier. Examples of the chain transfer agent include olefins such as propylene, butene and hexene; paraffins such as ethane, propane and butane; carbonyl compounds such as acetone, methyl ethyl ketone and methyl acetate; aromatic hydrocarbons such as toluene, xylene and ethylbenzene. And so on.

The components (A) and (B) thus produced are melted at a relatively low temperature and are rich in physical-chemical interaction and reactivity with various base materials. Demonstrates high adhesive strength with low-temperature molding to skin material layers and substrate material layers.

The component (C) of the thermoplastic resin composition of the present invention is a metal salt of an organic carboxylic acid. By further adding the component (C) to the component (A) and the component (B), the adhesive strength at high temperature can be improved.

The metal salt of an organic carboxylic acid is not particularly limited, but is usually a metal salt of lauric acid, myristic acid, stearic acid, palmitic acid, oleic acid, erucic acid or the like, or ethylene and acrylic acid, Examples thereof include those obtained by neutralizing a part or all of a copolymer such as methacrylic acid with a metal compound (hereinafter referred to as an ionomer). The metal is a metal of Group IA, IIA or IIB of the periodic table, and specifically, lithium, sodium, magnesium,
Potassium, calcium, zinc, etc.

Examples of the component (C) include sodium stearate, sodium palmitate, sodium oleate, magnesium stearate, magnesium palmitate, magnesium oleate, and partial neutralization of ethylene-methacrylic acid copolymer with sodium compounds. Or a partially neutralized product of an ethylene-acrylic acid copolymer with a zinc compound, particularly sodium stearate, sodium oleate, a partially neutralized product of an ethylene-methacrylic acid copolymer with a sodium compound, etc. Is preferred.

When an ionomer is used as the component (C), there is no particular limitation, but the MFR value is preferably 0.1 to 1000.

The adhesive layer of the present invention is basically a thermoplastic resin composition comprising the above-mentioned components (A), (B) and (C), and the mixing ratio thereof is a skin material and a substrate material to be laminated. Is appropriately selected depending on the type, required characteristics, and the like. Usually, the weight ratio of the component (A) and the component (B) is (A) component / (B).
Component = 1/9 to 9/1, the component (C) is a metal atom in which the number of acid anhydride units contained in the component (A) and the component (B) is contained in the component (C). The number of the acid anhydride units / the number of metal atoms = 10/1 to 2/1.

Various additives, compounding agents, fillers and the like can be added to the resin composition of the present invention within a range that does not impair the characteristics of the composition. If these are shown concretely, an antioxidant (heat resistance stabilizer), an ultraviolet absorber (light stabilizer),
Antistatic agent, antifogging agent, flame retardant, lubricant (slip agent, antiblocking agent), glass, inorganic filler such as filler, organic filler, reinforcing agent, colorant (dye, pigment), foaming agent, fragrance, etc. Is mentioned.

The resin composition for the adhesive layer of the present invention can be produced by various methods that are generally known. To illustrate the specific method, a method of dissolving and reprecipitating each component in a good solvent such as toluene at high temperature, a method of mixing each component in a molten state, that is, a commonly used pressure kneader , A roll, a Banbury mixer, a static mixer, a screw type extruder, etc. can be mentioned.

In some cases, the components may be dry blended during molding of the resin composition. That is, the respective components may be mixed in the form of pellets or powder and then melt mixed.

The laminated body of the present invention is a laminated body in which at least the above-mentioned skin material layer and substrate material layer are laminated via an adhesive layer, and various methods are possible in the production thereof. However, it can be efficiently manufactured especially by the vacuum forming method.

As a specific method thereof, a substrate material is heated to a predetermined temperature and placed on a vacuum forming mold, and a laminated material obtained by extrusion-coating the resin composition of the adhesive layer on the surface of the substrate is predetermined. A method of stacking and vacuum-molding after heating to a temperature; by heating a substrate material to a predetermined temperature and mounting it on a vacuum-molding die, and then inflation-molding or T-die molding the resin composition of the adhesive layer on it. Place the manufactured film, then stack the skin material that has been heated to a predetermined temperature in advance and press-bond it under vacuum; place the substrate material on the vacuum molding die and heat it to a predetermined temperature, and then attach the adhesive material to the skin. A method in which a laminate material extruded and coated with a resin composition of a layer is heated in advance to a predetermined temperature and then subjected to vacuum pressure bonding; a substrate material is placed on a vacuum molding die and heated to a predetermined temperature, and an adhesive layer is formed thereon. Of the resin composition of A method of forming a film by solution molding or T-die molding, then heat-laminating the laminated body at low pressure with a heat roll or a heating press to temporarily adhere the laminate to a predetermined temperature, and then stacking and vacuum-compression bonding. You can

The thickness of the film or coating layer of the resin composition of the adhesive layer used in vacuum forming may be appropriately selected according to the conditions of vacuum forming, but is usually 10 to 1.
It is 50 μm, preferably 15 to 100 μm. 10μ
If it is less than m, the adhesive strength is lowered, which is not preferable.
When it exceeds 50 μm, the thermal conductivity is lowered and sufficient adhesive strength cannot be obtained, which is not practical.

The heating temperature of the substrate material and the skin material at the time of vacuum forming varies depending on the conditions of vacuum forming, the kind of material, etc., but is at least the softening point of the resin composition of the adhesive layer, It may be appropriately selected at a temperature below the temperature at which the plate material and the skin material are not affected. Usually, the heating temperature is 40 to 200 ° C, preferably 50 to 180 ° C for the substrate material, and 50 to 180 ° C, preferably 60 to 160 ° C for the skin material.

The pressure bonding is vacuum forming, which is 1k.
g / cm ² or less, preferably 0.01 to 0.8 kg / cm ²
Strong bonding is possible at a relatively low pressure, and it can be manufactured without impairing the texture and feel of the materials of the skin material and the substrate material. Further, although lamination is possible at low temperature, the obtained laminate has cracks, warps,
Almost no deformation such as peeling or creep occurs.

[0045]

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples.

Reference Example 1 (Production of Ethylene-Methyl Methacrylate-Maleic Anhydride Terpolymer) Using the equipment of a high-pressure low-density polyethylene plant, the polymerization temperature was 200 ° C. and the polymerization pressure was 1800 kg / cm ² . Under the conditions, an ethylene-methyl methacrylate-maleic anhydride terpolymer was produced (hereinafter referred to as terpolymer a). MFR of this terpolymer (JIS-K721
0, Table 1, Condition 4, the same shall apply hereinafter) 15, the content of units derived from methyl methacrylate was 16% by weight, and the content of units derived from maleic anhydride was 2.2% by weight. . The composition of the comonomer was determined by infrared absorption spectrum.

Reference Example 2 (Production of ethylene-acrylic acid-n-butyl-maleic anhydride terpolymer) Polymerization temperature 200 ° C., polymerization pressure 1,600 kg / An ethylene-acrylic acid-n-butyl-maleic anhydride terpolymer was produced under the condition of cm ² (hereinafter referred to as terpolymer b). This terpolymer has an MFR of 10, acrylic acid-
The content of units derived from n-butyl was 12% by weight, and the content of units derived from maleic anhydride was 1.8% by weight. The composition of the comonomer was determined by infrared absorption spectrum.

Reference Example 3 (Ethylene-Methyl Acrylate-
Production of itaconic anhydride ternary copolymer) Using the equipment of a high-pressure low-density polyethylene plant, under the conditions of a polymerization temperature of 200 ° C and a polymerization pressure of 1,800 kg / cm ² , ethylene-methyl acrylate-itaconic anhydride A terpolymer was produced (hereinafter referred to as a terpolymer c).
The terpolymer had an MFR of 10, the content of units derived from methyl acrylate was 25% by weight, and the content of units derived from itaconic anhydride was 1.8% by weight. The composition of the comonomer was determined by infrared absorption spectrum.

Reference Example 4 (Production of Ethylene-Maleic Anhydride Binary Copolymer) Ethylene was produced under the conditions of a polymerization temperature of 190 ° C. and a polymerization pressure of 1,900 kg / cm ² using equipment of a high-pressure low-density polyethylene plant. -A maleic anhydride binary copolymer was produced (hereinafter referred to as binary copolymer a). The MFR of this binary copolymer was 10, and the content of units derived from maleic anhydride was 2.0% by weight.

Reference Example 5 (Ethylene-Itaconic Anhydride Binary Copolymer) Ethylene-anhydrous was used under the conditions of a polymerization temperature of 200 ° C. and a polymerization pressure of 1,800 kg / cm ² using equipment of a high-pressure low-density polyethylene plant. An itaconic acid binary copolymer was produced (hereinafter referred to as binary copolymer b). The MFR of this binary copolymer is 8, and the content of units derived from itaconic anhydride is
It was 1.0% by weight.

Reference Example 6 (Production of Sodium Partially Neutralized Product of Copolymer of Ethylene and Methacrylic Acid) A copolymer of ethylene and methacrylic acid (methacrylic acid content 20% by weight) was used as a solvent (water / methanol = 1 / Treated with sodium acetate in 1) at 50 ° C. for 2 hours, 5
It was neutralized by 5% to produce a partially neutralized product (hereinafter referred to as ionomer a).

