JPH05329983A - Laminated body and manufacturing method thereof - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a two-layer laminate having a high interlayer adhesion strength and capable of being heat-bonded to another substrate, a multilayer laminate using the same, and a method for producing the same. [Structure] (1) An adhesive resin composition comprising 10 to 100% by weight of an ethylene copolymer, which is a copolymer of ethylene and a radical-polymerizable acid anhydride, and 90 to 0% by weight of a polyolefin resin, and (2 ) A two-layer laminate is provided by co-extruding a thermoplastic elastomer, and another substrate is heat-sensitively adhered onto the adhesive resin composition layer of the two-layer laminate to provide a multilayer laminate. It is a thing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-bondable two-layer laminate, a multilayer laminate using the laminate, and a method for producing them.

[0002]

2. Description of the Related Art Conventionally, vehicle interior materials, automobile interior materials, architectural interior materials, display panel materials, furniture materials, home appliance housing materials, bag materials, sports equipment materials, office equipment materials, etc. In terms of scratch resistance, weather resistance, texture, etc., a multilayer laminate in which a soft or semi-hard polyvinyl chloride resin is adhesively bonded to various base materials is widely used as a skin material. However, recently, due to environmental problems, oozing out of plasticizers, generation of mold, and the like, thermoplastic elastomers, which are materials with excellent lightness, flexibility, surface scratches, and heat resistance, have been replaced by polyvinyl chloride. It has been widely used as a multilayer laminate with various base materials.

In the production of such a multi-layer laminate, since the thermoplastic elastomer itself has poor adhesion to other base materials, in many cases bonding with a solution adhesive is carried out. However, with such a bonding method, work is time-consuming and, in recent years, environmental issues are becoming more important,
There is a problem of occupational health and danger (fire etc.) due to organic solvent, and it cannot be said that it is an appropriate method. On the other hand, when the base material is made of a polyolefin-based material, for example, crosslinked polyethylene foam or crosslinked polypropylene foam, a heat bonding method such as roll pressure bonding may be used depending on the application (JP-A-57-20344). Gazette),
Depending on the case, the crimp deformation of the base material during roll crimping becomes a problem, and it cannot be applied to the base material such as urethane foam or nonwoven fabric due to insufficient adhesiveness, so its application range is limited. It was a thing.

Therefore, a method of exhibiting adhesiveness by using a polyolefin resin having a carboxyl group or an acid anhydride group as a constituent component of a thermoplastic elastomer (JP-A-59-59).
1561) or an ethylene-α-olefin copolymer rubber having a carboxyl group or an acid anhydride group to develop adhesiveness (Japanese Patent Laid-Open No. 59-27935). However, even if these methods are used, the adhesiveness cannot be said to be sufficient, and the processing method can be applied only to a limited use, and it is not a technology that can be widely applied.

In order to solve these problems, it has been proposed to use a resin obtained by copolymerizing ethylene with 24% by weight or more of an unsaturated ester or a modified resin thereof as an adhesive resin (JP-A-60-201140). Publication). Specifically, a method of thermocompression bonding the molding film of the adhesive resin,
Examples include a method of adhering by coextrusion molding, a method of adhering two kinds of substrates by a sandwich lamination method, a method of applying and adhering using a hot melt gun or the like. However, even if such an adhesive resin is used, the adhesive strength is insufficient in some cases, resulting in peeling during long-term use, or damage to the skin material due to the need for heat pressing at high temperature for a long time. There is a problem such as doing. In addition, a mineral oil-based softening agent is often added to the thermoplastic elastomer as a means for improving the decrease in fluidity. However, due to the bleeding of the mineral oil-based softening agent, the adhesive strength is significantly increased. Cause decline.

Due to the above-mentioned various difficulties, thermoplastic elastomers have been conventionally used for other substrates such as foamed polypropylene resin, polypropylene board, glass fiber-containing polypropylene board, resin felt, glass fiber-containing phenol board. However, it is difficult to adhere to a base material such as particle board or paper, and a special bonding method has to be selected for each base material such as using a special solvent-based adhesive.

[0007]

Therefore, the present invention solves the above-mentioned problems of the prior art, does not use a solvent-based adhesive, has a high interlayer adhesive strength, and is heat-bonded to another substrate. It is an object of the present invention to provide a two-layer laminate capable of being manufactured and a method for producing the same, and a multilayer laminate including the two-layer laminate and another substrate and a method for producing the same.

