JPH09176391A - Adhesive resin composition and laminate thereof - Google Patents

Abstract

(57) [Summary] (Modified) [PROBLEMS] An adhesive resin composition having high adhesive strength during high temperature molding and under thin film thickness. SOLUTION: In the presence of (A) a catalyst containing a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, ethylene or ethylene and 3 to 3 carbon atoms are contained.
20% by weight or more of an ethylene (co) polymer obtained by (co) polymerizing with 20 α-olefins,
(B) 80% by weight or less of a polyolefin resin other than the ethylene (co) polymer as the component (A), and 40% by weight of (C) rubber.
At least one of the component (A), the component (B), and the component (C) in the resin composition is a carboxylic acid group, an acid anhydride group, an ester group, a hydroxyl group, an amino group, and a silane. Graft-modified with at least one monomer containing a functional group selected from the groups, and the amount of the grafted monomer is 10 ^-8 to 1 per 1 g of the resin composition.
An adhesive resin composition having an amount of 0 ⁻³ mol.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to various substrates.
The present invention relates to an adhesive resin composition having excellent adhesiveness and a laminate comprising the adhesive resin composition and various substrates.

[0002]

2. Description of the Related Art Generally, polyethylene resin has a high strength, is resistant to chemicals and corrosion, is inexpensive, and so on.
It is used in a wide range of applications such as containers and blow bottles.
By further laminating it with a specific base material such as a gas barrier material, a container having a gas barrier property in addition to the above characteristics can be obtained. However, since polyethylene resin does not have a polar group in the molecule when these are laminated,
There is a drawback that the adhesiveness to other kinds of adhesive materials such as other synthetic resins and metal wood is extremely low. In order to improve these, it has been attempted to add an unsaturated carboxylic acid or the like to introduce a functional group to impart adhesiveness (see, for example, JP-A-50).
-4144).

Further, a composition obtained by modifying a polyolefin polymer with a solid rubber or an unsaturated carboxylic acid to further improve the adhesiveness (for example, JP-A-50-7848 and JP-A-54-1240), or A composition obtained by modifying an ethylene / α-olefin copolymer rubber with an unsaturated carboxylic acid (JP-A-52-49289) has been proposed. However, although these have achieved some results,
The high adhesive strength at the time of high-speed molding and under the thin film thickness, which has been recently demanded, is not sufficiently satisfied.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned drawbacks by providing an adhesive resin composition having a high adhesive strength during high-speed molding and under a thin film thickness, and a laminate using the same. To provide.

[0005]

Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a specific ethylene (co) polymer produced by a specific catalyst and a graft-modified resin is blended. They have found that the product gives excellent adhesive strength, and have completed the present invention.

That is, firstly, the present invention relates to (A) and (B).
In the presence of a catalyst containing at least a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, ethylene or ethylene and α- having 3 to 20 carbon atoms
Obtained by (co) polymerizing with an olefin,
(B) Density 0.86 to 0.97 g / cm ³ , (c) Melt flow rate 0.01 to 100 g / 10 minutes, (d) Molecular weight distribution Mw / Mn is 1.5 to 5.0, (e) 100 to 20% by weight of an ethylene (co) polymer having a composition distribution parameter Cb of 1.2 or less, 80% by weight or less of a polyolefin resin other than the ethylene (co) polymer of the component (B) (A), (C) Composition consisting of 40% by weight or less of rubber (A + B
+ C = 100% by weight), and (A) in the resin composition
Component, component (B), component (C) at least one component is graft modified with at least one monomer containing a functional group selected from a carboxylic acid group, an acid anhydride group, an ester group, a hydroxyl group, an amino group and a silane group. And the amount of the grafted monomer is 10 ^-8 to 1 g of the resin composition.
The present invention relates to an adhesive resin composition containing 10 ^-3 mol.

Secondly, the present invention comprises, as a single layer, a layer comprising the adhesive resin composition according to the above-mentioned first item, and comprises polyolefin, saponified ethylene vinyl acetate copolymer, polyamide, polyester, polyurethane, polystyrene, wood, fiber. And a layered body including at least two layers including at least one layer selected from metal foils as another layer.

Hereinafter, the present invention will be described in detail. The ethylene (co) polymer (A) of the present invention comprises a transition metal compound of Group IV of the Periodic Table containing the above-mentioned ligand having a cyclopentadienyl skeleton, and if necessary, a cocatalyst, an organoaluminum compound and / or Ethylene homopolymerization in the presence of a catalyst containing a carrier, or ethylene and α- with 3 to 20 carbon atoms
Obtained by copolymerizing with an olefin,
(B) An ethylene (co) polymer having a density of 0.86 to 0.97 g / cm ³ and (c) a melt flow rate of 0.01 to 100 g / 10 minutes. Further, the catalyst obtained by preliminarily polymerizing ethylene and / or the α-olefin with the above catalyst may be used as the catalyst.

The above α-olefin has 3 carbon atoms.
-20, preferably 3 to 12, specifically propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, and dodecene-1.
And so on. In addition, the content of these α-olefins used as the conomer of the copolymer is usually selected in the range of 30 mol% or less, preferably 20 mol% or less.

Cyclopentadienyl skeleton of a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton which is a catalyst for producing the above-mentioned (A) ethylene (co) polymer of the present invention Is a cyclopentadienyl group, a substituted cyclopentadienyl group, or the like. Examples of the substituted cyclopentadienyl group include a hydrocarbon group having 1 to 10 carbon atoms, a silyl group, a silyl-substituted alkyl group, a silyl-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, and a halosilyl group. And a substituted cyclopentadienyl group having at least one substituent selected from groups and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents may be bonded to each other to form a ring.

Examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like, specifically, methyl, ethyl,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group,
Examples thereof include alkyl groups such as decyl group; cycloalkyl groups such as cyclopentyl group and cycloalkyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group. Among these, an alkyl group is preferable.

Preferred substituted cyclopentadienyl groups include methylcyclopentadienyl group, ethylcyclopentadienyl group, n-hexylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
3-n-butylmethylcyclopentadienyl group, 1,3
Specific examples thereof include -n-propylmethylethylcyclopentadienyl group. Among these, the substituted cyclopentadienyl group of the present invention is preferably a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms,
A 1,3-substituted cyclopentadienyl group is particularly preferable.

