JP2000053819A - Modified resin material and laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin excellent in adhesiveness to other base materials and an affinity therefor and excellent in adhesive strength and heat resistance by selecting a modified copolymer prepared by grafting an unsaturated carboxylic acid onto an ethylene/α-olefin copolymer specified in properties such as density, MFR, and molecular weight distribution. SOLUTION: Use is made of a copolymer prepared by modifying, with an unsaturated carboxylic acid, an ethylene/5-12C α-olefin copolymer having a density of 0.92-0.96 g/cm3, an MFR of 0.01-200 g/10 min, and a molecular weight distribution of 1.5-5.0; giving a single-peak elution temperature vs. eluate amount curve in the continuous temperature rising elution fractionation method; satisfying the relationships: T75-T25>=-300×d+285, d<0.950 g/cm3 (wherein T25 is a temperature corresponding to the elution of 25% of the total eluate in an integrated elution curve corresponding to the above curve, T75 is a temperature corresponding to the elution of 75% of the total eluate in the integrated curve, and d is a density) and T75-T25>=0 and T75-T25>=-670×d+644, d>=0.950 /cm3; having at least one melting peak; and satisfying the relationship: Tm1>=150×d-17 (wherein Tm1 is the highest melting point; and d is a density).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive having good adhesion to other base materials, a compatibilizer for engineering plastics, a resin modifier for printing, dyeing, painting, etc., and a resin. The present invention relates to a polar group-containing resin which is used as a coupling agent for improving the strength with a filler or the like, or an electric material, and has excellent properties thereof, a composition thereof, and a laminate using the same. More specifically, despite having a narrow molecular weight distribution, it has a relatively broad composition distribution, tensile strength,
The present invention relates to polar group-containing resins that have good mechanical properties such as impact resistance, have both low-temperature heat sealability and high heat resistance, and have high adhesive strength, especially in the adhesive field, their compositions, and laminates using them. .

[0002]

2. Description of the Related Art In general, polyethylene resin is formed by injection molding, extrusion molding, blow molding, or the like because of its high strength, excellent chemical resistance and corrosion resistance, and low cost.
It is used for a wide range of applications such as containers and blow bottles.
Furthermore, by laminating with a specific base material such as a gas barrier material, it is possible to have a gas barrier property in addition to the above characteristics. Further, by being modified with various monomers such as maleic anhydride, it is used for a wide range of applications such as various functional resins such as adhesive resins and compatibilizers, and these functional resin films and molded products.

[0003]

As a modified polyethylene resin, for example, a modified polyethylene resin obtained by copolymerizing with an unsaturated carboxylic acid or the like to introduce a functional group to impart adhesiveness is disclosed in
No. 4144. Also, Japanese Patent Application Laid-Open
Japanese Patent Application Laid-Open No. -7848 and Japanese Patent Application Laid-Open Publication No. Sho 54-12408 propose a polymer obtained by modifying a polyolefin-based polymer with a solid rubber and an unsaturated carboxylic acid to improve adhesion. Further, JP-A-52-49289 proposes a method of modifying an ethylene / α-olefin copolymer rubber with an unsaturated carboxylic acid. Although these modified polyethylene resins have some degree of adhesiveness and affinity, they did not sufficiently satisfy the high adhesive strength required at the time of high-speed molding and thin-film molding. In addition, heat resistance was not sufficient.

An object of the present invention is to provide an adhesive having good adhesion to other substrates, a compatibilizer for engineering plastics, a resin modifier such as printability, dyeability, and paintability, and a resin and filler. It is an object of the present invention to provide a modified resin material which is used as a coupling agent for improving the strength of, for example, an electric material or the like, and which has high adhesive strength and heat resistance particularly in the adhesive field, and a laminate using the same.

[0005]

The inventors of the present invention have conducted intensive studies and have found that a copolymer of ethylene having a specific molecular structure and α-olefin having 5 to 12 carbon atoms contains an unsaturated carboxylic acid or an unsaturated carboxylic acid. The present inventors have found that a resin material containing a modified ethylene / α-olefin copolymer grafted with the derivative gives excellent adhesive strength, heat resistance and the like, and have completed the present invention.

That is, the modified resin material of the present invention comprises ethylene satisfying the following requirements (A) to (E) and having 5 to 5 carbon atoms.
12. A modified ethylene / α-olefin copolymer (a ′) obtained by grafting an unsaturated carboxylic acid or a derivative thereof to a copolymer (a) with α-olefin (12). (A) a density of 0.92 to 0.96 g / cm ³ (B) a melt flow rate (MFR) of 0.01 to 20
0 g / 10 min (C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0 (D) One peak of an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF), and the elution temperature - the difference T ₇₅ -T ₂₅ and the density d of the temperature T ₇₅ to 75% of the total temperature T ₂₅ to 25% of the total determined from the integral elution curve of elution amount curve is eluted elutes the following ( The relationship of equation a),
And satisfying the following formula (formula b) (formula a) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Equation b) T ₇₅ −T ₂₅ ≦ −670 × d + 644 (E) It has one or two melting point peaks, and the highest melting point T _m1 and density d satisfy the relationship of the following (Equation c). Satisfy (Equation c) T _m1 ≧ 150 × d−17

Further, the ethylene and α having 5 to 12 carbon atoms are used.
-The copolymer with olefin (a) further comprises the following (F)
It is desirable to satisfy the requirements of (F) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (formula d) (formula d) logMT ≦ −0.572 × logMFR +
0.3 The copolymer (a) of ethylene and an α-olefin having 5 to 12 carbon atoms contains at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table. In the presence of a catalyst, ethylene and α having 5 to 12 carbon atoms
-It is desirable that it is obtained by copolymerizing with an olefin. The ethylene and the carbon number 5
(G) is a copolymer with α-olefins (A) to (G).
It is desirable that the halogen concentration be 10 ppm or less.

Further, the modified resin material of the present invention further comprises another polyolefin resin (b) and a rubber (c),
And a modified ethylene / α-olefin copolymer (a ′) in which an unsaturated carboxylic acid or a derivative thereof is grafted to a copolymer of ethylene and α-olefin having 5 to 12 carbon atoms (a); %, The other polyolefin resin (b) may be 0 to 99% by weight, and the rubber (c) may be 0 to 40% by weight. Further, the other polyolefin resin (b) has a density of 0.86 to 0.97 g / cm ^3.
Ethylene (co) polymer, low-density polyethylene by high-pressure radical polymerization, ethylene-vinyl ester copolymer,
And at least one selected from the group consisting of a copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof.

The laminate of the present invention comprises a layer comprising any one of the above-mentioned modified resin materials and a polyolefin, a saponified ethylene-vinyl acetate copolymer, polyamide, polyester, polyurethane, polystyrene, wood, fiber and metal foil. And at least one layer selected from the group consisting of:

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The modified resin material of the present invention is a modified ethylene · α obtained by grafting an unsaturated carboxylic acid or a derivative thereof to a copolymer (a) of ethylene and α-olefin having 5 to 12 carbon atoms.
-An olefin copolymer (a ') (hereinafter referred to as a modified ethylene copolymer (a')), or the modified ethylene copolymer (a ') and another polyolefin resin (b), a rubber (c) It has.

