JPH0622969B2 - New stack - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Field of Industrial Application The present invention relates to a laminate having various synthetic resin base materials and a strong adhesive force.

(B) Conventional technology In general, polyolefin resin has high strength, good heat resistance, is inexpensive, and so on.
It is used in a wide range of applications such as blow bottles.

However, this polyolefin resin is excellent in chemical resistance and the like because it does not have a polar group in the molecule, but on the other hand, it has a drawback that the adhesion to different materials such as synthetic resin, metal and wood is extremely poor.

Therefore, various attempts have heretofore been made to impart adhesiveness to polyolefin resins. For example, there is a method of subjecting the adhesive surface of the polyolefin resin to surface treatment such as fire treatment, corona discharge treatment and solvent treatment. However, all of these methods not only complicate the treatment operation, but also provide sufficient adhesiveness. Can not do it.

In addition to these, various attempts have been made to add adhesiveness to a polyolefin resin by adding an unsaturated carboxylic acid or the like to the polyolefin resin in the presence of an organic peroxide or the like and introducing a functional group.

For example, a method of adding 1 to 20% by weight of a rubber compound to high-pressure low-density polyethylene, low-pressure high-density polyethylene or polypropylene and modifying it with an unsaturated carboxylic acid (JP-A-52-8035), high-pressure low Density polyethylene, low-pressure method High-density polyethylene or polypropylene 70 to 98% by weight and a mixture of 30 to 2% by weight of a copolymer of ethylene and α-olefin having a crystallinity of less than 30% are unsaturated carboxylic acids or their anhydrides. A method for laminating a modified polyolefin modified by (4) on a saponified product of nylon, polyester, and ethylene-vinyl acetate copolymer (JP-A-54-82 and JP-A-54-8).
No. 3) or ethylene-α- having a density of 0.915 to 0.935 g / cm ³ and a weight average molecular weight / number average molecular weight of 3 to 12
A method of using an adhesive resin composition obtained by reacting an unsaturated carboxylic acid or a derivative thereof with a mixture of an olefin copolymer and a synthetic rubber and modifying the mixture (JP-A-57-165469).
Etc., and has achieved some results.

Recently, polyethylene terephthalate molding bottles (P
These laminated materials are often used as ET bottles) and food packaging materials, and more severe molding conditions and usage conditions such as high-speed moldability, high stretchability and heat sealability are required, and at the same time, the physical properties of the laminated materials are Materials with higher performance are required.

However, it cannot be said that the conventional method as described above is sufficient.

(C) Problems to be Solved by the Invention In view of the above points, the present inventors have earnestly studied and, as a result, have achieved the present invention.

That is, the present invention is a laminate capable of improving the heat-sealing property, the delamination strength, and the mechanical strength of a molded product even in molding under severe molding conditions such as high stretching and high-speed molding. It is intended to provide the body.

(D) Means for Solving Problems The present invention relates to a laminate based on a laminate containing at least two layers of a synthetic resin layer and an adhesive layer, wherein the adhesive layer has a) a density of 0.86 to 0.91 g / cm 3. ³ , b) boiling n-hexane insoluble content is 10 wt% or more, c) maximum peak temperature (Tm) shown by differential scanning calorimetry (DSC) is 100 ° C or more, ethylene-α-olefin copolymer or An adhesive resin obtained by modifying an olefin-based polymer composition containing the copolymer as a main component in the presence of an unsaturated carboxylic acid or its derivative and an organic peroxide, or an olefin polymer containing the adhesive resin. The present invention provides a novel laminate characterized by being a united body.

The ethylene-α-olefin copolymer used in the present invention is a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms. Specific examples of α-olefins include propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1. Of these, propylene and butene-1 are particularly preferable. Α in ethylene-α-olefin copolymer
-The olefin content is preferably between 5 and 40 mol%.

The method for producing the ethylene / α-olefin copolymer used in the present invention will be described below.

