JP2000127304A - Laminate and manufacture of interior finishing material using it and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recyclable laminate having a light weight and a high heat resistance by using a base material made of a fiber material containing a specific crosslinkable resin composition. SOLUTION: An ethylene copolymer of a crosslinkable resin composition is a copolymer of an ethylene and a radical polymerizable acid anhydride. In the copolymer, a ratio of a unit caused by the radical polymerizable acid anhydride is 0.1 to 20 wt.%. A molar ratio of a hydroxyl group caused by a polyhydric alcohol compound having at least two or above hydroxyl groups in a molecule is set to 0.01 to 10. In this case, as a reaction accelerator, a metallic salt of the like of an organic carboxylic acid is used. Its using amount is 0.001 to 20 pts.wt. to 100 pts.wt. of the ethylene copolymer. This laminate comprises a fiber material layer made of 5 to 100 wt.% of a fiber material containing a crosslinkable resin composition and 0 to 95 wt.% of other fiber material and an another material layer, wherein the another fiber material is a polyethylene or the like and the another material layer is a base material or the like for an interior finishing material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having a fiber material layer using a fiber material containing a crosslinkable resin composition and another material layer, an interior material using the same, and a method of manufacturing the laminate. More particularly, the present invention relates to a lightweight, excellent rigidity, high heat resistance, recyclable laminate and a method for producing the same, and an interior material using the laminate.

[0002]

2. Description of the Related Art Hitherto, as an automotive interior material, a laminate having a structure in which a skin material or the like for obtaining a good appearance is bonded to a highly rigid base material is often used. Here, as the base material, resin felt in which various fibers are hardened with a phenol resin, a board in which wood powder is hardened with a resin, cardboard, and the like are often used. However, these base materials have poor thermoplasticity or are thermosetting, so that they are difficult to recycle, and have to be disposed of as shredder dust upon disposal.

In recent years, relatively high-melting fibers such as polypropylene and polyester have been replaced with relatively low-melting binder resins such as low-density polyethylene, high-density polyethylene, and low-melting polyester in order to ensure recyclability and reduce weight. A sheet-like base material that has been bonded and solidified is proposed. Since all of these components are made of a thermoplastic resin, these substrates have the characteristic that they can be heated and melted and can be recycled. However, at a temperature exceeding the softening point or melting point of the binder resin, for example, at a high temperature (about 80 ° C.) such as the temperature in a car under hot summer sun, the binder resin of the base material softens or melts, and the rigidity and shape of the laminate are reduced. There have been problems such as a remarkable decrease in retention and delamination.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a light-weight, good rigidity, high heat-resistant, recyclable laminate, an interior material using the laminate, and a method for producing the laminate. To provide.

[0005]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific ethylene-based copolymer, a polyhydric alcohol having two or more hydroxyl groups in the molecule. By using a substrate made of a fibrous material containing a compound and a crosslinkable resin composition made of a reaction accelerator, it is possible to obtain a lightweight, good rigidity, high heat resistance, and recyclable laminate. And completed the present invention.

That is, the laminate of the present invention comprises (a) an ethylene copolymer having ethylene and a radical polymerizable acid anhydride as essential components, and (b) a polyhydric alcohol having two or more hydroxyl groups in a molecule. A ratio of units derived from a radical polymerizable acid anhydride in the (a) ethylene-based copolymer, which comprises a compound and (c) a reaction accelerator, is 0.1 to 2;
0% by weight, the molar ratio of the hydroxyl group derived from the polyhydric alcohol compound (b) to the acid anhydride group (a) in the ethylene copolymer is in the range of 0.01 to 10, and (c) 5 to 100% by weight of a fiber material (I) containing a crosslinkable resin composition in which the reaction accelerator is in the range of 0.001 to 20 parts by weight per 100 parts by weight of the ethylene-based copolymer, and other It is characterized by having a fiber material layer composed of 0 to 95% by weight of the fiber material (II) and another material layer. Also,
Part or all of the fiber material (I) is a fiber material composed of multi-layered composite fibers, and at least one of the multi-layered composite fibers contains the crosslinkable resin composition. Good. Further, some or all of the composite fibers of the multilayer structure may be fibers having a core portion and a sheath portion covering the core portion, and the sheath portion may include a crosslinkable resin composition. .

In the laminate of the present invention, it is preferable that the fiber material layer is a layer formed by heating and pressing. Further, an interior material of the present invention is characterized by using the laminate. Further, the method for producing a laminate according to the present invention comprises the steps of: mixing 5 to 100% by weight of the fiber material (I) containing the crosslinkable resin composition with 0 to 95% by weight of another fiber material (II); After passing through at least one of the steps of lamination, another material layer is laminated thereon, and these are then subjected to heat and pressure molding.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The crosslinkable resin composition of the present invention not only has excellent adhesiveness, but also has excellent moldability without forming a crosslinked structure during thermoforming, and quickly forms a crosslinked structure in a cooling step after molding. The feature is that physical properties such as heat resistance and strength are greatly improved. Therefore, by using a fiber material layer containing a fiber material of this crosslinkable resin composition,
The obtained laminate can exhibit excellent heat resistance, rigidity, and the like.

[0009] The (a) of the crosslinkable resin composition of the present invention
The ethylene-based copolymer is a copolymer of ethylene and a radically polymerizable acid anhydride, and may be a multi-component copolymer containing another radically polymerizable comonomer component as needed. (A) Examples of the radical polymerizable acid anhydride used in the ethylene copolymer include maleic anhydride, itaconic anhydride, endic anhydride, citraconic anhydride, 1-
Butene-3,4-dicarboxylic anhydride, alkenyl succinic anhydride having at most 18 carbon atoms at the terminal having a double bond, alkadienyl succinic anhydride having at most 18 carbon atoms at the terminal. And the like. These may be used in combination of two or more. Among them, maleic anhydride and itaconic anhydride are preferably used in terms of reactivity and economy.

(A) In the ethylene copolymer, the ratio of units derived from the radically polymerizable acid anhydride is 0.1 to 0.1%.
It is in the range of 20% by weight, preferably in the range of 1 to 10% by weight. If the ratio of the unit derived from the radical polymerizable acid anhydride is less than 0.1% by weight, crosslinking becomes insufficient, and the heat resistance and rigidity of the obtained laminate are poor, which is not preferable.
On the other hand, if the content exceeds 20% by weight, the properties such as flexibility and moisture absorption resistance inherent to ordinary polyethylene resins are impaired.
It is not preferable because it is difficult to commercially manufacture and the cost increases.

Other radically polymerizable comonomers that can be used in combination with the above-mentioned radically polymerizable acid anhydrides include, for example, ethylenically unsaturated ester compounds, ethylenically unsaturated amide compounds, ethylenically unsaturated acid compounds, and ethylenically unsaturated acid compounds. Examples thereof include unsaturated ether compounds and ethylenically unsaturated hydrocarbon compounds.

Specific examples of the ethylenically unsaturated ester compound include vinyl acetate, methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, fumar Methyl ester, ethyl fumarate, propyl fumarate, butyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl maleate,
Examples thereof include ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, and dibutyl maleate.

Specific examples of the ethylenically unsaturated amide compound include (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. Specific examples of the ethylenically unsaturated acid compound include (meth) acrylic acid, maleic acid, fumaric acid, and the like.

Specific examples of the ethylenically unsaturated ether compound include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether,
Octadecyl vinyl ether, phenyl vinyl ether and the like can be mentioned. Specific examples of the ethylenically unsaturated hydrocarbon compound and other compounds include styrene,
Examples thereof include α-methylstyrene, norbornene, butadiene, acrylonitrile, methacrylonitrile, acrolein, crotonaldehyde, trimethoxyvinylsilane, triethoxyvinylsilane, vinyl chloride, and vinylidene chloride. These other radically polymerizable comonomers may be used in combination of two or more as needed.