In the present invention, ethylene and C 5 -C 12 are used.
(A) (hereinafter, referred to as ethylene copolymer (a)) with α-olefin satisfies the following requirements (A) to (E). (A) a density of 0.92 to 0.96 g / cm ³ (B) a melt flow rate (MFR) of 0.01 to 20
0 g / 10 min (C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0 (D) One peak of an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF), and the elution temperature - the difference T ₇₅ -T ₂₅ and the density d of the temperature T ₇₅ to 75% of the total temperature T ₂₅ to 25% of the total determined from the integral elution curve of elution amount curve is eluted elutes the following ( The relationship of equation a),
And satisfying the following formula (formula b) (formula a) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Equation b) T ₇₅ −T ₂₅ ≦ −670 × d + 644 (E) It has one or two melting point peaks, and the highest melting point T _m1 and density d satisfy the relationship of the following (Equation c). Satisfy (Equation c) T _m1 ≧ 150 × d−17

The α-olefin of the ethylene copolymer (a) in the present invention has 5 to 12 carbon atoms, preferably 5 to 12 carbon atoms.
, Specifically, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene,
-Decene, 1-dodecene and the like. The content of these α-olefins is usually 30 mol% in total.
Below, it is desirable to select in the range of preferably 3 to 20 mol% or less.

[0013] (A) The density of the ethylene copolymer in the present invention (i) is, 0.92~0.96g / cm ^3, preferably 0.925~0.94g / cm ^3, more preferably 0.925 ０．９0.935 g / cm ³ . When the density is less than 0.92 g / cm ³ , the resulting modified ethylene copolymer (a ′) has insufficient adhesive strength and heat resistance,
^{On the other hand} , if it exceeds 0.96 g / cm ³ , the adhesive strength of the modified ethylene copolymer (a ′) decreases, and the resulting multilayer film becomes too hard, resulting in low tear strength and impact strength of the multilayer film.

The melt flow rate (hereinafter referred to as MFR) of the ethylene copolymer (a) in the present invention is (B)
0.01 to 200 g / min, preferably 0.05 to 50 g
/ Min, more preferably 0.1 to 40 g / 10 min. MFR of less than 0.01 g / 10 minutes, or 2
If it exceeds 00 g / 10 minutes, the adhesive strength of the resulting modified ethylene copolymer (A ′) will be poor.

The (C) molecular weight distribution (Mw / Mn) of the ethylene copolymer (a) in the present invention is in the range of 1.5 to 5.0, preferably 1.7 to 4.0, and more preferably 1.
It is in the range of 8-3.0. If the Mw / Mn is less than 1.5, the molding processability is poor, and if it exceeds 5.0, the adhesive strength of the modified ethylene copolymer (A ′) decreases. In general, the molecular weight distribution (Mw / Mn) of an ethylene copolymer is obtained by determining the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC), and calculating the ratio (Mw / Mn). It can be obtained by calculating.

The ethylene copolymer of the present invention (a)
As shown in FIG. 1, (D) continuous heating elution fractionation method (T
REF) is a temperature at which there is one peak of the elution temperature-elution amount curve and 25% of the total amount determined from the integrated elution curve of the elution temperature-elution amount curve is eluted, that is, the elution temperature-elution amount curve. Are obtained by integrating the temperature T ₂₅ at which the area obtained by integrating is 25% of the total area and the temperature at which 75% of the total is eluted, ie, the area obtained by integrating the elution temperature-elution amount curve, The difference T ₇₅ -T _{25 from} the temperature T _75, which is an area of 75% of the above, and the density d satisfy the following relationship (formula a) and the following relationship (formula b). (Formula a) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Formula b) T ₇₅ −T ₂₅ When ≦ −670 × d + 644 T ₇₅ −T ₂₅ and the density d do not satisfy the relationship of the above (formula a), the adhesiveness and heat resistance of the modified ethylene copolymer (a ′) become inferior, and the above ( Even when the relationship of the formula b) is not satisfied, the adhesiveness is poor.

The method for measuring TREF according to the present invention is as follows. The sample was treated with orthodichlorobenzene (O 2
DCB) so that the sample concentration becomes 0.05% by weight, and heat and dissolve at 135 ° C. 5 ml of this sample solution
The sample is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, the sample is sequentially eluted while the column temperature is raised at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate. At this time, the concentration of the sample eluted in the solvent is continuously detected by measuring the absorption of the asymmetric stretching vibration of methylene at a wave number of 2925 cm ^-1 with an infrared detector. From this value, the concentration of the ethylene / α-olefin copolymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate. According to the TREF analysis, a change in the elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, so that a relatively fine peak which cannot be detected by the fractionation method can be detected.

Further, the ethylene copolymer (a) of the present invention has (E) one or two melting point peaks, and the highest melting point T _m1 and the density d of the ethylene copolymer (a) _satisfy the following relationship (formula c). To be satisfied. (Formula c) T _m1 ≧ 150 × d−17 If the melting point T _m1 and the density d do not satisfy the relationship of the above (Formula c), the heat resistance and the adhesive strength at high temperature of the modified ethylene copolymer (A ′) will be poor. Inferior.

Further, the ethylene copolymer (a) in the present invention preferably satisfies the following requirement (G). (G) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (formula d) (formula d) logMT ≦ −0.572 × logMFR +
When the 0.3 MT and the MFR satisfy the relationship of the above (formula d), the adhesion and the molding processability of the modified ethylene copolymer (a ') become more favorable.

The ethylene copolymer (a) in the present invention
Is a conventional metallocene-based catalyst, that is, ethylene copolymer obtained in the presence of a ligand having a cyclopentadienyl skeleton and at least one catalyst containing a transition metal compound of Group IV of the periodic table. Wider molecular weight distribution than polymer,
And low-density ethylene-α obtained with a Ziegler catalyst
It has better low-temperature moldability than olefin copolymers and is clearly distinguishable from these ethylene copolymers.

The ethylene copolymer of the present invention (a)
The catalyst, the production method, etc. are not particularly limited as long as the above specific parameters are satisfied, but preferably, at least an organic cyclic compound having at least a conjugated double bond and the periodic table
An ethylene copolymer obtained by copolymerizing ethylene or ethylene and an α-olefin having 5 to 12 carbon atoms in the presence of a catalyst containing a group IV transition metal compound is desirable. By using such a catalyst, it is possible to improve the adhesiveness and heat resistance of the modified ethylene copolymer (A ′) obtained from the ethylene copolymer (A).

