JP2007119608A - Composition for laminating use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hot-melt type composition for laminating use highly adhesive to polyester-coated steel plate and acrylic coated steel plate. <P>SOLUTION: The composition for laminating use contains a total of ≥60 wt.% of (A) an ethylene-based multicomponent copolymer, a copolymer of ethylene, a radical-polymerizable acid anhydride and another radical-polymerizable comonomer, wherein the proportion of units derived from the radical-polymerizable acid anhydride is 0.1-5 wt.% and that of units derived from the other radical-polymerizable comonomer, and (B) an ethylene-based copolymer, a copolymer formed by copolymerization between ethylene and an α-olefin in the presence of a metallocene-based polymerization catalyst, having a melt flow rate of 0.5-80 g/10min and a density of 870-900 kg/m<SP>3</SP>, with the compounding weight ratio A/B being (95:5) to (5:95). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminating composition that is applied by hot melt coating and exhibits adhesive strength by thermocompression bonding, and more particularly relates to a tack-free laminating composition that is excellent in adhesion to a polyester-coated steel sheet.

  The polyolefin-based hot-melt adhesive does not require the use of an organic solvent at the time of bonding, and since the work process is simple, it can be suitably used as a laminating composition that becomes an adhesive layer of a laminate. For this reason, the laminated body manufactured using this adhesive agent is used extensively.

  However, since this adhesive does not have sufficient adhesive strength depending on the type of substrate, a satisfactory laminate may not be obtained. For example, when a polyester coating is applied to the surface of the base material, a laminate using this adhesive tends to cause peeling of the base material layer. In such a case, it is necessary to perform a special treatment on the surface of the base material in advance or use a solvent-type adhesive instead of a hot-melt adhesive. It becomes complicated and increases the production cost. The latter causes adverse environmental and hygienic effects due to the use of organic solvents. As mentioned above, it has good adhesive strength regardless of the type of base material, so it can be widely used in a wide range of fields, and it does not have problems in manufacturing process such as workability and environmental problems. In fact, the composition has not yet been developed.

  For example, a multi-component copolymer composed of ethylene, a radically polymerizable acid anhydride and other radically polymerizable comonomers, a copolymerized nylon having a viscosity at 200 ° C. of 200 to 8,000 centipoise (cP), and a polyolefin resin Has already been proposed (see Patent Document 1), but in the case of the laminating composition used in this laminate, a polyester-coated steel sheet, Adhesion to acrylic-coated steel sheets is not sufficient.

JP-A-6-182922

  In view of the above circumstances, an object of the present invention is to provide a hot-melt type laminating composition having excellent adhesion to polyester-coated steel sheets and acrylic-coated steel sheets.

In order to achieve the above object, the laminating composition according to claim 1 of the present invention (hereinafter referred to as "composition of claim 1") is composed of ethylene, a radically polymerizable acid anhydride and other radicals. A copolymer of a polymerizable comonomer, wherein the proportion of units derived from the radical polymerizable acid anhydride is 0.1 to 5% by weight, and the proportion of units derived from other radical polymerizable comonomer is 3 to 3% by weight. A copolymer obtained by polymerizing ethylene and an α-olefin in the presence of a 50% by weight ethylene multi-component copolymer (A) and a metallocene polymerization catalyst, and having a melt flow rate of 0.5 to 80 g. / 10 minutes, the ethylene copolymer (B) having a density of 870 to 900 kg / m ³ , and 60% by weight or more of the total, and the ethylene multi-component copolymer (A) and the ethylene copolymer Coordination with copolymer (B) The combined ratio is characterized in that the weight ratio is 95: 5 to 5:95.

  The composition for laminating according to claim 2 of the present invention (hereinafter referred to as “composition of claim 2”) is characterized in that the composition of claim 1 contains a terpene phenol resin (C). .

  The laminate composition according to claim 3 of the present invention (hereinafter referred to as "composition of claim 3") is the composition of claim 2, wherein the total amount of terpene phenol resin (C) is 5 to 40 wt. % Is included.

  The ethylene-based multi-component copolymer (A) used in the present invention is a multi-component copolymer composed of ethylene, a radical polymerizable acid anhydride and another radical polymerizable comonomer. What is a radical polymerizable acid anhydride? Means a compound having at least one unsaturated bond and an acid anhydride group each capable of radical polymerization in the molecule, and capable of introducing an acid anhydride group into the molecule by polymerization. Those are preferred.

