JP2000238171A - Laminate for vehicle interior finish material, vehicle interior finish material and their manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain low temperature adhesion possibility, excellent heat resistance and good vent shut-off properties by incorporating an ethylenic copolymer containing an ethylene and an unsaturated carboxylic acid anhydride as indispensable components, a polyhydric alcohol compound having a hydroxyl group in a molecule and a reaction accelerator in a vent shut-off adhesive layer. SOLUTION: A vent shut-off adhesive layer is formed of an adhesive resin composition containing an ethylenic copolymer containing an ethylene and an unsaturated carboxylic acid anhydride as indispensable components, a polyhydric alcohol compound having at least two or above hydroxyl groups in a molecule and a reaction accelerator, and is extrusion laminated on a skin material layer. A ratio of the unit derivated from the unsaturated carboxylic acid anhydride in the ethylenic copolymer is 0.1 to 20 wt.%, a molar ratio of a hydroxyl group derivated from the polyhydric alcohol to the acid anhydride group in the copolymer is 0.01 to 10, and the accelerator is 0.001 to 20 pts.wt. to 100 pts.wt. of the copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vehicle interior having a skin layer and an adhesive layer capable of providing a remarkable improvement in performance and an economic effect when a skin material for a vehicle interior material is bonded to a substrate. Material laminate, vehicle interior material laminated with the substrate,
And its manufacturing method. Specifically, a vehicle interior material that can be bonded at a relatively low temperature, has excellent heat resistance, and achieves a required air-permeable barrier characteristic of a vehicle interior material without providing a special air-permeable barrier layer. TECHNICAL FIELD The present invention relates to a technology for providing a laminated body for vehicles or a vehicle interior material with high economic efficiency.

[0002]

2. Description of the Related Art Conventionally, in a vehicle interior material laminate or a vehicle interior material (hereinafter collectively referred to as a vehicle interior material laminate),
It is manufactured by bonding a skin material for enhancing the comfort and aesthetic appearance in a vehicle or a base material for maintaining and improving the functionality with a heat-fusion adhesive. The heat-fusible adhesive is different from the solvent-type adhesive, applied at the time of bonding, dried,
Work such as aging is not required, the work process is simple,
Since the use of organic solvents does not cause problems such as adverse effects on occupational health and danger of fire, the ceiling portion, which was easily adapted, has been widely put to practical use.

[0003]

However, the heat-sealing adhesive has an insufficient heat creep resistance, and when it is left at a high temperature (80 ° C.) such as the temperature in a car under the hot sun for a long time, it will not sag. It has a drawback that peeling, partial floating, and the like are likely to occur, and this has been a cause of deterioration of heat resistance of the laminate for vehicle interior materials. As a method of improving the heat resistance of the laminated body for vehicle interior materials, there is a method of increasing the melting point and the bonding temperature of the heat-fusible adhesive to improve the heat creep resistance of the heat-fusible adhesive. However, due to repeated demands for improving the heat resistance of the laminated body for vehicle interior materials, the melting point and the bonding temperature of the heat-fusible adhesive have reached the heat-resistant limit region of the thermoplastic resin.

[0004] In spite of such a situation, there is a demand for further improvement in heat resistance of the laminated body for vehicle interior materials, and it is no longer possible to cope with the conventional extension technology. To cope with the improvement of heat resistance, a method of introducing a cross-linking agent into the heat-fusible adhesive has been studied. However, the cross-linked heat-fusible adhesive has poor molding workability, so extrusion lamination is difficult. In addition, it has a disadvantage that it does not easily permeate into the skin material or the base material and the adhesive strength is not sufficiently increased.

[0005] On the other hand, when the heat creep resistance of the heat-fusible adhesive is improved, the laminating temperature of the heat-fusible adhesive also becomes high. This has the drawback that it is easy to cause damage. Furthermore, in recent years,
Due to environmental considerations, the use of conventional resin felt and resin board as a base material is being restricted, and the heat resistance of the base material tends to decrease due to the progress of deglassing fiber etc. Was in Therefore, there is a need for a heat-sealing adhesive that can be bonded at a relatively low temperature.

[0006] In addition to heat resistance, the laminate for vehicle interior materials is required to have a performance of blocking airflow. However, in the conventional lamination method using a heat-sealing adhesive,
There is a problem that a pinhole is always formed in the adhesive layer at the time of bonding, and it has been inevitable to form a multilayer structure with a resin having a high melting point, such as nylon, and provide a ventilation blocking layer. Therefore, there are problems such as an increase in the raw material cost due to the provision of the ventilation blocking layer and an increase in the manufacturing cost due to the addition of the step of providing the ventilation blocking layer.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a laminate for a vehicle interior material that can be bonded at a relatively low temperature, has excellent heat resistance, and can achieve good ventilation blocking without providing a special ventilation blocking layer. An object of the present invention is to provide a body, a vehicle interior material, and a manufacturing method capable of obtaining such a vehicle interior material laminate and a vehicle interior material at low cost.