The substituted cyclopentadienyl group in the case where the substituents, that is, the hydrocarbons, are bonded to each other to form one or two or more rings, is an indenyl group or a carbon number of 1
-Substituted indenyl group, naphthyl group having 1 to 8 carbon atoms, which is substituted by a substituent such as
Preferred are a substituted naphthyl group substituted by a substituent such as a hydrocarbon group (alkyl group) and a substituted fluorenyl group substituted by a substituent such as a hydrocarbon group having 1 to 8 carbon atoms (alkyl group). It is given as a thing.

Examples of the transition metal of the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton include zirconium, titanium and hafnium, and zirconium is particularly preferable.

The transition metal compound usually has 1 to 3 ligands having a cyclopentadienyl skeleton, and when they have 2 or more ligands, they may be bonded to each other by a bridging group. Examples of the crosslinking group include alkylene groups having 1 to 4 carbon atoms, alkylsilanediyl groups, and silanediyl groups.

As a ligand other than the ligand having a cyclopentadienyl skeleton in a transition metal compound of Group IV of the periodic table, hydrogen and C1 to C2 are typical.
And a hydrocarbon group of 0 (alkyl group, alkenyl group, aryl group, alkylaryl group, aralkyl group, polyenyl group, etc.), halogen, metaalkyl group, metaaryl group and the like.

The following are specific examples of the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton. Examples of monoalkyl metallocenes include bis (cyclopentadienyl) titanium methyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, bis (cyclopentadienyl) zirconium phenyl chloride, etc. There is. Examples of the dialkyl metallocene include bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl). Examples include phenyl) hafnium dimethyl and bis (cyclopentadienyl) hafnium diphenyl. As the trialkyl metallocene, cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium trimethyl, cyclopentadienyl zirconium triphenyl,
Cyclopentadienyl zirconium trineopentyl,
Examples include cyclopentadienyl hafconium trimethyl and cyclopentadienyl hafnium triphenyl.

Examples of monocyclopentadienyl titanocene include pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride, bis (pentamethylcyclopentadienyl) titanium diphenyl and the like.

Examples of the substituted bis (cyclopentadienyl) titanium compound include bis (indenyl) titanium diphenyl or dichloride, bis (methylcyclopentadienyl) titanium diphenyl or dihalide; dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopenta Examples of the dienyl titanium compound include bis (1,2-dimethylcyclopentadienyl) titanium diphenyl or dichloride, bis (1,2-diethylcyclopentadienyl) titanium diphenyl or dichloride or other dihalide complex; silicon, amine or Carbon-bonded cyclopentadiene complexes include dimethylsilyldicyclopentadienyl titanium diphenyl or dichloride, methylenedicyclopentadienyl Data chloride diphenyl or dichloride, other dihalide complexes and the like.

As the zirconocene compound, pentamethylcyclopentadienyl zirconium trichloride,
Pentaethylcyclopentadienyl zirconium trichloride, bis (pentamethylcyclopentadienyl)
Zirconium diphenyl: Alkyl-substituted cyclopentadiene includes bis (ethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, haloalkyl or dihalide thereof. Complexes; bis (pentamethylcyclopentadienyl) zirconium dimethyl as dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopentadiene, bis (1,2-dimethylcyclopentadienyl) zirconium dimethyl, and their dihalide complexes; silicon As the carbon-linked cyclopentadiene complex, dimethylsilyldicyclopentadienylzirconium dimethyl or dihalide, methylenedicyclopentene Dienyl zirconium dimethyl or dihalide, such as methylene dicyclopentadienyl zirconium dimethyl or dihalide and the like.

Further, as another example of the transition metal compound of Group IV of the periodic table, a ligand having a cyclopentadienyl skeleton represented by the following general formula and other ligands and a transition metal atom are cyclic. There are also those that form the.

[0022]

[Equation 1]

In the formula, Cp is a ligand having the cyclopentadienyl skeleton, X is hydrogen, halogen, and having 1 to 2 carbon atoms.
0 represents an alkyl group, an arylsilyl group, an aryloxy group, an alkoxy group, an amido group, a silyloxy group, etc., and Z is —O—, —S—, —NR—, —PR— or O.
A divalent neutral ligand selected from the group consisting of R, SR, NR ₂ and PR ₂ , Y is SiR ₂ , CR ₂ , SiR ₂ SiR
₂ , CR ₂ CR ₂ , CR = CR, SiR ₂ CR ₂ , BR
₂ represents a divalent group selected from the group consisting of BR. However, R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group, or two or more Rs from Y, Z or both Y and Z. The groups are those that form a fused ring system. M represents a transition metal atom of Group IV of the periodic table.

Examples of the metal coordination compound of the above formula I include (t
-Butylamido) (tetramethyl-cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (t-butylamido) (tetramethylcyclopentadienyl) -1,2-ethanediyl titanium dichloride, (methylamido) (tetra Methylcyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamido) (tetramethylcyclopentadienyl) -1,2-ethanediyltitanium dichloride,
(Ethylamido) (tetramethylcyclopentadienyl) -methylenetan dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silane zirconium Dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silane zirconium dibenzyl, (benzylamido) dimethyl- (tetramethylcyclopentadienyl) silane titanium dichloride, (phenylphosphide) dimethyl- (tetramethylcyclo Pentadienyl) silane titanium dichloride and the like.

As the co-catalyst of the present invention, a co-catalyst capable of effectively using the transition metal compound of Group IV of the periodic table as a polymerization catalyst or capable of balancing the ionic charge in a catalytically activated state is used. Examples of specific cocatalysts include benzene-soluble aluminoxanes of organoaluminum oxy compounds, organoaluminum oxy compounds insoluble in benzene, boron compounds, lanthanoid salts such as lanthanum oxide, and tin oxide. Of these, aluminoxane is most preferable.