  Examples of such radical polymerizable acid anhydrides include maleic anhydride, itaconic anhydride, endic acid anhydride, citraconic acid anhydride, dodecenyl succinic anhydride, 1-butene-3,4-dicarboxylic acid anhydride, carbon Examples thereof include alkenyl succinic anhydride having a double bond at the terminal having at most 18 and alkadienyl succinic anhydride having a double bond at the terminal having at most 18 carbon. Among them, maleic anhydride, itaconic anhydride, etc. Acid is preferred. These radical polymerizable acid anhydrides may be used alone or in combination of two or more.

  The proportion of units derived from the radically polymerizable acid anhydride in the ethylene-based multi-component copolymer (A) is in the range of 0.1 to 5% by weight, preferably in the range of 0.5 to 4.5% by weight. More preferably, it is in the range of 1.0 to 4.0% by weight, but the reason is that if the proportion of units derived from radically polymerizable acid anhydride is less than 0.1% by weight, the adhesive performance is insufficient and good. This is because if the adhesive strength is not obtained and the content exceeds 5% by weight, the effect of improving the adhesive strength is almost no longer economical, and the compatibility may be lowered when other resins are mixed.

  As the radical polymerizable comonomer (hereinafter referred to as “polymerizable comonomer”) other than the radical polymerizable acid anhydride used for the ethylene-based multi-component copolymer (A), there are various compounds such as an ethylenically unsaturated ester. Examples thereof include compounds, ethylenically unsaturated amide compounds, ethylenically unsaturated acid compounds, ethylenically unsaturated ether compounds, and other compounds.

  Specifically, as the ethylenically unsaturated ester compound, for example, 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 Examples include diethyl, dipropyl fumarate, dibutyl fumarate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, and dibutyl maleate. Here, methyl (meth) acrylate means methyl acrylate or methyl methacrylate.

  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- Examples thereof include 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.

Examples of other compounds include styrene, α-methylstyrene, norbornene, butadiene, (meth) acrylonitrile, acrolein, crotonaldehyde, trimethoxyvinylsilane, vinyl chloride, vinylidene chloride, and the like.
Among these polymerizable comonomers, vinyl acetate; (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; (meth) acrylic acid is particularly preferable. As a compound.

  These polymerizable comonomers may be used alone or in combination of two or more.

  The proportion of units derived from the polymerizable comonomer in the ethylene-based multi-component copolymer (A) is in the range of 3 to 50% by weight, preferably in the range of 5 to 40% by weight, more preferably 10 to 10%. The range is 35% by weight, but the reason is that if the proportion of the polymerizable comonomer is less than 3% by weight, the crystalline melting point of the ethylene-based multi-component copolymer is not sufficiently lowered and the low-temperature adhesiveness is sufficiently exhibited. This is because when the amount exceeds 50% by weight, it is difficult to handle the ethylene-based multi-component copolymer (A) and the heat resistance of the composition for laminating is lowered.

  In producing the above-mentioned ethylene-based multi-component copolymer (A), it is basically possible to use ordinary high-pressure low-density polyethylene production equipment and techniques.

  Generally, by a bulk polymerization method, at a polymerization pressure of 700 to 3000 atm, preferably 1000 to 2500 atm, and at a polymerization temperature of 100 to 300 ° C., preferably 140 to 290 ° C., more preferably 150 to 270 ° C. , Produced by radical polymerization. That is, when the polymerization pressure is less than 700 atm, the molecular weight of the resulting ethylene-based multi-component copolymer (A) is low, and the resin physical properties of the resulting laminate composition are deteriorated. On the other hand, if the polymerization pressure exceeds 3000 atm, it only increases the production cost and is essentially meaningless. In addition, when the polymerization temperature is less than 100 ° C., the polymerization reaction is not stable, the conversion rate to the ethylene-based multi-component copolymer (A) is lowered, and there is an economical problem. At the same time as the molecular weight of the copolymer (A) decreases, there is a risk of runaway reaction. As the polymerization apparatus, it is preferable to use a vessel type reactor. In particular, since radically polymerizable acid anhydrides have poor polymerization stability, a high degree of uniformity in the reactor is required. If necessary, a plurality of reactors can be connected in series or in parallel to perform multistage polymerization. Furthermore, more precise temperature control can be performed by dividing the inside of the reactor into a plurality of zones.