When the other radically polymerizable comonomer is used in combination, the content of the radically polymerizable comonomer component in (a) the ethylene copolymer is preferably 40% by weight or less. If it exceeds 40% by weight, the moldability is greatly reduced, and the melting point of (a) the ethylene copolymer is too low, so that practical heat resistance cannot be achieved.

(A) MFR of ethylene copolymer (JI
SK-7210 according to condition 4 in Table 1)
A range of 1000 g / 10 minutes is preferred. (A) When the MFR of the ethylene-based copolymer exceeds 1000 g / 10 minutes,
The resulting laminate has insufficient heat resistance and rigidity. (A)
If the MFR of the ethylene-based copolymer is less than 0.1 g / 10 minutes, the formability (draw-down property) during spinning will be poor.

(A) The ethylene copolymer is produced by a generally known polymerization method, for example, a polymerization process such as bulk, solution, suspension, or emulsion. Manufacturing equipment and technology can be used. The most common polymerization method is bulk polymerization, which is performed under a pressure of 700 to 3000 atm.
It is produced by radical polymerization in a temperature range of 300 ° C. The preferred range of polymerization pressure and polymerization temperature is 1
2,000-2,500 atm, average temperature in reactor is 150-
270 ° C. If the pressure is 700 atm or less, the molecular weight of the polymer becomes low, and the moldability and the resin properties of the composition deteriorate, which is not preferable. Pressures of 3000 atmospheres or more are practically meaningless and are not preferred because they increase manufacturing costs. When the average polymerization temperature is 100 ° C. or lower, the polymerization reaction is not stable, and the conversion into a copolymer is lowered, which is not economically preferable. 300
Exceeding the temperature is not preferred because the molecular weight of the copolymer decreases and the risk of runaway reaction arises.

It is desirable to use a vessel type reactor as the production apparatus. In particular, radically polymerizable acid anhydrides have poor polymerization stability, so the inside of the reactor needs to be highly uniform. Further, 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.

(A) The production of the ethylene copolymer is carried out under the above reaction conditions in the presence of at least one free radical initiator. As free radical initiators,
For example, oxygen; dialkyl peroxides such as di-t-butyl peroxide and t-butyl cumyl peroxide dicumyl peroxide; diacyl peroxides such as acetyl peroxide, i-butyl peroxide and octanoyl peroxide; Peroxycarbonates such as i-propylperoxycarbonate and di-2-ethylhexylperoxycarbonate; Peroxyesters such as t-butylperoxypivalate and t-butylperoxylaurate; methyl ethyl ketone peroxide and cyclohexanone peroxide Ketone peroxides such as;
1,1-bis-t-butylperoxycyclohexane,
Peroxy ketals such as 2,2-bis-t-butylperoxyoctane; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide;
And azo compounds such as -azo-i-butyronitrile.

In the polymerization, various chain transfer agents can be used as molecular weight regulators. 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 the like.

(B) Polyhydric alcohol compounds having at least two hydroxyl groups in the molecule (hereinafter referred to as (b) polyhydric alcohol compounds) include, for example, glycols such as ethylene glycol, diethylene glycol and triethylene glycol; 1,4-butanediol, 1,6-
Hexanediol, 1,8-octanediol, 1,1
Alcohol compounds such as 0-decanediol, trimethylolethane, trimethylolpropane, and pentaerythritol; albitol, sorbitol, xylose, arabinose, glucose, galactose, sorbose,
Saccharides such as fructose, palatinose, maltotriose, and mariezitose; saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyolefin-based oligomer having a plurality of hydroxyl groups, and hydroxyl groups such as ethylene-hydroxyethyl (meth) acrylate copolymer. And the like. (B) The melting point of the polyhydric alcohol compound is preferably 300 ° C. or lower from the viewpoint of easy mixing with the ethylene copolymer. Further, two or more of these polyhydric alcohol compounds may be used at the same time.

(B) The amount of the polyhydric alcohol compound used is
(A) The molar ratio of the hydroxyl group derived from the polyhydric alcohol compound to the acid anhydride group derived from the radical polymerizable acid anhydride of the ethylene copolymer is in the range of 0.01 to 10, more preferably It is in the range of 0.05 to 5 or less. If the molar ratio is less than 0.01, crosslinking is insufficient, and the desired heat resistance and rigidity cannot be obtained. Molar ratio of 10
Exceeding the range is not preferred because the crosslinked structure is not completely dissociated when molding at a high temperature and molding becomes extremely difficult.

(C) A reaction accelerator is used to activate (a) a carbonyl group contained in a unit derived from a radical polymerizable acid anhydride in an ethylene-based copolymer and to react a hydroxyl group with an acid anhydride group. Is a compound that promotes Such (c)
Examples of the reaction accelerator include metal salts of organic carboxylic acids.

Examples of the metal salts of organic carboxylic acids include acetic acid, butyric acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid, which are fatty acids having 1 to 30 carbon atoms. And the like, and metal salts (for example, Li, Na, K, Mg, Ca, Zn, Al, etc.) of metals belonging to IA, IIA, IIB, and IIIB of the periodic table. Specifically, lithium acetate, sodium acetate, magnesium acetate, aluminum acetate, potassium butyrate, calcium butyrate, zinc butyrate, sodium octanoate, calcium octanoate, potassium decanoate, magnesium decanoate, zinc decanoate, 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, Examples thereof include sodium oleate sulfate and sodium behenate.

Among them, lithium laurate, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, sodium stearate, stearic acid Potassium, calcium stearate, zinc stearate, and sodium oleate sulfate are preferably used.

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, IIA, IIB, and IIIB of ethylene and a radical polymerizable unsaturated carboxylic acid (eg, Li, Na, K, Mg, Ca, Zn, Al, etc.).
And those having a structure in which ethylene and a metal salt of the radically polymerizable carboxylic acid and another radically polymerizable unsaturated carboxylic acid and / or a derivative thereof are multiply copolymerized. Can be Further, those having a structure in which a metal salt of the radically polymerizable carboxylic acid is graft-polymerized on a polyolefin-based resin such as polyethylene, polypropylene, and ethylene-propylene copolymer; Examples thereof include those having a structure in which a salt and another radically polymerizable unsaturated carboxylic acid and / or a derivative thereof are simultaneously co-grafted and polymerized.

The radically polymerizable unsaturated carboxylic acids and derivatives thereof used herein include, for example, (meth)
Acrylic acid, maleic acid, fumaric acid, monomethyl maleate, monomethyl fumarate, monoethyl maleate, monoethyl fumarate, monobutyl maleate, monobutyl fumarate, methyl (meth) acrylate, dimethyl maleate, dimethyl fumarate, maleic acid Examples thereof include diethyl, diethyl fumarate, dibutyl maleate, and dibutyl fumarate.

(C) Another example of the reaction accelerator 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-phenetidine, 4-
t-butyl-N, N-dimethylaniline and the like.

Another example of the reaction accelerator (c) is a quaternary ammonium salt. Specific examples of the quaternary ammonium salt used here include tetramethylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetramethylammonium bromide, tetraethylammonium bromide, tetraethylammonium iodide, methyltri-n-butylammonium chloride, Examples include tetrabutylammonium bromide, tetrahexylammonium bromide, tetraheptylammonium bromide, phenyltrimethylammonium bromide, and benzyltriethylammonium chloride.

Further, other examples of the reaction accelerator (c) include hydroxides of metals belonging to Group IIA, IIB and IIIB. Specific examples include calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. Further, another example of (c) the reaction accelerator is IIA
And metal halides belonging to the genus IIB. Specific 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 or IIIB can be mentioned as another example of the reaction accelerator (c). Specific examples thereof include sodium 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,
And sodium iodate.

