JP3133835B2 - Laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate, and more particularly, to a laminate suitably used as an interior material for automobiles, vehicles, ships and the like.

[0002]

2. Description of the Related Art As interior materials for floors, walls, ceilings, etc. of automobiles, vehicles, ships, etc., the surface is generally embossed,
Laminates comprising a polyvinyl chloride layer having a leather pattern embossed thereon, which are successively lined with a foam layer and, if necessary, a substrate material, have conventionally been used.
Such a laminate is usually manufactured through the following steps. A step of calendering a flexible polyvinyl chloride to form a polyvinyl chloride sheet, a step of applying a mixture of a polyol and a polyisocyanate to the surface of the polyvinyl chloride sheet and performing a surface treatment by urethane treatment, and a step of embossing and embossing Forming the attached leather pattern on the front surface, flame-treating the back surface of the embossed PVC sheet and melting it, and pressing it by a separately supplied foam sheet and roll. A step of further providing an adhesive layer on the foamed sheet side of the laminated sheet, a step of forming a substrate material having a predetermined shape by a thermoforming method such as vacuum forming and compression molding, and preheating the PVC sheet-foamed sheet-adhesive laminated sheet After that, this is mounted on a substrate material molded product, and both are thermoformed and integrated. Here, a method of performing the above steps in reverse order is also a general manufacturing method.

However, such a method of manufacturing by laminating a PVC sheet and a foam sheet requires many operations as described above, and is not preferable in terms of cost. In recent years, due to growing interest in environmental issues, polyvinyl chloride, which emits a large amount of chlorine-based gas during combustion, has been replaced with other resins,
For example, efforts have been made to change to polyolefin resins. Among such PVC alternative materials, so-called thermoplastic polyolefin-based elastomers have been receiving attention. However, a large amount of mineral oil is mixed into the thermoplastic polyolefin-based elastomer in order to improve flexibility and processability, and this mineral oil bleeds and causes stickiness or adhesion to other base materials. It is not always a satisfactory material, for example, it may cause a decrease in the properties.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminate excellent in flexibility, workability and adhesiveness, which can be easily manufactured in a small number of operation steps.

[0005]

According to the present invention, a layer of a thermoreversible crosslinkable resin composition containing a specific ethylene-radical polymerizable acid anhydride copolymer, a specific polyhydric alcohol and a reaction accelerator is foamed. The object has been achieved by laminating with a body sheet. That is, the present invention relates to (A)
(A) An ethylene-based copolymer containing ethylene and a radically polymerizable acid anhydride as constituent monomers, wherein the component concentration of the radically polymerizable acid anhydride group in the copolymer is 0.1 to 20% by weight. A unit containing a copolymer, (b) a polyhydric alcohol compound having two or more hydroxyl groups in a molecule and (c) a reaction accelerator, and a unit derived from a radical polymerizable acid anhydride in the component (a). The molar ratio of hydroxyl units in the polyhydric alcohol compound as the component (b) is in the range of 0.01 to 10, and the reaction accelerator as the component (c) is an ethylene-based copolymer as the component (a). 0.001 based on 100 parts by weight of the polymer
An object of the present invention is to provide a laminate obtained by laminating a layer of a resin composition in an amount of from 20 to 20 parts by weight and a foam layer of a polyolefin or polyurethane (B).

Next, each component of the resin composition layer (A) constituting the laminate of the present invention will be described. First, the ethylene copolymer as the component (a) is a binary copolymer composed of ethylene and a radical polymerizable acid anhydride or a multicomponent copolymer composed of ethylene, a radical polymerizable acid anhydride and another radical polymerizable comonomer. It is a copolymer. Examples of the radical polymerizable acid anhydride constituting these ethylene copolymers include maleic anhydride, itaconic anhydride, endic anhydride, citraconic anhydride, 1-butene-3,4
-Dicarboxylic anhydrides, alkenyl succinic anhydrides having at most 18 carbon atoms having a double bond at the terminal, and alkadienyl succinic anhydrides having at most 18 carbon atoms having a double bond at the terminal. These may be used alone or in combination of two or more. Of these, maleic anhydride and itaconic anhydride are preferred.