Ethylene copolymer (a) in the present invention
Is preferably polymerized with a catalyst obtained by mixing the following compounds a1 to a4. a1: Compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr (where Me ¹ represents zirconium, titanium, or hafnium, and R ¹ and R ³ each represent a carbon number) 1 to
24 hydrocarbon groups, R ² is a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand,
A benzoylacetonate ligand or a derivative thereof, X ¹ represents a halogen atom, p, q and r each represent 0 ≦ p
≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, 0 ≦ p + q + r ≦ 4) a2: a compound represented by the general formula Me ² R ⁴ _m (OR ⁵ ) _n X ² _zmn (In the formula, Me ² is an element in Groups I to III of the periodic table, R ⁴
And R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, X
² represents a halogen atom or a hydrogen atom (however, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table), z represents a valence of Me ² , and m and n represent A is an integer satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z. A3: Organic cyclic compound having a conjugated double bond a4: Al—O—Al bond Containing modified organoaluminum oxy compound and / or boron compound

The details will be described below. The above-mentioned catalyst component a1
In the formula of the compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr , Me ¹ represents zirconium, titanium or hafnium, and the types of these transition metals are limited. It is not limited to this, and a plurality of them can be used, but it is particularly preferable that the copolymer contains zirconium having excellent weather resistance. R ¹ and R ³ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group;
Alkenyl groups such as vinyl group and allyl group; phenyl group,
Aryl groups such as tolyl, xylyl, mesityl, indenyl and naphthyl; benzyl, trityl,
And aralkyl groups such as phenethyl group, styryl group, benzhydryl group, phenylbutyl group, and neofuyl group. These may have branches. R ² is 2,
It shows a 4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonato ligand or a derivative thereof. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine. p and q are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, 0 ≦ p + q
An integer satisfying the range of + r ≦ 4 is an integer.

Examples of the compounds represented by the general formula of the above-mentioned catalyst component a1 include tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium, tetrapropoxy zirconium, tripropoxy monochlorodiconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrabutoxy titanium , Tetrabutoxy hafnium and the like, and especially Z such as tetrapropoxy zirconium and tetrabutoxy zirconium.
r (OR) ₄ compounds are preferred, and two or more of these may be used in combination. Specific examples of the 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonato ligand or derivative thereof include tetra (2,4-pentanedionato) zirconium. , Tri (2,4-pentanedionato)
Zirconium chloride, di (2,4-pentanedionato) dichloride zirconium, (2,4-pentanedionato) trichloride zirconium, di (2,4-pentanedionato) diethoxide zirconium, di (2,4- Pentanedionato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n
-Butoxide zirconium, di (2,4-pentanedionato) dibenzyl zirconium, di (2,4-pentanedionato) dineofylzirconium, tetra (dibenzoylmethanato) zirconium, di (dibenzoylmethanato) die Zirconium toxide, zirconium di (dibenzoylmethanato) di-n-propoxide, zirconium di (dibenzoylmethanato), zirconium di (n-butoxide), zirconium diethoxide zirconium, di (benzoylacetonate) ) Di-n-propoxide zirconium, di (benzoylacetonate)
And di-n-butoxide zirconium.

The general formula Me ² R ⁴ _m (O
R ⁵ ) _n X ^{2 In} the formula of the compound represented by _zmn , Me ² represents a group I-III element of the periodic table, and lithium, sodium,
Potassium, magnesium, calcium, zinc, boron,
Aluminum and the like. R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 1 carbon atoms.
2, more preferably 1 to 8, specifically alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, Aryl groups such as a xylyl group, a mesityl group, an indenyl group, and a naphthyl group; and aralkyl groups such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neofuyl group. These may have branches. X ² represents a halogen atom or a hydrogen atom such as fluorine, iodine, chlorine and bromine. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. Z represents the valence of Me ² , m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.

Examples of the compound represented by the general formula of the catalyst component a2 include organic lithium compounds such as methyllithium and ethyllithium; organic magnesium compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride and ethylmagnesium chloride; Organic zinc compounds such as zinc and diethyl zinc; organic boron compounds such as trimethyl boron and triethyl boron; trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum, tridecyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride , Ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl aluminum Derivatives of organoaluminum compounds such as Idoraido the like.

The organic cyclic compound having a conjugated double bond of the catalyst component a3 has one or more rings having two or more, preferably 2 to 4, more preferably 2 to 3, conjugated double bonds. A cyclic hydrocarbon compound having 2 or more and having a total carbon number of 4 to 24, preferably 4 to 12; wherein the cyclic hydrocarbon compound partially has 1 to 6 hydrocarbon residues (typically, carbon A cyclic hydrocarbon compound substituted with an alkyl group or an aralkyl group of the formulas 1 to 12; two or more, preferably 2 to 4, more preferably 2 to 2, conjugated double bonds.
One or more rings having three rings and a total carbon number of 4
An organosilicon compound having a cyclic hydrocarbon group of from 24 to 24, preferably 4 to 12; said cyclic hydrocarbon group being partially substituted by 1 to 6 hydrocarbon residues or an alkali metal salt (sodium or lithium salt) Organosilicon compounds. Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.

The preferred compounds include cyclopentadiene, indene, azulene and their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Further, a compound obtained by bonding (crosslinking) these compounds via an alkylene group (the number of carbon atoms of which is usually 2 to 8, preferably 2 to 3) is also preferably used.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. A _L SiR _4-L wherein A represents the above-mentioned cyclic hydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group, a propyl group. Alkyl groups such as methoxy, ethoxy, propoxy and butoxy groups; aryl groups such as phenyl groups; aryloxy groups such as phenoxy groups; aralkyl groups such as benzyl groups. And represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms or hydrogen, and L represents 1
≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound of the component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7- C5-C24 cyclopolyene or substituted cyclopolyene such as dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadienylsilane, biscyclopentadiene Examples include enylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.

The modified organoaluminum oxy compound containing an Al—O—Al bond of the catalyst component a4 is obtained by reacting an alkylaluminum compound with water to obtain a modified organoaluminum oxy compound usually called aluminoxane. The molecule usually contains 1 to 100, preferably 1 to 50 Al-O-Al bonds. The modified organic aluminum oxy compound may be linear or cyclic.

The reaction between the organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon,
Aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferred. The reaction ratio between water and the organoaluminum compound (water / Al molar ratio) is usually 0.25 / 1 to 1.2.
/ 1, preferably 0.5 / 1 to 1/1.

As the boron compound, triethylaluminum tetra (pentafluorophenyl) borate (triethylammoniumtetra (pentafluorophenyl)
Borate, dimethylanilinium tetra (pentafluorophenyl) borate (dimethylanilinium tetra (pentafluorophenyl) borate, butylammonium tetra (pentafluorophenyl) borate, N, N-
Dimethylanilinium tetra (pentafluorophenyl) borate, N, N-dimethylaniliniumtetra (3,5-difluorophenyl) borate and the like can be mentioned.

The above catalyst may be used by mixing and contacting a1 to a4, but it is preferable to use the catalyst by supporting it on an inorganic carrier and / or a particulate polymer carrier (a5). Examples of the inorganic carrier and / or the particulate polymer carrier (a5) include a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate or a mixture thereof, a thermoplastic resin, and a thermosetting resin. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. Specifically, Si
O ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ ,
CaO, ZnO, BaO, ₂ etc. ThO or mixtures thereof, can be _{mentioned, SiO 2 -Al 2 O 3,} SiO 2 -V 2
_{O 5, SiO 2 -TiO 2,} SiO 2 -V 2 O 5, SiO 2 -
MgO, SiO ₂ —Cr ₂ O _{3 and the} like. Among these, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable. Further, as the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, polymethyl (meth) acrylate, polystyrene, poly Examples include norbornene, various natural polymers, and mixtures thereof.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are converted to an organic aluminum compound or a modified organic aluminum compound containing an Al—O—Al bond. After the contact treatment, it can be used as the component a5.