The production of the ethylene-based multi-component copolymer (A) is carried out in the presence of at least one free radical initiator under the above reaction conditions. Examples of the free radical initiator include oxygen; di-t-butyl. Dialkyl peroxides such as peroxide, t-butylcumyl peroxide, dicumyl peroxide; diacyl peroxides such as acetyl peroxide, i-butyryl peroxide, octanoyl peroxide; di-i-propylperoxy-dicarbonate Peroxy-dicarbonates such as di-ethylhexyl peroxy-dicarbonate; peroxyesters such as t-butyl peroxypivalate and t-butyl peroxylaurate; ketone peroxyesters such as methyl ethyl ketone peroxide and cyclohexanone peroxide Oxide; 1,1-bis- -Peroxyketals such as butylperoxycyclohexane and 2,2-bis-t-butylperoxyoctane; hydroperoxides such as t-butylhydroperoxide and cumene hydroperoxide; 2,2-azo-i-butyronitrile And azo compounds.
In the polymerization of the ethylene-based multi-component copolymer (A), various chain transfer agents can be used as molecular weight regulators.

  Examples of the chain transfer agent include olefins such as propylene, butene and hexene, paraffins such as ethane, propane and butane, carbonyl compounds such as acetone, methyl ethyl ketone and methyl acetate, and aromatic carbonization such as toluene, xylene and ethylbenzene. Hydrogen etc. are mentioned.

  The ethylene-based multi-component copolymer (A) produced in this manner melts at a relatively low temperature, resulting in physicochemical interaction and reactivity with various base materials (including skin materials and substrate materials). Since it is rich, even when a laminate using the composition for laminating of the present invention is produced by low temperature molding, it plays a major role in ensuring high adhesive strength.

The ethylene copolymer (B) used in the present invention is a copolymer obtained by polymerizing ethylene and an α-olefin in the presence of a metallocene polymerization catalyst, and has a melt flow rate of 0.5 to 80 g / The density is 870 to 900 kg / m ³ for 10 minutes. Examples of the α-olefin include propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1, and decene-1. Preferred are butene-1, hexene-1, 4-methylpentene-1, and octene-1. Moreover, alpha-olefin may use 2 or more types together as needed.

  Specific examples of the ethylene copolymer (B) include, for example, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-4-methylpentene- 1 copolymer, ethylene-octene-1 copolymer, ethylene-propylene-butene-1 copolymer, etc., among which ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, ethylene- Octene-1 copolymers are preferred.

  The ethylene copolymer (B) used in the present invention has a melt flow rate of 0.5 to 80 g / 10 minutes, preferably 2 to 40 g / 10 minutes. When the melt flow rate of the copolymer (B) is less than 0.5 g / 10 minutes, the resulting laminate composition may be inferior in workability, and the melt flow rate of the ethylene copolymer (B) This is because the strength and workability when the laminate composition is used as a film may be inferior when the thickness exceeds 80 g / 10 min.

Furthermore, the ethylene copolymer (B) used in the present invention has a density of 870 to 900 kg / m ³ , preferably 875 to 895 kg / m ³ , for the reason that the ethylene copolymer ( When the density of B) is less than 870 kg / m ³ , the anti-blocking property and the slipping property may be inferior when the laminate composition is a film, and the density of the copolymer (A) is 900 kg / m ³ . This is because if it exceeds, the pinhole resistance and impact resistance may be inferior when the laminate composition is used as a film.

The metallocene catalyst used in the production of the ethylene-based copolymer (B) used in the present invention is a catalyst system using a transition metal compound having a group having a cyclopentadiene-type anion skeleton. _a X _na (wherein M is a group 4 or lanthanide series transition metal atom of the periodic table of elements. L is selected from a group having a cyclopentadiene-type anion skeleton and a group containing a hetero atom. , At least one is a group having a cyclopentadiene-type anion skeleton, a plurality of L may be mutually linked, X is a halogen atom, hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and n is a transition. It represents the valence of a metal atom, and a is an integer satisfying 0 <a ≦ n.) And can be used alone or in combination of two or more.

Furthermore, the metallocene-based catalyst includes an organoaluminum compound containing an alumoxane compound, an ionic compound such as trityl borate and anilinium borate, a transition metal compound having a group having a cyclopentadiene-type anion skeleton, SiO ₂ , Al ₂ One or more selected from particulate carriers including an inorganic carrier such as O ₃ and an organic polymer carrier such as an olefin polymer such as ethylene and styrene can also be used.