[0007] The component concentration of the radically polymerizable acid anhydride group in the ethylene copolymer as the component (a) must be in the range of 0.1 to 20% by weight, and 0.5 to 10% by weight. % Is preferred. The unit derived from the acid anhydride is
If the content is less than 0.1% by weight, the heat resistance and mechanical strength of the resin composition are undesirably reduced. On the other hand, if the content exceeds 20% by weight, the properties such as flexibility and moisture absorption resistance inherent to the polyethylene resin are impaired, and the cost is increased.

Other radically polymerizable comonomers (hereinafter referred to as third monomers) which can be used in combination with the above-mentioned radically polymerizable acid anhydrides include ethylenically unsaturated ester compounds, ethylenically unsaturated amide compounds, and ethylenically unsaturated amide compounds. Examples include unsaturated acid compounds, ethylenically unsaturated ether compounds, ethylenically unsaturated hydrocarbon compounds, and the like. Here, as the ethylenically unsaturated ester compound, for example, vinyl acetate, methyl (meth) acrylate [(meth)
Acrylic means acrylic and methacrylic. The same applies hereinafter), ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth) acryl Benzyl acid, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl maleate, ethyl maleate, propyl maleate,
Examples thereof include butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, and dibutyl maleate.

As the ethylenically unsaturated amide compound,
For example, (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 can be mentioned. Examples of the ethylenically unsaturated carboxylic acid compound include (meth) acrylic acid, maleic acid, fumaric acid, and the like. Further, as the ethylenically unsaturated ether compound,
For example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether,
Octadecyl vinyl ether, phenyl vinyl ether and the like can be mentioned. Examples of the ethylenically unsaturated hydrocarbon compound and other compounds include, for example, styrene, α-methylstyrene, norbornene, butadiene, acrylonitrile, methacrylonitrile, acrolein, crotonaldehyde, trimethoxyvinylsilane, triethoxyvinylsilane, vinyl chloride, and chloride. And vinylidene.

The above third monomer can be used in combination of two or more as necessary. When a third monomer is used in combination, the component concentration of the third monomer in the ethylene copolymer of the component (a) used in the present invention is preferably 40% by weight or less. If this concentration exceeds 40% by weight,
It is not preferable because the moldability is greatly reduced.

Further, the MFR (according to condition 4 in Table 1 of JIS-K7210) of the ethylene copolymer used in the present invention is preferably in the range of 0.1 to 1000 g / 10 minutes.
Outside this range, a resin composition meeting the purpose of the present invention cannot be obtained. Such an ethylene-based copolymer is in bulk,
Although it is produced by a polymerization method such as solution, suspension or emulsion, basically, ordinary low-density polyethylene production equipment and technology can be used. The most common is bulk polymerization, under pressures of 700-3000 atm.
It is produced by radical polymerization in a temperature range of up to 300 ° C. The preferred range of polymerization pressure and polymerization temperature is 10
00 to 2500 atm, average temperature in the reactor is 150 to 2
70 ° C. If the pressure is less than 700 atm, the molecular weight of the polymer becomes low, and the moldability and the resin properties of the composition deteriorate, which is not preferable. Pressures above 3000 atmospheres are substantially meaningless and are not preferred because they increase manufacturing costs. When the average polymerization temperature is lower than 100 ° C., the polymerization reaction is not stable, and the addition rate to the copolymer decreases, which is not economically preferable. On the other hand, if the temperature exceeds 300 ° C., the molecular weight of the copolymer decreases, and at the same time, the risk of a runaway reaction occurs.

As a production apparatus, it is preferable to use a vessel type reactor. In particular, radical polymerizable acid anhydrides have poor polymerization stability, and therefore, the inside of the reactor needs to be highly uniform. If necessary, a plurality of reactors can be connected in series or in parallel to carry out multistage polymerization. Further, by dividing the inside of the reactor into a plurality of zones, more precise temperature control can be performed.