The ethylene copolymer (a) in the present invention
Is manufactured using a catalyst that does not contain halogen such as chlorine in the above-mentioned catalyst components, so that the halogen concentration is at most 10 ppm or less, preferably 5 ppm or less,
More preferably, it can be substantially not contained (ND: 2 ppm or less). Such a halogen-free ethylene copolymer such as chlorine is preferably used because it has excellent chemical stability and does not cause corrosion or the like in a molding machine.

The process for producing the ethylene copolymer (a) in the present invention is carried out by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method or the like in the presence of the above-mentioned catalyst, which does not substantially contain a solvent. In a state where oxygen, water, etc. are turned off, it is converted to aliphatic hydrocarbons such as butane, pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. It is produced in the presence or absence of the exemplified inert hydrocarbon solvents. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C, preferably 20 to 200 ° C.
C., more preferably 50 to 110 ° C., and the polymerization pressure is usually normal pressure to 70 kg / cm ² G, preferably normal pressure to 20 kg / cm ² G in the case of the low and medium pressure method, and is usually 1500 kg / cm ^{2 in} the case of the high pressure method. cm 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, usually 1 minute to 3 minutes
0 minutes, preferably about 2 to 20 minutes is desirable. Also,
The polymerization is not particularly limited, such as a one-stage polymerization method, a two-stage or more multi-stage polymerization method in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, and catalyst are different from each other.

The modified ethylene copolymer (a ') in the present invention is obtained by graft-modifying the above ethylene copolymer (a) with an unsaturated carboxylic acid or a derivative thereof. Examples of the graft modification method include a melting method in which an unsaturated carboxylic acid or a derivative thereof is reacted with an ethylene copolymer (a) in an extruder in the presence of a radical initiator, or a solution method in which the reaction is performed in a solution. .

The unsaturated carboxylic acids or derivatives thereof in the present invention include, for example, α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, itaconic acid and anhydrides thereof; acrylic acid, methacrylic acid ,
Examples include unsaturated monocarboxylic acids such as furanic acid, crotonic acid, vinyl acetic acid, and pentenoic acid. Among them, maleic anhydride is particularly preferably used from the viewpoints of adhesive strength, economy, and the like.

Examples of the radical initiator include organic peroxides, dihydroaromatics, dicumyl compounds and the like.

Examples of the organic peroxide include hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide,
Dialkyl (allyl) peroxide, diisopropylbenzene hydroperoxide, dipropionyl peroxide, dioctanoyl peroxide, benzoyl peroxide, peroxysuccinic acid, peroxyketal, 2,5-di (t-butylperoxy) hexane,
2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butyloxyacetate, t-butylperoxy Oxyisobutyrate and the like are preferably used.

The dihydroaromatic includes dihydroquinoline or a derivative thereof, dihydrofuran, 1,2-dihydrobenzene, 1,2-dihydronaphthalene, 9,10-
Dihydrophenanthrene and the like. Examples of the dicumyl compound include 2,3-dimethyl-2,3-diphenylbutane, 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.
2,3-diphenylbutane is preferably used.

Examples of the other polyolefin resin (b) in the present invention include all ordinary polyolefin resins other than the ethylene copolymer (a). Among them,
Ethylene having a density of 0.86 to 0.97 g / cm ³ (co)
Polymer, low density polyethylene by high pressure radical polymerization,
Ethylene / vinyl ester copolymer, ethylene / α, β
-A copolymer with an unsaturated carboxylic acid or a derivative thereof,
It is preferable because it has excellent moldability, mechanical strength and the like.

The ethylene (co) polymer having a density of 0.86 to 0.97 g / cm ³ means a high-pressure method, a medium-pressure method, a low-pressure method or other known methods using a Ziegler-type, Phillips-type or Kaminsky-type catalyst. And a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms. It has a density between 0.86 and
Ultra low density polyethylene (hereinafter, referred to as VLDPE) having a density of 0.91 g / cm ^{3 or} less and 0.91 to 0.94 g
/ Cm ^{3 or} less linear low-density polyethylene (hereinafter LLD)
PE), medium-density polyethylene and high-density polyethylene having a density of 0.94 to 0.97 g / cm ³ (hereinafter, referred to as MDPE and HDPE, respectively).

Examples of the α-olefin having 3 to 12 carbon atoms include propylene, 1-butene and 4-methyl-1
-Pentene, 1-hexene, 1-octene, 1-dodecene and the like. Among these, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferred, and 1-butene is particularly preferred.
Butene or 1-hexene. The α-olefin content in the ethylene copolymer is preferably from 0.5 to 40 mol%.

The low-density polyethylene (LDPE) obtained by the high-pressure radical polymerization is an ethylene homopolymer having a density of 0.91 to 0.94 g / cm ³ obtained by a known high-pressure method.

The ethylene / vinyl ester copolymer is
Copolymerization with vinyl ester monomers such as vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate containing ethylene as a main component produced by the high-pressure radical polymerization method. It is a polymer. Among them, particularly preferred examples include an ethylene / vinyl acetate copolymer. That is, a copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl acetate, and 0 to 25% by weight of another copolymerizable unsaturated monomer is preferable.

The other copolymerizable unsaturated monomers include propylene, 1-butene, 1-hexene, 4-methyl-1-
3-1 carbon atoms such as pentene, 1-octene and 1-decene
0 olefins, vinyl esters of C2-C3 alkanecarboxylic acids, methyl (meth) acrylate, (meth)
(Meth) acrylates such as ethyl acrylate, propyl (meth) acrylate, and glycidyl (meth) acrylate; ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid and maleic anhydride; At least one selected from the group of anhydrides and the like
Is a seed.

Examples of the copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof include an ethylene / (meth) acrylate copolymer produced by a high-pressure radical polymerization method and ethylene / (meth) acrylate. ) Ethyl acrylate copolymer, ethylene / methyl (meth) acrylate / maleic anhydride copolymer, ethylene / ethyl (meth) acrylate / maleic anhydride copolymer, ethylene / maleic anhydride copolymer, etc. Can be mentioned. Further, a copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a (meth) acrylate and 0 to 25% by weight of an unsaturated dicarboxylic acid or an anhydride thereof is preferable.

Examples of the (meth) acrylic acid ester include acrylic acid, methacrylic acid, methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,
Isopropyl acrylate, isopropyl methacrylate,
N-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,
Examples thereof include lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, and glycidyl methacrylate. As the unsaturated dicarboxylic acid or its anhydride,
For example, maleic acid, fumaric acid, maleic anhydride and the like can be mentioned. Further, another copolymerizable unsaturated monomer may be copolymerized as long as its adhesiveness is not impaired.

The MFR of the other polyolefin resin (b) in the present invention is 0.01 to 100 g / 10 min, preferably 0.1 to 70 g / 10 min, more preferably 1 to 100 g / 10 min.
The range is 50 g / 10 minutes. MFR 0.01 g / 1
If the time is less than 0 minutes, the molding processability becomes poor, and 100 g / 10
If it exceeds minutes, the mechanical strength becomes insufficient.

The rubber (c) in the present invention includes, for example, ethylene propylene rubber, butadiene rubber, ethylene-butene rubber, isobutylene rubber, isoprene rubber, natural rubber, nitrile rubber and the like. These may be used alone. Or a mixture. Among these, ethylene propylene rubber and ethylene-butene rubber are preferred because of their good improvement in mechanical strength.