First, the catalyst system used is a combination of a solid catalyst component containing magnesium and titanium with an organoaluminum compound, and examples of the solid catalyst component include metal magnesium, magnesium hydroxide, magnesium carbonate,
Magnesium oxide, magnesium chloride, etc., also silicon,
Double salts, double oxides, carbonates, chlorides or hydroxides containing a metal selected from aluminum and calcium and a magnesium atom, and further inorganic solid compounds thereof are oxygen-containing compounds, sulfur-containing compounds, aromatic compounds. Examples thereof include those obtained by supporting a titanium compound on a magnesium-containing inorganic solid compound such as those treated or reacted with a hydrocarbon or a halogen-containing substance by a known method.

Examples of the oxygen-containing compound include water, alcohol,
Organic oxygen-containing compounds such as phenol, ketone, aldehyde, carboxylic acid, ester, polysiloxane, acid amide,
Examples thereof include inorganic oxygen-containing compounds such as metal alkoxides and metal oxychlorides. As the sulfur-containing compound, thiol, organic sulfur-containing compounds such as thioether,
Examples thereof include inorganic sulfur compounds such as sulfur dioxide, sulfur trioxide, and sulfuric acid. Examples of aromatic hydrocarbons include various monocyclic and polycyclic aromatic hydrocarbon compounds such as benzene, toluene, xylene, anthracene, and phenanthrene. As a halogen-containing substance,
Examples thereof include compounds such as chlorine, hydrogen chloride, metal chlorides and organic halides.

Examples of the titanium compound include titanium halides, alkoxy halides, alkoxides and halogenated oxides. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are preferable, and the tetravalent titanium compound is specifically represented by the general formula Ti (OR) n.
X4-n (wherein R represents an alkyl group, an aryl group or an aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, and n is 0 ≦ n ≦ 4) are preferred, and Titanium chloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, Monoisopropoxytrichlorotitanium,
Diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium. , Tetraphenoxytitanium and the like. As the trivalent titanium compound, titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide are hydrogen, aluminum, titanium or periodic table I to
Examples thereof include titanium trihalides obtained by reduction with an organometallic compound of Group III metal. In addition, the general formula Ti (O
R) m X4-m (wherein R represents an alkyl group, an aryl group or an aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, and m is 0 <m <4) A trivalent titanium compound obtained by reducing the halogenated alkoxytitanium of the above with an organometallic compound of a metal of Groups I to III in the periodic table.

Of these titanium compounds, tetravalent titanium compounds are particularly preferable.

Specific examples of these catalysts include MgO-
RX-Ti Cl ₄ system (JP-B 51-3514 discloses), Mg -
Si Cl ₄ -ROH-Ti Cl ₄ system (JP-B 50-23864 _{discloses), Mg Cl 2 -Al (OR} ) 3 -Ti Cl 4 system (JP-B 51-152 and JP-B-52-15111 ), Mg
Cl ₂ —Si Cl ₄ —ROH—Ti Cl ₄ system (JP-A-4
9-106581), Mg (OOCR) _2- Al (OR)
₃ -Ti Cl ₄ system (JP-B 52-11710 discloses), Mg -P
OCl ₃ -Ti Cl ₄ system (Japanese Patent Publication No. 51-153), Mg
Cl ₂ -AlOCl-Ti Cl ₄ system (JP-B 54-15316 _{discloses), Mg Cl 2 -Al (OR} ) n X 3-n-Si (O
'In) m X4-m -Ti Cl ₄ system (JP 56-95909 JP) a solid catalyst component such as (wherein, R, R' R is an organic residue, X in is a halogen atom) A combination of organoaluminum compounds is mentioned as an example of a preferred catalyst system.

