JPH06240064A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. which is excellent in adhesive strength at low temp. under low pressure and creep resistance at high temp. and is useful as an adhesive layer of a laminate by compounding a specific ethylene multicomponent copolymer with a specific ethylene binary copolymer in a specified wt. ratio. CONSTITUTION:This resin compsn. comprises 70-99wt.% ethylene multicomponent copolymer consisting of units derived from ethylene, 0.1-5wt.% units derived from a radical-polymerizable acid anhydride (e.g. maleic anhydride), and 3-50wt.% units derived from a radical-polymerizable monomer (e.g. methyl methacrylate) other than the foregoing two monomers and 30-1wt.% ethylene binary copolymer consisting of units derived from ethylene and 0.1-10wt.% units derived from the radical-polymerizable acid anhydride.

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a resin composition, and more specifically, it has excellent adhesiveness and heat resistance, and in particular, automobiles, houses, etc. which are required to have excellent adhesive strength at low temperature and low pressure adhesion and heat creep resistance at high temperature. The present invention relates to a resin composition of an ethylene-based multi-component copolymer, which can be suitably used as an adhesive layer of an interior material, and can also be widely used as an adhesive layer of a laminate used in various other fields. .

[0002]

2. Description of the Related Art Conventionally, hot-melt type adhesives have been used as an adhesive layer for various laminated bodies. Unlike solvent-based adhesives, this adhesive does not require work such as painting, drying, and aging during bonding, and the work process is simple. In addition, there are no adverse effects on occupational health and the risk of fire due to the use of organic solvents. Widely used because it causes no problems. On the other hand, hot-melt adhesives generally have lower adhesive strength than solvent-based adhesives, so they often lack heat-resistant creep resistance, and there is a problem that the adhesive strength is insufficient depending on the intended use of the laminate.
For example, as a material for the interior of automobiles, vehicles, ships, houses, other buildings, etc., a laminate in which a skin material for enhancing the habitability and aesthetics in the room and a substrate material for maintaining and enhancing the functionality are adhered. The ethylene-acrylic acid ester-maleic anhydride terpolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer conventionally used as an adhesive layer of this laminate is used. Or a hot-melt type adhesive such as low melting point copolymer nylon,
If it is left at a high temperature (around 80 ° C.) such as the temperature inside the car under the hot sun for a long time, it has a drawback that it is liable to sag or peel off. Further, if the adhesion temperature and the adhesion pressure are relatively high, the adhesiveness can be enhanced, but in this case, there is a drawback that the skin agent is likely to be damaged. On the other hand, there are hot-melt adhesives that do not have these drawbacks, but they have the drawback of being expensive and limiting their use due to cost. Further, the hot-melt adhesive has a problem that sufficient adhesive strength cannot be obtained depending on the type of base material (including skin material and substrate material). For example, when the surface of the base material is coated with urethane paint, when the base material is a foamed urethane type, or when the base material is injection-molded polypropylene and the surface is smooth, sufficient adhesiveness is obtained. And the base layer is easily peeled off. In such a case, it is necessary to perform a special treatment on the surface of the base material in advance, or to use a solvent-type adhesive instead of the hot-melt adhesive, but the former requires a work process. Since it has a drawback that it becomes complicated and raises the manufacturing cost, and the latter has a drawback that the use of an organic solvent has an adverse effect on the environment and hygiene, the benefit of using a hot-melt type adhesive can be obtained eventually. Can not. As described above, when used as an adhesive layer for interior materials for automobiles, houses, etc., it exhibits good heat-resistant creep resistance for a wide range of skin materials and substrate materials, and low temperatures that can prevent damage to the skin agents. It has good adhesiveness to a wide range of base materials and has good workability when used as an adhesive layer of a laminate used in various other fields. The reality is that an adhesive that does not have problems in use such as environmental problems and is satisfactory in terms of cost has not yet been developed.