As the ethylene-propylene rubber, for example, a random copolymer (EPR) containing ethylene and propylene as main components and a diene monomer (dicyclopentadiene, ethylidene norbornene, etc.) as a third component are mainly used. Random copolymer (E
PDM). The butadiene-based rubber refers to a copolymer containing butadiene as a constituent element, for example, a styrene-butadiene block copolymer (SBS) and a styrene-butadiene-ethylene copolymer (a hydrogenated or partially hydrogenated derivative thereof). SBES), 1,2-polybutadiene (1,2-PB), maleic anhydride-butadiene-
Examples thereof include a styrene copolymer and a modified butadiene rubber having a core-shell structure.

The modified resin material of the present invention comprises 1 to 100% by weight of a modified ethylene copolymer (A '), 0 to 99% by weight of another polyolefin resin (B), and 0 to 40% of rubber (C).
%, Preferably 1 to 50% by weight of a modified ethylene copolymer (a '), 10 to 99% by weight of another polyolefin resin (b), and 0 to 40% of a rubber (c).
%, More preferably 2 to 40% by weight of the modified ethylene copolymer (a '), 20 to 98% by weight of another polyolefin-based resin (B), and 0 to 40% by weight of a rubber (C). When the content of the modified ethylene copolymer (a ') is less than 1% by weight, the adhesive strength of the modified resin material becomes insufficient. On the other hand, if the content of the rubber (c) exceeds 40% by weight, the mechanical strength of the molded article is undesirably weak.

The concentration of unsaturated carboxylic acid or its derivative in the modified resin material of the present invention is 0.0001 to 1%.
It is preferably in the range of 0% by weight. Concentration is 0.00
When the concentration is less than 01% by weight, sufficient adhesive strength cannot be obtained, and when the concentration exceeds 10% by weight, the thermal stability of the composition is reduced, and a problem may occur in continuous productivity at the time of molding a multilayer film or the like. .

The modified resin material of the present invention may contain other thermoplastic resins, antioxidants, lubricants, pigments, ultraviolet absorbers, nucleating agents, etc. within a range that does not impair the properties of the modified resin material according to the intended use. May be added. In particular, antioxidants are effective for suppressing burning and gel formation.

The modified resin material of the present invention has good adhesiveness or affinity with various materials, and includes polyolefin, saponified ethylene-vinyl acetate copolymer, polyamide, polyester, polyurethane, polystyrene, wood, fiber and metal. It is suitable for being laminated on various base materials such as foils, or as a compatible dispersant of an inorganic or organic filler such as glass fiber, carbon black, wood flour or pigment and a thermoplastic resin.

The laminate of the present invention is selected from the group consisting of a layer composed of the modified resin material and a polyolefin, a saponified ethylene-vinyl acetate copolymer, polyamide, polyester, polyurethane, polystyrene, wood, fiber and metal foil. At least one type of layer. The laminate of the present invention has the adhesiveness of the modified resin material, the good workability of the polyolefin, water resistance, chemical resistance, and properties such as flexibility, or ethylene-
It is a material having both good gas barrier properties of saponified vinyl acetate copolymer, polyamide, polyester and metal foil, rigidity of polystyrene and metal foil, and mechanical strength of wood and fiber.

The polyolefin used in the laminate of the present invention includes, for example, polyethylene, polypropylene,
Olefin homopolymers such as poly-1-butene and poly-4-methyl-1-pentene; ethylene, propylene,
-Butene, 4-methyl-1-pentene, 1-hexene,
Mutual copolymers such as 1-octene; ethylene-vinyl ester copolymers such as a copolymer of ethylene and vinyl acetate; ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid Copolymers of ethylene with an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, or the like, such as an ethyl copolymer, and a mixture thereof are exemplified.

Examples of the polyamide include nylon 6, nylon 11, nylon 12, nylon 6-6, nylon 6-10, and nylon 6-12.
Examples of the wood include veneer, plywood, wood fiber board, and particle board. As the fiber, for example, various fibers made of carbon fiber or inorganic material, woven fabric,
Nonwoven fabrics and the like can be mentioned. Examples of the metal foil include foils of aluminum, iron, zinc, copper, and the like.

Among the above, a laminate having a layer made of saponified ethylene-vinyl acetate copolymer, polyamide, polyester or metal foil is particularly excellent in gas barrier properties, and is used for containers or packages for storing foods or drugs. And the like. In addition, these laminates have a small decrease in adhesive strength even at a relatively high temperature, and can withstand, for example, boiling for cooking and sterilization, and, depending on the use, exposure to high temperatures such as outdoors and in automobiles.

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

In particular, since the modified resin material of the present invention has good moldability, a layer made of the modified resin material of the present invention and a layer made of a saponified ethylene-vinyl acetate copolymer, polyamide or polyester are used. The method for producing a laminate is suitable for co-extrusion molding, and the modified resin material of the present invention has heat sealability, impact strength, water resistance, chemical resistance, and saponified ethylene vinyl acetate copolymer, polyamide And both of the gas barrier properties of the polyester. The lamination with a metal foil or the like is preferably performed by a lamination method.

The laminate of the present invention may be constituted such that the outer layer is composed of a layer made of saponified ethylene-vinyl acetate copolymer or a metal foil, and the inner layer is composed of a layer composed of a modified resin material. It is particularly preferable because the properties of the metal foil and the properties of the modified resin material can be utilized together. Also,
By forming another layer on this laminate, for example, a layer made of polyolefin inside, a laminate excellent in economy and the like can be obtained. Specific layer configurations include, for example, a layer (gas blocking layer) composed of saponified ethylene-vinyl acetate copolymer or metal foil / modified resin layer, gas barrier layer / modified resin layer / polyolefin layer, polyolefin layer / Modified resin layer / gas barrier layer / modified resin layer / polyolefin layer and the like.

[0065]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The test method in this example is as follows. (Physical property test method) [Density] Based on JIS K6760. [MFR] Based on JIS K6760. [Measurement of T _ml by DSC] A sheet having a thickness of 0.2 mm was formed by a hot press, a sample of about 5 mg was punched out, kept at 230 ° C for 10 minutes, cooled to 0 ° C at 2 ° C / min, and then again at 10 ° C / min.
The temperature was raised to 170 ° C. in minutes, and the temperature at the top of the highest temperature peak that appeared was defined as the highest peak temperature T _ml . [Mw / Mn] GPC (150C type manufactured by Waters)
And 135 ° C. ODCB was used as a solvent. The column used was GMH _HR- H (S) from Tosoh.