Further, LiBF ₄ , NaBF ₄ , KB
_{F 4, NaPF 6, KPF 6} , NaPCl 6, KPCl
₆ , NaFeCl ₄ , NaSnCl ₄ , NaSbF ₆ ,
Alkali metal salts of Lewis acids such as KSbF ₆ , NaAsF ₆ and KAsCl ₆ can also be mentioned as other examples of the (c) reaction accelerator. Among the (c) reaction accelerators exemplified above, a metal salt of an organic carboxylic acid is preferably used in terms of ease of handling and economy. Further, the reaction accelerator (c) exemplified above may be used in combination of two or more if necessary.

(C) The amount of the reaction accelerator used is in the range of 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, based on 100 parts by weight of the ethylene copolymer (a). is there. If the amount is less than 0.001 part by weight, the reaction becomes too slow and it becomes difficult to effectively introduce a crosslinked structure into the crosslinkable resin composition. On the other hand, if the amount exceeds 20 parts by weight, it is not only meaningless in terms of improving the reaction rate but also economically unfavorable.

The acid anhydride group contained in (a) the ethylene copolymer reacts with the hydroxyl group contained in (b) the polyhydric alcohol compound to form a monoester. It is considered that a crosslinked structure is introduced into the crosslinkable resin composition by this reaction. In a crosslinkable resin composition containing two components of (a) an ethylene-based copolymer containing an acid anhydride group and (b) a polyhydric alcohol compound, the crosslinked structure is dissociated at a high temperature by only these two components, and again upon cooling. Shows properties as a so-called thermo-reversible cross-linkable resin that forms a cross-linked structure. However, since the cross-linking reaction rate and cross-linking dissociation reaction rate are slow, sufficient performance cannot be exhibited under general thermoforming conditions. .

However, by adding the reaction accelerator (c), the rate of the cross-linking reaction or the rate of the cross-linking dissociation reaction can be increased, and a practically usable form can be obtained. This is because (c) the metal ion of the metal salt of the organic carboxylic acid in the reaction accelerator is (a) the acid anhydride group contained in the ethylene copolymer and (b) the hydroxyl group in the polyhydric alcohol compound. To increase the equilibrium reaction rate of
(C) The addition of a reaction accelerator provides, for the first time, a thermoreversible crosslinkable resin composition which exhibits sufficient physical properties even under general thermoforming conditions.

In the crosslinkable resin composition of the present invention, various additives, compounding agents and fillers can be used as long as the characteristics of the composition are not impaired. If these are concretely shown, an antioxidant (heat stabilizer), an ultraviolet absorber (light stabilizer), an antistatic agent, a tackifier, an antifogging agent, a flame retardant, a lubricant (slip agent, antiblocking agent) , Coloring agents (dyes and pigments), fragrances and the like.

The crosslinkable resin composition of the present invention can be used by blending it with another thermoplastic resin as long as the characteristics of the composition are not impaired. And a polyolefin-based resin is preferred. Examples of the polyolefin-based resin include polyethylene copolymers such as ultra-low density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene; ethylene-propylene copolymer rubber, ethylene -Olefin rubbers such as propylene-diene copolymer rubber and ethylene-butene-1 copolymer rubber; ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer; ethylene-acrylic acid alkyl ester copolymer , Ethylene-based copolymers such as copolymers with ethylene-α, β-carboxylic acid or a derivative thereof such as ethylene-alkyl methacrylate copolymer; polypropylene-based polymers such as polypropylene and propylene-ethylene copolymer; Polybutene polymers and the like can be mentioned. The other thermoplastic resin is used by being blended in a range of 50% by weight or less, preferably 30% by weight or less based on the crosslinkable resin composition. If the amount of the other thermoplastic resin exceeds 50% by weight, heat resistance is undesirably reduced.

As the method for producing the crosslinkable resin composition in the present invention, a generally known method of mixing various resins can be used. If a specific method is illustrated, a method of mixing each component in a molten state, that is, a method using a generally used pressure kneader, a roll, a Banbury mixer, a static mixer, a screw extruder, or the like can be mentioned. .

The laminate of the present invention comprises a fiber material layer comprising 5 to 100% by weight of the fiber material (I) containing the crosslinkable resin composition and 0 to 95% by weight of the other fiber material (II). It is a laminate having a material layer. Further, as the fibrous material layer, fibrous materials (I) 5 to 1 containing the crosslinkable resin composition may be used.
It is preferable that 00% by weight and 0 to 95% by weight of the other fiber material (II) are heated and pressed to melt and solidify a part or all of the crosslinkable resin composition in terms of excellent rigidity. . When the proportion of the fiber material (I) containing the crosslinkable resin composition is less than 5% by weight, the amount of the crosslinkable resin composition as a binder resin is insufficient, and the heat resistance and rigidity of the finally obtained laminate are reduced. Is not preferred because physical properties such as

The fibrous material layer only needs to use the fibrous material (I) containing the crosslinkable resin composition, and its shape and form are not particularly limited. Examples of the form of the fibrous material layer include a nonwoven fabric, a web, a primary molding mat in which the web is softened by a method such as needle punching, and a web in which another nonwoven fabric such as spunbond is laminated on the surface of the web.
A sheet formed by heating and compressing the primary molding mat again with a hot press and shaping the primary molding mat can be used.

The fibrous material (I) or other fibrous material (II) containing the crosslinkable resin composition used for the fibrous material layer is as follows:
Fibers or other fibers containing the crosslinkable resin composition, staples obtained from these fibers, webs, nonwoven fabrics, processed products such as mats, or sheets made thereof,
It includes products such as fabric and paper. The staple is formed by crimping or cutting a fiber containing a crosslinkable resin composition or another fiber, and the web is formed by a known carding method, an air lay method, a dry pulp method, or a wet staple method. It is processed into a sheet by the papermaking method.

The fiber containing the crosslinkable resin composition (hereinafter referred to as “fiber”)
Fiber (1) is obtained by spinning a crosslinkable resin composition by a known melt spinning method, and is a fibrillation in which a film made of the crosslinkable resin composition is fibrillated in a longitudinal direction. Thread etc. are also included. The single fiber fineness and the number of crimps of the fiber (1) used in the fiber material (I) containing the crosslinkable resin composition are not particularly limited, but the single fiber fineness is 0.1%.
It is preferably used in the range of 1 to 600 denier, 100 to 500 denier for monofilament use, 4 to 50 denier for multi-staple use, and 0.2 to 1.0 denier for melt blow use. However, in the case of a very thick multifilament, 600 to 10
It may be formed in the range of 000 denier, and may be formed in the range of 0.01 to 0.1 denier in ultra-fine melt blow molding. Therefore, the fiber (1) in the present invention is not substantially limited in thickness as long as various properties such as heat resistance can be utilized. Further, in the case of crimping, the number of crimps is preferably about 1 to 40 peaks / 25 mm.

Examples of other fibers used for the fiber material (I) containing the crosslinkable resin composition include a composite fiber having a multilayer structure and containing at least one layer of the crosslinkable resin composition. No. Usually, examples of the composite fiber having a multilayer structure include fibers having a parallel structure or a core-sheath structure. The side-by-side fiber has a configuration in which two or more resins having different melting points (low-melting resin and high-melting resin) are combined in parallel. With such a configuration, at the time of forming the molded body by heating, it is possible to thermally fuse a fiber made of a high melting point resin with a low melting point resin. Similarly, in the case of a core-sheath fiber, a fiber made of a resin having a high melting point in the core portion can be heat-sealed with a resin having a low melting point as a sheath component when the molded body is formed by heating. In the present invention, the crosslinkable resin composition is used as a resin having a low melting point in a parallel type fiber, and in a sheath portion in a core-sheath fiber. Further, a fiber material composed of a composite fiber having a multilayer structure such as the core-sheath fiber and a fiber material composed of the fiber (1) may be mixed and used in an arbitrary ratio according to the purpose. Moreover, you may mix and use a parallel type fiber and a core-sheath fiber in arbitrary ratios according to the objective.

Various materials can be used for the core portion (in the case of side-by-side fibers, the resin on the high melting point side) depending on the purpose. Examples of the material used for the core include polyethylene, polypropylene, copolymers of propylene and α-olefin, organic materials such as polyester, polyamide, acrylic, cellulose, rayon, acetate, and polyurethane; glass fiber, carbon fiber, and asbestos And inorganic fibers such as cotton, flax, silk, wool and the like. Among them, a thermoplastic resin is preferable because it is easy to recycle, and polypropylene, polyester, polyamide and the like are particularly preferable.

The composite fiber having such a multilayer structure is
Spinning can be performed by a known method. For example, the core-sheath fiber is filled into two extruders each heated to a predetermined temperature for the core portion and the sheath portion resin, and extruded from a two-layer nozzle,
After spinning the conjugate fiber and cooling it at a predetermined temperature, the core-sheath fiber can be produced by stretching it at a predetermined magnification in hot water at a predetermined temperature and winding it up, if necessary. When using the already spun fiber as the core portion, supply the thread-like core portion from the center discharge hole of the die, extrude and coat the resin for the sheath portion, and perform a stretching process or the like as necessary to perform the core process. Sheath fibers can be produced. There are no particular restrictions on the single-fiber fineness or the number of crimps of the core-sheath fiber, but the single-fiber fineness is preferably about 4 to 50 denier, and the number of crimps is preferably about 1 to 40 ridges / 25 mm.

The other fiber used in the other fiber material (II) is not particularly limited as long as it satisfies the required physical properties of the intended use, but is generally polyethylene, polypropylene, propylene and α-. Fibers of organic materials such as olefin copolymers, polyesters, polyamides, acrylics, cellulose, rayon, acetate, and polyurethane; inorganic fibers such as glass fibers, carbon fibers, and asbestos; and natural materials such as cotton, flax, silk, and wool Fibers and the like can be mentioned. Among them, a fiber made of a thermoplastic resin is preferable because it is easily recycled. By using such other fibrous material (II) or a fibrous material composed of multi-layered composite fibers, the fibrous material layer after heating and press molding remains in a fibrous state. The rigidity and heat resistance of the material layer and the laminate can be further improved.

The method for producing the fibrous material layer is not particularly limited, but the fibrous material (I) containing the crosslinkable resin composition alone or the fibrous material (I) containing the crosslinkable resin composition and other materials may be used. After at least one of the steps of mixing, papermaking, and laminating with the fibrous material (II), heat and pressure molding is performed to melt and solidify part or all of the crosslinkable resin composition. It is preferable because of its excellent rigidity. For example, a web made of a fiber material (I) containing a crosslinkable resin composition or a mixture of a fiber material (I) containing a crosslinkable resin composition and another fiber material (II) is processed by a method such as needle punching. Then, a flexible primary molding mat is formed, and then the primary molding mat is heated and compressed again by a hot press to form a rigid sheet-like molded body.

This flexible primary molding mat has a bulk density of about 0.05 to 0.3 g / cm ³ and a thickness of 10 to 30 mm.
Position is preferred. Further, as the primary forming mat, a material obtained by laminating a nonwoven fabric made of another fiber such as a spun bond on the surface of a web can be used. The material of the spun bond is not particularly limited, but polypropylene, polyester, polyamide and the like are preferable. The primary molding mat has advantages such as not only facilitating the handling until the next shaping, but also suppressing the bulkiness of the raw material fibers and saving the storage space by winding them in a roll shape.

The other material layers in the laminate of the present invention are not particularly limited, and include, for example, skin materials and substrate materials used for interior materials of automobiles and the like. Examples of the other material include, but are not particularly limited to, various papers such as synthetic paper, art paper, and coated paper; various woven or non-woven fabrics such as cotton, hemp, polyester, and nylon; plywood, particle board, and the like. Various wooden boards; various metals such as iron, aluminum, copper, and tinplate; polypropylene,
Various plastics such as polystyrene, polyethylene, polyester, nylon, polycarbonate, acrylic resin, phenol resin, polyurethane, styrene-butadiene block copolymer, styrene-acrylonitrile copolymer; various inorganic substances such as glass fiber and ceramic; Can be.

As the skin material, various skin materials generally used as materials for interior materials of automobiles and the like can be used, and there is no particular limitation. Specifically, polyester nonwoven fabric, brushed knit, fabric, suede-like synthetic leather, vinyl chloride leather, polyurethane leather, polypropylene-based thermoplastic elastomer, or a cushion material such as urethane foam, polyethylene foam, polypropylene foam, etc. And the like.

Specific examples of the substrate material include resin felt, resin wood, phenol resin plate containing glass fiber, corrugated cardboard, polypropylene honeycomb, polystyrene foam, glass fiber reinforced polypropylene plate, ABS resin plate, AS resin plate, and the like. What bonded a nonwoven fabric etc. is mentioned. These substrate materials may be subjected to surface treatment, printing, coating, etc., as necessary.

In manufacturing the laminate of the present invention,
Although various molding methods can be adopted, the method of laminating the fibrous material layer and another material layer, and pressurizing and heat-forming the adhesiveness between the fibrous material layer and the other material layer, and It is suitably used in that the rigidity and the like of the laminate are excellent. In addition, the fiber material (I) containing the crosslinkable resin composition is 5 to 100% by weight from the viewpoint of excellent adhesion between the fiber material layer and another material layer, rigidity of the laminate, and the like, and easy production. Other fiber materials (II)
0 to 95% by weight is subjected to at least one of the steps of cotton blending, papermaking, and lamination, and then another material layer is laminated thereon, and then these are heated and pressed to be more preferably used. Can be As a method for producing the laminate of the present invention, for example, a fiber material layer is heated to a predetermined temperature and set in a vacuum forming machine, and if necessary, an adhesive film formed thereon by inflation molding or T-die molding is formed. A method of placing an agent and then laminating another material layer heated to a predetermined temperature in advance and vacuum-pressing; a method of laminating a fiber material layer and another material layer and hot pressing; coating the fiber material layer with an adhesive A method of hot-pressing a laminated material to another material layer with a hot press or a hot roll; a method of hot-pressing a laminated material coated with an adhesive to another material layer with a hot press or a hot roll; A web of a mixture of fibers of the crosslinkable resin composition and fibers of the crosslinkable resin composition and other fibers is processed into a flexible primary molding mat by a method such as needle punching, Overlapping the other material layers on top of, and a method of shaping by heating and compressing a hot press and the like.

The heating temperature during the production of the laminate of the present invention varies depending on the type of other material layers used, the molding conditions, the composition of the crosslinkable resin composition and the like, and cannot be specified unconditionally. The temperature is appropriately selected at a temperature equal to or higher than the softening point of the material and equal to or lower than a temperature at which the other material layers are not affected. The thickness of each layer of the laminate of the present invention varies depending on its material, application, required physical properties and the like, and is not particularly limited.

The interior material of the present invention uses the laminate of the present invention, and is mainly used for interior materials of automobiles and the like (eg, ceiling materials, door members, dashboard members, console boxes, instool panel members, etc.). ) Or as interior materials for various vehicles, ships, houses, and the like.

Since the laminate of the present invention has a fiber material layer using the fiber material (I) containing the crosslinkable resin composition,
It is lightweight, has good rigidity, high heat resistance, and is recyclable. The reason for this is that the crosslinkable resin composition of the present invention can dissociate the crosslinks by selecting an appropriate molding temperature, exhibit good moldability, and rapidly undergo a crosslinking reaction during cooling and solidification. And
This is because the resulting molded article has a crosslinked structure introduced therein. Further, since the interior material of the present invention uses the laminate of the present invention, it is lightweight, has good rigidity,
It has high heat resistance and can be recycled.

[0056]

The present invention will be described more specifically with reference to the following examples.

The following evaluation method was used in the present example. (Evaluation of heat resistance) The heat resistance was evaluated by a heat sag test according to JIS K7195. Specifically, the obtained sample was cut out to a width of 10 mm and a length of 125 mm, held at a predetermined temperature and time in a cantilever state in which one end of the test piece was fixed, and the amount of deflection of the test piece due to heat was measured. . Judgment was evaluated as ○ when the amount of deflection was less than 1 mm, Δ when it was less than 1 mm to 3 mm, and X when it was 3 mm or more. (Hot Peel Strength) After conditioning the obtained sample at 23 ° C. and a relative humidity of 50% for 24 hours, it was cut into a test piece having a width of 25 mm and 180 ° at 120 ° C. using a tensile tester.
゜ A peeling test (peeling speed 200 mm / min) was performed.

Further, (a) an ethylene copolymer, (b)
The following were used as the polyhydric alcohol compound, the reaction accelerator (c), the other thermoplastic resin and the raw material resin for other fiber materials, and the other material layers. ((A) Ethylene copolymer) · Ethylene copolymer 1
(Abbreviation PE1): terpolymer of ethylene-maleic anhydride (2.5% by weight) -methyl acrylate (15% by weight), MFR = 12 g / 10 minutes (190 ° C., 2.16 k
g) Ethylene copolymer 2 (abbreviation PE2): ethylene-maleic anhydride (2.0% by weight) binary copolymer, MFR =
10 g / 10 minutes (190 ° C., 2.16 kg) ((b) polyhydric alcohol compound) trimethylolpropane (abbreviation TMP) ((c) reaction accelerator) ionomer: part of ethylene-methacrylic acid copolymer Neutralized product (methacrylic acid content 18% by weight, copolymer <sodium salt> in which about 10% of the methacrylic acid was neutralized), MFR 3.0 g / 10 minutes (190 ° C., 2.
16 kg) ・ Sodium stearate (StNa)

(Other thermoplastic resins) ・ Low density polyethylene (abbreviation L) by high pressure radical polymerization
DPE): density = 0.916 g / cm ³ , MFR = 7 g
/ 10 min (190 ° C, 2.16 kg) ・ Ethylene-vinyl acetate (V
A) Copolymer (abbreviation EVA): VA = 18% by weight, MF
R = 8.0 g / 10 min (190 ° C., 2.16 kg) Ethylene-methyl acrylate (MA) copolymer (EMA) by high pressure radical polymerization: MA = 16% by weight, M
FR = 10 g / 10 min (190 ° C., 2.16 kg) (raw resin for other fiber materials) Homopolypropylene (abbreviation PP): MFR = 10 g /
10 minutes (230 ° C, 2.16 kg) ・ Polyethylene terephthalate (abbreviation PET): [η]
= 0.65 (phenol / tetrachloroethane = 1 /
1,30 ° C)

(Other material layer) Polyethylene terephthalate nonwoven fabric (hereinafter referred to as PE
T is described as T non-woven fabric).
mm foamed polypropylene (hereinafter referred to as PVC / foamed PP) 2 mm thick foamed polypropylene (hereinafter referred to as TPO / foamed PP) to which a polypropylene-based thermoplastic elastomer having a thickness of 0.2 mm is attached.

Example 1 (a) 100 parts by weight of PE1 as an ethylene copolymer, (b) 1.5 parts by weight of TMP as a polyhydric alcohol compound, (c) 5 parts by weight of an ionomer as a reaction accelerator These were prepared and melt-kneaded at a resin temperature of 200 ° C. using a conventional twin-screw extruder to obtain a crosslinkable resin composition. TMP for acid anhydride groups in PE1
The molar ratio of the derived hydroxyl groups was 1.3. The obtained crosslinkable resin composition was spun to about 20 denier using a usual melt spinning molding machine to obtain a fiber. The fiber was crimped and cut to obtain staples. A web was formed from the obtained staples, formed into a thickness of 5 mm by hot pressing at 210 ° C., and cooled and solidified by a cooling press at 25 ° C. to obtain a fiber material layer. An adhesive (two-component mixed epoxy adhesive) is applied on the obtained fiber material layer, and a PET nonwoven fabric is laminated thereon as another material layer, and the heat is set to 120 ° C. for the upper plate and 70 ° C. for the lower plate. The laminate was pressed by a press under a condition of a substantial surface pressure of 2.5 kg / cm ² . The obtained laminate was evaluated. Table 2 shows the results
Shown in

[Examples 2 to 3] The same procedures as in Example 1 were carried out except that the composition of the crosslinkable resin composition was changed as shown in Table 1. Table 2 shows the results.

Example 4 (a) 100 parts by weight of PE1 as an ethylene copolymer, (b) 2.0 parts by weight of TMP as a polyhydric alcohol compound, (c) 5 parts by weight of an ionomer as a reaction accelerator These were prepared and melt-kneaded at a resin temperature of 200 ° C. using a conventional twin-screw extruder to obtain a crosslinkable resin composition. TMP for acid anhydride groups in PE1
The molar ratio of the derived hydroxyl groups was 1.8. The obtained crosslinkable resin composition was spun to about 20 denier using a usual melt spinning molding machine to obtain a fiber. The fiber was crimped and cut to obtain staples. Obtained staple (fiber material A) 50
% By weight and 50% by weight of staples of other fibers (PET) (fiber material B) to form a web,
It was shaped into a thickness of 5 mm by a hot press at 25 ° C., and cooled and solidified by a cooling press at 25 ° C. to obtain a fiber material layer. An adhesive (two-component mixed epoxy adhesive) is applied on the obtained fiber material layer, and a PET nonwoven fabric is laminated thereon as another material layer, and the heat is set to 120 ° C. for the upper plate and 70 ° C. for the lower plate. The laminate was pressed by a press under a condition of a substantial surface pressure of 2.5 kg / cm ² .
The heat resistance of the obtained laminate was evaluated. Table 2 shows the results.

Examples 5 to 9 Except that the composition of the crosslinkable resin composition, the kind of other fibers, the mixing ratio of the fiber material, and the other material layers were changed as shown in Tables 1 and 2, Performed as in Example 4. Table 2 shows the results.

Example 10 (a) 100 parts by weight of PE1 as an ethylene copolymer, (b) 1.5 parts by weight of TMP as a polyhydric alcohol compound, (c) 5 parts by weight of an ionomer as a reaction accelerator And 10 parts by weight of LDPE as another thermoplastic resin, and these were melt-kneaded at a resin temperature of 200 ° C. using a conventional twin-screw extruder to obtain a crosslinkable resin composition. The molar ratio of the hydroxyl group derived from TMP to the acid anhydride group in PE1 was 1.3. The obtained crosslinkable resin composition was spun to about 20 denier using a usual melt spinning molding machine to obtain a fiber. The fiber was crimped and cut to obtain staples. The obtained staple (fiber material A) 60% by weight and other fiber (PET) staple (fiber material B) 4
After mixing with 0% by weight, a web was formed, shaped into a thickness of 5 mm by a hot press at 220 ° C., and cooled and solidified by a cooling press at 25 ° C. to obtain a fibrous material layer. An adhesive (two-component mixed epoxy adhesive) is applied on the obtained fiber material layer, and PVC / foamed PP is laminated thereon as another material layer.
The laminate was pressed by a hot press set at 20 ° C. and a lower plate at 70 ° C. under the condition of a substantial surface pressure of 2.5 kg / cm ² . The obtained laminate was evaluated. Table 2 shows the results.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the amount of TMP was changed to 20 parts by weight. The molar ratio of the hydroxyl group derived from TMP to the acid anhydride group in PE1 was 18. The obtained laminate was evaluated. Table 2 shows the results. A laminate using a crosslinkable resin composition in which the molar ratio of (b) a hydroxyl group derived from a polyhydric alcohol compound to (a) an acid anhydride group in an ethylene-based copolymer exceeds 10, heat resistance and hot The peel strength was poor.