As another example of the catalyst system, a catalyst system in which a reaction product of an organomagnesium compound such as a so-called Grignard compound and a titanium compound is used as a solid catalyst component and an organoaluminum compound is combined therewith can be exemplified. Examples of the organomagnesium compound include organomagnesium compounds represented by the general formulas RMg X, R ₂ Mg, RMg (OR) (wherein R represents an organic residue having 1 to 20 carbon atoms, and X represents halogen), and Use of an ether complex or an organomagnesium compound obtained by modifying the organomagnesium compound with addition of various compounds such as other organometallic compounds such as organosodium, organolithium, organopotassium, organoboron, organocalcium, and organozinc. You can

Specific examples of these catalyst systems include, for example, RMg X
-Ti Cl ₄ system (JP-B 50-39470 Patent Publication) RMg X- phenol -ti Cl ₄ system (JP-B 54-12953 discloses), R
Mg X-halogenated phenol-TiCl ₄ system
54-12954 JP), mention may be made of a combination of an organoaluminum compound in the solid catalyst component such as _{RMg X-CO 2 -Ti Cl 4} ( JP 57-73009 JP).

Further, as another example of the catalyst system, as the solid catalyst component, S
with i O _2, Al 2 O ₃ or the like of the inorganic oxide and the solid substance obtained by contacting a solid catalyst component containing at least magnesium and titanium, which to illustrate a combination of an organoaluminum compound You can As the inorganic oxide, in addition to _CaO of _{Si O 2, Al 2 O 3} , B 2 O 3, Sn O 2 or the like can be cited, and also can be used without any trouble double oxides of these oxides. As a method for bringing these various inorganic oxides into contact with the solid catalyst component containing magnesium and titanium, known methods can be adopted. That is, a method of reacting in the presence or absence of an inert solvent at a temperature of 20 to 400 ° C, preferably 50 to 300 ° C for usually 5 minutes to 20 hours, a method of co-milling treatment, or a combination of these methods is appropriately used. You may make it react by.

Specific examples of these catalyst systems include, for example, SiO 2
_{2 -ROH-Mg Cl 2 -Ti Cl} 4 system (JP 56-474
No. 07), SiO ₂ -R-O-R'-Mg O-AlC.
l ₃ -Ti Cl ₄ system (JP 57-187305 JP), Si
_{O 2 -Mg Cl 2 -Al (OR} ) 3 -Ti Cl 4 -Si
(OR ') ₄ system (JP-A-58-21405) (in the above formula, R and R'represent a hydrocarbon residue) and the like in combination with an organoaluminum compound can be mentioned.

In these catalyst systems, the titanium compound can be used as an adduct with the organic carboxylic acid ester, or the inorganic solid compound containing magnesium described above can be used after being contact-treated with the organic carboxylic acid ester. Further, there is no problem even if the organoaluminum compound is used as an adduct with the organic carboxylic acid ester.
Furthermore, in all cases, it is possible to carry out without any problems using a catalyst system prepared in the presence of an organic carboxylic acid ester.

Here, as the organic carboxylic acid ester, various aliphatic,
Alicyclic and aromatic carboxylic acid esters are used, and aromatic carboxylic acid esters having 7 to 12 carbon atoms are preferably used. Specific examples thereof include alkyl esters of benzoic acid, anisic acid, toluic acid such as methyl and ethyl.

Specific examples of the organoaluminum compound to be combined with the above solid catalyst component include the general formulas R ₃ Al and R ₂
AlX, RAlX ₂ , R ₂ AlOR, RAl (OR) X
And an organic aluminum compound of R ₃ Al ₂ X ₃ (wherein R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, X is a halogen atom, and R may be the same or different). Preferred compounds are triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum,
Examples thereof include diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum sesquichloride, and mixtures thereof.

The amount of the organoaluminum compound used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 mol times that of the titanium compound.