[TREF] The column was kept at 140 ° C., the sample was injected, the temperature was lowered to 25 ° C. at 4 ° C./hr, and the polymer was deposited on glass beads. The concentration of the polymer eluted at each temperature was detected by an infrared detector. Solvent: ODCB, flow rate: 1 ml / min, heating rate: 5 ° C. /
Min, detector: infrared spectrometer (wavelength 3.42 μm), column: 0.8 cmφ × 12 cmL (filled with glass beads), sample concentration: 1 mg / ml [melt tension] The melted polymer was stretched at a constant speed. The stress at that time was determined by measuring with a strain gauge. The measurement sample was granulated into pellets and measured using an MT measuring device manufactured by Toyo Seiki Seisaku-sho. The orifice used has a hole diameter of 2.09 mmφ,
The length was 8 mm, and the measurement conditions were a resin temperature of 190 ° C., an extrusion speed of 20 mm / min, and a winding speed of 15 m / min. [Chlorine concentration] It was measured by a fluorescent X-ray method. When chlorine of 10 ppm or more was detected, this was taken as an analysis value.
When it was less than 10 ppm, it was measured with a TOX-100 type chlorine / sulfur analyzer manufactured by Dia Instruments Co., Ltd., and when it was 2 ppm or less, it was regarded as ND and was not substantially contained.

(Measurement of Adhesive Strength) [Adhesive Strength with Saponified Ethylene-Vinyl Acetate Copolymer] Using a small multilayer T-die, at a molding temperature of 230 ° C., a chill roll temperature of 25 ° C., and a take-up speed of 11 m / min. / Thickness ratio of adhesive layer / intermediate layer / adhesive layer / outer layer is 35/1
A laminate having a thickness of 100 μm was formed to have a thickness of 0/10/10/10/35. Here, LLDP is used for the inner layer and the outer layer.
E (density 0.935 g / cm ³ , MFR 2 g / 10
Minute), a modified resin material for the adhesive layer, and ethylene-
Saponified vinyl acetate copolymer (brand name: F101B, manufactured by Kuraray Co., Ltd.) was used. This laminate was cut into strips having a width of 15 mm, and the gap between the adhesive layer and the intermediate layer was cut at 300 mm / min.
゜ Peeling was performed and the load at that time was measured.

[Adhesive Strength with Nylon 6] Using a small multilayer T-die, a molding temperature of 230 ° C., a chill roll temperature of 25 ° C.,
Under the condition of a take-up speed of 13 m / min, a thickness of 60 μm is set so that the thickness ratio of the inner layer / adhesive layer / outer layer becomes 30/15/15
Was formed. Here, LLDPE (density 0.935 g / cm ³ , MFR 2 g / 10 min) for the inner layer, modified resin material for the adhesive layer, and nylon 6 (brand: CM) for the outer layer
1021, manufactured by Toray Industries, Inc.). 15 mm
The sheet was cut into strips each having a width, and the adhesive layer and the outer layer were separated by 90 ° at 300 mm / min, and the load at that time was measured.

(Production of ethylene copolymer (a)) [Preparation of solid catalyst] In a catalyst preparation apparatus equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen and tetraethoxyzirconium (Zr (OEt) ₄ ) were added. 22 g and 74 g of indene were added, and 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C.
Thereafter, the reaction was carried out at the same temperature for 2 hours. After cooling to 40 ° C., a toluene solution of methylalumoxane (concentration: 2.5 m
(mol / ml) and stirred for 2 hours.
Next, silica (manufactured by Grace, # 952, surface area 300 m ² / g) 2 previously calcined at 450 ° C. for 5 hours 2
After stirring at room temperature for 1 hour, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst having good fluidity.

[Gas Phase Polymerization] Using a continuous fluidized bed gas phase polymerization apparatus, ethylene and 1-hexene were copolymerized at a polymerization temperature of 80 ° C. and a total pressure of 20 kgf / cm ² G. The solid catalyst was continuously supplied, and ethylene, 1-hexene and hydrogen were supplied so as to be maintained at a predetermined molar ratio to carry out polymerization to obtain various ethylene copolymers (a) (PE1 to 3). . The physical properties of these ethylene copolymers were measured using the test methods described above. Table 1 shows the measurement results of each physical property.

[0071]

[Table 1]

(Ethylene copolymer using Ziegler catalyst or metallocene catalyst) Table 2 also shows the physical properties of the ethylene copolymer obtained under the following conditions. Ethylene copolymer (PE4) Using a catalyst composed of titanium tetrachloride and triethylaluminum, ethylene and 1-hexene were copolymerized by a gas phase method to obtain a linear low density polyethylene (LLDPE). Ethylene copolymer (PE5) Using a catalyst comprising titanium tetrachloride and diethylaluminum chloride, ethylene and 4-methyl-1-pentene are copolymerized by a solution method to obtain a linear low-density polyethylene (LLD).
PE) was obtained. Ethylene copolymer (PE6) A commercially available linear low-density polyethylene (brand name: Affinity HF1030, manufactured by Dow Chemical Co., Ltd.) using a metallocene catalyst was used.

[0073]

[Table 2]

(Example 1) Ethylene copolymer (PE1)
100 parts by weight of 2,5-di (t-butylperoxy)
Hexane (0.01 part by weight) was added, and dry blending was performed using a Henschel mixer for 2 minutes. Then, 0.4 parts by weight of maleic anhydride was added, and dry blending was further performed for 2 minutes. The resulting mixture was melt-kneaded using a single-shaft 50 mm kneader set at a temperature of 290 ° C. to obtain a modified ethylene copolymer. The amount of maleic anhydride added to the resulting modified ethylene copolymer was 0.30% by weight, and the MFR of the modified ethylene copolymer was 2.1 g / 10 minutes. LLDPE (density 0.922 g / c) produced by using 30% by weight of this modified ethylene copolymer and ordinary Ziegler catalyst
m ^3, MFR15g / 10 min) 40 wt%, EPR-rubber (propylene content 22 wt%, MFR2.1g / 10
Min) 30% by weight to obtain a modified resin material. Using this modified resin material, according to the method of measuring the adhesive strength,
The adhesive strength with the saponified ethylene-vinyl acetate copolymer was measured. Table 3 shows the results.

(Comparative Example 1) Ethylene copolymer (PE4)
Was modified in the same manner as in Example 1 to obtain a modified ethylene copolymer. The amount of maleic anhydride added to the resulting modified ethylene copolymer was 0.30% by weight, and the MFR was 1.2 g / 10 minutes. Example 1 using this modified ethylene copolymer
A modified resin material was prepared in the same manner as described above, and the adhesive strength with a saponified ethylene-vinyl acetate copolymer was measured. Table 3 shows the results
Shown in A modified resin material containing a modified ethylene copolymer obtained by graft-modifying an ethylene copolymer (PE4) having two peaks in an elution temperature-elution amount curve by TREF is as follows:
The adhesive strength was lower than that of the modified resin material of Example 1.

(Example 2) Ethylene copolymer (PE2)
910 g, together with 7 L of toluene, 15
L into the autoclave, and the temperature was increased while stirring.
When the temperature reached 7 ° C., 27.3 g of maleic anhydride dissolved in 400 ml of toluene and 375 ml of toluene
2.4 g of di-t-butyl peroxide dissolved in the above solution was added dropwise from different mouths over 6 hours. After dropping,
The reaction was carried out for 1 hour, and then cooled. When the temperature reached 105 ° C., 7 L of acetone was added to precipitate and recover the product, and the product was washed several times with acetone to obtain a modified ethylene copolymer. The amount of maleic anhydride added to the resulting modified ethylene copolymer was 0.50% by weight, and the MFR of the modified ethylene copolymer was 1.0 g / 10 minutes. LL produced with 5% by weight of this modified ethylene copolymer and ordinary Ziegler catalyst
DPE (density 0.922 g / cm ³ , MFR 15 g / 1
0 minutes) 70% by weight, and 25% by weight of EPR-rubber (propylene content 22% by weight, MFR 2.1 g / 10 minutes) 25% by weight,
A modified resin material was obtained. Using this modified resin material, the adhesive strength with the saponified ethylene-vinyl acetate copolymer was measured according to the above-mentioned method for measuring the adhesive strength. Table 3 shows the results.