[0008]

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 copolymer and a polyvalent polymer having at least two or more hydroxyl groups in the molecule. An alcohol compound and an adhesive resin composition having a reaction accelerator are extrusion-laminated to a skin material,
It has been found that it is possible to efficiently produce a laminate for vehicle interior materials having a practically no problem air-permeation barrier property, which can be bonded at a low temperature, has high heat resistance, and does not require a special air-permeation barrier layer, The present invention has been reached.

That is, the laminate for a vehicle interior material according to claim 1 is a laminate for a vehicle interior material having at least a skin material and a ventilation blocking adhesive layer, wherein the ventilation blocking adhesive layer (adhesion layer). Contains (a) an ethylene copolymer having ethylene and an unsaturated carboxylic anhydride as essential components, (b) a polyhydric alcohol compound having at least two hydroxyl groups in a molecule, and (c) a reaction accelerator. Wherein the proportion of units derived from the unsaturated carboxylic anhydride in the (a) ethylene-based copolymer is 0.1%.
(A) a molar ratio of (b) a hydroxyl group derived from a polyhydric alcohol compound to an acid anhydride group in the ethylene copolymer is in the range of 0.01 to 10, and (c)
The reaction accelerator is characterized by being in the range of 0.001 to 20 parts by weight based on 100 parts by weight of the ethylene copolymer (a). Further, the laminate for vehicle interior materials according to claim 2 is:
The air-permeable adhesive layer is formed by extrusion lamination two or more times. Claim 3
In the laminated body for vehicle interior materials according to the above, the thickness of the ventilation blocking adhesive layer is 20 μm or more. Further, in the laminate for vehicle interior materials according to claim 3, the ventilation barrier adhesive layer is composed of two or more layers, and the composition of the adhesive resin composition used for each ventilation barrier adhesive layer is different from each other. desirable.

Further, the vehicle interior material of the present invention is characterized in that a base material layer is provided on the laminated body for vehicle interior material, and the base material layer is laminated on the ventilation blocking adhesive layer. And Further, the method for manufacturing a laminate for vehicle interior materials of the present invention,
(A) an ethylene copolymer having ethylene and an unsaturated carboxylic anhydride as essential components, (b) a polyhydric alcohol compound having at least two hydroxyl groups in a molecule, and (c) a reaction accelerator. (A) the proportion of units derived from the unsaturated carboxylic anhydride in the ethylene-based copolymer is 0.1 to 20% by weight, and (a) based on the acid anhydride group in the ethylene copolymer; (B) The molar ratio of the hydroxyl group derived from the polyhydric alcohol compound is in the range of 0.01 to 10, and (c) the reaction accelerator is 0.1 to 100 parts by weight of the (a) ethylene-based copolymer. The adhesive resin composition in the range of 001 to 20 parts by weight is extrusion-laminated on the skin material layer to form a ventilation barrier adhesive layer on the skin material layer. It is preferable that the extrusion lamination is performed twice or more at an extrusion lamination thickness of 10 μm or more. Further, in the method for manufacturing a vehicle interior material according to the present invention, the base material layer is further laminated on the ventilation blocking adhesive layer of the vehicle interior material laminate obtained by the method for manufacturing a vehicle interior material laminate. It is characterized by the following.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The (a) ethylene-based copolymer according to the present invention is a copolymer containing at least ethylene and an unsaturated carboxylic anhydride as essential components, and optionally copolymerizes another radical polymerizable comonomer. You may let it. Specific examples of the unsaturated carboxylic anhydride used here include maleic anhydride, itaconic anhydride, citraconic anhydride, endic acid anhydride, 1-butene-3,4-dicarboxylic anhydride and the like. it can. These may be used in combination of two or more. Among them, maleic anhydride is preferably used in terms of reactivity and economy.

(A) In the ethylene copolymer, the unit derived from the unsaturated carboxylic anhydride is 0.1 to 20% by weight, preferably 0.1 to 10% by weight. Preferably, it is in the range of 0.3 to 5.0% by weight. When the unit derived from the unsaturated carboxylic anhydride is 0.1
If the amount is less than 10% by weight, sufficient bonding strength cannot be obtained due to insufficient bonding performance, and sufficient crosslink density required for heat creep resistance cannot be obtained. On the other hand, if it exceeds 10% by weight, the dissociation of the crosslink between the acid anhydride group and the (b) polyhydric alcohol compound upon heating becomes insufficient, resulting in poor moldability and adhesiveness.

(A) The ethylene copolymer may be used by copolymerizing another radical polymerizable comonomer as necessary. By using other radically polymerizable comonomers, it is possible to control the melting point and flexibility of the ethylene copolymer and compatibility with the adherend, and to design an adhesive resin composition suitable for the purpose. Becomes possible. Examples of other radical polymerizable comonomers include ethylenically unsaturated ester compounds, ethylenically unsaturated amide compounds, ethylenically unsaturated carboxylic acid compounds, ethylenically unsaturated ether compounds, ethylenically unsaturated hydrocarbon compounds, and the like. it can. Specific examples of these include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, benzyl (meth) acrylate, and fumaric acid. Methyl acetate, ethyl fumarate, dimethyl maleate, diethyl maleate, vinyl acetate,
(Meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethylacrylamide, (meth) acrylic acid, fumaric acid, methyl vinyl ether, methyl allyl ether, styrene, butadiene, acrylonitrile and the like can be mentioned. These other radically polymerizable comonomers may be used in combination of two or more as needed. Also, two or more (a) ethylene copolymers separately polymerized using different radical polymerizable comonomers may be mixed and used.