Examples 1 and 2 60 parts by weight of the terpolymer a obtained in Reference Example 1, 35 parts by weight of the binary copolymer a obtained in Reference Example 4 and the ionomer obtained in Reference Example 6 a 5 parts by weight, 0.1 part by weight of magnesium silicate and 0.01 part by weight of erucic acid amide as additives were further added and dry blended, and then 180 using a 37 mmφ twin-screw extruder in the same direction.
Melt kneading was performed at 0 ° C. to obtain pellets of the thermoplastic resin composition. Then, the obtained resin composition was treated with an inflation film molding machine having a 45 mmφ extruder to obtain 7
A film having a thickness of 5 μm was formed to obtain a film having a width of 80 cm.
The film obtained by the heat roll laminating treatment was laminated on the skin material side of the skin material shown in Table 1 of 2 mm to which 0.2 mm vinyl chloride leather was stuck. The hot roll at this time was a Teflon coat roll heated to 130 ° C., sandwiching the skin material and the film, and the heating was performed at a speed of 5 m / min. Further, the substrate material shown in Table 1 having a thickness of 3 mm was heated at 60 ° C. for 3 minutes, and the skin material obtained by laminating the films produced above was heated to 120 ° C. and bonded by the vacuum forming method. After bonding, after conditioning for 24 hours at 23 ° C. and 50% relative humidity, cut into 25 mm width test pieces and use a tensile tester to
An 80 degree peel test (23 ° C) was performed to measure the adhesive strength. The value of the adhesive strength is the average value of the five test pieces (maximum,
The minimum is omitted). The results are shown in Table 1. Further, suspend a load of 100 g on the test piece peeled halfway,
The peeling distance when left in an atmosphere of 24 ° C. for 24 hours was measured and used as a measure of heat-resistant creep resistance. The heat creep resistance is an average value of three test pieces. The results are shown in Table 1. In all cases, workability was good and adhesion was also good.

[0053]

[Table 1]

Examples 3 and 4 In Example 1, the ionomer a obtained in Reference Example 6 was used.
Sodium stearate was used instead of, and the blending ratio was 60 parts by weight of the terpolymer a obtained in Reference Example 1, 39.5 parts by weight of the binary copolymer a obtained in Reference Example 4, and stearin. A laminate was obtained in the same manner as in Example 1 except that the substrate material and the skin material shown in Table 2 were used as 0.5 part by weight of sodium acid salt. The evaluation of the adhesive strength and the heat-resistant creep resistance was performed in the same manner as in Example 1. The results are shown in Table 2. In all cases, workability was good and adhesion was also good.

[0055]

[Table 2]

Examples 5 and 6 In Example 1, the terpolymer a obtained in Reference Example 1 was used.
A laminate was obtained in the same manner as in Example 1 except that the terpolymer b obtained in Reference Example 2 was used instead of and the substrate material and the skin material shown in Table 3 were used. The evaluation of the adhesive strength and the heat-resistant creep resistance was performed in the same manner as in Example 1. The results are shown in Table 3. Workability is good in both cases,
Adhesion was also good.

[0057]

[Table 3]

Examples 7 and 8 In Example 1, 50 parts of the thermoplastic resin composition obtained was used.
It was extruded to a thickness of 50 μm with a laminator having an mmφ extruder and laminated with a 0.2 mm polyethylene teraphthalate non-woven fabric (PET non-woven fabric) on the foam sheet side of the 2 mm skin material shown in Table 4 and the table. A laminate was obtained in the same manner as in Example 1 except that the substrate material shown in 4 was used. The evaluation of the adhesive strength and the heat-resistant creep resistance was performed in the same manner as in Example 1. The results are shown in Table 4. In all cases, workability was good and adhesion was also good.

[0059]

[Table 4]

Examples 9 and 10 In Example 1, the terpolymer a obtained in Reference Example 1 was used.
A laminate was obtained in the same manner as in Example 1 except that the terpolymer c obtained in Reference Example 3 was used instead of and the substrate material and skin material shown in Table 5 were used. The evaluation of the adhesive strength and the heat-resistant creep resistance was performed in the same manner as in Example 1. The results are shown in Table 5. Workability is good in both cases,
Adhesion was also good.

[0061]

[Table 5]

Examples 11 and 12 In Example 1, the terpolymer a obtained in Reference Example 1 was used.
The terpolymer c obtained in Reference Example 3 was used instead of the above, and the binary copolymer b obtained in Reference Example 5 was used instead of the binary copolymer a obtained in Reference Example 4. Was used, and the compounding ratio was 45 parts by weight of the terpolymer c obtained in Reference Example 3, 50 parts by weight of the binary copolymer b obtained in Reference Example 5, and the ionomer a obtained in Reference Example 6. A laminate was obtained in the same manner as in Example 1 except that the amount was 5 parts by weight and the substrate material and the skin material shown in Table 6 were used. The evaluation of the adhesive strength and the heat-resistant creep resistance was performed in the same manner as in Example 1. The results are shown in Table 6. In all cases, workability was good and adhesion was also good.