[0008]

Means for Solving the Problems The present inventor uses a copolymer of ethylene and a radical-polymerizable acid anhydride as an adhesive resin to form a two-layer laminate having a thermoplastic elastomer and an extremely high interlayer adhesive strength. It has been found that it can be formed and can be heat-bonded to other substrates. The present invention has been completed based on such findings.

That is, according to the present invention, (1) 10 to 100% by weight of an ethylene copolymer, which is a copolymer of ethylene and a radical-polymerizable acid anhydride, and a polyolefin resin 9
An adhesive resin composition comprising 0 to 0% by weight and (2) a two-layer laminate comprising a thermoplastic elastomer, and the above (1)
The present invention provides a method for producing a two-layer laminate, which comprises coextrusion molding a component and the component (2).

The present invention further includes a multilayer laminate obtained by laminating another base material on the adhesive resin composition layer of the two-layer laminate of the present invention and the adhesive resin of the two-layer laminate of the present invention. It is intended to provide a method for producing a multilayer laminate, which comprises heat-bonding another substrate onto the composition layer.

The adhesive resin composition of component (1) in the present invention comprises one or two components, and an ethylene-based copolymer which is a copolymer of ethylene and a radical-polymerizable acid anhydride as an essential component. Including. Here, the radical-polymerizable acid anhydride is a compound having at least one radical-polymerizable unsaturated bond and at least one acid anhydride group in the molecule, and capable of introducing an acid anhydride group into the molecule by polymerization. Is. Specific examples of such compounds include maleic anhydride, itaconic anhydride, endic anhydride, citraconic anhydride, 1-
Butene-3,4-dicarboxylic acid anhydride, alkenylsuccinic anhydride having a double bond at the terminal having at most 18 carbon atoms, alkadienyl succinic anhydride having a double bond at the terminal having at most 18 carbon atoms Etc. can be mentioned. These may be used in combination of two or more kinds at the same time. Of these, maleic anhydride and itaconic anhydride are particularly preferable.

In producing the above-mentioned ethylene-based copolymer, basically, ordinary low-density polyethylene production equipment and techniques can be used. Generally, it is a bulk polymerization, and it is 100 at a pressure of 700 to 3000 atm.
It is produced by radical polymerization in the temperature range of up to 300 ° C. The preferred polymerization pressure and polymerization temperature range is 1000 to 2
The pressure may be 500 atm, and the average temperature in the reactor may be 150 to 270 ° C.

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

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

The production of the ethylene copolymer used in the present invention is carried out under the above reaction conditions in the presence of at least one free radical initiator. Examples of the free radical initiator include oxygen; di-t-butyl peroxide,
t-butyl cumyl peroxide, dialkyl peroxide such as dicumyl peroxide; acetyl peroxide,
Diacyl peroxides such as i-butyryl peroxide and octanoyl peroxide; peroxycarbonates such as di-i-propylperoxycarbonate and di-2-ethylhexylperoxycarbonate; t-butylperoxypivalate and t-butyl Peroxyesters such as peroxylaurate; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis-t-butylperoxycyclohexane, 2,2-bis-t-butylperoxyoctane and the like. Peroxyketals; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; azo compounds such as 2,2-azo-i-butyronitrile.

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

The ethylene-based copolymer satisfying the above-mentioned conditions, which is produced in this manner, melts at a relatively low temperature and is rich in physical-chemical interaction and reactivity with various base materials. High adhesive strength even when coextruded at low temperature with a plastic elastomer.

The adhesive resin composition of the component (1) in the present invention may contain a polyolefin resin as the second component. Here, as the polyolefin resin,
High-density polyethylene, low-density polyethylene, polypropylene, polybutene, polyisoprene, poly-3-methylbutene-1, poly-4-methylpentene-1, polybutadiene, a copolymer of the resin constituent units, and more specifically, Propylene, butene-1,4-methylpentene-
1, low-density polyethylene copolymer using a comonomer selected from 1, hexene-1 and octene-1, and selected from ethylene, butene-1,4-methylpentene-1, hexene-1 and octene-1. Examples thereof include a propylene-based copolymer (including a block copolymer) using a comonomer, a mixture of these resins, and the like.

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

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

The adhesive resin composition used in the present invention may contain various additives, compounding agents, fillers and the like within a range that does not impair the characteristics of the composition. Specific examples of these include antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), glass, fillers. Inorganic filler, organic filler, reinforcing agent, colorant (dye,
Pigments), foaming agents, fragrances and the like.