The polyhydric alcohol compound having two or more hydroxyl groups in the molecule as component (b) is not particularly limited, and various compounds can be used. For example, glycols such as ethylene glycol, diethylene glycol, and triethylene glycol;
1,4-butanediol, 1,6-hexanediol,
1,8-octanediol, 1,10-decanediol, trimethylolethane, trimethylolpropane,
Alcohol compounds such as pentaerythritol; saccharides such as albitol, sorbitol, xylose, arabinose, glucose, galactose, sorbose, fructose, palatinose, maltotriose, and mariezitose;
Saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyolefin oligomer having a plurality of hydroxyl groups, ethylene-hydroxyethyl (meth) acrylate [(meth) acrylate means methacrylate and acrylate. The same applies to the following.) There are polymers having a plurality of hydroxyl groups in the molecule such as copolymers.

The polyhydric alcohol compound usable as the component (b) further includes the following general formula (I) or (I)
I) (R) _a C (CH ₂ OH) _b (I) wherein R represents hydrogen, a linear or cyclic alkyl group having 1 to 12 carbon atoms or an aralkyl group, and a represents 0 to 2
B represents an integer of 2 to 4, and a + b =
4 is selected. ]

Embedded image [In the formula, n is an integer of 0 to 10. A polyoxyalkylene compound having a structure in which ethylene oxide or propylene oxide is added to the polyhydric alcohol represented by the formula (1). More specifically, these polyoxyalkylene compounds include 1,3-dihydroxypropane; 2,2-dimethyl-1,3-dihydroxypropane; trimethylolethane; 1,1,1-trimethylolpropane; 1,1-trimethylolhexane;
1,1,1-trimethyloldodecane; 2-cyclohexyl-2-methylol-1,3-dihydroxypropane; 2- (p-methylphenyl) -2-methylol-
1,3-dihydroxypropane; pentaerythritol,
Polyoxyalkylene compounds obtained by adding ethylene oxide or propylene oxide to glycerin, diglycerin, hexaglycerin, octaglycerin, decaglycerin, or the like.

Further, as the component (b), a general formula (III) R ¹ —COOH (III) wherein R ¹ represents a linear or cyclic alkyl group or aralkyl group having 2 to 25 carbon atoms. . And a polyglycerol ester having two or more hydroxyl groups in the molecule, which is obtained by dehydration-condensation of the organic carboxylic acid compound represented by the general formula (II) and the polyglycerin represented by the general formula (II). Specific examples of such polyglycerin esters include glycerin monostearate, glycerin monooleate, glycerin monolaurate, glycerin monocaprylate, glycerin monohexanoate, glycerin monophenethyl ester, glycerin monopropionate, Glycerin monostearate, diglycerin distearate, diglycerin monooleate, diglycerin monohexanoate, diglycerin dioctanoate, tetraglycerin monostearate,
Tetraglycerin tristearate, tetraglycerin tetrastearate, tetraglycerin trihexanoate, tetraglycerin monophenethyl ester, hexaglycerin monostearate, hexaglycerin distearate, hexaglycerin pentastearate, hexaglycerin trioleate, hexaglycerin Monolaurate, hexaglycerin pentalaurate, decaglycerin monostearate, decaglycerin octastearate, decaglycerin pentaoleate, decaglycerin dilaurate, pentadecaglycerin distearate, pentadecaglycerin decaoleate, octadecaglycerin tetra And polyglycerin alkyl esters such as stearate.

Still other polyhydric alcohol compounds include, for example, sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan monocaprylate, sorbitan monohexanoate,
And sorbitan alkyl esters such as sorbitan monophenethyl ester, sorbitan monopropionate, sorbitan tristearate, and sorbitan tetrastearate.