Furthermore, the composition for laminating of the present invention contains the ethylene multi-component copolymer (A) and the ethylene-based copolymer (B) in a total of 60% by weight or more, and the ethylene multi-component copolymer. It is essential that the blending ratio of the union (A) and the ethylene-based copolymer (B) is 95: 5 to 5:95 (preferably 80:10 to 10:80) in weight ratio. Is as follows.
That is, if the total amount of the ethylene-based multi-component copolymer (A) and the ethylene-based copolymer (B) is less than 60% by weight, pinhole resistance, This is because the impact property may be inferior.

In addition, if the blending ratio of the ethylene-based multi-component copolymer (A) is too large, it is not possible to give good adhesive strength to the laminate using the laminating composition during low-temperature molding, and a sticky phenomenon occurs. Take time.
If the blending ratio of the ethylene-based multi-component copolymer (A) is too small, sufficient adhesive strength cannot be secured for a wide range of base materials, and therefore the laminate composition has good adhesive strength regardless of the type of base material. It is not possible to provide a laminate using this.

  In addition, said (A) component and (B) component may mix | blend only 1 type, respectively, and may use 2 or more types together.

The laminate composition of the present invention preferably further contains a terpene phenol resin (C) as in the composition of claim 2.
The terpene phenol resin (C) is obtained by copolymerizing a terpene monomer and phenols in the presence of a Friedel-Craft type catalyst in an organic solvent. Moreover, the hydrogenated terpene phenol resin which hydrogenated the obtained terpene phenol resin may be sufficient.

Examples of the terpene monomer include α-pinene, β-pinene, dipentene, d-, 1-limonene and the like.
Examples of the phenols include phenol, cresol, bisphenol A and the like.

Moreover, as such a terpene phenol resin (C), for example, commercially available products such as “YS Polyster” and “Mighty Ace” manufactured by Yashara Chemical Co., Ltd. can be used.
The blending ratio of the terpene phenol resin (C) is not particularly limited, but is preferably 5 to 40% by weight, more preferably 10 to 30% by weight as in the composition of claim 3. .

  That is, if the blending ratio of the terpene phenol resin (C) is too small, sufficient adhesive strength may not be obtained when the laminating composition is used for bonding the polyester-coated steel sheet, and the blending of the terpene phenol resin (C). When the ratio is too large, the glass transition temperature of the entire laminating composition is increased, so that it becomes brittle and the handling property when the laminating composition is used as a film may be deteriorated.

  The laminating composition according to the present invention can contain other components as necessary as long as the object of the present invention is not impaired. Such other components include adhesion improvers, sensitizers, dehydrating agents, anti-aging agents, stabilizers, plasticizers, waxes, fillers, flame retardants, foaming agents, antistatic agents, antifungal agents, A viscosity modifier etc. can be mentioned. Other components that can be added are not limited to the above components, and two or more other components that can be added may be added.

  The composition for laminating of the present invention comprises an ethylene-based multi-component copolymer (A), an ethylene-based copolymer (B), and, if necessary, a terpene phenol resin (C) and other components at an appropriate blending ratio. Although it is prepared by mixing, various commonly known methods can be used for mixing. Specifically, for example, each component is dissolved in a solvent such as high-temperature toluene and reprecipitated, each component is mixed in a molten state, a commonly used pressure kneader, roll, Banbury mixer, Examples thereof include a method using a static mixer, a screw type extruder and the like.

  The laminating composition of the present invention can be suitably used for laminating polyester coated steel sheets, acrylic coated steel sheets, etc., which are difficult to bond with ordinary laminating compositions, but for the same applications as ordinary hot melt adhesives. Can also be used.

  Polyester-coated steel sheets, acrylic-coated steel sheets, and the like can be obtained by using the laminating composition of the present invention, such as fine paper, kraft paper, glassine paper, Japanese paper, cardboard base paper, synthetic paper, art paper, coated paper, etc. Paper; Various woven or non-woven fabrics made of cotton, hemp, polyester, nylon, etc .; Wood board; Various metal plates or foils such as iron, aluminum, copper, tinplate, etc .; Polypropylene, polystyrene, polyethylene, polyester, nylon, polycarbonate, acrylic resin, Plates, molded products, films or foams made of various plastics such as phenol resin and polyurethane; various inorganic materials such as glass fibers and ceramics, and those whose surfaces are surface treated, coated, printed, etc. It can be laminated to various things.