In the production of the adhesive resin composition used in the present invention, the blending ratio of the ethylene copolymer and the polyolefin resin varies depending on the finally required requirements, and therefore cannot be specified unconditionally. Is an ethylene-based copolymer 10 to 100% by weight and a polyolefin resin 0 to 9
It is preferably in the range of 0% by weight. If the proportion of the polyolefin-based resin exceeds 90% by weight, the performance of the ethylene-based copolymer cannot be exhibited, which is not preferable.

Further, the adhesive resin composition produced as described above has a ratio of units derived from the radical-polymerizable acid anhydride in the ethylene-based copolymer which is an essential constituent of the adhesive resin composition. Of the adhesive resin composition as a whole.
It is preferably in the range of 1 to 5% by weight, and more preferably in the range of 0.5 to 4% by weight. If the proportion of the radical-polymerizable acid anhydride is less than 0.1% by weight based on the whole adhesive resin composition, the adhesive performance is insufficient and a good two-layer laminate cannot be produced. On the contrary, even if the amount of the unit derived from the radical-polymerizable acid anhydride exceeds 5% by weight, it does not affect the improvement of the adhesiveness, which is a feature of the present invention, and is economically meaningless. Is not preferable.

Next, as the thermoplastic elastomer which is the component (2) in the present invention, a blend of at least partially cross-linked ethylene / α-olefin copolymer rubber and polyolefin resin is used. preferable. Examples of such blends include the following.

Various polyolefin resins represented by a homopolymer of ethylene or propylene or a copolymer with a small amount of another comonomer, and ethylene and a carbon number of 3 to 1
No. 4, a binary copolymer rubber with an α-olefin or a terpolymer rubber obtained by further copolymerizing various polyene compounds with the ethylene / α-olefin copolymer rubber partially crosslinked product and / or complete A thermoplastic composition comprising a mixture of crosslinked materials.

Polyolefin resin and ethylene / α
A thermoplastic composition obtained by dynamically heat treating a composition with an olefinic copolymer rubber.

Polyolefin resin and ethylene / α
A thermoplastic composition obtained by dynamically blending a polyolefin obtained by dynamically heat-treating a composition with an olefin-based copolymer rubber.

A composition of various peroxide cross-linkable polyolefin resins represented by a homopolymer of ethylene or propylene or a copolymer of these with a small amount of a comonomer and an ethylene / α-olefin copolymer rubber is dynamically used. A thermoplastic composition obtained by heat treatment.

Further, the thermoplastic elastomer used in the present invention may contain a mineral oil softening agent, if necessary.
Mineral oil-based softeners usually weaken the intermolecular force of rubber during roll processing to facilitate processing, accelerate the dispersion of carbon black, white carbon, etc., or increase the hardness of vulcanized rubber. Is a petroleum fraction used for the purpose of reducing the oil content and increasing flexibility and rubber elasticity.
It is classified into naphthene type and aromatic type. Of these, paraffinic process oils are preferred.

The mineral oil-based softening agent can be used in the thermoplastic elastomer in the range of 0 to 60% by weight. That is, a thermoplastic comprising (a) 100 to 40% by weight of a blend of an at least partially crosslinked ethylene-α-olefin copolymer rubber and a polyolefin-based resin, and (b) 0 to 60% by weight of a mineral oil-based softening agent. Elastomers can be used. If the mineral oil-based softening agent is used in an amount of more than 60% by weight, the strength of the thermoplastic elastomer is lowered, and the mineral oil-based softening agent oozes out to cause problems such as appearance deterioration, which is not preferable.

In the thermoplastic elastomer used in the present invention, other additives, compounding agents, fillers and the like can be used as long as the characteristics of the composition are not impaired. Specific examples of these are glass, carbon black, zinc oxide,
In addition to inorganic fillers such as clay, talc, ground calcium carbonate, kaolin, diatomaceous earth, silica, alumina, asbestos, and graphite, organic fillers, antioxidants (heat resistance stabilizers), ultraviolet absorbers (light stabilizers), Antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), reinforcing agents, colorants (dyes, pigments), foaming agents, fragrances and the like can be mentioned.

In order to produce a laminate of the adhesive resin composition and the thermoplastic elastomer according to the present invention, a method called coextrusion molding method is usually used. Specifically, it is a method in which a T-die having a two-layer structure and two extruders directly connected to the T-die are used to simultaneously perform multilayer extrusion molding of the adhesive resin composition and the thermoplastic elastomer. According to this method, a two-layer laminate having an extremely high adhesive strength between the adhesive resin composition layer and the thermoplastic elastomer layer can be produced.