When the above-mentioned other radically polymerizable comonomer is used in combination, the content of (a) the other radically polymerizable comonomer component in the ethylene copolymer is in the range of 30% by weight or less, preferably 25% by weight or less. Range. If it exceeds 30% by weight, the melting point of the ethylene copolymer (a) is too low, and practical heat resistance cannot be achieved. Also,
(A) Melt flow rate (MF) of ethylene copolymer
R) is not particularly limited, but 0.1 to 50 g /
Desirably, the range is 10 minutes. (A) When the MFR of the ethylene copolymer exceeds 50 g / 10 minutes, the resistance to molecular pull-out at the time of peeling is remarkably reduced, so that heat creep resistance does not increase. If the MFR of the (a) ethylene-based copolymer is less than 0.1 g / 10 minutes, the moldability (draw-down property) during extrusion lamination will be poor.

(A) The ethylene copolymer can be produced by a generally known method, that is, a polymerization process such as bulk, solution, suspension, and emulsification. And manufacturing technology.

Specific examples of (b) a polyhydric alcohol compound having at least two hydroxyl groups in the molecule (hereinafter referred to as (b) polyhydric alcohol compound) include ethylene glycol, diethylene glycol, triethylene glycol, 4-butanediol, 1,6-hexanediol, 1,8-octanediol, trimethylolethane, trimethylolpropane, pentaerythritol,
Albitol, sorbitol, xylose, glucose, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyolefin oligomer having two or more hydroxyl groups in one molecule, ethylene-hydroxyethyl (meth) acrylate copolymer, etc. And polyoxyalkylene compounds and polyglycerin esters obtained by adding ethylene oxide or propylene oxide to the above alcohol compounds. These may be used in combination of two or more kinds. Further, the melting point of (b) the polyhydric alcohol compound is desirably 300 ° C. or less.
In particular, trimethylolpropane, pentaerythritol, a polyoxyalkylene compound, or a polyglycerol ester is preferably used because of its excellent recyclability and economic efficiency.

(B) The amount of the polyhydric alcohol compound used is
(A) for the acid anhydride group in the ethylene-based copolymer,
(B) the molar ratio of hydroxyl groups derived from the polyhydric alcohol compound is
0.01 to 10, more preferably 0.05
It is desirably で 5. If the molar ratio is less than 0.01, crosslinking is insufficient, and the desired heat resistance cannot be obtained. On the other hand, when the molar ratio exceeds 10, the dissociation of the cross-link between the acid anhydride group and the (b) polyhydric alcohol compound during heating becomes insufficient, and molding processing becomes difficult.

(C) Examples of the reaction accelerator include a metal salt of a carboxylic acid and a metal salt of a polymer containing a carboxyl group. Examples of metal salts of carboxylic acids include acetic, butyric, octanoic, decanoic, lauric, myristic, palmitic, stearic, oleic, behenic, succinic, benzoic, terephthalic, and pyromellitic acids. And carboxylic acids such as IA group, IIA group,
Group IIB, IIIB elements (eg Li, Na, K, M
g, Ca, Zn, Al, etc.).

Examples of the metal salt of the polymer containing a carboxyl group include a part or all of the carboxyl group of the ethylene- (meth) acrylic acid copolymer, and a group IA or II of the periodic table.
Group A, IIB, IIIB elements (eg, Li, Na,
K, Mg, Ca, Zn, Al, etc.)
Copolymers of ethylene and ethylene- (meth) acrylic acid metal salt can be mentioned. At this time, (a) other radical polymerizable comonomer used in the ethylene copolymer may be used. Further, a resin obtained by graft-polymerizing a metal salt of an unsaturated carboxylic acid to a polyolefin resin such as polyethylene or polypropylene may be used.

(C) Other examples of the reaction accelerator include triethylamine, trimethylamine, tetramethylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetramethylammonium bromide, tetraethylammonium bromide and the like. Among the reaction accelerators (c) exemplified above, metal carboxylate has the highest accelerating effect and is preferably used. However, even if it is a low molecular weight or a high molecular weight, the effect remains unchanged. . Further, the reaction accelerator (c) exemplified above may be used in combination of two or more if necessary.

(C) Since the amount of the reaction accelerator used varies depending on the type, it is difficult to unconditionally define it. However, generally, the amount of the reaction accelerator is 0.1 to 100 parts by weight of the ethylene copolymer (a).
The range is preferably 001 parts by weight or more and 20 parts by weight or less, more preferably 0.01 parts by weight or more and 15 parts by weight or less. If the amount is less than 0.001 part by weight, the reaction is too slow to effectively introduce the crosslinking, and the heat resistance is poor. When the amount exceeds 20 parts by weight, not only does the reaction rate of crosslinking not increase, but also reversible crosslinking reaction hardly occurs, resulting in poor moldability and adhesiveness.