[0003]

Therefore, the present inventors have
In view of the above situation, the inventors have conducted intensive research to develop an adhesive that eliminates the conventional defects. As a result, the resin composition containing the specific ethylene-based multi-component copolymer and the specific ethylene-based binary copolymer as the main components is suitable for a wide variety of base materials (including skin materials and substrate materials). It was found to have adhesiveness and heat resistance. The present invention has been completed based on such findings. That is, the present invention provides an ethylene-based multi-component copolymer comprising (A) ethylene, a radical-polymerizable acid anhydride and a radical-polymerizable comonomer other than the above, wherein the radical-polymerizable acid anhydride in the multi-component copolymer is 70-99% by weight of an ethylene-based multi-component copolymer having a proportion of units derived from 0.1 to 5% by weight and a proportion of units derived from other radically polymerizable comonomer of 3 to 50% by weight, and (B ) An ethylene-based binary copolymer comprising ethylene and a radical-polymerizable acid anhydride, wherein the ratio of the units derived from the radical-polymerizable acid anhydride in the binary copolymer is 0.1 to 1
30% to 1% by weight of an ethylene-based binary copolymer which is 0% by weight
The present invention provides a resin composition comprising:

The resin composition of the present invention, as described above,
The ethylene-based multi-component copolymer which is the component (A) and the ethylene-based binary copolymer which is the component (B) are essential components.
Further, if necessary, copolymerized nylon as the component (C),
The component (D) may contain one or more components selected from the organic carboxylic acid metal salts and other components.

The ethylene-based multicomponent copolymer constituting the component (A) of the resin composition of the present invention comprises ethylene, a radical-polymerizable acid anhydride and a radical-polymerizable comonomer other than the above radical-polymerizable acid anhydride. It is a multi-component copolymer.
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. Means The acid anhydride group is preferably cyclic. Examples of such compounds include maleic anhydride, itaconic anhydride, endic acid anhydride, citraconic anhydride, dodecenyl succinic anhydride, 1-butene-3,4.
-Dicarboxylic acid anhydrides, alkenylsuccinic anhydrides having a double bond at the terminal having at most 18 carbons, alkadienyl succinic anhydride having a double bond at the terminal having at most 18 carbons, and the like. These alone
Alternatively, two or more kinds may be used in combination. Among these, maleic anhydride and itaconic anhydride are particularly preferable. The proportion of the units derived from the radical-polymerizable acid anhydride in the component (A) is in the range of 0.1 to 5% by weight, preferably 0.5 to 4.5% by weight, more preferably 1 It is in the range of 0.0 to 4.0% by weight. Here, if the proportion of the radical-polymerizable acid anhydride is less than 0.1% by weight, the adhesiveness is insufficient and good adhesive strength cannot be obtained. On the other hand, if it exceeds 5% by weight, it becomes difficult to produce an ethylene-based copolymer, which is not practical.

There are various compounds as radical-polymerizable comonomers other than radical-polymerizable acid anhydrides, such as ethylenically unsaturated ester compounds, ethylenically unsaturated amide compounds, ethylenically unsaturated acid compounds, ethylenically unsaturated compounds. Examples include saturated ether compounds and other compounds. Specifically describing these, 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, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, dimethyl fumarate, fumaric acid Diethyl, dipropyl fumarate, dibutyl fumarate,
Examples include methyl maleate, ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate and the like. 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. Examples of the ethylenically unsaturated acid compound include (meth) acrylic acid, fumaric acid, maleic acid and the like. 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. In addition to the above, other compounds such as styrene and α-
Methylstyrene, (meth) acrylonitrile, acrolein, crotonaldehyde, trimethoxyvinylsilane, triethoxyvinylsilane, vinyl chloride, vinylidene chloride, norbornene, butadiene and the like can be mentioned. Among these, (meth) acrylic acid esters and (meth) acrylic acid are mentioned as particularly preferable compounds. These comonomers may be used alone or in combination of two or more. The ratio of the units derived from the radically polymerizable comonomer in the component (A) is 3 to.
It is in the range of 50% by weight, preferably in the range of 4 to 45% by weight, more preferably in the range of 5 to 40% by weight. Here, if the proportion of the radical-polymerizable comonomer is less than 3% by weight, the crystal melting point of the ethylene-based multi-component copolymer is not sufficiently lowered, and the low-temperature adhesiveness which is a feature of the present invention cannot be sufficiently exhibited. On the other hand, if it exceeds 50% by weight, it becomes difficult to handle the resin and the heat resistance of the product deteriorates.

In producing the ethylene-based multi-component copolymer which is the above-mentioned component (A), it is possible to basically utilize ordinary production equipment for high-pressure low-density polyethylene and its technology. Generally, by the bulk polymerization method, 70
Polymerization pressure of 0 to 3,000 atm, preferably 1,000 to 2,500 atm, and 100 to 300 ° C., preferably 15
It is produced by radical polymerization at a polymerization temperature of 0 to 270 ° C. When the polymerization pressure is less than 700 atm, the molecular weight of the polymer becomes low, and the moldability and the resin physical properties of the resin composition deteriorate.
On the other hand, when the pressure exceeds 3,000 atm, the manufacturing cost is increased and it is practically meaningless. Also, the polymerization temperature is 10
If the temperature is lower than 0 ° C, the polymerization reaction is not stable and the conversion rate to the copolymer is lowered, which is economically problematic. On the other hand, when the temperature exceeds 300 ° C, the molecular weight of the copolymer decreases, and at the same time, the risk of a runaway reaction occurs. As the polymerization apparatus, it is preferable to use a vessel type reactor. Particularly, since radical-polymerizable acid anhydrides have poor polymerization stability, a high degree of homogenization within the reactor is required. If necessary, a plurality of reactors may be connected in series or in parallel to carry out multistage polymerization.
Further, by partitioning the inside of the reactor into a plurality of zones, more precise temperature control can be performed.

The ethylene-based multi-component copolymer is produced under the above reaction conditions in the presence of at least one free radical initiator. Here, as the free radical initiator, specifically, for example, oxygen; dialkyl peroxides such as di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide; acetyl peroxide, i-butane Diacyl peroxides such as noyl peroxide and octanoyl peroxide; peroxy-dicarbonates such as di-i-propyl peroxy-dicarbonate and di-2-ethylhexyl peroxy-dicarbonate; t-butyl peroxypivalate, Peroxyesters such as t-butylperoxylaurate; ketone peroxides such as methylethylketone peroxide and cyclohexanone peroxide; 1,1-bis-t-butylperoxycyclohexane, 2,2-bis-t-butylperoxy Peroki such as octane Ketal; t-
Examples thereof include hydroperoxides such as 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 the molecular weight modifier. As the chain transfer agent, for example,
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 are listed.

The ethylene-based multi-component copolymer produced in this manner melts at a relatively low temperature and is rich in physicochemical interaction and reactivity with various base materials (including skin material and substrate material). Therefore, the resin composition of the present invention plays a large role in exerting a high adhesive force even during low temperature molding. The component (A) can be used in combination of two or more kinds.

The ethylene-based binary copolymer which constitutes the component (B) of the resin composition of the present invention is a binary copolymer comprising ethylene and a radical-polymerizable acid anhydride. Here, examples of the radical-polymerizable acid anhydride include the above-mentioned radical-polymerizable acid anhydride that can be used for producing the component (A). These may be used alone or in combination of two or more kinds. Among these, maleic anhydride and itaconic anhydride are particularly preferable. The proportion of units derived from the radical-polymerizable acid anhydride in the component (B) is in the range of 0.1 to 5% by weight, preferably 0.5 to 4.5% by weight, more preferably 1 0.0-4.0
It is in the range of% by weight. Here, if the proportion of the radical-polymerizable acid anhydride is less than 0.1% by weight, high heat-resistant creep resistance cannot be obtained. On the other hand, if it exceeds 5% by weight, the flexibility of the obtained ethylene-based binary copolymer is significantly lowered and the production cost is increased, which is not preferable. The MFR value of the component (B) is not particularly limited, but from the viewpoint of ensuring good moldability when producing a laminate using the resin composition of the present invention, 0.1 to 500 g / 10 It is preferably set to minutes. The component (B) can be used in combination of two or more kinds.

The component (B) can be produced by the same method as the production of the component (A), and can be produced, for example, by using the above-mentioned production method of the component (A). That is,
In producing the component (B), it is possible to basically utilize a conventional high-pressure low-density polyethylene production facility and its technology, and generally 70% by the bulk polymerization method.
It is produced by radical polymerization at 0 to 3,000 atm and 100 to 300 ° C. As the polymerization apparatus, it is preferable to use a vessel type reactor. The polymerization is carried out in the presence of at least one free radical initiator and various chain transfer agents can be used as molecular weight regulators.

The ethylene-based binary copolymer produced in this manner has a melting point of 100 ° C. or higher and plays a role of improving the heat-resistant creep property of the resin composition of the present invention. Generally, when a polymer having a high melting point is blended with a resin composition, the heat-resistant creep property of the resin composition can be improved, but on the other hand, it has a drawback that the adhesive strength at the time of low temperature molding is lowered. . On the other hand, when the above binary copolymer is blended with the ethylene-based multi-component copolymer which is the component (A), it is possible to improve the heat-resistant creep property without lowering the adhesive strength during low temperature molding. This is a major feature of the present invention. Although the action mechanism is not always clear, it is presumed that the above binary copolymer suppresses the decrease in the content of the acid anhydride group in the entire resin composition. That is, when the resin composition of the present invention exerts excellent adhesive strength during low temperature molding, the interaction between a large amount of acid anhydride groups contained in the ethylene-based multicomponent copolymer (A) and the substrate. Or, although the reaction is a major factor, it is possible to suppress a decrease in the content of the acid anhydride group with respect to the entire resin composition because the binary copolymer also contains an acid anhydride group, It is presumed that it is possible to prevent a decrease in adhesive strength during low temperature molding.