Further, a method of simultaneously performing multi-layer injection molding of the adhesive resin composition and the thermoplastic elastomer, or inserting the adhesive resin composition or the thermoplastic elastomer into a mold and then applying the thermoplastic elastomer or the adhesive It can also be manufactured by a method of injection molding a resin composition.

On the other hand, as another molding method, after the adhesive resin composition and the thermoplastic elastomer are formed into a film or sheet by inflation molding or T-die molding, the polyolefin resin composition and the thermoplastic elastomer are hot-pressed or hot-rolled. A method of thermocompression bonding with, a film or sheet of an adhesive resin composition or a thermoplastic elastomer, a method of laminating a thermoplastic elastomer or an adhesive resin composition is also conceivable, but in these methods, in particular, a mineral The adhesive strength with the thermoplastic elastomer containing the oil-based softening agent is lower than that of the laminate produced by the coextrusion molding, which is not preferable.

The two-layer laminate of the present invention is a material in which a thermoplastic elastomer having extremely poor heat-sensitive adhesiveness is provided with adhesiveness to various substrates by a copolymer of ethylene and a radical-polymerizable acid anhydride. .. Therefore, the two-layer laminate can be used to easily produce a multilayer laminate with various base materials by a heat-sensitive adhesive method such as a hot roll, a hot press, and a hot vacuum press. The heating temperature for heat bonding is
It cannot be unconditionally specified because it varies depending on conditions such as the type of base material, thickness, and time required for adhesion, but it is preferably at least the melting point of the adhesive resin composition or higher. Therefore, the temperature is preferably 120 ° C. or higher, and more preferably 140 ° C. or higher.

The other base material which can be heat-sensitively bonded onto the adhesive resin composition layer of the two-layer laminate of the present invention is 1
A substrate having a heat resistance of 20 ° C. or higher, more preferably a heat resistance of 140 ° C. or higher is preferably used. The multilayer laminate heat-bonded to these base materials can be applied to various uses, and can be particularly suitably used as a vehicle or automobile interior material. Currently, soft vinyl chloride resin is mainly used as a skin material for vehicles or automobiles, but due to environmental problems, expectations for a polyolefin-based thermoplastic elastomer as a skin material replacing soft vinyl chloride are increasing. Therefore, a multilayer laminate of the thermoplastic elastomer and various base materials such as those mentioned above, which are currently used for interior materials, is a suitable material for interior materials of vehicles or automobiles. Specific examples of the base material include foamed polypropylene resin, polypropylene board, glass fiber-containing polypropylene board, resin felt, glass fiber-containing phenol board and particle board.

Among them, the multi-layer laminate using the foamed polypropylene resin or the polypropylene board as a base material also has an advantage that it is a recyclable material when used as a vehicle or automobile interior material. ..

As the other base material capable of heat-sensitive adhesion to the two-layer laminate of the adhesive resin composition and the thermoplastic elastomer according to the present invention, a cross-linked polyethylene which is mainly used in addition to the above-mentioned vehicle or automobile interior materials. Form,
Examples include foamed resins such as PVC foam, polystyrene foam, and polyurethane foam, as well as cardboard paper boards impregnated with a resin and cured. Further, a board or sheet made of synthetic resin such as polyamide, PET, polycarbonate, polysulfone, polyimide, cellophane, phenol resin, unsaturated polyester cured resin, ABS, AES, HIPS, etc. may be mentioned. Moreover,
Fabrics such as nylon, polyester, wool, cotton, silk or blends thereof; nylon non-woven fabric, PET non-woven fabric, glass fiber non-woven fabric, polyolefin non-woven fabric, non-woven fabric such as regenerated cellulose non-woven fabric; Japanese paper, pulp paper, high-quality paper,
Examples include YUPO, decorative paper, kraft paper and the like. In addition to plywood, metal plates such as aluminum, iron, brass, galvanized iron, tin plate and the like, metal foils, and the like, cloth manufactured from a polyolefin resin such as polypropylene can also be used.

The multilayer laminate obtained by using the above-exemplified base materials is a material for automobiles, a material for vehicles, a material for ships, a material for construction, a material for display panels, a material for furniture, a housing material for home appliances. , It can be preferably used in a wide range of fields such as bag materials, sports equipment materials and office equipment materials.

[0040]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to these.