The adhesive resin composition used in the present invention includes:
Various adhesive components can be added as necessary.
By adding the tacky component, the adhesiveness of the adhesive resin composition can be improved. Examples of the added adhesive component include a cyclopentadiene-based hydrogenated petroleum resin, a copolymerized polyamide resin, a terpene phenol resin, a hydrogenated terpene resin, a rosin-based resin, and the like. The amount of the adhesive component is not particularly limited, but is preferably in the range of 1 to 25% by weight. If the amount is less than 1% by weight, the effect of improving the adhesion cannot be obtained, and if it exceeds 25% by weight, the processing becomes difficult because the tackiness is too high. Various additives can be added to the adhesive resin composition used in the present invention, if necessary, as long as the properties are not impaired. Specific examples include antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, lubricants, antiblocking agents, flame retardants, antifoggants, inorganic fillers, pigments, foaming agents, and the like. No.

The adhesive resin composition used in the present invention comprises:
The main components are (a) an ethylene copolymer, (b) a polyhydric alcohol compound, (c) a reaction accelerator, and an adhesive component, which are essential components. Can be blended. The polyolefin-based resin can additionally provide properties such as processability, mechanical properties, and low-temperature adhesiveness. Specific examples of the polyolefin resin to be blended include polyethylene, polypropylene, polystyrene, ethylene propylene copolymer, ethylene vinyl acetate copolymer, ethylene-methyl acrylate copolymer and the like. The blending amount of the polyolefin-based resin is not particularly limited, but is preferably 1% in total of a composition comprising (a) an ethylene-based copolymer, (b) a polyhydric alcohol compound, and (c) a reaction accelerator.
Less than 100 parts by weight to 00 parts by weight. If the amount exceeds 100 parts by weight, the amount of (a) the ethylene-based copolymer becomes too small, and the heat resistance and the adhesiveness decrease.

The adhesive resin composition of the present invention may contain, if necessary, an adhesive component in addition to the essential components (a) an ethylene copolymer, (b) a polyhydric alcohol compound, and (c) a reaction accelerator. , Each additive and a polyolefin resin, and melt-mixing them by a general kneading method such as an extruder, a Banbury mixer, a static mixer, and a roll. The kneading temperature is usually in the range of 150 to 280C, preferably in the range of 180 to 240C.

The acid anhydride group in the (a) ethylene copolymer used in the resin composition of the present invention reacts with the hydroxyl group contained in the (b) polyhydric alcohol compound to form a half ester (monoester). Form the structure. However, with only these two components, the reaction rate of dissociation of crosslinks by heat and recrosslinking upon cooling is extremely slow, and it is difficult to achieve a desired crosslinked state under general processing conditions. Therefore, by using the reaction accelerator (c), a thermoreversible crosslinked resin that can be practically used for the first time can be obtained.

As described above, the heat-resistant creep property of the adhesive resin composition according to the present invention is determined by the fact that (a) the acid anhydride group in the ethylene copolymer is crosslinked by (b) the polyhydric alcohol compound. Express. On the other hand, under certain conditions, the acid anhydride group and the (b) polyhydric alcohol compound are dissociated, and the adhesive resin composition is in a non-crosslinked state, and can be subjected to molding such as extrusion lamination as a complete thermoplastic resin. It becomes possible to perform bonding at a relatively low temperature by controlling the cooling conditions. (B) Since the crosslinking by the polyhydric alcohol compound is reversible, by forming a crosslinked structure in the cooling process of the adhesive resin composition after the molding process, the heat-resistant creep property of the adhesive resin composition is exhibited again. . At this time, if the quenching condition is used, the non-crosslinked state is fixed, so that the level of crosslinking can be controlled according to the cooling condition. After fixing the non-crosslinked state by quenching, the laminating temperature / time, annealing temperature /
By adjusting the time, the level of crosslinking of the final laminate, ie, the heat resistance, can be controlled.

The air-permeable barrier adhesive layer (hereinafter, referred to as an adhesive layer) constituting the laminate for a vehicle interior material of the present invention is composed of the above-mentioned adhesive resin composition and has a thickness of at least 20 μm and is formed as a single layer. In this case, the thickness is preferably 40 μm or more, more preferably 50 μm or more, and the molding method such as press bonding is not particularly limited, but is preferably formed by direct lamination. The thickness of the adhesive layer is 20 μm
If it is less than 10, there is a possibility that the ventilation barrier property of the laminate for vehicle interior materials may be insufficient. In the case where the adhesive layer is formed by extrusion lamination two or more times, the thickness of the extrusion laminate per one time is 1 in consideration of the amount of penetration into the skin material and the base material.
It is preferable that the thickness be 0 μm or more. Therefore, when the adhesive layer is formed by two or more extrusion laminations, if the thickness of each extrusion laminate is 10 μm or more and the total thickness of the formed adhesive layer is at least 20 μm, a single layer is formed. It is possible to make the laminated body for a vehicle interior material excellent in ventilation blocking property while making the adhesive layer thinner than that of the laminated body. Further, the adhesive layer may have a structure of two or more layers composed of two or more adhesive resin compositions having different compositions within the scope of the present invention. In this case, for the adhesive layer in contact with the skin material layer, an adhesive resin composition having excellent adhesion to the skin material is used, and for the adhesive layer in contact with the base material layer, an adhesive having excellent adhesion to the base material is used. By using the conductive resin composition, it is possible to obtain a laminate for a vehicle interior material having excellent adhesiveness of each layer.