[0063]

[Table 6]

Comparative Examples 1 and 2 In Example 1, the ionomer a obtained in Reference Example 6 was used.
Ternary copolymer a 70 obtained in Reference Example 1 without blending
A laminate was obtained in the same manner as in Example 1 except that 30 parts by weight of the binary copolymer a obtained in Reference Example 4 and 3 parts by weight of the substrate material and the skin material shown in Table 7 were used. The adhesive strength and the thermal creep resistance were the same as in Example 1. The results are shown in Table 7.

[0065]

[Table 7]

Comparative Examples 3 and 4 In Example 1, the terpolymer a obtained in Reference Example 1 was used.
Of the binary copolymer a 95 obtained in Reference Example 4 without blending
A laminate was obtained in the same manner as in Example 1 except that 5 parts by weight of the ionomer a obtained in Reference Example 6 and 5 parts by weight of the substrate material and the skin material shown in Table 8 were used. The adhesive strength of this laminate was not sufficient at room temperature, and deformation and peeling occurred without performing heat-resistant creep measurement, so that the laminate was not practically usable. The adhesive strength and the thermal creep resistance were the same as in Example 1. The results are shown in Table 8.

[0067]

[Table 8]

[0068]

As described above, the laminate for an automobile door interior material according to the present invention can be laminated by a treatment at a relatively low temperature and a low pressure by using a specific adhesive material layer, and can be adhered. It has excellent workability and workability, and because it can be processed at low temperature, it does not damage the texture of the skin material, has high aesthetics, has high adhesive strength at room temperature and high temperature, and does not deform in a wide temperature range. It has excellent heat resistance and creep resistance. Further, it can be manufactured efficiently by thermocompression bonding of vacuum forming. Therefore, the laminate of the present invention can be suitably used as a material for interior materials of automobile doors.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI technical display location C08J 5/12 9267-4F // B29L 31:58 4F (72) Inventor Kunio Iwasaki Oita City, Oita Prefecture Nakanozu 2 Showa Denko Co., Ltd. Oita Laboratories (72) Inventor Hirotaka Tagoshi Oita City, Oita Prefecture Nakanozu 2 Showa Denko Co. Ltd. Oita Laboratories (72) Inventor Shogo Okado Kasugai City, Aichi 2-10-4 Towa Textile Industry Co., Ltd. (72) Inventor Keiji Imai 2-10-4 Ajimi Hakusancho Kasugai City, Aichi Prefecture Toyo Textile Industry Co., Ltd.

Claims (3)

[Claims] 1. A laminate in which a substrate material layer and a skin material layer selected from resin felt or resin wood are laminated via an adhesive layer, wherein the adhesive layer is (A) ethylene, a radical-polymerizable acid anhydride. And an ethylene-based multi-component copolymer comprising a radical-polymerizable comonomer other than the above, wherein the ratio of units derived from the radical-polymerizable acid anhydride in the ethylene-based multi-component copolymer is 0.1 to 5 % By weight, the proportion of units derived from other radically polymerizable comonomers is 3 to
An ethylene-based binary copolymer comprising 50% by weight of an ethylene-based multi-component copolymer, (B) ethylene and a radical-polymerizable acid anhydride, wherein the radical-polymerizable acid in the ethylene-based binary copolymer is The ratio of units derived from anhydride is 0.1 to 5
An interior material for a vehicle door, which is a thermoplastic resin composition comprising a metal salt of an ethylene-based binary copolymer (C) and an organic carboxylic acid (I), a group (IIA), or a group (IIB) of the periodic table of (C) in an amount of 1% by weight. Laminate. 2. The thermoplastic resin composition, wherein the weight ratio of (A) ethylene-based multi-component copolymer and (B) ethylene-based binary copolymer is (A) ethylene-based multi-component copolymer / (B) ethylene. System binary copolymer = in the range of 1/9 to 9/1,
(C) The number of units of the acid anhydride contained in the (A) ethylene-based multi-component copolymer and (B) the ethylene-based two-component copolymer of the organic carboxylic acid metal salt, and the number of metal atoms of the organic carboxylic acid salt. Is used in the interior material of an automobile door according to claim 1, wherein the ratio of the number of units of acid anhydride / the number of metal atoms of organic carboxylate is 10/1 to 1/2. Laminate. 3. A method for producing a laminate for an automobile door interior material, which comprises thermally bonding the layers according to claim 1 by vacuum forming.