The melting point of the polyhydric alcohol compound used as the component (b) is desirably 300 ° C. or lower.
Two or more of the above polyhydric alcohol compounds may be used in combination. Among the above polyhydric alcohol compounds, a polyoxyalkylene compound is particularly preferably used. The amount of the polyhydric alcohol compound used as the component (b) is
The molar ratio of the hydroxyl group contained in the polyhydric alcohol compound to the unit derived from the unsaturated carboxylic acid anhydride contained in the ethylene copolymer of the component (a) is in the range of 0.01 to 10. Is required, and is preferably in the range of 0.05 to 5. If the molar ratio is less than 0.01, it is insufficient to introduce a crosslinked structure into the composition in an effective amount, and if it exceeds 10, it is meaningless in that the crosslinked structure is effectively introduced. In addition, it is not preferable because the cost increases.

The reaction accelerator of the component (c) of the resin composition refers to a compound which activates a carbonyl group contained in a unit derived from an unsaturated carboxylic acid anhydride contained in an ethylene copolymer, and forms a hydroxyl group and an acid anhydride. It is a compound that promotes the reaction with the basic group. There are various types of such reaction accelerators. One example is a metal salt of an organic carboxylic acid. As the metal salt of the organic carboxylic acid, one having 1 carbon atom
Metal salts of up to 30 fatty acids, such as acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like, and the genus IA, IIA of the periodic table Genus, genus IIB, IIIB
Metals (eg, Li, Na, K, Mg, Ca, Z)
n, Al, etc.). More specific examples include lithium acetate, sodium acetate, magnesium acetate, aluminum acetate, potassium butyrate, calcium butyrate, zinc butyrate, sodium octanoate, calcium octanoate, potassium decanoate, magnesium decanoate, zinc decanoate, and lauric acid. Lithium, sodium laurate, calcium laurate, aluminum laurate,
Potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, sodium stearate, potassium stearate, calcium stearate, zinc stearate, sodium oleate,
And sodium behenate. Of these,
Lithium laurate, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, sodium stearate, potassium stearate, calcium stearate,
Zinc stearate, sodium oleate and the like are preferred.

Another example of a metal salt of an organic carboxylic acid is a resin having a metal salt structure of a carboxylic acid. Examples of such a resin include metals of Group IA, Group IIA, Group IIB and Group IIIB of ethylene and a radical polymerizable unsaturated carboxylic acid (eg, Li, Na, K, Mg, Ca, Zn, Al, etc.).
One having a structure in which a salt is copolymerized, or one having a structure in which ethylene and a metal salt of a radically polymerizable carboxylic acid and another radically polymerizable unsaturated carboxylic acid and / or a derivative thereof are multi-component copolymerized. .

Further, polyethylene, polypropylene,
A structure in which a metal salt of a radically polymerizable unsaturated carboxylic acid (a free unsaturated carboxylic acid may be polymerized and then neutralized) is graft-polymerized on a polyolefin resin such as a free ethylene-propylene copolymer. And those having a structure in which a metal salt of a radically polymerizable carboxylic acid and another radically polymerizable unsaturated carboxylic acid and / or a derivative thereof are simultaneously co-grafted and polymerized on a polyolefin resin. Examples of the radical polymerizable unsaturated carboxylic acid and derivatives thereof used herein include (meth) acrylic acid, maleic acid, fumaric acid, monomethyl maleate, monomethyl fumarate, monoethyl maleate, monoethyl fumarate, monobutyl maleate, fumarate Monobutyl acrylate, methyl (meth) acrylate, dimethyl maleate, dimethyl fumarate, diethyl maleate, diethyl fumarate, dibutyl maleate, dibutyl fumarate and the like can be mentioned.

Another example of the reaction accelerator used in the resin composition of the present invention is a tertiary amine compound. Specific examples of the tertiary amine compound used here include trimethylamine, triethylamine, triisopropylamine, trihexylamine, trioctylamine, trioctadecylamine, dimethylethylamine,
Methyldioctylamine, dimethyloctylamine, diethylcyclohexylamine, N, N-diethyl-4-
Methylcyclohexylamine, diethylcyclododecylamine, N, N-diethyl-1-adamantanamine, 1
-Methylpyrrolidine, 1-ethylpiperidine, quinuclidine, triphenylamine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-m
-Phenethazine, 4-t-butyl-N, N-dimethylaniline and the like.

Other examples of the reaction accelerator include quaternary ammonium salts. Examples of the quaternary ammonium salt used here include tetramethylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetramethylammonium bromide, tetraethylammonium bromide, tetraethylammonium iodide, methyltri-n-butylammonium chloride, Butylammonium bromide, tetrahexylammonium bromide, tetraheptylammonium bromide, phenyltrimethylammonium bromide, benzyltriethylammonium chloride and the like.

Further, a hydroxide of a metal belonging to Group IIA, IIB or IIIB or a halide of a metal belonging to Group IIA or IIB can be used as a reaction accelerator. Where IIA
Examples of the hydroxides of metals belonging to the genus, IIB and IIIB include calcium hydroxide, magnesium hydroxide and aluminum hydroxide, and the halides of metals belonging to the genus IIA and IIB include, for example, Examples include calcium chloride, calcium bromide, and magnesium chloride.

Further, oxo acids and genus IA, IIA, IIB
A salt of a metal belonging to the group IIIB can be used as the reaction accelerator. Specific examples thereof include aluminum nitrate, calcium nitrate, zinc nitrate, magnesium nitrate, aluminum nitrate, sodium phosphate, calcium phosphate, sodium carbonate, calcium carbonate, magnesium carbonate, sodium sulfate, zinc sulfate, magnesium sulfate, aluminum sulfate, and chloric acid. Sodium, potassium chlorate, sodium iodate and the like. In addition, Li BF ₄ , Na BF
_{4, KBF 4, Na PF 6} , KPF 6, Na PCl 6, N
a Fe Cl ₄ , Na Sn Cl ₄ , Na Sb F ₆ , KSb
Alkali metal salts of Lewis acids such as F ₆ , Na As F ₆ , and Na As Cl ₆ can also be used as the reaction accelerator.

Among the reaction accelerators exemplified above, metal salts of organic carboxylic acids are preferably used. In addition, two or more of the above various reaction accelerators can be used in combination as needed. The amount of these reaction accelerators used depends on the amount of component (a)
0.001 to 100 parts by weight of the ethylene copolymer
It is in the range of 20 parts by weight, more preferably in the range of 0.01 to 15 parts by weight. If this amount is less than 0.001 parts by weight,
The reaction becomes so slow that it is difficult to effectively introduce a crosslinked structure into the composition, and if it exceeds 20 parts by weight, it is not only meaningless in terms of improving the reaction rate, but also economically preferable. Absent.

The resin composition used in the present invention may contain various additives, compounding agents, fillers, etc. as long as the properties of the composition are not impaired. If these are concretely described, antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), glass fillers, etc. Inorganic fillers, organic fillers, reinforcing agents, coloring agents (dyes and pigments), foaming agents, fragrances and the like.

In order to produce the resin composition used in the present invention, the components (a) to (c) and additives used as necessary may be mixed by various means. As a mixing method, a generally known mixing method of various resins can be used. For example, dry blending may be performed using a mixer such as a Henschel mixer or a tumbler, or a Banbury mixer, a pressure kneader, or the like. A method of melt-kneading using a kneading machine such as an extruder and a roll mill may be mentioned. At this time, a uniform mixture can be obtained by dry-blending in advance and melt-kneading the resulting mixture. In addition, each component can be melt-mixed at the time of molding the resin composition. That is, the respective components can be mixed (dry-blended) in the form of pellets or powder, and can be melt-mixed by utilizing the stage of manufacturing a sheet or the like.

The resin composition is melt-kneaded and molded, but no crosslinked structure is formed during the molding process. Then, after this is formed into a sheet, a crosslinked structure is formed in the cooling and solidifying process, the cohesive force is increased, and the heat resistance and the mechanical strength are improved. Also, once a crosslinked structure is formed, it melts to dissociate this structure to restore moldability, and to form a crosslinked structure again in the cooling and solidifying process after newly forming, resulting in a high-strength sheet. . If an example of molding conditions is specifically shown, by setting the extruder and the die temperature so that the resin temperature becomes 200 ° C. or higher, the crosslinking in the composition is dissociated, and melt molding becomes possible. Then, at the time of cooling and solidification, the crosslinking reaction proceeds promptly due to the effect of the reaction accelerator, and a resin composition molded article having a crosslinked structure is obtained. Therefore, the strength of the resin is improved, and heat resistance is also provided.

The laminate of the present invention is obtained by extruding and extruding a sheet-shaped resin composition layer in a molten state by a T-die method from an extruder at about 200 to 250 ° C. with a polyethylene,
In a state of being laminated on a foam sheet of polyolefin or polyurethane such as polypropylene, by passing the resin composition layer to the embossing roll side, by passing between a pair of rolls such that the foam sheet is normally in contact with the roll side. Manufactured. As a result, the steps corresponding to the above-mentioned steps in the case of using soft polyvinyl chloride are greatly simplified, and a laminated body whose surface has been embossed can be manufactured in one step. That is, the laminate can be bonded to the foam sheet simultaneously with the embossing.

As foams of polyolefin or polyurethane, such as polyethylene and polypropylene, lined with a skin layer formed of the resin composition, foams cross-linked by radiation or electron beam are known.
These foams preferably have an expansion ratio of about 10 to 50 times when the laminate is used as an interior material for automobiles, vehicles, ships, and the like.

The thicknesses of the resin composition layer and the foam layer of the laminate of the present invention differ depending on the use of the molded laminate. For example, when the laminate is used as an interior material for automobiles, vehicles, ships, etc. Generally, the resin composition layer is about 0.1 to 2 mm,
The thickness of the foam layer is about 1 to 30 mm. Even in the case of the same automobile, the thickness of the skin layer is relatively thin for ceiling materials, and is relatively thick for dashboards, wheel house covers, various pillars, sheets and the like. Is used.

The laminate of the present invention can be used by further laminating with a substrate material. Specific examples of the substrate material include resin wood, plastic cardboard, resin felt, phenolic resin plate with glass, corrugated cardboard, and polypropylene honeycomb. , A polystyrene foam, a glass fiber reinforced polypropylene plate or a material obtained by bonding a nonwoven fabric to these plates.

[0033]

The resin composition constituting the laminate of the present invention is characterized by being flexible, having high strength, and having excellent heat resistance. This is an acid anhydride group contained in the ethylene-based copolymer,
It is considered that a hydroxyl group contained in the polyhydric alcohol compound reacts to introduce a crosslinked structure.

[0034]

Next, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited by these examples.

Example 1 10 g of MFR (condition 1 in Table 1 of JIS-K7210) using a high pressure polyethylene production facility having a tank type reactor.
/ 10 minutes, the unit derived from maleic anhydride is 3.0% by weight
Was produced from a copolymer of ethylene and maleic anhydride. The composition of the copolymer was determined by an infrared absorption spectrum. 94% by weight of this copolymer, propylene oxide (3.0 mol%) adduct of trimethylolpropane
1.0 wt% (hydroxyl group / acid anhydride group = 0.32) and MFR (condition 4 in Table 1 of JIS-K7210) as a metal salt of organic carboxylic acid 3.0 g / 10 min, density 0.94 g / cm ³ (Hereinafter abbreviated as metal salt (a)) (methacrylic acid content 1)
8% by weight and 5% by weight of a copolymer obtained by neutralizing about 10% of the methacrylic acid with sodium ions (metal atom / acid anhydride group = 0.30) were mixed. Upon mixing, the three components were dry-blended with a Henschel mixer, and then mixed for 30 minutes.
The mixture was melt-kneaded at 250 ° C. using a mmφ different direction twin-screw extruder and pelletized. MFR of composition (JIS-K72
The condition 14) in Table 1 for 10 was 3.2 g / 10 min.

This composition is described in JIS-K7113
A test piece molded at 250 ° C. was conditioned at 23 ° C. and 50% relative humidity for 24 hours in accordance with the method described above, and the tensile strength was measured. As a result, a breaking strength of 207 kg / cm ² was observed. Was 560%.

Separately, to measure the heat resistance of the resin composition, a single-layer sheet having a thickness of 30 μm was formed using a 25 mmφ extruder and a sheet forming machine having a 200 mm wide T-die. The single-layer sheet (Shore A 94) was placed in an oven at 120 ° C. for 1 hour, and the shrinkage was measured.
% Value.

Next, lamination of the resin composition and the foam was performed. Molding was performed using a 25 mmφ extruder and a sheet molding machine having a 200 mm wide T-die.
Extruded into a sheet at 5 ° C. and a take-up speed of 6 m / min. The extruded sheet-shaped resin composition layer in a molten state is crosslinked with a polypropylene crosslinked foam sheet (“Toray Pef-
PP (foaming ratio 30 times, thickness 3 mm), in a state of being laminated, the resin composition layer is passed through a pair of rolls that are configured to contact the embossing roll side and the foam sheet to the normal roll side, A laminate having a skin layer having a thickness of 30 μm was manufactured, and when the interlayer adhesion strength of the obtained laminate was measured in accordance with a 180-degree peel test of JIS-K6854, it was found that the foam layer was broken. When the laminate was placed in an oven at 120 ° C. for 2 hours, almost no deformation such as curling occurred, and when the laminate was placed in an oven at 150 ° C. for 1 hour, the grain shape was maintained. Was.

The composition of the resin composition is shown in Table 1. Abbreviations relating to the components of the composition mean the following substances. BA = Butyl acrylate MA = Methyl acrylate TP-30P = Propylene oxide adduct of trimethylolpropane PE-50E = Ethylene oxide adduct of pentaerythritol Metal salt (a) = Partially neutralized ethylene-methacrylic acid copolymer Metal Salt (b) = calcium stearate

The physical properties of the obtained laminate are shown in Table 2, and the shrinkage was measured by heating a single layer sheet of the resin composition at 120 ° C. for 1 hour. Further, the change in the heat-resistant appearance of the laminated body is such that the laminated body is heated at 120 ° C. for 1 hour, has almost no thermal deformation such as curl, and is heated at 150 ° C. for 1 hour, and the crimped shape is maintained. ○,
The case where the deformation is remarkable or the grain shape is lost is indicated by x.

Example 2 As an ethylene copolymer, ethylene-maleic anhydride-butyl acrylate (2.2% by weight of units derived from maleic anhydride, 1 unit derived from butyl acrylate)
4% by weight), a resin composition was prepared in the same manner as in Example 1, and a laminate was produced.
The measurement was performed in the same manner as described above. Table 1 shows the composition of the resin composition.
Table 2 shows the physical properties of the laminate.

Example 3 In the same manner as in Example 1 except that an ethylene oxide (5.0 mol) adduct of pentaerythritol (hydroxyl group / acid anhydride group = 0.55) was used as the polyhydric alcohol compound. A resin composition was prepared, a laminate was produced, and its physical properties were measured in the same manner as in Example 1. Table 1 shows the composition of the resin composition, and Table 2 shows the physical properties of the laminate.

Example 4 A resin composition was prepared and a laminate was prepared in the same manner as in Example 2 except that calcium stearate was used as the reaction accelerator, and the physical properties were measured in the same manner as in Example 1. did. Table 1 shows the composition of the resin composition and Table 2 shows the physical properties of the laminate.
It is shown in the table.

Example 5 As a foam layer, a crosslinked polyurethane sheet of polyurethane (“Sfranboard” manufactured by Toyo Tire & Rubber Co., Ltd., foaming ratio: 20 times,
A resin composition was prepared and a laminate was produced in the same manner as in Example 3 except that the thickness was 3 mm), and the physical properties were measured in the same manner as in Example 1. Table 1 shows the composition of the resin composition, and Table 2 shows the physical properties of the laminate.

Comparative Example 1 A resin composition was prepared and a laminate was prepared in the same manner as in Example 1 except that the polyhydric alcohol compound was not added, and the physical properties were measured in the same manner as in Example 1. Table 1 shows the composition of the resin composition, and Table 2 shows the physical properties of the laminate. The obtained laminate has poor heat resistance and is placed in an oven at 120 ° C. for 1 hour.
It melted over time and was not usable.

Comparative Example 2 A resin composition was prepared and a laminate was prepared in the same manner as in Example 1 except that no reaction accelerator was added, and the physical properties were measured in the same manner as in Example 1. Table 1 shows the composition of the resin composition, and Table 2 shows the physical properties of the laminate.

Comparative Example 3 A resin composition was prepared in the same manner as in Example 1 except that an ethylene-methyl acrylate binary copolymer was used as the ethylene copolymer, and a laminate was produced. Was measured in the same manner as in Example 1. The first composition of the resin composition
Table 2 shows the physical properties of the laminate.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

The laminate of the present invention can be easily manufactured with a small number of operation steps, and is excellent not only in lightness, flexibility, workability and adhesiveness, but also in the resin composition layer and foam used. Since the body layers are all excellent in heat resistance, the laminate as a whole is also excellent in heat resistance. Furthermore, since the used resin composition is thermoreversible crosslinkable, it can be recycled, and is excellent in cost reduction and environmental protection.
The laminate of the present invention has excellent properties such as light weight, flexibility, heat resistance and the like as described above, and is expected to be effectively used as an interior material for automobiles, vehicles, ships, and the like.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (6)

(57) [Claims] (A) (a) a copolymer containing ethylene and a radical polymerizable acid anhydride as constituent monomers, wherein the component concentration of the radical polymerizable acid anhydride group in the copolymer is
0.1 to 20% by weight of an ethylene copolymer, (b) a polyhydric alcohol compound having two or more hydroxyl groups in a molecule, and (c) a reaction accelerator, and a radical in the component (a). The molar ratio of the unit of the hydroxyl group in the polyhydric alcohol compound as the component (b) to the unit derived from the polymerizable acid anhydride is
Resin in the range of 0.01 to 10 and the reaction accelerator of the component (c) is in the range of 0.001 to 20 parts by weight based on 100 parts by weight of the ethylene copolymer of the component (a) A laminate comprising a composition layer and a (B) polyolefin or polyurethane foam layer. 2. The ethylene-based copolymer as the component (a) is a copolymer comprising ethylene, a radically polymerizable acid anhydride and another radically polymerizable comonomer, and the radically polymerizable acid in the copolymer. When the component concentration of the anhydride group is 0.1 to
The laminate according to claim 1, wherein the content is 20% by weight, and the concentration of the other radically polymerizable comonomer groups is 40% by weight or less. 3. The polyhydric alcohol compound of the component (b),
(I) or (II) (R) _a C (CH ₂ OH) _b (I) wherein R is hydrogen, a linear or cyclic alkyl group having 1 to 12 carbon atoms or an aralkyl group; And a is 0 to 2
B represents an integer of 2 to 4, and a + b =
4 is selected. [Formula 1] [In the formula, n is an integer of 0 to 10. A polyoxyalkylene compound having a structure in which ethylene oxide or propylene oxide is added to a polyhydric alcohol compound represented by the following general formula (III): R ¹ —COOH (III) wherein R ¹ is a group having 2 to 25 carbon atoms. Represents a chain or cyclic alkyl group or aralkyl group. One of the polyglycerol esters having two or more hydroxyl groups in the molecule, which are obtained by dehydration-condensation of the organic carboxylic acid compound represented by the general formula (II) and the polyglycerin represented by the general formula (II).
The laminate according to claim 1, which is at least one kind. 4. The laminate according to claim 1, wherein the reaction accelerator of the component (c) is a metal salt of a polymer containing a carboxyl group or a metal salt of an organic carboxylic acid. 5. The resin composition layer according to claim 1, wherein said resin composition layer has a cross-linked structure in a cooling step during melt molding.
The laminate according to any one of the above. 6. The laminate according to claim 1, wherein the foam layer is a layer formed from a crosslinked foam.