Further, by using the above catalyst system in the polymerization reaction after contacting it with the α-olefin, the polymerization activity can be greatly improved, and the operation can be more stable than that in the untreated case. As the α-olefin used at this time, various ones can be used, but preferably having 3 to 12 carbon atoms.
Α-olefin, more preferably 3 to 3 carbon atoms
An α-olefin of 8 is desirable. Examples of these α-olefins include, for example, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1,
Examples thereof include decene-1, dodecene-1 and the like, and mixtures thereof. The temperature and time for contacting the catalyst system with the α-olefin can be selected within a wide range, for example, 0 to 2
The contact treatment can be performed at 00 ° C, preferably 0 to 110 ° C for 1 minute to 24 hours. The amount of α-olefin to be contacted can be selected within a wide range, but usually, it is usually per 1 g of the solid catalyst component.
Treated with 1 to 50,000 g, preferably about 5 to 30,000 g of α-olefin, and 1 to 500 g per 1 g of the solid catalyst component.
It is desirable to react the α-olefin of At this time, the pressure at the time of contact can be arbitrarily selected, but normally,
It is desirable to contact under a pressure of -1 to 100 kg / cm ² · G.

During the α-olefin treatment, all the organoaluminum compound used was combined with the solid catalyst component and then α-
It may be contacted with an olefin, or a part of the organoaluminum compound used may be combined with the solid catalyst component and then contacted with an α-olefin, and the rest of the organoaluminum compound may be added separately during the polymerization. A polymerization reaction may be performed. Further, at the time of contact between the catalyst system and the α-olefin, there is no problem even if hydrogen gas coexists, and nitrogen,
There is no problem even if other inert gases such as argon and helium coexist.

The polymerization reaction is carried out in the same manner as the usual olefin polymerization reaction using a Ziegler type catalyst. That is, all of the reactions are carried out in a state where oxygen, water, etc. are substantially cut off, in the gas phase, in the presence of an inert solvent, or using the monomer itself as a solvent. The olefin polymerization conditions are a temperature of 20 to 300 ° C., preferably 40 to 200 ° C., and a pressure of normal pressure to 70 kg / cm ²
G, preferably 2 kg / cm ² · G to 60 kg / cm ² · G. The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but it is effectively performed by adding hydrogen to the polymerization system.
Of course, different polymerization conditions such as hydrogen concentration and polymerization temperature
It is possible to carry out a multi-step polymerization reaction of two steps or more without any trouble.

In the present invention, when the density of the ethylene-α-olefin copolymer exceeds 0.91 g / cm ³ , the adhesive resin does not have excellent adhesiveness, and when the density is less than 0.86 g / cm ³ ,
The melting point of the adhesive resin is low and it can not withstand high temperature use,
In addition, the strength of the adhesive layer itself is reduced, and the apparent adhesive strength is low.

On the other hand, when the boiling n-hexane insoluble content of the ethylene-α-olefin copolymer is less than 10% by weight, the amount of amorphous parts and low molecular weight components increases, and the adhesive strength required as an adhesive cannot be sufficiently exhibited.

On the other hand, when the maximum peak temperature (Tm) of differential scanning calorimetry (DSC) is less than 100 ° C, the heat resistance of the adhesive is inferior.

The boiling n-hexane insoluble matter and D
The SC measuring method is as follows.

[Method for measuring boiling n-hexane insoluble matter] Using a heat press, form a sheet with a thickness of 200 μm, cut three 20 mm x 30 mm sheets in each length and width, and use a double-tube Soxhlet extractor. Using, boiling
Extract with n-hexane for 5 hours. The n-hexane insoluble matter was taken out and dried under vacuum (7 hours, under vacuum, 50 ° C.),
Calculate the boiling n-hexane insoluble matter by the following formula.

Boiling n-hexane insoluble matter (weight%) = (weight of extracted sheet / weight of unextracted sheet) x 100 (weight%) [Measurement method by DSC] Weighing about 5 mg of sample from 100 μm thick film hot-press molded Then, set it in the DSC device, raise the temperature to 170 ° C, hold at that temperature for 15 minutes, and then decrease the temperature by 2.5 ° C /
Cool to 0 ° C in minutes. Next, from this state
Measure at 170 ° C in ° C / min. 0 ° C to 1
Let Tm be the temperature at the position of the maximum apex of the peak that appeared while heating to 70 ° C.