As the copolymerized nylon constituting the component (C) of the resin composition of the present invention, various types can be used, but preferably, a higher nylon salt having 10 or more carbon atoms, ω-amino acid or lactam. It is a nylon containing a structure derived from it. Specifically, for example, nylon 6/66
Copolymer, Nylon 6/12 Copolymer, Nylon 6/6
6/610 copolymer, nylon 6/66/12 copolymer, nylon 6/612/12 copolymer, nylon 6 /
610/12 copolymer, nylon 6/66/11 copolymer, nylon 6/66/610/12 copolymer and the like. Examples of the component (C) other than the above include dimer acid obtained by heat-condensing unsaturated fatty acids such as tall oil fatty acid and soybean oil fatty acid, and ethylenediamine, hexamethylenediamine, isophoronediamine, xylylenediamine, 4 , 4'-diaminodicyclohexylmethane,
Examples thereof include condensation polymers with diamines such as p, p′-methylenedianiline, piperazine and trimethylhexamethylenediamine. Among these, particularly preferable copolymer nylons are nylon 6/66/12 and nylon 6/612.
/ 12, a condensation polymer of dimer acid obtained by heat-condensing unsaturated fatty acid such as tall oil fatty acid and diamine such as ethylenediamine, and the like. And, these copolymerized nylons can be used not only alone but also in combination of two or more kinds.

The copolymer nylon as the component (C) is 20
Viscosity at 0 ° C is 200-8,000 centipoise (c
P), preferably in the range of 300 to 7,000 cP, more preferably in the range of 500 to 6,500 cP. The viscosity here means a value measured by a cylindrical rotary viscometer. If the viscosity is less than 200 cP, stickiness and heat resistance of the resin composition are deteriorated, while 8,000 cP
When it exceeds, the compatibility or the miscibility with the component (A) or the component (B) decreases, and it becomes difficult to produce the resin composition. Further, from the viewpoint of operability and adhesiveness at low temperature adhesion, the melting point or softening point of the copolymerized nylon is preferably 180 ° C. or lower.

The above-mentioned component (C) does not impair the adhesiveness based on the component (A) or the component (B), and has high adhesion to a substrate which cannot be obtained with a conventional adhesive resin. It is mixed in order to obtain strength or to improve the adhesive strength at low temperature bonding. The resin composition consisting of the component (A) and the component (B) may not have sufficient adhesiveness depending on the type of the substrate and the bonding temperature. In such a case, the component (C) may be blended. It is valid. Although the detailed mechanism of the action of the component (C) is not clear, in the resin composition of the present invention, the amide group in the copolymerized nylon has an affinity with the base material, and under an appropriate viscosity condition. It is presumed that the dispersion of the component (C) and the transfer to the adhesive interface are favorably performed.

The metal salt of an organic carboxylic acid which constitutes the component (D) of the resin composition of the present invention means a compound in which the organic carboxylic acid is completely or partially neutralized with a metal. As the above-mentioned organic carboxylic acid, various ones can be used, and examples thereof include lauric acid, myristic acid, stearic acid, palmitic acid, decanoic acid, pentadecanoic acid, eicosanoic acid, docosanoic acid. Saturated fatty acids having 10 or more carbon atoms (usually 10 to 40) such as acid, tricosanoic acid, triacontanoic acid, suberic acid, azelaic acid, sebacic acid, and hexadecanedioic acid; oleic acid, erucic acid, linolein Examples thereof include unsaturated fatty acids having 10 or more carbon atoms (usually 10 to 40) such as acids, linolenic acid, and arachidonic acid; and polymeric carboxylic acids such as copolymers of ethylene and (meth) acrylic acid. on the other hand,
The metal forming a salt with an organic carboxylic acid is not particularly limited, but a metal belonging to Group IA, IIA or IIB of the periodic table is preferably used. Among the components (D), preferred are sodium stearate, sodium oleate, calcium oleate, and metal salts of high molecular weight carboxylic acids generally called ionomers (for example, ethylene- (meth) acrylic acid copolymer). Partially neutralized with a sodium compound or a zinc compound). These (D) components may be used alone or in combination of two or more.

The above-mentioned component (D) is added in order to improve the heat resistance of the resin composition of the present invention or to improve the adhesive strength to a special substrate. The resin composition consisting of only the components (A) and (B) may not have sufficient heat resistance depending on the type of the base material and the intended use of the finally obtained laminate. In such a case, Is (A)
It is effective to incorporate the component (D), which enhances the adhesive strength of the resin composition at high temperature due to the interaction with the components.

The resin composition of the present invention includes the above (A),
In addition to the components (B), (C), and (D), various additives, as long as the characteristics of the resin composition of the present invention are not impaired,
A compounding agent, a filler, etc. can be compounded. Specifically, for example, inorganic materials such as antioxidants (heat resistance stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), glass fillers, etc. Examples include fillers, organic fillers, reinforcing agents, colorants (dyes and pigments), foaming agents, cross-linking agents, and fragrances. These additives and the like may be added at the time of producing the resin composition of the present invention, or may be added to the component (A), (B), (C) or (D) from the beginning. .

The resin composition of the present invention is obtained by blending the components (A) and (B) in a certain ratio. The mixing ratio of both components is such that the component (A) is 70 to 99% by weight, preferably 72 to 97% by weight, more preferably 75 to 95% by weight, based on the total amount of the resin composition of the present invention.
On the other hand, the content of the component (B) is 30 to 1% by weight, preferably 28 to 3% by weight, and more preferably 25 to 5% by weight. If the component (A) is less than 70% by weight or the component (B) exceeds 30% by weight, the adhesive strength is insufficient. On the other hand, when the amount of the component (A) exceeds 99% by weight or when the amount of the component (B) is less than 1% by weight, good heat creep resistance cannot be obtained, and it cannot be put to practical use. The mixing ratio of the component (C) and the component (D) can be changed according to the required characteristics of the resin composition of the present invention to be produced, but generally, the adhesiveness of the resin composition of the present invention is From the viewpoint of ensuring the same, the total amount of the component (C) and the component (D) is preferably 50% by weight or less of the resin composition. The components (C) and (D) may be used in combination of two or more kinds.

The resin composition of the present invention is prepared by mixing the above-mentioned components (A) and (B) according to the respective mixing ratios. Further, the resin composition of the present invention is (A)
In addition to the component and the component (B), if necessary, the component (C),
It is also prepared by mixing the component (D) or other components. Various commonly known methods can be used for mixing the components. Specifically, for example, a method of dissolving and reprecipitating each component in a solvent such as high temperature toluene, a method of mixing each component in a molten state, that is, a commonly used pressure kneader, roll, Banbury mixer , A method using a static mixer, a screw type extruder or the like. In some cases, the components may be dry blended to form a composition during molding.

The resin composition of the present invention can be applied to various uses and molding methods as an adhesive layer of a laminate. As the molding method, various conventionally known methods, for example, a method of sandwiching the resin composition formed into a film by inflation molding or T-die molding between base materials and thermally adhering it, the above resin composition Examples of the method include a method of coating a base material by extrusion lamination molding, followed by heat adhesion to another base material, a method of sprinkling the above resin composition as a powder adhesive on the base material, and the like. The resin composition of the present invention exhibits good adhesion to a wide range of substrates, which is one of the features of the present invention. Examples of such a bondable base material include various papers such as high-quality paper, kraft paper, glassine paper, Japanese paper, cardboard base paper, synthetic paper, art paper, coated paper; cotton, linen, polyester, nylon, etc. Various woven or non-woven fabrics; wood boards; iron,
Various metal plates or foils of aluminum, copper, tinplate, etc .; Plates, molded products, films or foams made of various plastics such as polypropylene, polystyrene, polyethylene, polyester, nylon, polycarbonate, acrylic resin, phenol resin, polyurethane, etc .; Examples include various inorganic substances such as glass fiber and ceramics. Further, these base materials may be subjected to surface treatment, coating, printing or the like, if necessary.

The resin composition of the present invention is particularly excellent in adhesion at low temperature adhesion and heat creep resistance at high temperature,
It is one of the features of the present invention that both of these contradictory properties are compatible. Therefore, the resin composition of the present invention can be used as an interior material for automobiles (for example, a ceiling member, a door member, a dashboard member, etc.) or an interior material for a house by using a skin material and a substrate material as a base material. Can be suitably used as the adhesive layer. Here, the skin material and the substrate material that can be adhered are not particularly limited, and the present invention can be applied to various materials that are currently generally used as interior materials for automobiles, vehicles, ships, houses and the like. For example, as the skin material, polyester non-woven fabric, brushed knit, fabric, suede-like synthetic leather, vinyl chloride (polyvinyl chloride) leather, polyurethane leather, polypropylene thermoplastic elastomer, or urethane foam, foamed to these materials to provide cushioning properties. Examples include those obtained by adhering polypropylene, foamed polyethylene, foamed polyvinylidene, and the like. On the other hand, examples of the substrate material include resin felt, glass fiber-containing phenol resin plate, corrugated board, polypropylene honeycomb, polystyrene foam, or a material obtained by laminating a non-woven fabric to these materials.

When the resin composition of the present invention is used to manufacture interior materials for automobiles and the like, various molding methods can be adopted. For example, a substrate material is heated to a predetermined temperature, set in a vacuum forming machine, the above resin composition formed into a film by inflation molding, T-die molding or the like is placed thereon, and then the skin is heated to a predetermined temperature in advance. A method of stacking materials and vacuum-pressing; a method of sandwiching the above film between a skin material and a substrate material and hot pressing; a laminate material obtained by coating the skin material with the resin composition of the present invention by extrusion molding and a substrate material. Method of hot pressing with a hot press or hot roll; powdering the resin composition of the present invention, sprinkling it on a substrate material placed on a hot press, and hot pressing a skin material thereon; Examples include a method of previously laminating the above film on the adhesive side with a hot roll, and then thermocompression bonding with a hot press or a hot roll.

[0024]

EXAMPLES Further, the present invention will be specifically described with reference to Examples, Comparative Examples, Application Examples and Reference Examples. Example 1 An ethylene-maleic anhydride-methyl methacrylate terpolymer was used as the ethylene-based multi-component copolymer (A). This ternary copolymer (hereinafter referred to as "terpolymer (a)") uses equipment of a high-pressure process low-density polyethylene plant and has a polymerization temperature of 200 ° C and a polymerization pressure of 1,800 kg / c.
It was manufactured under the condition of m ² . MF of this terpolymer (a)
R (JIS-K7210, Table 1, Condition 4, hereinafter, all MFRs use this condition.) Is 15 g / 10 minutes, the proportion of units derived from maleic anhydride is 2.2% by weight, and derived from methyl methacrylate. The proportion of units was 16% by weight. The composition of the comonomer was determined by infrared absorption spectrum. Further, as the ethylene-based binary copolymer (B),
An ethylene-maleic anhydride binary copolymer was used. This binary copolymer (hereinafter referred to as "binary copolymer (a)").
Uses the equipment of the high pressure low density polyethylene plant,
It was produced under the conditions of a polymerization temperature of 195 ° C. and a polymerization pressure of 1,900 kg / cm ² . This binary copolymer (a) has an MFR of 10
g / 10 minutes, the ratio of units derived from maleic anhydride is 2.
It was 0% by weight. The composition of the comonomer was determined by infrared absorption spectrum. Weight ratio of the above two components ((A)
/ (B)) is set to 80/20, and 0.2% by weight of magnesium silicate and 0.2% by weight of erucic acid amide as additives are dry blended in a tumbler with respect to the total amount of the components (A) and (B). After that, it was melt-kneaded at 170 ° C. using a 65 mmφ single screw extruder to obtain pellets of the resin composition.

Example 2 A terpolymer (a) was used as the ethylene-based multi-component copolymer (A), and a binary copolymer (a) was used as the ethylene-based terpolymer (B). . In addition, as the copolymerized nylon (C), Tomeide # 13 manufactured by Fuji Kasei Kogyo Co., Ltd.
50 was used. This is a condensation polymer of dimer acid obtained by heating and condensing unsaturated fatty acid such as tall oil fatty acid and diamine such as ethylenediamine, and the viscosity at 200 ° C was 2,900 cP and the softening point was 150 ° C. . The weight ratio ((A) / (B) / (C)) of the above three components is 75/15/10
In the same manner as in Example 1, pellets of the resin composition were obtained.

Example 3 A terpolymer (a) was used as the ethylene-based multi-component copolymer (A), and a binary copolymer (a) was used as the ethylene-based terpolymer (B). As the copolymerized nylon (C), Tomeide # 1350 manufactured by Fuji Kasei Kogyo Co., Ltd. was used, and as the metal salt (D) of the organic carboxylic acid, the ionomer (a) was used. This ionomer (a) was prepared by mixing an ethylene-methacrylic acid copolymer (methacrylic acid content 20% by weight) in a solvent of water: methanol = 1: 1 at 50 ° C.
Prepared by treating with sodium acetate for 2 hours and neutralizing 55 mol%. Weight ratio of the above 4 components ((A) / (B) / (C) /
(D) was set to 70/10/10/10 and the same operation as in Example 1 was carried out to obtain pellets of the resin composition.

Comparative Example 1 A resin composition pellet was obtained in the same manner as in Example 1 except that the binary copolymer (a) was not added.

Comparative Example 2 A resin composition pellet was obtained in the same manner as in Example 1 except that the terpolymer (a) was not added.

Application Example 1 The pellets obtained in Example 1 were formed into a film having a thickness of 50 μm by an inflation film molding machine. Using this film as an adhesive layer, a skin material and a substrate material which are actually used as interior materials for automobiles were adhered and the adhesiveness was tested. As the skin material, a foamed polypropylene (PVC leather / PPF) having a thickness of 2 mm with polyvinyl chloride leather having a thickness of 0.2 mm was used, and as the substrate material, a resin felt (RF) having a thickness of 3 mm was used. The adhesion was performed by hot pressing under the conditions of 120 ° C., a substantial surface pressure of 2 kg / cm ² , and 20 seconds. After the bonding, it was cooled at 30 ° C. for 4 minutes, cut into a test piece having a width of 25 mm, and subjected to a 180 ° peel test at room temperature (25 ° C.) using a tensile tester. As a general rule, the adhesive strength (kg / 25 mm width) at the time of peeling was measured, but if the skin material or the substrate material was broken before peeling, the strength at break was measured. Furthermore, a 100 g load was hung on the test piece that had been partially peeled, and the peeling distance (mm) was measured when the test piece was left standing in an atmosphere of 80 ° C. for 24 hours, and used as a measure of heat-resistant creep resistance. The value of the adhesive strength is the average value (maximum,
(Minimum 2-point cut), and the thermal creep resistance is the average value of 3 test pieces. The results are shown in Table 1.

Application Examples 2 to 3 As shown in Table 1, the same operation as in Application Example 1 was performed except that the film of Application Example 1 was used as the adhesive layer and the kinds of the skin material and the substrate material were changed. . The results are shown in Table 1.

Application Example 4 The film obtained in Application Example 1 was used as the adhesive layer, and the skin material was a foamed polypropylene (PVC leather / PP) having a thickness of 0.2 mm and a polyvinyl chloride leather having a thickness of 0.2 mm.
F) was used, and the substrate material was a polypropylene plate (PP) with a thickness of 2 mm coated with an anchor coating agent. For the adhesion, first, the outer skin and the film were sandwiched by a Teflon coat roll heated to 130 ° C., and a heat roll laminating process was performed at a speed of 5 m / min to bond them. Next, the substrate material is heated to 80 ° C. for 3 minutes, and the skin is heated to 120 ° C.,
Bonded by a vacuum bonding method. This laminate was tested for adhesion in the same manner as in Application Example 1. The results are shown in Table 1.

Application Example 5 As shown in Table 1, the same operation as in Application Example 1 was performed except that the film of Application Example 1 was used as the adhesive layer and the kinds of the skin material and the substrate material were changed. The results are shown in Table 1.

Application Examples 6 to 7 As shown in Table 1, the resin composition of Example 2 was used as the resin composition for the adhesive layer, and the same operation as in Application Example 1 was performed to obtain the adhesive layer. I got a film. Next, the types of the skin material and the substrate material were changed, the same operation as in Application Example 1 was performed, and the adhesiveness was tested. The results are shown in Table 1.

Application Examples 8 to 10 As shown in Table 1, the resin composition of Example 3 was used as the resin composition for the adhesive layer, and the same operation as in Application Example 1 was performed to obtain the adhesive layer. I got a film. Next, the types of the skin material and the substrate material were changed, the same operation as in Application Example 1 was performed, and the adhesiveness was tested. The results are shown in Table 1.

Application Example 11 As shown in Table 1, the film of Application Example 8 was used as the adhesive layer, the kinds of skin material and substrate material were changed, and vacuum adhesion was performed in the same manner as in Application Example 4, Adhesion was then tested in the same manner as in Application Example 1. The results are shown in Table 1.

Application Example 12 As shown in Table 1, the same operation as in Application Example 1 was performed except that the film of Application Example 8 was used as the adhesive layer and the types of the skin material and the substrate material were changed. The results are shown in Table 1.

Reference Examples 1-2 A film was produced from the pellets obtained in Comparative Example 1 in the same manner as in Application Example 1. Using this film as an adhesive layer, the types of skin material and substrate material were changed as shown in Table 1, and the same operation as in Application Example 1 was performed. The results are shown in Table 1.

Reference Examples 3 to 4 Films were produced from the pellets obtained in Comparative Example 2 in the same manner as in Application Example 1. Using this film as an adhesive layer, as shown in Table 1, the types of skin material and substrate material were changed, and the same operation as in Application Example 1 was performed. The results are shown in Table 1.

[0039]

[Table 1]

* 1 PVC leather: 0.2 mm thick polyvinyl chloride leather * 2 PPF: 2 mm thick expanded polypropylene * 3 PET non-woven fabric: 2 mm thick polyethylene terephthalate non-woven fabric * 4 SBR coat: styrene butadiene rubber Adhesive * 5 PUF: 2 mm thick urethane foam * 6 RF: 3 mm thick resin felt * 7 GFP: 3 mm thick glass fiber phenolic plate * 8 PP: 2 mm thick polypropylene coated with anchor coating agent Board

[0041]

[Table 2]

Looking at the results of the adhesion test shown in Table 1, when the resin compositions of Examples 1 to 3 were used as the adhesive layer (Application Examples 1 to 12), the adhesive strength at room temperature was high. And the heat-resistant creep resistance were both good. That is, the resin composition of the present invention is applied to various base materials (including skin material and substrate material) including urethane foam base materials and polypropylene injection-molded plates that have not been able to obtain sufficient adhesive strength in the past. Shows good adhesion. In addition, the resin composition of the present invention has a pattern peculiar to vinyl chloride leather when adhering a skin material on which vinyl chloride leather (vinyl chloride leather) is applied (application examples 1, 4 to 6, 8, 11, 12). It could be manufactured without causing damage to the skin material. Further, the bonding work was very easy and hygienic, and the workability was good. On the other hand, in the case of the resin composition of Comparative Example 1 (Reference Examples 1 and 2), the adhesive strength was relatively good, but the thermal creep resistance was significantly poor,
There is a big problem in using it as an interior material for automobiles. In the case of the resin composition of Comparative Example 2 (Reference Example 3,
In 4), before the measurement of the heat-resistant creep resistance, the adhesive strength was completely insufficient, and a practically durable laminate could not be obtained.

[0043]

As described above, the resin composition of the present invention is
It exhibits good adhesiveness to a wide range of substrates and can be suitably used as an adhesive layer of various laminated bodies. Also,
Since it can be bonded at low temperature and low pressure without damaging the skin material, it does not impair the texture of the skin material, has excellent aesthetics, and has high adhesive strength in a wide temperature range from normal temperature to high temperature. Therefore, since it does not cause deformation or the like and is excellent in heat-resistant creep resistance, it can be suitably used as an interior material for automobiles, houses and the like. Moreover, there is no need to use an organic solvent when bonding,
Moreover, since the working process is simple, there is no problem in use. Further, since it can be manufactured using the same method and equipment as those of the conventional adhesive resin, it can be manufactured relatively inexpensively and easily. Therefore, the resin composition of the present invention is
It is effectively used as an adhesive layer for various laminates including interior materials for homes.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hirotaka Takoshi 2nd Nakanosu, Oita City, Oita Prefecture Showa Denko Oita Laboratory

Claims (3)

[Claims] 1. An ethylene-based multi-component copolymer comprising (A) ethylene, a radical-polymerizable acid anhydride and a radical-polymerizable comonomer other than the above, wherein the radical-polymerizable acid anhydride in the multi-component copolymer is The ratio of derived units is 0.1-5
70% to 99% by weight of an ethylene-based multi-component copolymer having a weight percentage of 3 to 50% by weight of units derived from other radically polymerizable comonomers, and (B) ethylene and a radical polymerizable acid anhydride. An ethylene-based binary copolymer having the following ratio, wherein the ratio of the units derived from the radical-polymerizable acid anhydride in the binary copolymer is 0.1 to 10% by weight. A resin composition containing from 1 to 1% by weight. 2. (C) The viscosity at 200 ° C. is 200 to
The resin composition according to claim 1, which contains a copolymerized nylon having a weight of 8,000 centipoise (cP). 3. (C) The viscosity at 200 ° C. is from 200 to
The resin composition according to claim 1, which contains a copolymerized nylon having 8,000 centipoise (cP) and (D) a metal salt of an organic carboxylic acid.