The catalyst may be an inorganic compound or an organic compound.
It may be supported on a carrier for use. Inorganic as the carrier
A compound or a porous oxide of an organic compound is preferable.
Physically SiO_Two, Al_TwoO_Three, MgO, ZrO_Two, T
iO_Two, B_TwoO_Three, CaO, ZnO, BaO, ThO_Two
Etc. or a mixture of these, for example, SiO_Two-Al_Two
O_Three, SiO_Two-V_TwoO_Five, SiO_Two-TiO_Two, Si
O_Two-V_TwoO_Five, SiO_Two-MgO, SiO_Two−Cr_Two
O_ThreeAnd the like. Among them, SiO _TwoAnd A
l_TwoO_ThreeAt least one selected from the group consisting of
Those containing minutes as the main component are preferable.

As the organic compound, either a thermoplastic resin or a thermosetting resin can be used, and specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, poly (meth) acrylate, Examples thereof include polystyrene, polynorbornene, various natural polymers, and mixtures thereof.

As the organoaluminum compound of the present invention,
Trialkyl aluminums such as triethyl aluminum and triisopropyl aluminum; dialkyl aluminum halides; alkyl aluminum sesquihalides;
Alkyl aluminum dihalide; alkyl aluminum hydride, organic aluminum alkoxide and the like.

The ethylene (co) polymer (A) of the present invention is
In the presence of the catalyst, it is produced by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method or the like substantially without a solvent, butane, pentane, hexane, heptane are substantially cut off with oxygen, water and the like. And the like, and aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C,
Preferably 20 to 200 ° C., more preferably 50 to 1
The polymerization pressure is usually atmospheric pressure to 70 kg / cm ² G, preferably atmospheric pressure to 20 kg / c in the case of the low and medium pressure method.
m ² G, usually 1500 kg / c in case of high pressure method
m ² G or less is desirable. The polymerization time is usually from 3 minutes to 10 hours, preferably from 5 minutes to 5 hours in the case of the low and medium pressure method. In the case of the high pressure method, it is usually 1 minute to 30 minutes, preferably 2 minutes to 20 minutes. Further, the polymerization is not limited to the one-step polymerization method, and is not particularly limited to a two-step or more multi-step polymerization method in which the polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature and catalyst are different from each other.

The ethylene (co) polymer (A) of the present invention has a (b) density of 0.86 to 0.97 g / cm ³ , preferably 0.89 to 0.95 g / cm ³ , and more preferably It is in the range of 0.90 to 0.94 g / cm ³ . If the density is less than 0.86 g / cm ³ , the heat resistance of the obtained adhesive resin is poor, and if it is 0.97 g / cm ³ or more, the adhesive strength is insufficient. Particularly, the density range of 0.90 to 0.94 g / cm ³ is most preferable because a composition having a balance between heat resistance and adhesive strength can be obtained.

The (A) ethylene (co) polymer (c) melt flow rate is 0.01 to 100 g / 10.
Min, preferably 0.03 to 50 g / 10 min, more preferably 0.1 to 30 g / 10 min. If the MFR is less than 0.01 g / 10 minutes or 100 g / 10 minutes or more, the adhesive strength is insufficient.

The ethylene (co) polymer (A) of the present invention is
The properties are different from those of ethylene (co) polymers obtained by conventional Ziegler type catalysts and Phillips type catalysts. That is, the ethylene (co) polymer of the present invention obtained by the above catalyst has a narrow active mass of the catalyst and thus has a narrow molecular weight distribution and composition distribution, and (d) a molecular weight distribution Mw / Mn of 1.5.
.About.5.0, and (e) the composition distribution parameter Cb is 1.2 or less. Due to the characteristics of this molecular structure, as the amount of branching increases, the crystalline lamella of the resin becomes thinner and the melting point becomes lower. In addition, since the crystal lamella thickness is thin, the number of tie molecules across the lamella is large, and the crystal size is small and uniform, so that the solidification rate upon cooling from the molten state is high. Therefore, it is difficult to form a low melting point component having a low molecular weight or a highly branched structure. These characteristics contribute to the improvement of the adhesive strength of the adhesive resin composition of the present invention.

The above-mentioned method (d) for calculating the molecular weight distribution (Mw / Mn) is to calculate by calculating the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC). , Mw / Mn is in the range of 1.5 to 5.0, preferably 1.8 to 4.5. If Mw / Mn is less than 1.5, the workability during molding of the laminate is not sufficient, and if 5.0 or more, the adhesive strength is poor. Mw /
When Mn is in the above range, an adhesive resin composition and a laminate having significantly better moldability and adhesive strength than those obtained by using a conventional polyolefin resin can be obtained.

The measurement method of the above (e) composition distribution parameter Cb is as follows. Add a heat stabilizer to the sample and add
Dissolve in DCB by heating at 135 ° C. to a concentration of 0.2% by weight. The solution is transferred to a column packed with diatomaceous earth (Celite 545) and cooled to 25 ° C at 0.1 ° C / min to deposit a sample on the surface of Celite. Next, ODCB
Column temperature at 5 ℃ increments
The temperature is raised stepwise to 20 ° C. to elute the sample and separate the sample. The solution is reprecipitated with methanol, filtered and dried to obtain a sample at each elution temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) of each sample are measured. The degree of branching (measured value) is determined by 13 C-NMR.

The fraction of 30 ° C. to 90 ° C. is subjected to the following correction of branching degree by the above method.
That is, the measured branching degree is plotted against the elution temperature, and the correlation is approximated to a straight line by the method of least squares to create a calibration curve. The correlation coefficient of this approximation is large enough. The value obtained from this calibration curve is defined as the degree of branching of each fraction. If the elution temperature is 95 ° C. or higher, a linear relationship does not always hold between the elution temperature and the degree of branching, so this correction is not performed.

Next, the weight fraction w of each fraction
The _i, the amount of change in the degree of branching b _i per the elution temperature 5 ° C. (b _i
Obtaining the relative concentration c _i is divided by -b _i-1), by plotting the relative concentration against the branching degree to obtain a composition distribution curve. This composition distribution curve is divided by a certain width, and the composition distribution parameter Cb is calculated from the following equation.

[0037]

[Equation 2]

Here, c _j and b _j are the relative density and branching degree of the j-th section, respectively. Composition distribution parameter Cb
Is 1 when the composition of the sample is uniform, and the value increases as the composition distribution spreads.