As the skin material for the skin material layer constituting the laminate for a vehicle interior material of the present invention, various skin materials generally used as materials for an interior material of an automobile can be used, and particularly limited. Is not done. For example, polyester non-woven fabric, brushed knit, fabric, suede-like synthetic leather, vinyl chloride leather, polyurethane leather, polypropylene-based thermoplastic elastomer, or those obtained by laminating a cushion material such as urethane foam, polyethylene foam, or polypropylene foam to these materials And the like.

As the material of the substrate used for the substrate layer,
Various materials generally used as materials for interior materials of automobiles can be used, and there is no particular limitation. For example, various papers such as synthetic paper, art paper, coated paper, etc .; various woven or non-woven fabrics made of cotton, hemp, polyester, nylon, etc .; various wooden boards such as plywood, particle board; various kinds of iron, aluminum, copper, tinplate, etc. Metals; polypropylene, polystyrene, polyethylene, polyester, nylon, polycarbonate, acrylic resin, phenolic resin, polyurethane, styrene-butadiene block copolymer, styrene-acrylonitrile copolymer, and other plastics; glass fiber, ceramic, etc. Examples include inorganic substances. Specific examples of the base material include resin felt, resin wood, phenolic resin plate containing glass fiber, corrugated cardboard, polypropylene honeycomb, polystyrene foam, glass fiber reinforced polypropylene plate, ABS resin plate, AS resin plate, or a nonwoven fabric bonded to these. And the like. These substrates may be subjected to surface treatment, printing, coating, etc., as necessary.

Next, a method of manufacturing the laminate for a vehicle interior material according to the present invention will be described. The production of the laminated body for a vehicle interior material of the present invention is not particularly limited, and can be performed by an extrusion laminating method, a heat laminating method, or a method of thermocompression bonding using a generally used hot press or hot roll. The heating temperature at the time of bonding differs depending on the composition of the adhesive resin composition, the skin material, the type of the base material, the molding conditions and the like, and cannot be specified unconditionally, but is at least equal to or higher than the softening point of the adhesive resin composition. , The skin material and the base material are appropriately selected within a temperature range that does not affect the base material. In particular, in the present invention, it is desirable to be manufactured by an extrusion lamination method. The laminate for a vehicle interior material of the present invention is preferably manufactured by extrusion laminating the above adhesive resin composition on a skin material layer and forming an adhesive layer on the skin material layer. When the adhesive layer is a single layer, it is desirably extruded once with a laminate thickness of 20 μm or more, preferably 40 μm, to form an adhesive layer on the skin material layer. More preferably, it is desirably manufactured by extruding and laminating an extruded laminate on the skin material layer two or more times and a plurality of times to form an adhesive layer on the skin material layer. If extrusion lamination is performed twice or more, 10 μm
It is desirable to perform the above extrusion lamination a plurality of times. When forming a plurality of adhesive layers, the adhesive composition may be the same or different. Extrusion lamination can be performed by a generally used method. It is desirable that the resin temperature during extrusion lamination be in the range of 210 to 300 ° C.

The vehicle interior material of the present invention is manufactured, for example, by laminating a base material layer by bonding on an adhesive layer formed on a skin material layer. The bonding conditions at this time are the same as those for the laminate for vehicle interior materials.

At the time of extrusion lamination, the resin temperature is set at 210 to
Except in the range of 300 ° C., both neck-in and draw-down are in accordance with the conditions at the time of extrusion lamination of low-density polyethylene, and no special attention is required. In addition, in consideration of the compatibility of the adhesive with the skin material and the substrate, the composition of each adhesive resin composition at the time of extrusion lamination two or more times,
Each may be different within the scope of the present invention. When performing extrusion lamination twice or more, extrusion lamination may be performed off-line or may be performed by a tandem machine (in-line). When performing extrusion lamination, a process for treating the substrate layer or the surface of the adhesive layer is introduced in-line or off-line for the purpose of improving the extruded laminate adhesive strength or the heat-sensitive adhesive strength at the time of lamination with the substrate. No problem. Specific examples of the process for assisting the adhesive strength include a corona treatment, an ozone treatment, a flame treatment, and a heat treatment with a heater.

[0033] The problem of the air-permeability in the conventional laminated body for vehicle interior materials is that when extruding and laminating the adhesive layer on the skin material layer, a pinhole generated in the adhesive layer or a defect causing the pinhole is generated. In most cases, it is stretched and expanded at the time of bonding with the base material layer. That is,
At least if there is no pinhole in the adhesive layer immediately before lamination,
Substantial ventilation barrier is not a problem. Therefore, when the thickness of the extruded laminate is a single layer of one-time lamination, the thickness is preferably 20 μm or more or 40 μm or more from the viewpoint of safety. Further, when the extrusion laminate is formed a plurality of times, even if the thickness of the extrusion laminate per one time is about 10 μm, the pinhole can be completely eliminated by performing the extrusion lamination twice or more. The ventilation barrier property of the laminate for a material is good.

The thicknesses of the skin material layer and the base material layer vary depending on the material, required physical properties and the like, and are not particularly limited. The vehicle interior material laminate or vehicle interior material of the present invention is:
It is composed of at least two layers of the above-mentioned skin material layer and adhesive layer, or three layers of the skin material layer, the adhesive layer and the base material layer, and if necessary, further comprises the adhesive resin composition according to the present invention. A laminate in which another material is laminated via an adhesive layer made of, or via another adhesive layer, or without an adhesive layer may be used.

[0035]

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

The following evaluation method was used in the present embodiment. (Air permeability) The air permeability was measured at 23 ° C. using a Frazier-type air permeability tester manufactured by Toyo Seiki, and was 0.1 cc / cm.
○ ² s or less, 1 cc / cm ² / s or more, 5 cc / cm
Less than ² / s was rated as ×, and 5 cc / cm ² / s or more was rated as XX. (Initial adhesive strength) A sample having a width of 25 mm was cut out and measured three days after bonding at a peeling speed of 300 mm / min. (Heat-resistant creep resistance) Cut out a sample to a width of 25 mm, expose the skin material, and hang a 100 g weight
It was left in a constant temperature room at 20 ° C. for 24 hours, and the peeling distance after that was 5 mm or less, 、, 20 mm or more and less than 40 mm, x, 40
mm or more was designated as XX.

In this embodiment, (a) an ethylene copolymer, (b) a polyhydric alcohol compound, (c) a reaction accelerator,
The following were used as the adhesive component and the polyolefin resin. ((A) Ethylene copolymer) a-1: Ethylene-maleic anhydride (1.5% by weight)-
Methyl acrylate (25% by weight) terpolymer, MF
R = 12 g / 10 min a-2: Ethylene-maleic anhydride (2.0% by weight)-
Methyl acrylate (15% by weight) terpolymer, MF
R = 12 g / 10 min a-3: Ethylene-maleic anhydride (2.5% by weight) 2
Original copolymer, MFR = 15g / 10min

((B) Polyhydric alcohol compound) b-1: 1,1,1-trimethylolpropane b-2: pentaerythritol b-3: tris (2-hydroxybutanoic acid) glycerin triester ((c) Reaction Accelerator) c-1: Ionomer (Himilan 1605, manufactured by Mitsui DuPont Polychemicals) c-2: Sodium stearate c-3: Calcium stearate (adhesive component) Viscosity-1: Alcon P-125 (Arakawa Chemical Co., Ltd.) Viscosity-2: Terpene phenol YP902 (manufactured by Yasuhara Chemical Co., Ltd.) (polyolefin resin) JH606N: Low-density polyethylene by high-pressure radical polymerization (density = 0.916 g / cm ³ , MFR = 7 g / 1)
0 minutes, manufactured by Nippon Polyolefin)

Example 1 Ethylene copolymer (a-
1) 100 parts by weight of a polyhydric alcohol compound (b-1) 2
Parts by weight and 5 parts by weight of the reaction accelerator (c-1) were melt-kneaded by a co-directional twin-screw extruder set at 180 ° C to obtain an adhesive resin composition. The molar ratio of the hydroxyl group derived from the polyhydric alcohol compound (b-1) to the acid anhydride group in the ethylene copolymer (a-1) was 2.9. This adhesive resin composition was applied to a line speed of 4 using a 65 mmφ laminator.
Under conditions of 0 m / min and a temperature of 270 ° C., 180
Extrusion lamination was performed twice on a g / m ² polyester nonwoven fabric. The thickness of the extruded laminate was 20 μm for the first time, 2
The second round was 20 μm.

A sample after lamination was prepared with a thickness of 50 mm.
160 ° C on polypropylene / glass fiber mixed substrate
Lamination was carried out by micro-pressure heat pressing under the condition of 30 seconds.
The obtained vehicle interior material was measured for air-permeability, initial adhesive strength, and heat creep resistance. Table 2 shows the results.

[Examples 2 to 9] (a) an ethylene copolymer, (b) a polyhydric alcohol compound, (c) a reaction accelerator,
A laminate for a vehicle interior material was obtained in the same manner as in Example 1 except that the amount of the adhesive component, the amount of the polyolefin-based resin, and the number and the thickness of the extrusion lamination were changed as shown in Table 1. The air-permeable barrier property, initial adhesive strength, and heat creep resistance of the obtained laminate for vehicle interior materials were measured. Table 2 shows the results.

Comparative Example 1 Ethylene copolymer (a-
2) 100 parts by weight, 0.3 parts by weight of a reaction accelerator (c-2), and 5 parts by weight of an adhesive component (viscosity-2), except that the thickness of the extrusion laminate was changed to 40 μm for the first time and 40 μm for the second time. Was performed in the same manner as in Example 1 to obtain a laminate for vehicle interior materials. The air-permeable barrier property, initial adhesive strength, and heat creep resistance of the obtained laminate for vehicle interior materials were measured. Table 2 shows the results. The laminate for vehicle interior materials in which the adhesive layer did not contain (b) the polyhydric alcohol compound was inferior in ventilation blocking properties and heat creep resistance.

Comparative Example 2 Ethylene copolymer (a-
2) 100 parts by weight of a polyhydric alcohol compound (b-3)
Except that 0.005 parts by weight, 0.3 parts by weight of the reaction accelerator (c-2), and 5 parts by weight of the adhesive component (viscosity-2) were used, and the thickness of the extrusion laminate was changed to 30 μm for the first time and 30 μm for the second time. Was performed in the same manner as in Example 1 to obtain a laminate for vehicle interior materials. The air-permeable barrier property, initial adhesive strength, and heat creep resistance of the obtained laminate for vehicle interior materials were measured. Table 2 shows the results. (A) for the acid anhydride group in the ethylene copolymer,
(B) A laminate for a vehicle interior material using an adhesive resin composition having a molar ratio of hydroxyl groups derived from a polyhydric alcohol compound of less than 0.01 was inferior in ventilation blocking property and heat creep resistance.

Comparative Example 3 Polyhydric alcohol compound (b-
Comparative Example 2 except that the amount of 3) was changed to 40 parts by weight.
In the same manner as described above, a laminate for vehicle interior materials was obtained. The air-permeable barrier property, initial adhesive strength, and heat creep resistance of the obtained laminate for vehicle interior materials were measured. Table 2 shows the results. A laminate for vehicle interior materials using an adhesive resin composition having a molar ratio of (b) a hydroxyl group derived from a polyhydric alcohol compound to (a) an acid anhydride group in an ethylene copolymer of more than 10 is initially bonded. Poor strength and heat creep resistance.

Comparative Example 4 Polyhydric alcohol compound (b-
3) was changed to 1.5 parts by weight, and the reaction accelerator (c
A laminate for vehicle interior material was obtained in the same manner as in Comparative Example 3, except that the blending amount of -2) was changed to 0.0001 parts by weight. The air-permeable barrier property, initial adhesive strength, and heat creep resistance of the obtained laminate for vehicle interior materials were measured. Table 2 shows the results. (A) relative to 100 parts by weight of ethylene copolymer,
(C) The laminate for vehicle interior materials using the adhesive resin composition containing less than 0.001 part by weight of the reaction accelerator was inferior in the ventilation barrier property and the heat creep resistance.

Comparative Example 5 A laminate for vehicle interior materials was obtained in the same manner as in Comparative Example 5, except that the amount of the reaction accelerator (c-2) was changed to 25 parts by weight. The air-permeable barrier property, initial adhesive strength, and heat creep resistance of the obtained laminate for vehicle interior materials were measured. Table 2 shows the results. (A) 100 parts by weight of ethylene copolymer, (c) the amount of the reaction accelerator is 2
A laminate for vehicle interior materials using an adhesive resin composition exceeding 0 parts by weight was inferior in initial adhesive strength and heat creep resistance.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

As described above, the laminate for a vehicle interior material of the present invention comprises the above-mentioned (a) an ethylene copolymer, and (b)
Having a ventilation barrier adhesive layer composed of an adhesive resin composition containing a polyhydric alcohol compound and (c) a reaction accelerator,
(A) the proportion of units derived from the unsaturated carboxylic anhydride in the ethylene copolymer is 0.1 to 20% by weight, and (b) based on the acid anhydride groups in the (a) ethylene copolymer The molar ratio of the hydroxyl group derived from the polyhydric alcohol compound is in the range of 0.01 to 10, and the (c) reaction accelerator is 0.0% based on 100 parts by weight of the (a) ethylene-based copolymer.
Since it is in the range of 01 to 20 parts by weight, bonding at a relatively low temperature is possible, excellent in heat resistance, and good air-permeability can be achieved without providing a special air-permeation barrier layer. Further, since there is no need to provide a special ventilation blocking layer, a laminate for vehicle interior materials can be obtained at low cost.