Reference Example 1 (Production of Ethylene-Maleic Anhydride Binary Copolymer) Ethylene-anhydrous was prepared under the conditions of a polymerization temperature of 220 ° C. and a polymerization pressure of 1900 Kg / cm ² using equipment of a high-pressure low-density polyethylene plant. A maleic acid binary copolymer was produced. MFR (J of the ethylene-maleic anhydride binary copolymer (hereinafter referred to as ethylene-based copolymer (A))
IS-K7210, Table 1, Condition 4) was 10, and the content of units derived from maleic anhydride was 2.1% by weight.
The composition was determined by infrared absorption spectrum.

Reference Example 2 (Production of Ethylene-Maleic Anhydride Binary Copolymer) Using the equipment of a high-pressure low-density polyethylene plant, ethylene-anhydrous was prepared under the conditions of a polymerization temperature of 200 ° C. and a polymerization pressure of 1900 Kg / cm ^2. A maleic acid binary copolymer was produced. MFR (J of the ethylene-maleic anhydride binary copolymer (hereinafter referred to as ethylene-based copolymer (B))
IS-K7210, Table 1, Condition 4) was 8, and the content of units derived from maleic anhydride was 0.5% by weight. The composition was determined by infrared absorption spectrum.

Reference Example 3 (Production of Ethylene-Maleic Anhydride Binary Copolymer) Ethylene-anhydrous was used under the conditions of a polymerization temperature of 220 ° C. and a polymerization pressure of 2000 kg / cm ² using equipment of a high-pressure low-density polyethylene plant. A maleic acid binary copolymer was produced. This ethylene-maleic anhydride binary copolymer (hereinafter, referred to as ethylene-based copolymer (C)) has MFR (J
IS-K7210, Table 1, Condition 4) was 36, and the content of units derived from maleic anhydride was 3.8% by weight.
The composition was determined by infrared absorption spectrum.

Reference Example 4 (Preparation of thermoplastic elastomer) Ethylene / propylene / ethylidene norbornene terpolymer [Ethylene / propylene molar ratio 70/30, iodine value 14, Mooney viscosity (ML _{1 + 4,} 121 ° C) 59] 4
9% by weight, polypropylene [MFR (JIS-K721
0, Table 1, Conditions 14) 15 g / 10 min] 20 wt%, naphthene-based process oil 30 wt% and 1,3-bis (tertiary butylperoxyisopropyl) benzene / trimethylolpropane triacrylate / paraffinic mineral oil 1% by weight of the mixture, which is 2/3/5 by weight, is mixed in a Henschel mixer, after which this mixture is mixed with 12
The mixture was put into a Banbury mixer preheated to 0 to 140 ° C. and kneaded at 180 to 190 ° C. for 10 minutes to carry out a crosslinking reaction. This product is referred to below as thermoplastic elastomer (1)
Called.

Reference Example 5 (Preparation of thermoplastic elastomer) Ethylene / propylene / ethylidene norbornene terpolymer [Ethylene / propylene molar ratio 70/30, iodine value 14, Mooney viscosity (ML _{1 + 4,} 121 ° C.)] 59] 6
9% by weight, polypropylene [MFR (JIS-K721
0, Table 1, condition 14) 15 g / 10 min] 30 wt% and 1,3-bis (tertiary butylperoxyisopropyl) benzene / trimethylolpropane triacrylate / paraffinic mineral oil in a weight ratio of 2/3/5. Mixture 1 which is
% By weight was mixed in a Henschel mixer, and then this mixture was put into a Banbury mixer preheated to 120 to 140 ° C. and kneaded at 180 to 190 ° C. for 10 minutes to carry out a crosslinking reaction. Hereinafter, this product is referred to as a thermoplastic elastomer (2).

Example 1 An extruder 2 equipped with a screw having a diameter of 35 mm was prepared by using the adhesive resin composed of the ethylene-based copolymer (A) produced in Reference Example 1 and the thermoplastic elastomer (1) produced in Reference Example 4. Using a sheet forming machine having a table and a two-layer T-die, a two-layer sheet having a T-die portion temperature of 190 ° C. and a thickness of 400 μm (of which the thickness of the ethylene-based copolymer (A) is 80 μm) was obtained. .. The peel strength at the interface between the adhesive resin layer and the thermoplastic elastomer layer of the obtained sheet was not peelable and could not be measured. The workability was good and the adhesion was good.

Example 2 The same as Example 1 except that the adhesive resin made of the ethylene copolymer (B) prepared in Reference Example 2 and the thermoplastic elastomer (1) prepared in Reference Example 4 were used. Thickness 40
A two-layer sheet having a thickness of 0 μm (of which the thickness of the ethylene-based copolymer (B) is 80 μm) was obtained. The peel strength at the interface between the adhesive resin layer and the thermoplastic elastomer layer of the obtained sheet was not peelable and could not be measured. The workability was good and the adhesion was good.