The ethylene-α-olefin copolymer used in the present invention is clearly distinguished from the ethylene-α-olefin copolymer obtained by using the one containing vanadium as the solid catalyst component.

That is, conventional ethylene-propylene copolymers and the like have almost no crystallinity, and even if a crystal part exists, the amount is extremely small, and the maximum peak temperature (m) by DSC is 1
It is less than 00 ℃.

This means that it cannot be used for an adhesive resin used for applications requiring heat resistance and adhesive strength. Furthermore, vanadium, which exists in the copolymer as a catalyst residue, poses a problem of toxicity, unlike titanium, so that the catalyst removal step is indispensable, whereas when titanium is used, the toxicity problem of the catalyst residue does not occur. The copolymer of the present invention which uses a highly active catalyst in combination with a magnesium carrier does not require a catalyst removal step, which is extremely economical and preferable.

Further, in the present invention, the olefin polymer composition containing ethylene-α-olefin as a main component can also be used as the base polymer of the adhesive resin, but the ethylene-α-olefin copolymer and the olefin polymer are used. The composition ratio of the polymer is such that the ethylene-α-olefin copolymer is 60% by weight or more, preferably 70% by weight or more.

Examples of the above-mentioned olefin polymer include polyethylene, polypropylene, polybutene-1, poly-4-methyl-pentene.
-1, such as an olefin homopolymer, or ethylene, propylene, butene-1, 4-methyl-pentene-1, hexene-1, octene-1, etc. from which the ethylene-α-olefin copolymer in the above specific range has been removed. Copolymers of ethylene, ethylene-propylene copolymer rubber (EPR), ethylene-propylene-diene copolymer rubber (EPDM), copolymerization of ethylene and vinyl ester, unsaturated carboxylic acid, unsaturated carboxylic acid ester, etc. Examples thereof include coalesce, polyisobutylene and mixtures thereof.

Examples of the unsaturated carboxylic acid used in the present invention include monobasic acids and dibasic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and citraconic acid. As the unsaturated carboxylic acid derivative, a metal salt of the above unsaturated carboxylic acid, an amide, an imide,
Examples thereof include esters and anhydrides, of which maleic anhydride is most preferable.

The amount of the above-mentioned unsaturated carboxylic acid or its derivative (hereinafter simply referred to as unsaturated carboxylic acid) added to the ethylene-α-olefin copolymer or the olefin-based polymer composition containing the copolymer as a main component is not specified. Saturated carboxylic acid amount 0.05 ~
5% by weight, preferably 0.1 to 3% by weight, is added and heated in the presence of an organic peroxide to form a reaction.

The reaction is carried out by melt-mixing in an extruder or a kneading machine such as a Banbury mixer in the absence of a solvent to cause a reaction, or an aromatic hydrocarbon such as benzene, xylene and toluene, and an aliphatic hydrocarbon such as hexane, heptane and octane. There is a method of heating and mixing in a solvent such as, and is not particularly limited, but it can be carried out in the extruder because of its simple operation, excellent economical efficiency, continuity with subsequent steps, etc. preferable.

If the amount of the unsaturated carboxylic acid exceeds 5% by weight, decomposition and crosslinking reactions may occur in addition to the addition reaction.
If it is less than 0.05% by weight, the object of improving the adhesiveness of the present invention cannot be achieved.