Comparative Example 2 The same operation as in Example 1 was carried out except that no ionomer was added. The obtained laminate was evaluated. Table 2 shows the results. (C) The laminate using the crosslinkable resin composition containing no reaction accelerator had poor heat resistance and hot peel strength.

Comparative Example 3 Except that TMP was not blended,
Performed in the same manner as in Example 1. The obtained laminate was evaluated. Table 2 shows the results. (B) A laminate using a crosslinkable resin composition containing no polyhydric alcohol compound has heat resistance,
Hot peel strength was poor.

Comparative Example 4 The same operation as in Example 1 was carried out except that TMP and the ionomer were not blended. The obtained laminate was evaluated. Table 2 shows the results. The laminate using the crosslinkable resin composition not containing (b) the polyhydric alcohol compound and (c) the reaction accelerator had poor heat resistance and hot peel strength.

Comparative Example 5 (a) 100 parts by weight of PE1 as an ethylene copolymer, (b) 1.5 parts by weight of TMP as a polyhydric alcohol compound, (c) 5 parts by weight of an ionomer as a reaction accelerator These were prepared and melt-kneaded at a resin temperature of 200 ° C. using a conventional twin-screw extruder to obtain a crosslinkable resin composition. TMP for acid anhydride groups in PE1
The molar ratio of the derived hydroxyl groups was 1.3. The obtained crosslinkable resin composition was spun to about 20 denier using a usual melt spinning molding machine to obtain a fiber. The fiber was crimped and cut to obtain staples. 3% by weight of obtained staple (fiber material A) and staple of other fibers (PET) (fiber material B)
After mixing with 97% by weight, a web was formed, formed into a thickness of 5 mm by a hot press at 220 ° C, and cooled and solidified by a cooling press at 25 ° C to obtain a fiber material layer. An adhesive (two-component mixed type epoxy adhesive) is applied on the obtained fiber material layer, and a PET non-woven fabric is laminated thereon as another material layer.
With a hot press set at 0 ° C and a lower plate at 70 ° C, a substantial surface pressure of 2.
Crimping was performed under the condition of 5 kg / cm ² to obtain a laminate. The obtained molded body was evaluated. Table 2 shows the results. The laminate having a fiber material layer containing less than 5% by weight of the fiber material made of the crosslinkable resin composition was inferior in heat resistance and hot peel strength.

[Comparative Example 6] (a) 100 parts by weight of PE1 as an ethylene copolymer and (b) 1.5 parts by weight of TMP as a polyhydric alcohol compound were prepared. The resin was melt-kneaded at a resin temperature of 200 ° C. to obtain a crosslinkable resin composition. The obtained crosslinkable resin composition was spun to about 20 denier using a usual melt spinning molding machine to obtain a fiber. The fiber was crimped and cut to obtain staples. After mixing 80% by weight of the obtained staples (fiber material A) and 20% by weight of staples (fiber material B) of other fibers (PET), a web was formed, and 5 mm was formed by a 220 ° C. hot press.
It was shaped into a thickness and cooled and solidified by a cooling press at 25 ° C. to obtain a fiber material layer. An adhesive (two-component mixed epoxy adhesive) is applied on the obtained fiber material layer, and a PET non-woven fabric is laminated thereon as another material layer.
Was pressed under the condition of a substantial surface pressure of 2.5 kg / cm ² by a hot press set as described above to obtain a laminate. The obtained laminate was evaluated. Table 2 shows the results. (C) The laminate using the crosslinkable resin composition containing no reaction accelerator had poor heat resistance and hot peel strength.

[Comparative Example 7] (a) 100 parts by weight of PE1 as an ethylene copolymer and (c) 5 parts by weight of an ionomer as a reaction accelerator were prepared at a temperature of 200 ° C using a conventional twin-screw extruder. The mixture was melt-kneaded at a resin temperature to obtain a crosslinkable resin composition. The obtained crosslinkable resin composition was spun to about 20 denier using a usual melt spinning molding machine to obtain a fiber. The fiber was crimped and cut to obtain staples. 80% by weight of the obtained staple (fiber material A) and other fibers (PET)
Was mixed with 20% by weight of a staple (fiber material B), and a web was formed, formed into a thickness of 5 mm by a hot press at 220 ° C., and cooled and solidified by a cooling press at 25 ° C. to obtain a fibrous material layer. An adhesive (two-component mixed epoxy adhesive) is applied on the obtained fiber material layer, and P is used as another material layer thereon.
The VC / foamed PP were stacked and pressed by a hot press set at 120 ° C. on the upper plate and 70 ° C. on the lower plate under the condition of a substantial surface pressure of 2.5 kg / cm ² to obtain a laminate. The obtained laminate was evaluated. Table 2 shows the results. (B) A molded article using a crosslinkable resin composition containing no polyhydric alcohol compound has heat resistance,
Hot peel strength was poor.

[Comparative Example 8] LDPE was spun into a denier of about 20 denier using a conventional melt spinning molding machine to obtain a fiber. The fiber was crimped and cut to obtain staples. After mixing 80% by weight of the obtained staples (fiber material A) and 20% by weight of staples (fiber material B) of other fibers (PET), a web is formed, and a web is formed by a hot press at 220 ° C. to a thickness of 5 mm. Shape
The fiber material layer was obtained by cooling and solidifying with a cooling press at 25 ° C. An adhesive (two-component mixed type epoxy adhesive) is applied on the obtained fiber material layer, and PV
C / foamed PP were stacked and pressed by a hot press set at 120 ° C. on the upper plate and 70 ° C. on the lower plate under the condition of a substantial surface pressure of 2.5 kg / cm ² to obtain a laminate. The obtained laminate was evaluated. Table 2 shows the results. The laminate having a fiber material layer containing no fiber material of the crosslinkable resin composition was inferior in heat resistance and hot peel strength.

[Comparative Examples 9 to 10] E instead of LDPE
Comparative Example 8 was carried out except that VA or EMA was used, and PP was used as another fiber. Table 2 shows the results.
The laminate having a fiber material layer containing no fiber material of the crosslinkable resin composition was inferior in heat resistance and hot peel strength.

[0075]

[Table 1]

[0076]

[Table 2]

Example 11 (a) 100 parts by weight of PE1 as an ethylene copolymer, (b) 1.5 parts by weight of TMP as a polyhydric alcohol compound, and (c) 5 parts by weight of an ionomer as a reaction accelerator And prepare these as usual 2
The mixture was melt-kneaded at a resin temperature of 200 ° C. with a screw extruder to obtain a crosslinkable resin composition. TM for the acid anhydride group in PE1
The molar ratio of hydroxyl groups derived from P was 1.3. The obtained crosslinkable resin composition was used as a sheath portion, and PP was used as a core portion, and spun to about 20 denier using a usual core-sheath fiber molding machine to obtain a core-sheath fiber. The fiber was crimped and cut to obtain staples. Forming a web from the resulting staples, 22
It was shaped into a thickness of 5 mm by a hot press at 0 ° C. and solidified by cooling with a cooling press at 25 ° C. to obtain a fiber material layer. An adhesive (two-component mixed epoxy adhesive) is applied on the obtained fiber material layer, and a PET nonwoven fabric is laminated thereon as another material layer, and the heat is set to 120 ° C. for the upper plate and 70 ° C. for the lower plate. The laminate was pressed by a press under a condition of a substantial surface pressure of 2.5 kg / cm ² .
The obtained laminate was evaluated. Table 4 shows the results.