Composition of ethylene / α-olefin copolymer
Many proposals have been made for methods of measuring distribution. example
For example, in JP-A-60-88016, a sample is obtained by solvent separation.
The cumulative weight fraction is specified for the number of branches of each separated sample.
Performs numerical processing assuming a distribution (lognormal distribution)
Of the weight average branching degree (Cw) and the number average branching degree (Cn)
Seeking ratio. This approximate calculation is based on the number of samples
If the weight fraction deviates from the lognormal distribution, the accuracy decreases and the market
When measuring LLDPE for sale, the correlation coefficient R _TwoHaka
Very low, the accuracy of the value is not sufficient. Also, of Cw / Cn
Although the measuring method is different from that of Cb of the present invention,
The value of Cw / Cn is much larger than that of Cb.
It will be good.

The composition distribution parameter Cb of the (A) ethylene (co) polymer must be 1.2 or less. When the composition distribution parameter is 1.2 or more, improvement in adhesive strength is not observed.

As the component (B) of the present invention, all polyolefins other than the ethylene (co) polymer of the component (A) can be used, and among them, the (B1) density is 0.86 to 0.9.
At least one polyolefin resin selected from 7 g / cm ^{3 of} an ethylene (co) polymer, (B2) an ethylene (co) polymer by a high-pressure radical polymerization method, and (B3) a polypropylene resin is preferred. To be

The (B1) density is 0.86 to 0.97 g.
/ Cm ³ of ethylene homopolymer or ethylene / α-olefin copolymer means an ethylene homopolymer obtained by the high-middle / low pressure method and other known methods using a Ziegler-based or Phillips-based catalyst, ethylene and 3 carbon atoms. ~ 12
Is a copolymer of α-olefin with a density of 0.86 to
Ultra low density polyethylene (hereinafter referred to as VLDPE) of less than 0.91 g / cm ³ , and density of 0.91 to 0.94
Linear low density polyethylene less than g / cm ³ (hereinafter LLD
PE), and medium to high density polyethylene (hereinafter referred to as MDPE or HDPE) having a density of 0.94 to 0.97 g / cm ³ .

Specific α-olefins include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-dodecene. Of these, preferred is 1-butene, 4-
Methyl-1-pentene, 1-hexene, 1-octene, and particularly preferred is 1-butene. The content of α-olefin in the ethylene copolymer is 0.5 to 40.
Preferably it is mol%.

Examples of the ethylene (co) polymer (B2) produced by the high pressure radical polymerization method include ethylene homopolymers and ethylene / vinyl ester copolymers having a density of 0.91 to 0.94 g / cm ³ produced by the high pressure radical polymerization method. ,ethylene·
Examples thereof include copolymers with α, β-unsaturated carboxylic acids or their derivatives.

Density 0.9 by the high-pressure radical polymerization method
The ethylene homopolymer of 1 to 0.94 g / cm ³ is low density polyethylene by a known high pressure method.

The above ethylene / vinyl ester copolymer is produced by a high pressure radical polymerization method and contains ethylene as a main component, vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, It is a copolymer with vinyl ester monomers such as trifluorovinyl acetate and other unsaturated monomers. Among them, ethylene / vinyl acetate copolymers are particularly preferable. That is, ethylene 50 to 99.5% by weight, vinyl acetate 0.5
Copolymers consisting of .about.50% by weight and 0 to 25% by weight of other unsaturated monomers are preferred.

The other unsaturated monomer is propylene,
1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, olefins having 3 to 10 carbon atoms such as 1-decene, vinyl esters of C ₂ -C ₃ alkane carboxylic acid, (meth) (Meth) acrylic acid esters such as methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and glycidyl (meth) acrylate, (meth) acrylic acid, maleic acid, fumaric acid and maleic anhydride It is at least one selected from the group consisting of ethylenically unsaturated carboxylic acids or their anhydrides.

The copolymer with the above ethylene / α, β-unsaturated carboxylic acid or its derivative is produced by a high pressure radical polymerization method. The α, β-unsaturated carboxylic acid or its derivative is an unsaturated dicarboxylic acid. An acid or an anhydride thereof is also included, and at least one of these monomers is copolymerized with ethylene. Specific examples thereof include ethylene / methyl (meth) acrylate copolymer, ethylene / ethyl (meth) acrylate copolymer,
Examples thereof include ethylene / methyl (meth) acrylate / maleic anhydride copolymer, ethylene / ethyl (meth) acrylate / maleic anhydride copolymer, ethylene / maleic anhydride copolymer and the like. That is, ethylene 50-
99.5% by weight, (meth) acrylic acid ester 0.5 to
Copolymers consisting of 50% by weight and 0 to 25% by weight of unsaturated dicarboxylic acids or their anhydrides are preferred. Further, other monomers may be copolymerized within a range that does not impair the adhesiveness.

The above-mentioned (B1) ethylene (co) polymer, (B
2) MFR of low density polyethylene, ethylene / vinyl ester copolymer, copolymer with ethylene / α, β-unsaturated carboxylic acid or its derivative by high pressure radical polymerization
Is 0.01 to 100 g / 10 min. , Preferably 0.1 to 70 g / 10 min. , And more preferably 1 to 5
0 g / 10 min. Is selected from the range. MFR is 0.01 g / 10 min. If it is less than 100 g / 10 min. If it exceeds, the strength becomes insufficient.

Examples of the rubber as the component (C) of the present invention include ethylene propylene rubber, butadiene rubber, isobutylene rubber, isoprene rubber, natural rubber and nitrile rubber, and these may be used alone or as a mixture.

As the above ethylene propylene rubber,
Random copolymer (EPM) containing ethylene and propylene or butene-1 as a main component, and random copolymer containing a diene monomer (dicyclopentadiene, ethylidene norbornene, etc.) as a third component as a main component ( EPDM).

The above-mentioned butadiene rubber means a copolymer having butadiene as a constituent element, and is a styrene-butadiene block copolymer (SBS) and its hydrogenated or partially hydrogenated styrene-butadiene-ethylene copolymer. Combined (SBES), 1,2-polybutadiene (1,
2-PB), a maleic anhydride-butadiene-styrene copolymer, a modified butadiene rubber having a core-shell structure, and the like. Among these, ethylene-propylene rubber and ethylene-butene-1 rubber are preferable because they have a good improvement in strength.