Examples of the organic peroxide include benzoyl peroxide, lauryl peroxide, azobisisobutyronitrile, dicumyl peroxide, t-butylhydroperoxide, α, α′-bis (t-butylperoxydiisopropyl). Benzene, di-t-butylperoxide, 2,5-di (t-butylperoxy) hexine, etc. are preferably used, and the adhesive resin or the olefin polymer containing the adhesive resin is added to 100 parts by weight. To 0.005
It is used in an amount of up to 0.2 parts by weight, preferably 0.01 to 1.0 parts by weight. If the amount of the organic peroxide added is less than 0.005 parts by weight, the modifying effect is not substantially exerted, and even if it is added in excess of 2.0 parts by weight, it is difficult to obtain a further effect and it is excessive. This may cause decomposition or crosslinking reaction.

The laminate of the present invention is basically a laminate including at least two layers of a synthetic resin layer and the adhesive layer, and the synthetic resin layer includes a polyamide resin, polyvinylidene chloride resin, ethylene-acetic acid. Saponification product of vinyl copolymer, polyester resin, polyvinyl chloride resin, polystyrene resin, ABS resin, polycarbonate resin, polyvinyl alcohol resin, fluorine resin, polyphenylene oxide resin, polyphenylene sulfide resin , Polyether / etherketone resin, polyamideimide resin, polyacetal resin, polysulfone resin, polyarylate resin, polyetherimide resin, polyparabanic acid resin, etc., and other different materials as a multilayer structure include ethylene- Propylene copolymer rubber, ethylene-propylene Diene copolymer rubber, polybutadiene rubber, butadiene - styrene copolymer rubber, butadiene - acrylonitrile rubber, polychloroprene rubber,
Synthetic rubber such as acrylic rubber and silicone rubber, rubber such as natural rubber, metal such as aluminum, iron, zinc, copper, wood such as veneer and plywood, glass such as glass and ceramic, ceramics, concrete, plaster Although woven fabrics, non-woven fabrics, papers and the like made of mineral fibers such as Acbest, FRP, natural fibers, synthetic fibers or carbon fibers, aramid fibers and metal fibers can also be used, synthetic resins such as polyethylene terephthalate, Polyester such as polybutylene terephthalate, polyamide, vinylidene chloride resin,
Laminates that combine resins with low gas permeability such as vinyl chloride resin or synthetic resins with good oil resistance are
It is preferable as a food container, a food packaging material, a gasoline container and the like.

In the present invention, as described above, the synthetic resin layer (A) and the adhesive layer (B) are used.
Based on a laminate containing at least two layers of
/ B, B / A / B, A / B / C (where C is another dissimilar material layer), A / B / C / B, B / A / B /
3 layers of A, C / B / A / B, C / B / A / B / C, 4
It includes layers or multi-layer laminates such as five layers.

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.

In addition to the co-extrusion molding method such as an inflation method or a multilayer T-die method, which uses a multi-layer die, a resin melted by an extruder is joined at a tip of a die to form a laminated structure, as a method for producing a laminate of the present invention. Ordinary molding methods such as a multi-layer blow molding method and an injection molding method are applied, and are not particularly limited.

(E) Action / Effect of the Invention Since the laminate of the present invention uses the synthetic resin layer (A) as a substrate, a layer formed by graft-modifying a conventional olefin polymer with an unsaturated carboxylic acid, or The adhesive strength is superior to that using a layer composed of a mixture of the graft modified product and an olefin polymer, and particularly excellent in maintaining the adhesive strength during deformation such as stretching.
Further, since the adhesive layer (B) has the above-mentioned characteristics, it can be suitably used for multilayer stretch blow molding which is difficult to realize with the conventional laminated structure.

Of course, the laminate of the present invention is excellent by using a material having a small gas permeability such as a saponified product of ethylene-vinyl acetate copolymer, polyester, or polyvinylidene chloride as the synthetic resin layer (A) having excellent heat sealability. As a packaging material, it is effectively used in many fields such as food, medicine and cosmetics.

(F) Example Hereinafter, the effect of the present invention will be described more specifically with reference to Examples and Comparative Examples.

Examples 1 to 3 Polymerization of ethylene and propylene was carried out using a solid catalyst component obtained from substantially anhydrous magnesium chloride, 1,2-dichloroethane and titanium tetrachloride and a catalyst consisting of triethylaluminum, and Three kinds of ethylene-propylene copolymers were obtained.