Example 3 The same as Example 1 except that the adhesive resin made of the ethylene-based copolymer (C) prepared in Reference Example 3 and the thermoplastic elastomer (2) prepared in Reference Example 5 were used. Thickness 40
A two-layer sheet having a thickness of 0 μm (of which the thickness of the ethylene-based copolymer (C) is 80 μm) was obtained. The peel strength at the interface between the adhesive resin layer and the thermoplastic elastomer layer of the obtained sheet was not peelable and could not be measured. The workability was good and the adhesion was good.

Example 4 70 wt% of the ethylene-based copolymer (A) produced in Reference Example 1 and low density polyethylene Shorex (registered trademark) L182 [MFR (JIS-K7210, Table 1,
Condition 4) 8, density 0.917] After dry blending two components of 30% by weight, 18 by a 37 mm twin-screw extruder in the same direction.
A thickness of 400 μm was obtained in the same manner as in Example 1 except that the adhesive resin composition melt-kneaded at 0 ° C. into pellets and the thermoplastic elastomer (2) prepared in Reference Example 5 were used.
(Of these, the thickness of the adhesive resin composition layer was 80 μm) to obtain a two-layer sheet. The peel strength at the interface between the adhesive resin layer and the thermoplastic elastomer layer of the obtained sheet was not peelable and could not be measured. The workability was good and the adhesion was good.

Example 5 25 wt% of the ethylene-based copolymer (B) produced in Reference Example 2 and low-density polyethylene Shorex (registered trademark) L182 [MFR (JIS-K7210, Table 1,
Condition 4) 8, density 0.917] After dry-blending two components of 75% by weight, 18 with a 37 mm twin-screw extruder in the same direction.
A thickness of 400 μm was obtained in the same manner as in Example 1 except that the adhesive resin composition melt-kneaded at 0 ° C. to form pellets and the thermoplastic elastomer (1) prepared in Reference Example 4 were used.
(Of these, the thickness of the adhesive resin composition layer was 80 μm) to obtain a two-layer sheet. The peel strength at the interface between the adhesive resin layer and the thermoplastic elastomer layer of the obtained sheet was not peelable and could not be measured. The workability was good and the adhesion was good.

Example 6 90% by weight of the ethylene-based copolymer (C) produced in Reference Example 3 and SHOWAROMER (registered trademark) FD432 [MFR (JIS
-K7210, Table 1, condition 14) 9, ethylene unit 8% by weight] 10% by weight of two components were dry-blended, and then 3
In the same manner as in Example 1 except that the adhesive resin composition that was melt-kneaded into pellets by a 7 mm twin-screw extruder at 200 ° C. and the thermoplastic elastomer (2) prepared in Reference Example 5 were used. A two-layer sheet having a thickness of 400 μm (of which the thickness of the adhesive resin composition layer is 80 μm) was obtained. The peel strength at the interface between the adhesive resin layer and the thermoplastic elastomer layer of the obtained sheet was not peelable and could not be measured. The workability was good and the adhesion was good.

Comparative Example 1 Instead of the ethylene-based copolymer (A) in Example 1, an ethylene-vinyl acetate binary copolymer [MFR (JI
S-K7210, Table 1, condition 14) 12, unit 12% by weight derived from vinyl acetate] was used in the same manner as in Example 1 to obtain a thickness of 400 μm (of which, ethylene-based copolymer (A)). A two-layer sheet having a thickness of 80 μm) was obtained.

After conditioning for 24 hours in a thermostatic chamber at a temperature of 23 ° C. and a humidity of 60%, the adhered sample was cut into a width of 15 mm and peeled at a rate of 300 mm / min using a tensile tester at 180 °.
The adhesive strength by peeling was measured. As a result, the peel strength at the interface between the adhesive resin layer and the thermoplastic elastomer layer was 72.
It was 0 g / mm, which was insufficient.

Comparative Example 2 Instead of the ethylene copolymer (A) in Example 1, an ethylene-ethyl acrylate binary copolymer [MFR
(JIS-K7210, Table 1, Condition 14) 8, unit 5% by weight derived from ethyl acrylate] was used in the same manner as in Example 1 to obtain a thickness of 400 μm (of which ethylene-ethyl acrylate 2 (The thickness of the original copolymer is 80 μm)
A two-layer sheet of

When the interlayer adhesive strength was measured by the same method as in Comparative Example 1, the adhesive strength at the interface between the adhesive resin layer and the thermoplastic elastomer layer was 610 g / 15 mm, which was insufficient.

Comparative Example 3 2 parts by weight of the ethylene-based copolymer (A) produced in Reference Example 1 and Sholex (registered trademark) L182 [MFR (JIS-K7210, Table 1, Condition 4) 8 which is a low density polyethylene 8] , Density 0.917] 98 parts by weight of the two components were dry blended, and then 180 mm with a 37 mm twin-screw extruder in the same direction.
An adhesive resin composition that is melt-kneaded at 0 ° C. to form pellets,
A two-layer sheet having a thickness of 400 μm (of which the thickness of the adhesive resin composition layer is 80 μm) was obtained in the same manner as in Example 1 except that the thermoplastic elastomer (1) prepared in Reference Example 4 was used. It was

When the interlayer adhesive strength was measured by the same method as in Comparative Example 1, the adhesive strength at the interface between the adhesive resin layer and the thermoplastic elastomer layer was 540 g / 15 mm, which was insufficient.

Comparative Example 4 An adhesive resin comprising the ethylene-based copolymer (B) produced in Reference Example 2 and 29% by weight of an ethylene / propylene / ethylidenenorbornene terpolymer in Reference Example 4 and 5% by weight of polypropylene , Naphthenic process Eucil 6
The thermoplastic elastomer produced by the same method as in Reference Example 4 except that 5% by weight was used, using a sheet molding machine having two extruders equipped with a screw having a diameter of 35 mm and a two-layer T die. 400 μm thick at 190 ° C
(Of these, the thickness of the ethylene-based copolymer (B) is 80μ
A two-layer sheet of m) was obtained.

When the interlayer adhesive strength was measured by the same method as in Comparative Example 1, the adhesive strength at the interface between the adhesive resin layer and the thermoplastic elastomer layer was 380 g / 15 mm, which was insufficient.

Comparative Example 5 The ethylene copolymer (A) produced in Reference Example 1 was used in an extruder equipped with a screw having a diameter of 35 mm and a T-die to obtain a film of 40 μm at a T-die temperature of 180 ° C. It was Further, the thermoplastic elastomer (1) prepared in Reference Example 4 was extruded under the same manufacturing conditions to obtain a thickness of 400 μm.
m sheets were obtained.

The obtained film of ethylene copolymer (A) and the sheet of thermoplastic elastomer (1) were each cut into a size of 10 cm × 10 cm, and ethylene was cut using a heat sealer manufactured by Tester Sangyo Co., Ltd. Seal bar temperature of the system copolymer (A) side 150 ° C, seal bar temperature of the thermoplastic elastomer (1) side 40 ° C, gauge pressure 2K
Adhesion was performed under heat-sealing conditions of g / cm ² and a heating time of 1 second.

When the interlayer adhesive strength was measured by the same method as in Comparative Example 1, the adhesive strength was 370 g / 15 mm,
It was insufficient.

Comparative Example 6 Molding and adhesion were carried out in the same manner as in Comparative Example 5 except that the ethylene copolymer (C) produced in Reference Example 3 and the thermoplastic elastomer (2) prepared in Reference Example 5 were used. I went.
When the interlayer adhesive strength was measured by the same method as in Comparative Example 1, the adhesive strength was 210 g / 15 mm, which was insufficient.

Example 7 Using the two-layer sheet obtained in Example 1, foamed polypropylene (crosslinking type) was adhered as a base material to the adhesive resin side of the two-layer sheet to obtain a multilayer laminate. .. For adhesion, a hot press was used, a base material was placed on the lower surface of the press, and the two-layer sheet obtained in Example 1 was overlaid thereon with the adhesive resin surface side facing downward. The press temperature was 150 ° C., the press bottom surface temperature (press temperature on the substrate side) was room temperature, and the press gauge pressure was 0.2 Kg / cm ² for 3 seconds.

The obtained multi-layer laminate of 10 cm × 10 cm was conditioned in a thermostatic chamber at a temperature of 23 ° C. and a humidity of 60% for 24 hours, cut into a width of 1.5 cm, and stretched with a Toyo Baldwin tensile tester at 300 mm / The adhesive strength between the adhesive resin and the substrate was evaluated at a pulling rate of minutes. The results are shown in Table 1.
The workability was good and the adhesion was good.