The proportions of the above components (A), (B) and (C) are usually 20 to 100% by weight of the component (A), 80% by weight or less of the component (B), 40% by weight or less of the component (C) (however, (A) + (B) + (C) = 100% by weight,
When the content of the ethylene (co) polymer as the component (A) is less than 20% by weight, the adhesive strength and affinity which are the objects of the present application are insufficient. Further, the rubber as the component (C) is used in the range of 40% by weight or less. If it exceeds 40% by weight, the strength of the molded article becomes weak, which is not preferable.

Within the above range, the component (A) is preferably used alone or in an amount of 50% by weight or more when the adhesive strength or the affinity and the high temperature stability are emphasized, and when the economical efficiency is emphasized (B1). It is desirable that the components are blended in the above range, and further, the component (B2) is blended in the above range in order to improve the processability in the molding by the inflation method and the blow molding method.

In the present invention, the above (A), (B),
(C) Each component is used by graft-modifying it with a specific monomer in the form of a single composition or a combination of plural components, depending on the purpose.

Regarding the resin component to be graft-modified, the entire resin component is graft-modified when the adhesive strength is important, but (A), (B ) And (C) are preferably blended in an unmodified state. The compounding ratio of these graft-modified resin and unmodified resin is 100: 0 to 1: 9.
Although it is 9 and not particularly limited, the monomer concentration in the composition must be within the range described below.

The first method of combining the modified resin and the unmodified resin is the graft-modified (A) component, (A +
It is a combination of component B), component (A + C), component (A + B + C) and unmodified resin component.

The second method for combining the modified resin and the unmodified resin is the graft-modified resin of any one of the components (A), (B) and (C) and the component (A),
It is a combination of at least one unmodified resin of component (B) and component (C).

The third combination method is (A +
Component (B), component (B + C), component (A + C), a graft-modified resin, and component (A), component (B),
It is a combination of at least one unmodified resin of the component (C).

The fourth combination method is (A +
A graft-modified resin comprising (B + C) component and (A) component,
It is a combination of at least one unmodified resin of component (B) and component (C).

The above graft modification is graft modification of a polymerized resin component by a melting method of reacting a reactive monomer in an extruder in the presence of a radical initiator or a solution method of reacting in a solution.

Examples of the radical initiator include organic peroxides, dihydroaromatics and dicumyl compounds.
Examples of the organic peroxide include hydroperoxide, dicumyl peroxide, t-butylcumyl peroxide, dialkyl (allyl) peroxide, diisopropylbenzene hydroperoxide, dipropionyl peroxide, dioctanoyl peroxide,
Benzoyl peroxide, peroxysuccinic acid, peroxyketal, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexane, t-butyloxyacetate, t-butylperoxyisobutyrate and the like are preferably used.

As the dihydroaromatic, dihydroquinoline or a derivative thereof, dihydrofuran, 1,2-dihydrobenzene, 1,2-dihydronaphthalene, 9,10-
Dihydrophenanthrene and the like can be mentioned.

Examples of the dicumyl compound include 2,3-dimethyl-2,3-diphenylbutane and 2,3-diethyl-
2,3-diphenylbutane, 2,3-diethyl-2,3
-Di (p-methylphenyl) butane, 2,3-diethyl-2,3-di (p-bromophenyl) butane and the like are exemplified, and 2,3-diethyl-2,3-diphenylbutane is particularly preferably used. .

The monomer used for grafting in the present invention is a monomer having the above-mentioned functional group, that is, a: a carboxylic acid group- or acid anhydride group-containing monomer, b: an ester group-containing monomer, c: a hydroxyl group-containing monomer, d: amino. Group-containing monomer, e: at least one monomer selected from silane group-containing monomers.

Examples of the a-containing carboxylic acid group or acid anhydride group-containing monomer include α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid and itaconic acid, or anhydrides thereof, acrylic acid and methacrylic acid. And unsaturated monocarboxylic acids such as furanic acid, crotonic acid, vinylacetic acid, and pentenoic acid.

Examples of the above-mentioned b: ester group-containing monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and the like. Particularly preferred is methyl acrylate. Can be raised.

Examples of the c: hydroxyl group-containing monomer include hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

As the above-mentioned d: amino group-containing monomer,
Examples thereof include aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate and the like.

As the above-mentioned e: silane group-containing monomer,
Examples of unsaturated silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, and vinyltrichlorosilane.

Among these graft monomers, a: α, β-, such as maleic acid, fumaric acid, citraconic acid and itaconic acid, which are carboxylic acid group- or acid anhydride group-containing monomers.
Unsaturated dicarboxylic acids or their anhydrides are preferred,
In particular, maleic anhydride is preferably used from the viewpoint of adhesive strength, economy and the like.

The graft monomer concentration is the same as that of resin component 1
10 ^-8 to 10 ^-3 mol, preferably 10 ^-7 to g
It must be in the range of 10 ⁻⁴ mol. These monomers may be introduced into the resin component by blending the ethylene / vinyl ester copolymer or the ethylene / α, β-unsaturated carboxylic acid or its copolymer as the component (B2), Those introduced by graft modification have stronger adhesive strength than those introduced by copolymerization. Graft monomer concentration is 10 ^-8
If it is less than mol, the adhesive strength of the laminated base material and the affinity with the filler are poor, and if it exceeds 10 ⁻³ mol, “burn” or “gel” may occur in the composition, and it is not economical.

The above-mentioned adhesive resin composition may be added with other thermoplastic resins, antioxidants, lubricants, pigments, ultraviolet absorbers, nucleating agents, etc. within the range not departing from the gist of the present invention depending on the purpose of use. You may mix | blend an agent. In particular, the antioxidant is effective for suppressing the burning and the generation of gel.

The adhesive resin composition of the present invention has good adhesiveness or affinity with various materials, and is suitable for being laminated with various base materials and blending various fillers. Regarding lamination, it is laminated with a layer comprising at least one selected from polyolefin, saponified ethylene vinyl acetate copolymer, polyamide, polyester, polyurethane, polystyrene, wood, fiber and metal foil, and is in the form of film, sheet or tube. The shape of hollow containers is formed, and food packaging materials, medicines, cosmetics, etc. are effectively used in the field. It is also effectively used as a compatibilizing dispersant between an inorganic or organic filler such as glass fiber, carbon black, wood powder, and a pigment and a thermoplastic resin.

The laminate of the second aspect of the present invention is a laminate of saponified vinyl acetate copolymer, polyamide, polyester, polystyrene, metal foil, wood, woven fabric, non-woven fabric, etc., and has a polyolefin. Good processability, water resistance, chemical resistance, flexibility and other properties of other materials, for example, saponified ethylene vinyl acetate copolymer, polyamide, polyester, metal foil and other gas barrier properties, polystyrene , Rigidity such as metal foil or wood,
It is a material that has strength and the like such as woven cloth and non-woven cloth.

First, various polyolefin resins are used as the base material, and examples thereof include olefin homopolymers such as polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene; or ethylene, propylene. , 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like interpolymers;
Copolymer of ethylene and vinyl ester such as ethylene and vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-
Examples thereof include copolymers of ethylene such as ethyl methacrylate copolymer with unsaturated carboxylic acid, unsaturated carboxylic acid ester and the like, and a mixture thereof.

Other base materials include saponified ethylene vinyl acetate copolymers, synthetic resins such as polyamide, polyester, polyurethane and polystyrene, wood such as veneer and plywood, various fibers made of carbon fibers and inorganic materials, aluminum and iron. , Metals such as zinc and copper.

Among the above, when a laminate with a saponified product of ethylene-vinyl acetate copolymer, polyamide, polyester, metal foil, etc. is used as a container or a package for storing food or medicines having excellent gas barrier properties, It is the most preferable because it has a strong adhesive strength with these materials. Further, they are required to withstand, for example, boiling for cooking or sterilization, or, depending on the application, use that is exposed to high temperatures such as outdoors or inside automobiles, and it is required that the adhesive strength is not significantly reduced even at relatively high temperatures.

The form of the laminate of the present invention may be any of film form, plate form, tubular form, foil form, woven fabric form, bottle, container, injection molded product, etc., and is not particularly limited. The method for producing the laminate of the present invention includes a preformed film, a method of laminating an extrusion lamination method, a dry lamination method, a sand lamination method, etc. on a sheet, or a resin melted by an extruder using a multilayer die. In addition to the co-extrusion molding method such as the multilayer inflation method and the multilayer T-die which are joined at the tip of the die to form a laminated structure, ordinary molding methods such as the multilayer blow molding method and the injection molding method are applied and are not particularly limited. .

Of the above, the laminate of the saponified ethylene vinyl acetate copolymer, polyamide and polyester is suitable for coextrusion molding because the adhesive resin composition of the present invention has good moldability. The adhesive resin composition of the present invention has both heat sealability, impact strength, water resistance, chemical resistance, and gas barrier properties of saponified ethylene vinyl acetate copolymer, polyamide, and polyester. Further, it is preferable that the lamination with the metal foil or the like is formed by a lamination method.

It is particularly preferable that the laminated body has a saponified ethylene vinyl acetate copolymer or a metal foil as an outer layer and a layer made of an adhesive resin composition as an inner layer, because the above characteristics can be utilized. In addition, these include at least the above-mentioned two layers, and it is economically advantageous to form another layer, for example, a layer made of a polyolefin resin inside.

As a concrete layer structure, EVOH / adhesion,
EVOH / Adhesive / PO, PO / Adhesive / EVOH / Adhesive /
PO or EVOH / adhesion / PO / adhesion / EVOH etc. can be considered (provided that EVOH: saponified ethylene vinyl acetate copolymer, metal foil, etc., adhesion: adhesive resin composition of the present invention, PO: polyolefin resin) .

[0083]

[Production Example 1]

A1: Polymerization of ethylene / butene-1 copolymer A stainless steel autoclave equipped with a stirrer was replaced with nitrogen, and then a predetermined amount of purified toluene was added as a solvent. Then, butene-1 was added, and bis (n-butylcyclopentadienyl) zirconium dichloride (Zr of 0.
02 mmol) Methylalumoxane [MAO] (MAO /
After adding a mixed solution of Zr = 500 [molar ratio], 80 ° C.
The temperature was raised to 1, ethylene was supplied, and the polymerization was carried out while continuously maintaining the pressure at a constant pressure. The physical properties of the obtained ethylene / butene-1 copolymer (A1) were as follows. MFR: 4.4 g / 10 min. Density: 0.918 g / cm ³ Molecular weight distribution (Mw / Mn): 2.5 Composition distribution parameter (Cb): 1.03

[Preparation Example 2] A2: Polymerization of ethylene / butene-1 copolymer In the same manner as in Preparation Example 1, ethylene / α- with different MFR.
An olefin copolymer was obtained. MFR: 2.0 g / 10 min. Density: 0.921 g / cm ³ Molecular weight distribution (Mw / Mn): 2.6 Composition distribution parameter (Cb): 1.02

(B) Ethylene Polymer B1-1: Linear Low Density Polyethylene (LLDPE) with a Ti Catalyst [Density = 0.925 g / cm ³ , MFR
= 2.0 g / 10 min. , Product Name: J-LEX L
LBF3310, manufactured by Nippon Polyolefin Co., Ltd.] B1-2: linear low density polyethylene (LLDPE) with a Ti-based catalyst [density = 0.925 g / cm ³ , MFR
= 23.0 g / 10 min. , Product Name: Jay Lex
LL BJ6420, manufactured by Nippon Polyolefin Co., Ltd.] B1-3: Low density polyethylene (LDP by high pressure method)
E) [Density = 0.924 g / cm ³ , MFR = 2.0 g
/ 10 min. , Product name: J-LEX LD F3
1. Made by Nippon Polyolefin Co., Ltd.]

(C) Rubber C1: ethylene-propylene rubber (EP-01, Nippon Synthetic Rubber Co., Ltd.) Mooney viscosity ML _{1 + 4} (100 ° C.) = 19 Propylene content = 22 wt% Type (JIS-A) = 73

(Evaluation method) In the evaluation, under the following conditions,
A three-kind five-layer T-die film composed of LLDPE / adhesive resin / ethylene-saponified vinyl acetate / adhesive resin / LLDPE was molded and various measurements were performed. Film molding conditions Molding machine: 3 types, 5 layers T-die Molding temperature: 210 ° C Inner and outer layers LLDPE: MFR 2.0 g / 10 min, density 0.
937 g / cm ³ Adhesion layer: Various intermediate layers: Saponified ethylene-vinyl acetate copolymer Kuraray Eval F101B Membrane thickness: 100 μm, outside (35/10/10)
/ 10/35) Adhesive strength measurement conditions: Tensilon tensile tester (manufactured by Toyo Seiki Co., Ltd.) T peeling, sample 15 mm width, peeling speed 300 m
m / min atmosphere was performed at two points of normal temperature and 60 ° C.

Example 1 The ethylene / butene-1 copolymer (A
1) 70% by weight, ethylene-propylene rubber (EP0
1) 100 parts by weight of a resin component consisting of 30% by weight, 0.25 part by weight of maleic anhydride, 0.02 part by weight of 2,5-di (t-butylperoxy) hexine, antioxidant Irganox 1010 (Ciba Geigy) 0.1 part by weight of Irgafos 168 (Ciba-Geigy) and sufficiently mixed with a Henschel mixer, and then kneaded at a preset temperature of 230 ° C. using a 50 mm single screw extruder for modification. The resin composition obtained had an MFR of 3.1 g / 10 min and an addition rate of maleic anhydride of 1.8 × 10 ⁻⁵ mol / g.

Example 2 The ethylene / butene-1 copolymer (A
2) 50% by weight, LLDPE (B1-1) 30% by weight,
100 parts by weight of a resin component consisting of 20% by weight of ethylene-propylene rubber (EP01), 0.25% of maleic anhydride
Parts by weight, 2,5-di (t-butylperoxy) hexine 0.02 parts by weight, antioxidant Irganox 1010
(Ciba Geigy) 0.1 part by weight, Irgafoss 168
(Ciba Geigy) 0.1 part by weight was added, and the mixture was thoroughly mixed with a Henschel mixer and then kneaded at a preset temperature of 230 ° C. using a 50 mm single-screw extruder for modification. The resin composition obtained had an MFR of 1.3 g / 10 min and an addition rate of maleic anhydride of 1.8 × 10 ⁻⁵ mol / g.

Example 3 Ethylene / butene-1 copolymer (A obtained in Production Example 2
2) 70% by weight, ethylene-propylene rubber (EP0
1) 100 parts by weight of a resin component consisting of 30% by weight, 0.2 parts by weight of maleic anhydride, 0.015 parts by weight of 2,5-di (t-butylperoxy) hexine, and antioxidant Irganox 1010 (Ciba Geigy) 0.1 part by weight of Irgafos 168 (Ciba-Geigy) and sufficiently mixed with a Henschel mixer, and then kneaded at a preset temperature of 230 ° C. using a 50 mm single screw extruder for modification. The resin composition thus obtained had an MFR of 1.2 g / 10 minutes and an addition rate of maleic anhydride of 1.8 × 10 ⁻⁵ mol / g.

Example 4 760 g of LLDPE (B1-2) was placed in a 15-liter autoclave equipped with a stirrer together with 7 liters of toluene, and the temperature was raised with stirring. When 127 ° C. was reached, anhydrous maleic acid was dissolved in 483 g of toluene. Acid 42
g and 5.6 g of dicumyl peroxide dissolved in 320 g of toluene are added via separate ports over 6 hours. After dropping, the mixture was reacted for 3 hours, and then cooled to precipitate and collect the product, which was washed several times with acetone, and a maleic anhydride-modified ethylene / butene-1 copolymer (maleation rate = 0.
9%, MFR = 4 g / 10 minutes) was obtained.

7% by weight of this maleic anhydride-modified ethylene / butene-1 copolymer was prepared according to Production Example 2
100 parts by weight of a resin component consisting of 63% by weight of butene-1 copolymer (A2) and 30% by weight of ethylene-propylene rubber (EP01), and an antioxidant Irganox 1010
(Ciba Geigy) 0.1 part by weight, Irgafoss 168
(Ciba Geigy) 0.1 part by weight was added, and the mixture was thoroughly mixed with a Henschel mixer and then kneaded at a preset temperature of 180 ° C. using a 50 mm single screw extruder. The resin composition thus obtained had an MFR of 2.0 g / 10 minutes and a maleic anhydride addition rate of 7 × 10.
It was ^-6 mol / g.

Comparative Example 1 Resin component 10 comprising 70% by weight of LLDPE (B1-1) and 30% by weight of ethylene-propylene rubber (EP01)
0 parts by weight, maleic anhydride 0.25 parts by weight, 2,5-
0.02 parts by weight of di (t-butylperoxy) hexine,
Antioxidant Irganox 1010 (Ciba Geigy)
0.1 parts by weight, Irgafos 168 (Ciba Geigy)
Add 0.1 parts by weight and thoroughly mix with a Henschel mixer,
Using a 50 mm single-screw extruder, kneading was performed at a set temperature of 230 ° C. for modification. The MFR of the obtained resin composition is 1.4 g.
/ 10 minutes, the addition rate of maleic anhydride is 1.8 × 10 ^-5 m
ol / g.

Comparative Example 2 The ethylene / butene-1 copolymer (A
2) 15% by weight, LLDPE (B1-1) 65% by weight,
100 parts by weight of a resin component consisting of 20% by weight of ethylene-propylene rubber (EP01), 0.25% of maleic anhydride
Parts by weight, 2,5-di (t-butylperoxy) hexine 0.02 parts by weight, antioxidant Irganox 1010
(Ciba Geigy) 0.1 part by weight, Irgafoss 168
(Ciba Geigy) 0.1 part by weight was added, and the mixture was thoroughly mixed with a Henschel mixer and then kneaded at a preset temperature of 230 ° C. using a 50 mm single-screw extruder for modification. The resin composition obtained had an MFR of 1.4 g / 10 min and an addition rate of maleic anhydride of 1.8 × 10 ⁻⁵ mol / g.