(A) Density 0.870 g / cm ³ , DSC maximum peak (Tm
) An ethylene-propylene copolymer having an n-hexane insoluble content of 45% at 119.0 ° C.

(B) Density 0.887 g / cm ³ , DSC maximum peak (Tm
) An ethylene-propylene copolymer having an n-hexane insoluble content of 50% at 119.5 ° C.

(C) Density 0.908 g / cm ³ , DSC maximum peak (Tm
) An ethylene-propylene copolymer having an n-hexane insoluble content of 50% at 121.5 ° C.

Maleic anhydride was added to 100 parts by weight of the above three copolymers.
0.25 parts by weight and organic peroxide (2,5-dimethyl-2,5-
Di (tert-butylperoxy) hexyne-3) 0.0
Two parts by weight were added, and the mixture was kneaded with a Banbury mixer for 200 and 15 minutes to obtain an adhesive resin.

Next, using a multi-layer T-die, a saponified ethylene-vinyl acetate copolymer (trade name: Eval ED-F, manufactured by Kuraray Co., Ltd.) (hereinafter EV
AL) and high-density polyethylene (density 0.948, melt index 0.03 g / 10 minutes, trade name: Nisseki Staflen E 903, manufactured by Nippon Petrochemical Co., Ltd.) are supplied to a multi-layer die at a die temperature of 220 ° C. Before joining the die lip, they were joined together and laminated to form a three-layer T-die sheet. At that time, the thickness of the laminated film is Evar layer 30μ / adhesive resin layer 2
It was 00μ / high density polyethylene layer 750μ.

A 25 mm wide test piece was made from the above laminated film, and using a Tensilon tensile tester, an angle of 180 degrees and a take-up speed of 50 mm /
Delamination strength when pulled at a speed of minute is the adhesive strength (1)
The results are shown in Table 1. As a more severe test method, the peel strength (adhesive strength (2)) measured after the test piece was stretched 4.5 times in advance is also shown in Table 1.

Comparative Example 1 Ethylene-butene-1 copolymer outside the scope of the present invention (density
0.922 g / cm ³ , melt index 2.0 g / 10 min, trade name: Nisseki Linirex AF3340, manufactured by Nippon Petrochemical Co., Ltd. (hereinafter referred to as LLDPE) 100 parts by weight of maleic anhydride 0.25 parts by weight and organic Peroxide (2,5-dimethyl-2,5 di (tert-butyl-peroxy) hexyne
-3) 0.02 parts by weight was added to obtain an adhesive resin in the same manner as in Example 1, a test piece was prepared in the same manner as in Example 1, and the results of the same test are shown in Table 1.

Example 4 100 parts by weight of the adhesive resin of Example 2 was added to a linear low density polyethylene (hereinafter referred to as LLDPE) (ethylene-butene 1-).
Copolymer, density 0.922 g / cm ³ , melt index 2.
30 g by weight of 0 g / 10 minutes, trade name: Nisseki Linilex AF3320, manufactured by Nippon Petrochemical Co., Ltd.) was mixed with a Banbury mixer to prepare an adhesive resin composition, and the composition was used as an adhesive layer. A laminated body was prepared in the same manner as in Example 2 and the adhesive strength was measured. The results are shown in Table 1.

Comparative Example 2 Ethylene-propylene copolymer rubber (trade name: EPR
EP01-P, manufactured by Nippon Synthetic Rubber Co., Ltd.) 0.25 parts by weight of maleic anhydride and 100 parts by weight of organic peroxide (2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3) ) 0.02 part by weight was added, and the mixture was kneaded in a Banbury mixer at 200 ° C for 15 minutes to modify. A laminated body was prepared using this modified product as an adhesive layer in the same manner as in Example 1 and the adhesive strength was measured. The results are shown in Table 1.