Examples 12 and 13 The same procedures as in Example 11 were carried out except that the composition of the crosslinkable resin composition was changed as shown in Table 3. Table 4 shows the results.

[Example 14] Using the crosslinkable resin composition of Example 11 as a sheath and PP as a core, a core-sheath fiber was spun to about 20 denier using an ordinary core-sheath fiber molding machine. The fiber was crimped and cut to obtain staples. After mixing 50% by weight of the obtained staples (fiber material A) and 50% by weight of staples (fiber material B) of other fibers (PP), a web is formed, and a web is formed to a thickness of 5 mm by a 220 ° C. hot press. It was cooled and solidified by a cooling press at 25 ° C. to obtain a fiber material layer. An adhesive (two-component mixed epoxy adhesive) is applied on the obtained fiber material layer, and a PET nonwoven fabric is laminated thereon as another material layer, and the heat is set to 120 ° C. for the upper plate and 70 ° C. for the lower plate. The laminate was pressed by a press under a condition of a substantial surface pressure of 2.5 kg / cm ² . The obtained laminate was evaluated. Table 4 shows the results.

[Examples 15 to 19] The composition of the crosslinkable resin composition, the type of core portion, the type of other fibers, the mixing ratio of the fiber material, and the other material layers were changed as shown in Tables 3 and 4. Except having performed, it carried out similarly to Example 14. Table 4 shows the results.

Example 20 (a) 100 parts by weight of PE1 as an ethylene copolymer, (b) 1.5 parts by weight of TMP as a polyhydric alcohol compound, (c) 5 parts by weight of an ionomer as a reaction accelerator And 10 parts by weight of LDPE as another thermoplastic resin, and these were melt-kneaded at a resin temperature of 200 ° C. using a conventional twin-screw extruder to obtain a crosslinkable resin composition. The molar ratio of the hydroxyl group derived from TMP to the acid anhydride group in PE1 was 1.3. Using the obtained crosslinkable resin composition as a sheath portion, PET as a core portion,
The fiber was spun to about 20 denier using a conventional core-sheath fiber molding machine to obtain a core-sheath fiber. The fiber was crimped and cut to obtain staples. 50% by weight of the obtained staple (fiber material A) and 50% by weight of other fiber (PET) staples (fiber material B)
Was mixed, and a web was formed, shaped into a thickness of 5 mm by a hot press at 220 ° C., and cooled and solidified by a cooling press at 25 ° C. to obtain a fiber material layer. An adhesive (two-component mixed epoxy adhesive) is applied on the obtained fiber material layer, and PVC / foamed PP is laminated thereon as another material layer.
With a hot press set at a lower plate temperature of 70 ° C, a substantial surface pressure of 2.5 kg
/ Cm ² to obtain a laminate. The obtained laminate was evaluated. Table 4 shows the results.

Comparative Example 11 The same procedure as in Example 11 was carried out except that the amount of TMP was changed to 20 parts by weight. PE
The molar ratio of the hydroxyl group derived from TMP to the acid anhydride group in 1 was 18. The obtained laminate was evaluated. Table 4 shows the results. A laminate using a crosslinkable resin composition in which the molar ratio of (b) a hydroxyl group derived from a polyhydric alcohol compound to (a) an acid anhydride group in an ethylene-based copolymer exceeds 10, heat resistance and hot The peel strength was poor.

[Comparative Example 12] The same operation as in Example 11 was carried out except that no ionomer was added. The obtained laminate was evaluated. Table 4 shows the results. (C) A laminate using a crosslinkable resin composition containing no reaction accelerator has heat resistance,
Hot peel strength was poor.

[Comparative Example 13] The same operation as in Example 11 was carried out except that TMP was not blended. The obtained laminate was evaluated. Table 4 shows the results. (B) The laminate using the crosslinkable resin composition containing no polyhydric alcohol compound was inferior in heat resistance and hot peel strength.

[Comparative Example 14] By using PE1 as a sheath,
P is used as a core part, and about 20
The fiber was spun into denier to obtain a core-sheath fiber. This fiber is crimped,
It was cut to obtain staples. After mixing 50% by weight of the obtained staples (fiber material A) and 50% by weight of staples (fiber material B) of other fibers (PP), a web is formed, and a web is formed by a hot press at 220 ° C. to a thickness of 5 mm. It was cooled and solidified by a cooling press at 25 ° C. to obtain a fiber material layer. An adhesive (two-component mixed epoxy adhesive) is applied on the obtained fiber material layer, and a PET nonwoven fabric is laminated thereon as another material layer, and the heat is set to 120 ° C. for the upper plate and 70 ° C. for the lower plate. The laminate was pressed by a press under a condition of a substantial surface pressure of 2.5 kg / cm ² . The obtained laminate was evaluated. Table 4 shows the results
Shown in A laminate using the (b) polyhydric alcohol compound and (c) a crosslinkable resin composition containing no reaction accelerator,
Heat resistance and hot peel strength were poor.

Comparative Example 15 (a) 100 parts by weight of PE1 as an ethylene copolymer, (b) 1.5 parts by weight of TMP as a polyhydric alcohol compound, (c) 5 parts by weight of an ionomer as a reaction accelerator And prepare these as usual 2
The mixture was melt-kneaded at a resin temperature of 200 ° C. with a screw extruder to obtain a crosslinkable resin composition. TM for the acid anhydride group in PE1
The molar ratio of hydroxyl groups derived from P was 1.3. The obtained crosslinkable resin composition was used as a sheath portion, and PP was used as a core portion, and spun to about 20 denier using a usual core-sheath fiber molding machine to obtain a core-sheath fiber. The fiber was crimped and cut to obtain staples. 3% by weight of the obtained staple (fiber material A),
Staple of other fiber (PP) (Fiber material B) 97% by weight
Was mixed, and a web was formed, shaped into a thickness of 5 mm by a hot press at 220 ° C., and cooled and solidified by a cooling press at 25 ° C. to obtain a molded body. An adhesive (2) is applied on the obtained fiber material layer.
A liquid mixture type epoxy adhesive) is applied, and PVC / foamed PP is layered thereon as another material layer, and a hot press set at 120 ° C. on the upper plate and 70 ° C. on the lower plate is used to apply a substantial surface pressure of 2.5 kg / c.
Crimp under the condition of m ^2, and to obtain a laminate. The obtained laminate was evaluated. Table 4 shows the results. The laminate having a fiber material layer containing less than 5% by weight of the fiber material made of the crosslinkable resin composition was inferior in heat resistance and hot peel strength.

[Comparative Example 16] (a) 100 parts by weight of PE1 as an ethylene-based copolymer and (b) 1.5 parts by weight of TMP as a polyhydric alcohol compound were prepared. The resin was melt-kneaded at a resin temperature of 200 ° C. to obtain a crosslinkable resin composition. The resulting crosslinkable resin composition was used as a sheath portion, and PET was used as a core portion, and spun to about 20 denier using an ordinary core-sheath fiber molding machine to obtain a core-sheath fiber. The fiber was crimped and cut to obtain staples. 80% by weight of the obtained staple (fiber material A) and other fibers (PE
A web is formed after mixing 20% by weight of the staple (fibrous material B) of T), formed into a thickness of 5 mm by a hot press at 220 ° C., and cooled and solidified by a cooling press at 25 ° C. to obtain a fibrous material layer. Was. An adhesive (two-component mixed epoxy adhesive) is applied on the obtained fiber material layer, and PVC / foamed PP is laminated thereon as another material layer, and the upper plate is set at 120 ° C and the lower plate at 70 ° C. By using a hot press, compression bonding was performed under the condition of a substantial surface pressure of 2.5 kg / cm ² to obtain a laminate. The obtained laminate was evaluated. Table 4 shows the results. (C) A laminate having a fiber material layer using a crosslinkable resin composition containing no reaction accelerator had poor heat resistance and hot peel strength.