Examples 8 to 14 Various materials listed in Table 1 were used as the base material and adhered in the same manner as in Example 7 to obtain multilayer laminates. Table 1 shows the evaluation results of the adhesive strength between the adhesive resin and the base material of the obtained multilayer laminate. In all cases, workability was good and adhesion was also good.

[0067]

[Table 1]

The abbreviations of the base materials listed in Table 1 mean the following. PP board: Polypropylene board GF-containing PP board: Glass fiber-containing polypropylene board GF-containing PH board: Glass fiber-containing phenol board

Examples 15 to 20 The two-layer sheet obtained in Example 2 was used, and Table 2 was used as a substrate.
Adhesion was performed in the same manner as in Example 7 except that the various materials listed in 1 above were used to obtain a multilayer laminate. Table 2 shows the evaluation results of the adhesive strength between the adhesive resin and the base material of the obtained multilayer laminate. In all cases, workability was good and adhesion was also good.

[0070]

[Table 2]

The abbreviations of the base materials listed in Table 2 mean the following. PP board: Polypropylene board PC board: Polycarbonate board PP cloth: Polypropylene cloth

Examples 21 to 26 The two-layer sheet obtained in Example 5 was used, and Table 3 was used as a substrate.
Adhesion was performed in the same manner as in Example 7 except that the various materials listed in 1 above were used to obtain a multilayer laminate. Table 3 shows the evaluation results of the adhesive strength between the adhesive resin and the base material of the obtained multilayer laminate. In all cases, workability was good and adhesion was also good.

[0073]

[Table 3]

The abbreviations of the base materials listed in Table 3 mean the following. PH board with GF: Phenol board with glass fiber

Examples 27 to 32 The two-layer sheets obtained in Example 6 were used and Table 4 was used as a substrate.
Adhesion was performed in the same manner as in Example 7 except that the various materials listed in 1 above were used to obtain a multilayer laminate. Table 4 shows the evaluation results of the adhesive strength between the adhesive resin and the base material of the obtained multilayer laminate. In all cases, workability was good and adhesion was also good.

[0076]

[Table 4]

[0077]

INDUSTRIAL APPLICABILITY The two-layer laminate of the present invention has high interlayer adhesion strength and high thermal adhesiveness to various other substrates, and is useful for producing various multilayer laminates. .. The multilayer laminate according to the present invention can be used for vehicle interior materials, automobile interior materials, architectural interior materials, display panel materials, furniture materials, home appliance housing materials, bag materials, sports equipment materials, office equipment materials, etc. Expected to be used for a wide range of purposes.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location B32B 27/32 Z 8115-4F // B29K 23:00 B29L 9:00 4F (72) Inventor Tsutsumi Katsuaki 2 Nakanosu, Oita City, Oita Prefecture Showa Denko Oita Plant (72) Inventor Shintaro Inazawa 2 Nakanosu, Oita City, Oita Prefecture Showa Denko Oita Laboratory

Claims (7)

[Claims] 1. An ethylene-based copolymer 10 to 100 which is a copolymer of (1) ethylene and a radical-polymerizable acid anhydride.
A two-layer laminate comprising an adhesive resin composition comprising 2% by weight and a polyolefin resin of 90 to 0% by weight and (2) a thermoplastic elastomer. 2. The unit derived from a radical-polymerizable acid anhydride of an ethylene-based copolymer is contained in an amount of 0.1 to 5% by weight based on the adhesive resin composition. Two-layer laminate. 3. A thermoplastic elastomer comprising: (a) a blend of at least partially cross-linked ethylene-α-olefin copolymer rubber and a polyolefin resin, 100 to 40% by weight, and (b) a mineral oil-based softener. The two-layer laminate according to claim 1, which comprises -60% by weight. 4. An ethylene-based copolymer 10 to 100 which is a copolymer of (1) ethylene and a radical-polymerizable acid anhydride.
A method for producing a two-layer laminate, which comprises co-extruding an adhesive resin composition comprising 90% by weight of a polyolefin resin and 90% by weight of a polyolefin resin and (2) a thermoplastic elastomer. 5. A multilayer laminate obtained by laminating another base material layer on the adhesive resin composition layer of the two-layer laminate according to claim 1. 6. The multilayer laminate according to claim 5, wherein the other substrate is a foamed polypropylene resin, a polypropylene board, a glass fiber-containing polypropylene board, a resin felt, a glass fiber-containing phenol board or a particle board. 7. A method for producing a multi-layer laminate, which comprises thermally adhering another base material layer onto the adhesive resin composition layer of the two-layer laminate according to claim 1.