Examples 5 to 8 The adhesive resin prepared in Example 1 and EVAL as a substrate,
Aluminum plate (hereinafter abbreviated as Al), nylon-6 (trade name: Toray Milan 1046) (hereinafter abbreviated as PA), polyethylene terephthalate (trade name: kodar PETG 6763)
, Eastman Chemical Product Inc. Made)
(Hereinafter, abbreviated as PET), the adhesive resin sheet (thickness 500μ) is overlaid on the base material preheated to 220 ° C, and pressurized at 100kg / cm ³ for 5 minutes in the oven at 220 ° C. After slow cooling, a test piece (25 mm width) was prepared, and the value obtained by peeling 180 ° at a tensile speed of 50 mm / min by a tensile tester is shown in Table 2 as the adhesive strength.

Comparative Examples 3 to 6 Comparative Examples 3 to 6 were performed in the same manner as in Examples 5 to 8 except that the resin of Comparative Example 1 was used, and the results are shown in Table 2.

Examples 9 to 10 and Comparative Examples 7 to 8 As a base material, polyvinylidene chloride resin (manufactured by Kureha Chemical Co., Ltd.) (hereinafter abbreviated as PVDCl) and polyvinyl chloride resin (trade name: Aron Compound BL, 2M-11VI-P) are used. ,
Toa Gosei Co., Ltd. (hereinafter abbreviated as PVC) was used, and the same procedure as in Examples 5 to 8 was carried out except that the test piece molding temperature was 160 ° C., and the results are shown in Table 2. In addition, as a comparative example, the base materials of Examples 9 to 10 were used, and the resin of Comparative Example 1 was used as the resin, and the results were shown in Table 2 in the same manner as in Examples 9 to 10.

Continuation of front page (56) Reference JP-A-56-109758 (JP, A) JP-A-58-59060 (JP, A) JP-A-58-140248 (JP, A) JP-A-58-18260 (JP , A) JP-A-56-92902 (JP, A) JP-A-55-56111 (JP, A) JP-A-55-56110 (JP, A)

Claims (5)

[Claims] 1. A laminate based on a laminate comprising at least two layers of a synthetic resin layer and an adhesive layer, wherein the adhesive layer has a) a density of 0.86 to 0.91 g / cm ³ , b) boiling n- Hexane-insoluble matter is 10% by weight or more, c) The maximum peak temperature (Tm) shown by differential scanning calorimetry (DSC) is 100 ° C or more, and the main component is an ethylene-α-olefin copolymer or the copolymer. And an olefin polymer containing the adhesive resin obtained by modifying the olefin-based polymer composition to be modified in the presence of an unsaturated carboxylic acid or its derivative and an organic peroxide. A new laminated body. 2. The synthetic resin layer comprises a polyolefin resin, a polyamide resin, a polyester resin, a polycarbonate resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polystyrene resin, an ethylene-vinyl acetate copolymer. Saponified product, polyvinyl alcohol resin,
Fluorine resin, polyphenylene oxide resin, polyphenylene sulfide resin, polyether / etherketone resin, polyamideimide resin, polyimide resin, polyacetal resin, polysulfone resin, polyarylate resin, polyetherimide resin, polybarabanic acid resin,
At least 1 selected from the group consisting of phenolic resins
A novel laminate according to claim 1 comprising seeds. 3. The laminate is selected from the group consisting of rubber, metal, FRP plate, wood, glass, ceramic, concrete, plaster, woven fabric, non-woven fabric and paper via a synthetic resin layer and an adhesive layer. The novel laminate according to claim 1 or 2, which comprises at least one multilayer structure. 4. The novel laminate according to any one of claims 1 to 3, wherein the amount of the unsaturated carboxylic acid or its derivative added is in the range of 0.05 to 5% by weight. 5. The novel laminate according to any one of claims 1 to 4, wherein the unsaturated carboxylic acid or its derivative is maleic anhydride.