  The laminate using the laminating composition of the present invention is not particularly limited. For example, the laminating composition is laminated on one side or both sides of one arbitrarily selected substrate, or arbitrarily. It can be manufactured by adhering two or more selected substrates with a laminating composition. That is, in the case of the former laminate, for example, the laminate composition is first formed into a film by, for example, inflation molding or T-die molding, and this film-like molded body is formed into a hot roll laminate. A method of coating by laminating a composition for extrusion onto a substrate; a method of using the composition for laminating on a substrate as a powder adhesive, and the like. In the case of the latter laminate, for example, a method of laminating the film-like molded body between substrates and thermally bonding the composition; a composition for laminating the laminate obtained by hot roll laminate molding or extrusion laminate molding Examples include a method in which the layer side is further heat-pressed to another substrate by hot pressing or hot roll.

As described above, the laminating composition of the present invention is a copolymer of ethylene, a radically polymerizable acid anhydride and another radically polymerizable comonomer, which is a unit derived from the radically polymerizable acid anhydride. An ethylene multi-component copolymer (A) having a proportion of 0.1 to 5% by weight and a proportion of units derived from other radical polymerizable comonomers of 3 to 50% by weight;
An ethylene-based copolymer obtained by polymerizing ethylene and α-olefin in the presence of a metallocene polymerization catalyst, having a melt flow rate of 0.5 to 80 g / 10 min and a density of 870 to 900 kg / m ³ Copolymer (B) in a total of 60% by weight or more, and the blending ratio of the ethylene-based multi-component copolymer (A) and the ethylene-based copolymer (B) is 95: Since it is 5-5: 95, it is excellent in adhesiveness, such as a polyester coated steel plate. Moreover, it is easy to handle because there is little surface tack.

  Moreover, if the terpene phenol resin (C) is further contained like the composition of Claim 2, the adhesive force to a polyester coating steel plate and an acrylic coating steel plate will improve further.

  Furthermore, if the terpene phenol resin (C) is contained in an amount of 5 to 40% by weight as in the composition of claim 3, the adhesive force to the polyester coated steel sheet and the acrylic coated steel sheet is further improved, and the cold-resistant adhesion is achieved. Power also improves.

  Specific examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1
Trade name Bondine HX8210 manufactured by Arkema as the ethylene-based multi-component copolymer (A) (ternary of ethylene, maleic anhydride as a radical polymerizable acid anhydride, and ethyl acrylate as another radical polymerizable comonomer) A copolymer in which the proportion of units derived from maleic anhydride is 3% by weight, the proportion of units derived from ethyl acrylate is 6% by weight) is 30% by weight,
Trade name EXCELEN FX CX4002 manufactured by Sumitomo Chemical Co., Ltd. as an ethylene copolymer (B)
(Ethylene and α-olefin (C6) are polymerized in the presence of a metallocene polymerization catalyst, and the melt flow rate is 8 g / 10 min, the density is 880 kg / m ³ ) and 70 wt%. The composition for lamination was prepared by melt-kneading.

(Example 2)
Trade name Bondine AX8390 (ethylene, maleic anhydride as a radical polymerizable acid anhydride, and ethyl acrylate as the other radical polymerizable comonomer as an ethylene-based multi-component copolymer (A) manufactured by Arkema 30% by weight of a copolymer having a proportion of units derived from maleic anhydride of 1.7% by weight and a proportion of units derived from ethyl acrylate of 30% by weight)
Exelene FX CX5508 manufactured by Sumitomo Chemical Co., Ltd. as an ethylene copolymer (B) (ethylene and α-olefin (C4 system) are polymerized in the presence of a metallocene polymerization catalyst, and the melt flow rate is 75 g / A composition for laminating was prepared by blending for 10 minutes such that the density was 890 kg / m ³ ) being 70% by weight, and melt-kneading.

(Example 3)
Arkema brand name Bondine HX8210 is 30% by weight, Sumitomo Chemical brand name Excellen FX CX4002 is 50% by weight, and Yashara Chemical brand name PL-5 as terpene phenol resin is 20% by weight. Thus, the composition for lamination was prepared by mix | blending in this way and melt-kneading.

Example 4
Arkema brand name Bondine AX8390 is 30% by weight, Sumitomo Chemical brand name Excellen FX CX5508 is 50% by weight, and Yashara Chemical brand name PL-5 as terpene phenol resin is 20% by weight. Thus, the composition for lamination was prepared by mix | blending in this way and melt-kneading.

(Example 5)
A composition for laminating was prepared by blending so that the product name Bondine HX8210 manufactured by Arkema Co., Ltd. was 5% by weight and the product name Exelen FX CX4002 manufactured by Sumitomo Chemical Co., Ltd. was 95% by weight, and melt-kneaded.

(Example 6)
Arkema brand name Bondine HX8210 is 5% by weight, Sumitomo Chemical brand name Excellen FX CX4002 is 90% by weight, and Yashara Chemical brand name PL-5 as terpene phenol resin is 5% by weight. Thus, the composition for lamination was prepared by mix | blending in this way and melt-kneading.

(Comparative Example 1)
A composition for laminating was prepared by blending so that 80% by weight of the trade name Bondine HX8210 manufactured by Arkema Co., Ltd. and 20% by weight of the product name PL-5 manufactured by Yasuhara Chemical Co., Ltd. were melted and kneaded.

(Comparative Example 2)
A composition for laminating was prepared by blending so that 80% by weight of trade name Exelen FX CX4002 manufactured by Sumitomo Chemical Co., Ltd. and 20% by weight of product name PL-5 manufactured by Yashara Chemical Co., Ltd. may be 20% by weight.

(Comparative Example 3)
A laminating composition was prepared by blending 3 wt% of the trade name Bondine HX8210 manufactured by Arkema Co., Ltd. and 97 wt% of the trade name EXCELEN FX CX4002 manufactured by Sumitomo Chemical Co., Ltd.

(Evaluation of Examples and Comparative Examples)
About the composition for lamination obtained as mentioned above, (1) normal state adhesiveness and (2) surface tack were evaluated in the following ways.

(1) Normal adhesiveness The laminate composition obtained above is sandwiched between release PET and crushed to a thickness of about 100 microns with a heating press heated to 160 ° C. to obtain a laminate composition film. Obtained.
(Adhesion between polyester coated steel sheets)
In an atmosphere of 23 ° C. and 50% relative humidity, two 1 cm wide and about 5 cm polyester coated steel sheets were prepared as adherends, and the laminate composition film was sandwiched between the polyester coated steel sheets with a width of 1 cm and a length of 2 cm. The plate was placed on an ironing board set at 160 ° C., and a weight was placed thereon for 2 seconds so as to be 500 g / cm ² , followed by pressure bonding. And after peeling this test piece for 24 hours at 23 degreeC, the peeling test was done with the pulling speed of 300 mm / min.
(Adhesion between polyester-coated steel sheet and canvas)
In an atmosphere of 23 ° C. and 50% relative humidity, a 1 cm wide, approximately 5 cm polyester coated steel sheet and canvas are prepared as an adherend, and the laminate composition film is 1 cm wide between the polyester coated steel sheet and the canvas. The sample was sandwiched between 2 cm lengths and placed on an ironing board set at 160 ° C., and a weight was applied for 2 seconds so as to be 500 g / cm ² , followed by pressure bonding. And after peeling this test piece for 24 hours at 23 degreeC, the peeling test was done with the pulling speed of 300 mm / min.

(2) Surface Tack The normal adhesion test piece of (1) was placed in a dryer at 40 ° C. for 24 hours, and immediately after removal, the presence or absence of tack of the laminating composition was evaluated by finger pitting. Those without tack were marked with ◯, and those without tack were marked with ×.

    As can be seen from Table 1 above, Comparative Examples 1 and 2 lack the essential component, and Comparative Example 3 lacks the necessary amount of the essential component, indicating that the adhesiveness is insufficient.

Claims (3)

A copolymer of ethylene, radically polymerizable acid anhydride and other radically polymerizable comonomer, wherein the proportion of units derived from the radically polymerizable acid anhydride is 0.1 to 5% by weight, An ethylene-based multi-component copolymer (A) in which the proportion of units derived from the radical polymerizable comonomer is 3 to 50% by weight;
An ethylene-based copolymer obtained by polymerizing ethylene and α-olefin in the presence of a metallocene polymerization catalyst, having a melt flow rate of 0.5 to 80 g / 10 min and a density of 870 to 900 kg / m ³ Copolymer (B);
Including 60% by weight or more of the total, and
A composition for laminating, wherein the blending ratio of the ethylene multi-component copolymer (A) and the ethylene copolymer (B) is 95: 5 to 5:95 by weight.   The composition for laminating according to claim 1, comprising a terpene phenol resin (C).   The composition for laminating according to claim 2, comprising 5 to 40% by weight of the terpene phenol resin (C).