Further, the thickness of the ventilation blocking adhesive layer is 20
If it is not less than μm, the ventilation blocking property is further improved. Further, when the air-permeable barrier adhesive layer is formed by two or more extrusion laminations, the air-permeable barrier properties are further improved. Further, when two or more air-permeable adhesive layers are provided, and the composition of the adhesive resin composition used for each of the air-permeable adhesive layers is different from each other, the adhesive resin composition may be different from the base material layer of the skin material or the vehicle interior material. It is possible to obtain a laminate for vehicle interior materials having excellent adhesiveness. Further, since the vehicle interior material of the present invention is provided with a base material layer on the laminate for vehicle interior material, it can be bonded at a relatively low temperature, has excellent heat resistance, and has good ventilation. The barrier properties can be achieved without providing a special ventilation barrier layer.

The method for producing a laminate for a vehicle interior material according to the present invention is a method in which the adhesive resin composition is extrusion-laminated on a skin material layer, and a ventilation-blocking adhesive layer is formed on the skin material layer. Because of this, a laminate for vehicle interior materials that can be bonded at a relatively low temperature, has excellent heat resistance, and can achieve good ventilation barrier properties without providing a special ventilation barrier layer at low cost. Can be obtained at Further, in the method for manufacturing a vehicle interior material of the present invention, the adhesive resin composition is extrusion-laminated on a skin material layer, and a ventilation barrier adhesive layer is formed on the skin material layer. Since it is a method of laminating the base material layer on the top, lamination at a relatively low temperature is possible,
In addition, it is possible to obtain a vehicle interior material which is excellent in heat resistance and can achieve good ventilation blocking properties without providing a special ventilation blocking layer at low cost. In addition, when extrusion lamination is performed twice or more with an extrusion lamination thickness of 10 μm or more, the obtained vehicle interior material laminate and the vehicle inner layer material can be further improved in the ventilation blocking property.

Continuation of front page (72) Inventor Koji Okamoto 2-3-2, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan F-term in Kawasaki Research Laboratory of Polyolefin Co., Ltd. 3D023 BA05 BB01 BB02 BD01 BE05 BE06 4F100 AH02B AH02C AH02J AK04B AK04C AK04J AK04K AL01B AL01C AL01K AL07B AL07C AR00A AR00B AR00C AT00D BA02 BA03 BA04 BA07 BA10A BA10C BA10D BA13 BA27 CA02B CA02C EC182 EH23B EH23C EH232 GB31 HB00A JD02 JD02B JD11B00JJLY

Claims (8)

[Claims] 1. A laminate for vehicle interior materials having at least a skin material and a ventilation barrier adhesive layer, wherein the ventilation barrier adhesive layer comprises (a) ethylene and an unsaturated carboxylic anhydride as essential components. Ethylene copolymer,
(B) an adhesive resin composition containing a polyhydric alcohol compound having at least two hydroxyl groups in a molecule and (c) a reaction accelerator, wherein (a) the unsaturated carboxylic acid in the ethylene-based copolymer The ratio of the unit derived from the acid anhydride is 0.1 to 20% by weight, and (a) based on the acid anhydride group in the ethylene copolymer,
(B) the molar ratio of hydroxyl groups derived from the polyhydric alcohol compound is
0.01 to 10; and (c) the reaction accelerator is (a) ethylene copolymer 1
A laminate for vehicle interior materials, wherein the amount is 0.001 to 20 parts by weight with respect to 00 parts by weight. 2. The laminate for a vehicle interior material according to claim 1, wherein the ventilation blocking adhesive layer is formed by extrusion lamination two or more times. 3. The method according to claim 1, wherein the thickness of the ventilation blocking adhesive layer is 20 μm.
The laminated body for a vehicle interior material according to claim 1 or 2, wherein: 4. The vehicle interior according to claim 3, wherein the ventilation barrier adhesive layer comprises two or more layers, and the composition of the adhesive resin composition used for each ventilation barrier adhesive layer is different from each other. Laminate for materials. 5. The vehicle interior material laminate according to any one of claims 1 to 4, further comprising a substrate layer, and the substrate layer is laminated on the ventilation blocking adhesive layer. Vehicle interior material characterized by: 6. An ethylene copolymer having (a) ethylene and an unsaturated carboxylic anhydride as essential components, (b) a polyhydric alcohol compound having at least two hydroxyl groups in a molecule, and (c). It contains a reaction accelerator, and the proportion of units derived from the unsaturated carboxylic anhydride in the (a) ethylene-based copolymer is 0.1 to 20% by weight;
(A) (b) for the acid anhydride group in the ethylene copolymer
The molar ratio of the hydroxyl group derived from the polyhydric alcohol compound is 0.0
In the range of 1 to 10, and (c) a reaction accelerator,
(A) 0.0 to 100 parts by weight of the ethylene copolymer
A laminate for a vehicle interior material, wherein an adhesive resin composition in an amount of from 0.01 to 20 parts by weight is extrusion-laminated on a skin material layer to form a ventilation blocking adhesive layer on the skin material layer. Manufacturing method. 7. The method according to claim 6, wherein the extrusion laminating is performed twice or more with a thickness of 10 μm or more. 8. A method of manufacturing a laminate for a vehicle interior material according to claim 6 or 7, further comprising laminating a base material layer on the ventilation blocking adhesive layer of the laminate for a vehicle interior material. A method for manufacturing vehicle interior materials.