Comparative Example 2 Ethylene Copolymer (PE5)
Was modified in the same manner as in Example 2 to obtain a modified ethylene copolymer. The amount of maleic anhydride added to the resulting modified ethylene copolymer was 0.40% by weight, and the MFR was 0.6 g / 10 minutes. Example 2 using this modified ethylene copolymer
A modified resin material was prepared in the same manner as described above, and the adhesive strength with a saponified ethylene-vinyl acetate copolymer was measured. Table 3 shows the results
Shown in A modified resin material blended with a modified ethylene copolymer obtained by graft-modifying an ethylene copolymer (PE5) having two peaks in an elution temperature-elution amount curve by TREF,
The adhesive strength was lower than that of the modified resin material of Example 2.

[0078]

[Table 3]

Example 3 Ethylene Copolymer (PE2)
910 g, together with 7 L of toluene, 15
L into the autoclave, and the temperature was increased while stirring.
When the temperature reached 7 ° C., 27.3 g of maleic anhydride dissolved in 400 ml of toluene and 375 ml of toluene
2.4 g of dicumyl peroxide, which had been dissolved in the above, was added dropwise from different mouths over 6 hours. After the completion of the dropwise addition, the reaction was carried out for 1 hour. Then, when the temperature reached 105 ° C., 7 L of acetone was added to precipitate and collect the product, and the product was washed several times with acetone to obtain a modified ethylene copolymer. The amount of maleic anhydride added to the resulting modified ethylene copolymer was 0.45% by weight, and the MFR of the modified ethylene copolymer was 1.2 g / 10 minutes. LLDPE produced with 5% by weight of this modified ethylene copolymer and ordinary Ziegler catalyst
(Density 0.922 g / cm ³ , MFR 15 g / 10 min)
95% by weight was kneaded to obtain a modified resin material. Using this modified resin material, the adhesive strength with nylon 6 was measured according to the above-mentioned method of measuring adhesive strength. Table 4 shows the results.

Comparative Example 3 Ethylene Copolymer (PE5)
Was modified in the same manner as in Example 3 to obtain a modified ethylene copolymer. The amount of maleic anhydride added to the modified ethylene copolymer obtained was 0.4% by weight, and the MFR was 0.6 g / 10 minutes. Using this modified ethylene copolymer, a modified resin material was prepared in the same manner as in Example 3, and the adhesive strength to nylon 6 was measured. Table 4 shows the results. The modified resin material containing the modified ethylene copolymer obtained by graft-modifying the ethylene copolymer (PE5) having two peaks of the elution temperature-elution amount curve by TREF has an adhesive strength as compared with the modified resin material of Example 3. Was inferior.

Comparative Example 4 Ethylene Copolymer (PE2)
Was modified in the same manner as in Example 3 to obtain a modified ethylene copolymer. The amount of maleic anhydride added to the modified ethylene copolymer obtained was 0.45% by weight, and the MFR was 1.7 g / 10 minutes. Example 3 using this modified ethylene copolymer
A modified resin material was prepared in the same manner as described above, and the adhesive strength with nylon 6 was measured. Table 3 shows the results. 0.5% by weight of this modified ethylene copolymer, L produced with a usual Ziegler catalyst
LDPE (density 0.922 g / cm ³ , MFR 15 g /
10 minutes) 99.5% by weight was kneaded to obtain a modified resin material. Using this modified resin material, the adhesive strength with nylon 6 was measured according to the above-mentioned method of measuring adhesive strength. Table 4 shows the results. 1% by weight of modified ethylene copolymer
The following modified resin materials were inferior in adhesive strength.

[0082]

[Table 4]

(Example 4) Ethylene copolymer (PE2)
100 parts by weight of 2,5-di (t-butylperoxy)
Hexane (0.015 parts by weight) was added, and dry blending was performed using a Henschel mixer for 2 minutes. Next, 0.8 parts by weight of maleic anhydride was added, and dry blending was further performed for 2 minutes. The resulting mixture was melt-kneaded using a single-shaft 50 mm kneader set at a temperature of 290 ° C. to obtain a modified ethylene copolymer. The amount of maleic anhydride added to the resulting modified ethylene copolymer was 0.51% by weight, MF
R was 1.7 g / 10 minutes. LLD produced with 20% by weight of this modified ethylene copolymer and ordinary Ziegler catalyst
PE (density 0.922 g / cm ³ , MFR 15 g / 10
55% by weight) and 25% by weight of EPR-rubber (propylene content 22% by weight, MFR 2.1 g / 10 minutes) to obtain a modified resin material. Using this modified resin material, the adhesive strength with the saponified ethylene-vinyl acetate copolymer was measured according to the above-mentioned method for measuring the adhesive strength. Table 5 shows the results.

Comparative Example 5 Ethylene Copolymer (PE5)
Was modified in the same manner as in Example 4 to obtain a modified ethylene copolymer. The amount of maleic anhydride added to the resulting modified ethylene copolymer was 0.50% by weight, and the MFR was 0.9 g / 10 minutes. Example 4 using this modified ethylene copolymer
A modified resin material was prepared in the same manner as described above, and the adhesive strength with a saponified ethylene-vinyl acetate copolymer was measured. Table 5 shows the results
Shown in A modified resin material blended with a modified ethylene copolymer obtained by graft-modifying an ethylene copolymer (PE5) having two peaks in an elution temperature-elution amount curve by TREF,
The adhesive strength was lower than that of the modified resin material of Example 4.

Example 5 Ethylene Copolymer (PE3)
100 parts by weight of 2,5-di (t-butylperoxy)
Hexane (0.01 part by weight) was added, and dry blending was performed using a Henschel mixer for 2 minutes. Then, 0.4 parts by weight of maleic anhydride was added, and dry blending was further performed for 2 minutes. The resulting mixture was melt-kneaded using a single-shaft 50 mm kneader set at a temperature of 290 ° C. to obtain a modified ethylene copolymer. The amount of maleic anhydride added to the resulting modified ethylene copolymer was 0.30% by weight, MFR
Was 1.5 g / 10 minutes. LLDP prepared by using a modified Ziegler catalyst with 20% by weight of this modified ethylene copolymer
E (density 0.922 g / cm ³ , MFR 15 g / 10
55% by weight) and 25% by weight of EPR-rubber (propylene content 22% by weight, MFR 2.1 g / 10 minutes) to obtain a modified resin material. Using this modified resin material, the adhesive strength with the saponified ethylene-vinyl acetate copolymer was measured according to the above-mentioned method for measuring the adhesive strength. Table 5 shows the results.