Comparative Example 3 Resin component 100 consisting of 70% by weight of LDPE (B1-3) and 30% by weight of ethylene-propylene rubber (EP01).
In parts by weight, maleic anhydride 0.25 parts by weight, 2,5-di (t-butylperoxy) hexine 0.02 parts by weight, antioxidant Irganox 1010 (Ciba Geigy)
0.1 parts by weight, Irgafos 168 (Ciba Geigy)
Add 0.1 parts by weight and thoroughly mix with a Henschel mixer,
Using a 50 mm single-screw extruder, kneading was performed at a set temperature of 230 ° C. for modification. The MFR of the obtained resin composition is 0.7 g.
/ 10 minutes, the addition rate of maleic anhydride is 1.8 × 10 ^-5 m
ol / g.

Comparative Example 4 The ethylene / butene-1 copolymer (A
100 parts by weight of a resin composition consisting of 2), 0.2 parts by weight of maleic anhydride, 0.015 parts by weight of 2,5-di (t-butylperoxy) hexine, and antioxidant Irganox 1076 (Ciba Geigy). 0.2 parts by weight was added and thoroughly mixed with a Henschel mixer, and then kneaded at a preset temperature of 230 ° C. using a 50 mm single screw extruder to carry out modification.

0.1% by weight of this modified resin, 69.9% by weight of unmodified ethylene / butene-1 copolymer (A2) and 30% by weight of ethylene-propylene rubber (EP01).
To 100 parts by weight of the resin composition consisting of 0.1 part by weight of the antioxidant Irganox 1010 (Ciba-Geigy) and 0.1 parts by weight of Irgafos 168 (Ciba-Geigy), and thoroughly mixed with a Henschel mixer, 50 mm uniaxial Kneading was performed at a preset temperature of 180 ° C. using an extruder. The resin composition thus obtained had an MFR of 1.9 g / 10 minutes and an addition rate of maleic anhydride of 3 × 10 ⁻⁹ mol / g.

(Measurement of Adhesive Strength) The adhesive strengths at room temperature and 60 ° C. are summarized in Tables 1 and 2. The adhesive resin compositions of Examples 1 to 4 satisfying the claims of the present application are compared with Comparative Examples. An improvement in the adhesive strength of 10 to 30% was obtained.

[0099]

The adhesive resin composition of the present invention is obtained by graft-modifying an ethylene (co) polymer produced by a specific catalyst or a composition containing the (co) polymer. Maintains high adhesive strength and strong affinity with materials,
It is possible to obtain a laminate having good adhesive strength during high-speed molding or thin film formation. By laminating a layer made of the composition and a layer made of another base material, it is possible to provide a laminate having both the characteristics of the present composition and the characteristics of another base material.

[0100]

[Table 1]

[0101]

[Table 2]

[Brief description of the drawings]

FIG. 1 shows an elution temperature-elution amount curve of the copolymer of the present invention.

FIG. 2 shows an elution temperature-elution amount curve of a copolymer with a typical metallocene catalyst.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B32B 27/28 102 B32B 27/28 102 27/30 27/30 B 27/32 27/32 Z C08L 21/00 LBG C08L 21/00 LBG 23/04 LCB 23/04 LCB 51/04 LKY 51/04 LKY 51/06 LLE 51/06 LLE (72) Inventor Tatsuo Yamaguchi 3 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture No. 2 Nihon Polyolefin Co., Ltd., Kawasaki Laboratory

Claims (7)

[Claims] 1. (A) (a) cyclopentadienyl skeleton
Group IV transition metal compounds containing ligands containing
Ethylene or ethylene and carbon in the presence of catalysts containing
(Co) polymerizing with α-olefin of several 3 to 20
(B) Density of 0.86 to 0.97 g /
cm^Three, (C) Melt flow rate is 0.01 to 100
g / 10 minutes, (d) molecular weight distribution Mw / Mn of 1.5 to
5.0, (e) Composition distribution parameter Cb is 1.2 or less
20% by weight or more of the ethylene (co) polymer, which is a polymer other than the ethylene (co) polymer (B) and (A)
80% by weight or less of reffin resin, 40% by weight of rubber (C)
A composition (A + B + C = 100% by weight) consisting of:
Thus, the component (A), the component (B), and the component (C) in the resin composition
At least one of the components is a carboxylic acid group, an acid anhydride group,
From ter, hydroxyl, amino and silane groups
At least one monomer containing selected functional groups
Graft-modified with, and the amount of the graft monomer is
10 per 1 g of resin composition^-8-10 ^-3be mol
A characteristic adhesive resin composition. 2. The composition is graft-modified (A) component, (A + B) component, (A + C) component, (A +)
The adhesive resin composition according to claim 1, which comprises any one of components B + C). 3. The composition comprises a graft-modified resin of any one of the components (A), (B) and (C) and at least one of the components (A), (B) and (C). The adhesive resin composition according to claim 1, wherein the adhesive resin composition comprises the unmodified product. 4. The composition comprises a component (A + B), a component (B +)
The adhesive according to claim 1, which comprises a graft-modified resin of any one of component C) and component (A + C) and at least one unmodified resin or rubber of component (A), component (B), and component (C). Resin composition. 5. The graft-modified resin comprising the component (A + B + C), the component (A), the component (B),
The adhesive resin composition according to claim 1, which comprises at least one unmodified resin of component (C). 6. The polyolefin resin (B) is
(B1) ethylene / α-olefin copolymer having a density of 0.86 to 0.97 g / cm ³ , (B2) low-density polyethylene by high-pressure radical polymerization, ethylene / vinyl ester copolymer, ethylene / α, β-non-polymer It is at least 1 sort (s) selected from the copolymer with a saturated carboxylic acid or its derivative (s), The adhesive resin composition in any one of Claims 2-5 characterized by the above-mentioned. 7. A layer comprising the adhesive resin composition according to any one of claims 1 to 6 as a single layer, and a polyolefin, saponified ethylene vinyl acetate copolymer, polyamide, polyester, polyurethane, polystyrene, wood. A laminate comprising at least two layers including a layer made of at least one selected from fibers and metal foils as another layer.