[Comparative Example 17] (a) 100 parts by weight of PE1 as an ethylene copolymer and (c) 5 parts by weight of an ionomer as a reaction accelerator were prepared at 200 ° C. using a conventional twin-screw extruder. The mixture was melt-kneaded at a resin temperature to obtain a crosslinkable resin composition. The resulting crosslinkable resin composition was used as a sheath portion, and PET was used as a core portion, and spun to about 20 denier using an ordinary core-sheath fiber molding machine to obtain a core-sheath fiber. The fiber was crimped and cut to obtain staples. After mixing 80% by weight of the obtained staples (fiber material A) and 20% by weight of staples (fiber material B) of other fibers (PET), a web is formed, and a web is formed by a hot press at 220 ° C. to a thickness of 5 mm. Shape
The fiber material layer was obtained by cooling and solidifying with a cooling press at 25 ° C. An adhesive (two-component mixed type epoxy adhesive) is applied on the obtained fiber material layer, and PV
C / foamed PP were stacked and pressed by a hot press set at 120 ° C. on the upper plate and 70 ° C. on the lower plate under the condition of a substantial surface pressure of 2.5 kg / cm ² to obtain a laminate. The obtained laminate was evaluated. Table 4 shows the results. (B) A laminate using a crosslinkable resin composition containing no polyhydric alcohol compound has heat resistance,
Hot peel strength was poor.

Comparative Example 18 Using LDPE as a sheath part
Using PP as the core part, about 2
It was spun to 0 denier to obtain a core-sheath fiber. The fiber was crimped and cut to obtain staples. After mixing 80% by weight of the obtained staples (fiber material A) and 20% by weight of staples (fiber material B) of other fibers (PET), a web is formed, and a web is formed by a hot press at 220 ° C. to a thickness of 5 mm. Shape, 25
The resulting mixture was cooled and solidified by a cooling press at ℃ to obtain a fiber material layer. An adhesive (two-component mixed epoxy adhesive) is applied on the obtained fiber material layer, and a PET nonwoven fabric is laminated thereon as another material layer, and the heat is set to 120 ° C. for the upper plate and 70 ° C. for the lower plate. The laminate was pressed by a press under a condition of a substantial surface pressure of 2.5 kg / cm ² . The obtained laminate was evaluated. Table 4 shows the results. The laminate having a fiber material layer containing no fiber material of the crosslinkable resin composition was inferior in heat resistance and hot peel strength.

[Comparative Examples 19 to 20] The same procedure as in Comparative Example 18 was carried out except that EVA or EMA was used instead of LDPE and PP was used as another fiber. Table 4 shows the results. The laminate having a fiber material layer containing no fiber material of the crosslinkable resin composition was inferior in heat resistance and hot peel strength.

[0091]

[Table 3]

[0092]

[Table 4]

[0093]

As described above, the laminate of the present invention is a laminate having a fiber material layer and another material layer, wherein the fiber material layer comprises the specific crosslinkable resin composition. Containing 5 to 100% by weight of the fiber material (I) and the other fiber material (II)
0-95% by weight, so it is lightweight, has good rigidity,
It has high heat resistance and can be recycled. Further, a part or all of the fiber material (I) is a fiber material composed of multi-layered composite fibers, and at least one of the multi-layered composite fibers contains the crosslinkable resin composition. Lightweight, good rigidity,
It has high heat resistance and can be recycled. In addition, even when a part or all of the composite fiber having the multilayer structure is a fiber having a core portion and a sheath portion covering the core portion, the sheath portion may include a crosslinkable resin composition. It is lightweight, has good rigidity, high heat resistance, and is recyclable.

When the laminate of the present invention is formed by pressing and heating the fiber material layer and another material layer, the laminate has excellent adhesion and rigidity. Also,
Since the interior material of the present invention uses the laminate of the present invention, it is lightweight, has good rigidity, high heat resistance, and is recyclable. In addition, the method for producing a laminate of the present invention is characterized in that the fiber material (I) 5 containing the crosslinkable resin composition
100% by weight and 0 to 95% by weight of the other fiber material (II)
Cotton blending, papermaking, after at least one of the steps of lamination, after laminating another material layer, and then heat and pressure molding these methods, lightweight, good rigidity,
A laminate having high heat resistance and being recyclable can be easily obtained. Such laminates and interior materials,
Mainly lightweight and high rigidity, such as interior materials for automobile interior parts,
Very useful for applications requiring high heat resistance. Also,
Although it can be suitably used for interior materials for automobiles and the like, it can be used for various applications as long as the laminate and interior material of the present invention can make use of the feature of high heat resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/08 C08L 23/08 // B60R 13/02 B60R 13/02 B C08J 5/04 CES C08J 5 / 04 CES (72) Inventor Koji Okamoto 2-2-2, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Polyolefin Co., Ltd. Kawasaki Laboratory F-term (reference) 3D023 BA01 BB03 BC00 BD01 BE04 BE06 BE31 4F072 AB04 AB15 AB29 AC06 AK06

Claims (6)

[Claims] 1. An ethylene copolymer having (a) ethylene and a radical polymerizable acid anhydride as essential components, (b) a polyhydric alcohol compound having two or more hydroxyl groups in a molecule,
And (c) a reaction accelerator, wherein the proportion of units derived from the radically polymerizable acid anhydride in the (a) ethylene-based copolymer is 0.1 to 20% by weight, and the (a) ethylene For the acid anhydride group in the copolymer,
(B) the molar ratio of hydroxyl groups derived from the polyhydric alcohol compound is
A crosslinkable resin composition in the range of 0.01 to 10 and the (c) reaction accelerator is in the range of 0.001 to 20 parts by weight based on 100 parts by weight of the ethylene copolymer (a) Material (I) containing 5 to 100
A laminate comprising: a fiber material layer composed of 0 to 95% by weight of another fiber material (II); and another material layer. 2. Part or all of the fiber material (I) is:
2. The laminate according to claim 1, wherein the laminate is a fibrous material composed of multi-layered composite fibers, wherein at least one of the multi-layered composite fibers contains the crosslinkable resin composition. 3. 3. A fiber having a core part and a sheath part covering the core part, wherein the sheath part comprises a crosslinkable resin composition. 3. The laminate according to claim 2, wherein: 4. The laminate according to claim 1, wherein the fiber material layer is a layer formed by heating and pressing. 5. An interior material using the laminate according to any one of claims 1 to 4. 6. (a) an ethylene copolymer having ethylene and a radical polymerizable acid anhydride as essential components, (b) a polyhydric alcohol compound having two or more hydroxyl groups in a molecule,
And (c) a reaction accelerator, wherein the proportion of units derived from the radically polymerizable acid anhydride in the (a) ethylene-based copolymer is 0.1 to 20% by weight, and the (a) ethylene For the acid anhydride group in the copolymer,
(B) the molar ratio of hydroxyl groups derived from the polyhydric alcohol compound is
A crosslinkable resin composition in the range of 0.01 to 10 and the (c) reaction accelerator is in the range of 0.001 to 20 parts by weight based on 100 parts by weight of the ethylene copolymer (a) Material (I) containing 5 to 100
Weight% and other fiber material (II) 0-95% by weight,
A method for producing a laminated body, comprising, after at least one of the steps of papermaking and laminating, laminating another material layer thereon, and then heating and pressing them.