Comparative Example 6 Ethylene Copolymer (PE6)
Was modified in the same manner as in Example 5 to obtain a modified ethylene copolymer. The amount of maleic anhydride added to the resulting modified ethylene copolymer was 0.31% by weight, and the MFR was 1.3 g / 10 minutes. Example 5 using this modified ethylene copolymer
A modified resin material was prepared in the same manner as described above, and the adhesive strength with a saponified ethylene-vinyl acetate copolymer was measured. Table 5 shows the results
Shown in T ₇₅ -T ₂₅ and a density d relationships described above (equation a),
Ethylene copolymer (PE) not satisfying the relationship of (Formula b)
The modified resin material containing the modified ethylene copolymer obtained by graft-modifying 6) was inferior in adhesive strength to the modified resin material of Example 5.

[0087]

[Table 5]

[0088]

As described above, in the modified resin material of the present invention, a copolymer of ethylene and α-olefin having 5 to 12 carbon atoms which satisfies the above-mentioned specific requirements (a)
Which has a modified ethylene / α-olefin copolymer (a ′) grafted with an unsaturated carboxylic acid or a derivative thereof, so that it has excellent adhesion and affinity with other base materials, and particularly high-speed molding It has sufficient adhesive strength required at the time of molding and at the time of forming a thin film, and also has excellent heat resistance.

Further, the ethylene and α having 5 to 12 carbon atoms are used.
-When the melt tension (MT) and the melt flow rate (MFR) of the copolymer (a) with the olefin further satisfy the requirement of the above (F), the adhesiveness and the moldability become more excellent. . The ethylene and the carbon number 5
To α-olefins (a) to (c) in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound belonging to Group IV of the periodic table. When it is obtained by copolymerizing α-olefins of No. 1 to No. 12, the adhesiveness and heat resistance are further improved. Further, when the halogen concentration of the copolymer (a) of the ethylene and the α-olefin having 5 to 12 carbon atoms is 10 ppm or less, the copolymer has excellent chemical stability and does not cause corrosion or the like to a molding machine. Become.

Further, the modified resin material is a copolymer of ethylene and α-olefin having 5 to 12 carbon atoms (a),
Modified ethylene / α-olefin copolymer (a ′) 1 to 10 onto which unsaturated carboxylic acid or its derivative is grafted
0% by weight and other polyolefin-based resin (II) 0 to 99
% By weight and a composition having 0 to 40% by weight of rubber (c), the modified ethylene / α-olefin copolymer (a ′) has excellent adhesion and other polyolefin-based resin (b) The rubber (c) has various characteristics. Further, the other polyolefin-based resin (b) may be an ethylene (co) polymer having a density of 0.86 to 0.97 g / cm ³ , a low-density polyethylene obtained by high-pressure radical polymerization, an ethylene / vinyl ester copolymer, When it is at least one selected from the group consisting of copolymers of α, β-unsaturated carboxylic acids or derivatives thereof, the moldability, mechanical strength and the like are more excellent. Such a modified resin material is an adhesive having good adhesion to other base materials, a compatibilizing agent for engineering plastics, a resin modifier for printing, dyeing, painting, etc., and a resin and filler, etc. Used as a coupling agent for improving the strength, etc., or compounded with various resins such as electric materials, extruded, injected, functional resin film by various molding methods such as hollow, molded products such as containers, etc. Can be used for applications.

The laminate of the present invention comprises a layer comprising the modified resin material and a layer comprising a polyolefin, saponified ethylene vinyl acetate copolymer, polyamide, polyester, polyurethane, polystyrene, wood, fiber and metal foil. Since the modified resin material has at least one selected layer, the modified resin material has both the excellent adhesiveness and the properties of another substrate.

[Brief description of the drawings]

FIG. 1 shows TREF of an ethylene copolymer in the present invention.
It is a graph which shows an example of a curve.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shinji Miwa 2-2-2, Yasuko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Inside the Japan Polyolefin Co., Ltd.Kawasaki Research Laboratories No. 3-2 F-term (reference) in Kawasaki Research Laboratory, Japan Polyolefin Co., Ltd. YY00A 4J002 AB01Z AC01Y AC02Y AC03Y AC06Y AC07Y AH00Z BB00Z BB03W BB03Z BB04W BB05W BB05X BB05Y BB06W BB06Z BB07Z BB08W BB08Z BB12Z BB15Y BB17Z BB18Z CF03Z BB18W CF03Z BB18W BB18Z

Claims (7)

[Claims] 1. An unsaturated carboxylic acid or a derivative thereof is grafted onto a copolymer (a) of ethylene and α-olefin having 5 to 12 carbon atoms satisfying the following requirements (A) to (E). A modified resin material comprising a modified ethylene / α-olefin copolymer (a ′). (A) a density of 0.92 to 0.96 g / cm ³ (B) a melt flow rate (MFR) of 0.01 to 20
0 g / 10 min (C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0 (D) One peak of an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF), and the elution temperature - the difference T ₇₅ -T ₂₅ and the density d of the temperature T ₇₅ to 75% of the total temperature T ₂₅ to 25% of the total determined from the integral elution curve of elution amount curve is eluted elutes the following ( The relationship of equation a),
And satisfying the following formula (formula b) (formula a) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Equation b) T ₇₅ −T ₂₅ ≦ −670 × d + 644 (E) It has one or two melting point peaks, and the highest melting point T _m1 and density d satisfy the relationship of the following (Equation c). Satisfy (Equation c) T _m1 ≧ 150 × d−17 2. The modified resin material according to claim 1, wherein the copolymer (a) of ethylene and an α-olefin having 5 to 12 carbon atoms further satisfies the following requirement (F). . (F) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (formula d) (formula d) logMT ≦ −0.572 × logMFR +
0.3 3. The copolymer (a) of ethylene and an α-olefin having 5 to 12 carbon atoms contains at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table. In the presence of a catalyst, ethylene and C5-C5
The modified resin material according to claim 1, wherein the modified resin material is obtained by copolymerizing the α-olefin of No. 12 with an α-olefin of No. 12. 4. The copolymer (A) of ethylene and an α-olefin having 5 to 12 carbon atoms, wherein (G) the halogen concentration is 10 ppm or less. The modified resin material according to the above item. 5. The modified resin material according to claim 1, further comprising another polyolefin-based resin (b) and a rubber (c), and ethylene and α- having 5 to 12 carbon atoms. Modified ethylene / α in which an unsaturated carboxylic acid or a derivative thereof is grafted on a copolymer with olefin (a)
A modified resin, characterized in that the olefin copolymer (a ') is 1 to 100% by weight, the other polyolefin-based resin (B) is 0 to 99% by weight, and the rubber (C) is 0 to 40% by weight. material. 6. The other polyolefin resin (b)
Is an ethylene (co) polymer having a density of 0.86 to 0.97 g / cm ³ , a low-density polyethylene obtained by high-pressure radical polymerization, an ethylene / vinyl ester copolymer, and ethylene and an α, β-unsaturated carboxylic acid or a mixture thereof. The modified resin material according to claim 5, wherein the modified resin material is at least one selected from the group consisting of a copolymer with a derivative. 7. A layer comprising the modified resin material according to claim 1 and a polyolefin, a saponified ethylene-vinyl acetate copolymer, polyamide, polyester, polyurethane, polystyrene, wood, fiber, and metal foil. A layer comprising at least one layer selected from the group consisting of: