CN109563385A - Polyolefin adhesive composition - Google Patents
Polyolefin adhesive composition Download PDFInfo
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- CN109563385A CN109563385A CN201780047590.5A CN201780047590A CN109563385A CN 109563385 A CN109563385 A CN 109563385A CN 201780047590 A CN201780047590 A CN 201780047590A CN 109563385 A CN109563385 A CN 109563385A
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- adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
- C09J123/30—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides that a kind of laundering period property is good, and the good adhesive composition containing improved polyalkene and epoxy resin of adhesiveness of metal base and polyolefin resin substrate.It is containing crystallinity acid modified polyolefin (A) that acid value is 5~50mgKOH/g resin, glycidyl amine type epoxy resin (B1), chelate modified epoxy resin (B2) and organic solvent (C) adhesive composition.
Description
Technical field
The present invention relates to a kind of adhesive compositions for bonding polyolefin resin substrate and metal base.More specifically
Ground is related to a kind of adhesive composition containing crystallinity acid modified polyolefin, epoxy resin and organic solvent.
Background technique
Traditionally, it is used always in the metal bases such as dress component in household electrical appliances external application plate, furniture raw material, building
(hereinafter, also referred to as " PVC " with vinyl chloride resin by its surface.) after coating, laminated body made of being laminated；Nowadays,
Environmental problem is attracted attention, and there has been proposed replace PVC using polyolefin resin.Since polyolefin resin is nontoxic, show pair
The strong durability of acid, alkali, organic solvent etc., mechanical strength, abrasion performance are also excellent, cheap, therefore are widely used in
Each field.
However, the bonding with metal base is difficult since polyolefin resin is nonpolarity.There has been proposed various viscous in the past
Mixture is for the bonding between polyolefin resin and metal base.It, can be for by phenolic resin, melamine as typical adhesive
The thermosetting resins such as polyimide resin, epoxy resin or thermoplastic resin are dissolved in basis made of organic solvent (base) adhesive
In, adhesive made of the dispersed modified polyolefin resin of mixed solvent.However, it is difficult to think that these adhesives can have sufficiently
Adhesiveness.In addition, there has been proposed the adhesives for mixing catechol etc. into crystallinity acid modified polyolefin and epoxy resin
Composition (patent document 1), and the adhesive combination of the maleic acid modified chlorinated polypropylene of mixing, chelating epoxy resin and solvent
Object (patent document 2).
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2003-261847 bulletin
Patent document 2: Japanese Patent Laid-Open 2009-292853 bulletin
Summary of the invention
Invent solved project
However, there is a situation where that the mixed working life property of acid modified polyolefin solution is bad in the above method, or i.e.
Make working life property without very big problem, it is vital insufficient with the adhesiveness and chemical-resistant of metal base.That is, not depositing
In the adhesive for meeting working life property, adhesiveness and chemical-resistant.Particularly, even if (being hereinafter also referred to as using polypropylene
For PP.) in the case where substrate, also there is no can be bonded in a low temperature of such as being heat-shrinked etc. influences low 80 DEG C or less with
The adhesive of aging (solidification).Herein, working life property refers to mixed cross-linker or curing agent in improved polyalkene, is mixing
Even the stability worked as by the solution after a certain period of time afterwards.
The present invention is the invention made in view of above-mentioned traditional problem, for the viscous of polyolefin resin substrate and metal base
Mixture, present inventor has performed further investigations, as a result, it has been found that containing crystallinity acid modified polyolefin, epoxy resin and organic solvent
Adhesive composition, working life property can be taken into account, and be bonded at 80 DEG C or less, aging when adhesiveness and chemicals-resistant
Property, it has thus completed the present invention.
That is, the object of the present invention is to provide a kind of adhesive composition, in mixed crystallization acid modified polyolefin and
Laundering period property after curing agent is good, and be bonded at low temperature, aging when have to polyolefin resin substrate and Metal Substrate
The good adhesive property and chemical-resistant of material both sides.
Means for solving the problems
To reach the above subject, the present inventor is furtherd investigate, and thus proposes following invention.
A kind of adhesive composition, containing acid value be 5~50mgKOH/g resin crystallinity acid modified polyolefin (A),
Glycidyl amine type epoxy resin (B1), chelate modified epoxy resin (B2) and organic solvent (C).
Preferably, the glycidyl amine type epoxy resin (B1) is the glycidyl in 1 molecule with 2 or more
Epoxy resin.
Preferably, the glycidyl amine type epoxy resin (B1) is general formula (1) compound represented.
[changing 1]
(in general formula (1), R is the aryl that can have substituent group, and X1 and X2 are each independently the carbon atom number that can have substituent group
1~5 alkylidene, m are 1 or 2, and n is 1 or 2.)
Preferably, the chelate modified epoxy resin (B2) is the glycidyl in 1 molecule with 2 or more, and is had
There is 1 or more the functional group with chelate effect, not the epoxy resin of nitrogen atom.
Preferably, relative to 100 mass parts of crystallinity acid modified polyolefin (A), contain glycidyl amine type epoxy resin
(B1) 0.01~20 mass parts, 1~20 mass parts of chelate modified epoxy resin (B2), 80~1000 mass parts of organic solvent (C).
Preferably, organic solvent (C) is the mixed liquor of solvent (C1) and solvent (C2), and solvent (C1) is selected from by aromatic series
The solvent of one or more of the group that hydrocarbon, aliphatic hydrocarbon, clicyclic hydrocarbon and halogenated hydrocarbons are constituted, solvent (C2) are selected from molten by alcohol system
The solvent of one or more of the group that agent, ketone series solvent, ester series solvent and glycol ether series solvent are constituted, solvent (C1)/solvent (C2)
=50~97/50~3 (mass ratioes).
Adhesive composition described in above-mentioned any one is used for viscous between polyolefin resin substrate and metal base
It closes.
The polyolefin resin substrate and metal base being bonded using adhesive composition described in above-mentioned any one
Laminated body.
Invention effect
Adhesive composition of the present invention contains crystallinity acid modified polyolefin, two kinds of epoxy resin and organic molten
Agent will not generate thickening or gelation long-term preservation, can maintain good working life property.Further, though
It is bonded in a low temperature of such as small on the thermal contraction influence of polyolefin base material 80 DEG C or less, aging, polyolefin can also be taken into account
Good adhesive property and chemical-resistant between resin base material and metal base.
Specific embodiment
Hereinafter, embodiments of the present invention are described in detail.
< crystallinity acid modified polyolefin (A) >
Crystallinity acid modified polyolefin (A) used in the present invention is unrestricted, but preferably by polyethylene, polypropylene and
On at least one of propylene-alpha-olefin copolymers, be grafted α, at least one of beta-unsaturated carboxylic acid and its acid anhydrides and obtain
Crystallinity acid modified polyolefin (A).
Propylene-alpha-olefin copolymers are to make itself and polymer made of alpha-olefin copolymer based on propylene.As α-alkene
Hydrocarbon can be used one of such as ethylene, 1- butylene, 1- heptene, 1- octene, 4-methyl-1-pentene, vinyl acetate or more
Kind.Among these alpha-olefins, optimal ethylene, 1- butylene.The propylene ingredient of propylene-alpha-olefin copolymers and the ratio of α-olefin content
Example is unrestricted, but preferably propylene ingredient is 50 moles of % or more, more preferable 70 moles of % or more.
As α, at least one of beta-unsaturated carboxylic acid and its acid anhydrides can be enumerated for example, maleic acid, itaconic acid, lemon health
Acid and their acid anhydrides.Preferred anhydrides among these, more preferable maleic anhydride.Specifically, maleic anhydride modified poly- third can be enumerated
Alkene, maleic anhydride modified propylene-ethylene copolymers, maleic anhydride modified propene-1-butene copolymer, maleic anhydride modified propylene-
These one or more kinds of crystallinity acid modified polyolefins can be applied in combination for ethylene-butene copolymer etc..Wherein, excellent
Select maleic anhydride modified propene-1-butene copolymer.Propylene ingredient/1- fourth as maleic anhydride modified propene-1-butene copolymer
Alkene ingredient (molar ratio), preferably 90~50/10~50, more preferable 85~60/15~40, further preferred 80~55/20~45,
Particularly preferred 75~60/25~40.By making its above range, can express especially excellent working life property, adhesiveness and
Chemical-resistant.
The acid value of crystallinity acid modified polyolefin (A), between working life property and polyolefin resin substrate and metal base
Adhesiveness angle, lower limit is it is necessary for more than 5mgKOH/g resin, preferably more than 10mgKOH/g resin, more preferably
It is more than 14mgKOH/g resin, further preferably more than 16mgKOH/g resin, particularly preferably more than 18mgKOH/g resin,
Most preferably more than 20mgKOH/g resin.If it is less than described value, low with the compatibility of epoxy resin, cannot show to glue
Intensity is closed, additionally, there are crosslink density reduction, the insufficient situations of chemical-resistant.The upper limit it is necessary for 50mgKOH/g resin with
Under, preferably 48mgKOH/g resin is hereinafter, more preferably 46mgKOH/g resin is hereinafter, further preferably 44mgKOH/g tree
Rouge is hereinafter, particularly preferably 42mgKOH/g resin is hereinafter, most preferably below 40mgKOH/g resin.If more than described value, then
The viscosity or stability of solution reduce, and working life property is low.Further, manufacture efficiency also reduces, thus not preferred.Acid value can
By α, the grafting amount (additive amount) of at least one of beta-unsaturated carboxylic acid and its acid anhydrides is controlled.
The weight average molecular weight (Mw) of crystallinity acid modified polyolefin (A) is preferably 40,000~180,000 range.It is more excellent
It is selected as 50,000~160,000 range, further preferably 60,000~150,000, particularly preferably 70,000~140,
000 range, most preferably 80,000~130,000 range.If it is less than the value, there are cohesiveness to weaken adhesiveness
The situation of difference.On the other hand, if it is greater than the value, the operational feelings led to the problem of there are mobility reduction, when bonding
Shape.If it is in the range, due to can use its curing reaction with epoxy resin, thus preferably.
The crystallinity of crystallinity acid modified polyolefin (A) refers to using differential scanning type calorimeter (DSC), with 20 DEG C/minute
From -100 DEG C be warming up to 250 DEG C until, the substance of specific melting peakss is shown in the temperature-rise period.
By making acid modified polyolefin crystallinity, compared to amorphism, since cohesiveness is strong, adhesiveness and chemicals-resistant
Property it is excellent thus advantageous.
The fusing point (Tm) of crystallinity acid modified polyolefin (A) is preferably 50 DEG C~120 DEG C of range.More preferably 60 DEG C~
100 DEG C of range, most preferably 70 DEG C~90 DEG C of range.If it is less than the value, there is crystallization bring cohesiveness and subtract
It is weak, the situation of adhesiveness and chemical-resistant difference.On the other hand, if it is greater than the value, there are stabilities of solution, mobility
It reduces, the operational situation led to the problem of when bonding.
The heat of fusion (Δ H) of crystallinity acid modified polyolefin (A) is preferably the range of 5J/g~60J/g.More preferably
The range of 10J/g~50J/g, the most preferably range of 20J/g~40J/g.If there are zone of a crystal if it is less than the value
The cohesiveness come weakens, the situation of adhesiveness and chemical-resistant difference.On the other hand, if it is greater than the value, there are solution
Stability, mobility reduce, the operational situation led to the problem of when bonding.
It as the manufacturing method of crystallinity acid modified polyolefin (A), is not particularly limited, such as free radical grafting can be enumerated
Reaction (that is, generating free radical species on the polymer as main chain, using the free radical species as polymerization initiation point, makes not
The reaction that saturated carboxylic acid and acid anhydrides are graft-polymerized) etc..
It as radical initiator, is not particularly limited, but it is preferable to use organic peroxides.As organic peroxy
Object is not particularly limited, can enumerate phthalic peroxide di tert butyl carbonate, tert-butyl hydroperoxide, cumyl peroxide,
Benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxide -2-ethyl hexanoic acid tert-butyl, tert-Butyl peroxypivalate, mistake
Aoxidize the peroxide such as methyl ethyl ketone, di-tert-butyl peroxide, lauroyl peroxide；Azodiisobutyronitrile, azo two are different
Azos nitrile such as propionitrile etc..
< glycidyl amine type epoxy resin (B1) >
Glycidyl amine type epoxy resin used in the present invention (B1) is if the glycidyl in 1 molecule with 1 or more
Epoxy resin if, then be not particularly limited.There is 2 or more glycidyls in preferably 1 molecule epoxy resin, it is more excellent
Select in 1 molecule epoxy resin with 3 or more glycidyls, have in further preferably 1 molecule epoxy resin 4 with
On glycidyl.
In addition, glycidyl amine type epoxy resin (B1) is by using the following general formula (1) compound represented, further
Improve chemical-resistant and it is preferred that.
[changing 1]
In general formula (1), R is the aryl that can have substituent group, can preferably have the phenyl of substituent group.As taking for the aryl
Dai Ji is not particularly limited, but can enumerate the alkyl below of carbon atom number 1 or more 5, the alcoxyl below of carbon atom number 1 or more 5
Base, hydroxyl, amino, glycidyl, glycidol amino or glycidyl ether.X1 and X2 are each independently carbon atom
The straight-chain alkyl-sub with substituent group below of number 1 or more 5, preferably carbon atom number are for 4 hereinafter, more preferably 3 hereinafter, into one
Step preferably 2 or less.It as the substituent group of the alkylidene, is not particularly limited, but carbon atom number 1 or more 5 or less can be enumerated
Alkyl, carbon atom number 1 or more 5 alkoxy or amino below.M is 1 or 2, and n is 1 or 2.Preferably, one of m or n are 2,
It is highly preferred that m, n are 2.
Concrete example as glycidyl amine type epoxy resin (B1) is not particularly limited, but can enumerate four glycidyl group
Diaminodiphenyl-methane, triglycidyl group para-aminophenol, four glycidyl group double aminomethyl cyclohexanones, N, N, N ',
Glycidols amine systems such as N '-four glycidyl group m-xylene diamine etc..Wherein, preferably N, N, N ', between N '-four glycidyl group
Dimethylphenylene diamine.These glycidyl amine type epoxy resins (B1) can be used alone or and with two or more.
The combined amount of glycidyl amine type epoxy resin (B1), relative to 100 mass of crystallinity acid modified polyolefin (A)
Part, more than preferably 0.01 mass parts, more than more preferably 0.05 mass parts, more than further preferably 0.1 mass parts, especially
More than preferably 1 mass parts, more than most preferably 2 mass parts.If it is less than the range, make in the presence of catalysis cannot be shown
With, be bonded at 80 DEG C or less, aging when adhesiveness and the low situation of chemical-resistant.Furthermore it is preferred that it is 20 mass
Part hereinafter, more preferably 18 below the mass, further preferably 16 below the mass, and particularly preferably 14 below the mass,
Most preferably 12 below the mass.If it is greater than the range, tends to cross-linking reaction and excessively carry out rigid raising, adhesiveness drop
It is low.In addition, the solution for tending to adhesive composition save in be easy to carry out cross-linking reaction, working life reduces.
The chelate modified epoxy resin of < (B2) >
Chelate modified epoxy resin (B2) used in the present invention has the asphalt mixtures modified by epoxy resin of the functional group of chelate effect if intramolecular
It if rouge, is not particularly limited, but is preferably 1 molecule from reactivity, the angle of adhesiveness, chemical-resistant is improved
With 2 or more glycidyls, 1 or more the functional group with chelate effect in epoxy resin, and not nitrogen atom
Epoxy resin.That is, the rust-preventing characteristic of the metal bases such as aluminium, chemically-resistant can be improved by mixing chelate modified epoxy resin (B2)
Moral character increases accordingly.Even if not implementing the surface treatment (for example, chromic acid salt treatment) of metal base as a result, also can express viscous
The excellent adhesiveness of mixture composite and the chemical-resistant of metal base.
Chelating, which refers to, is bonded (coordination) via ligand (multidentate ligand) and metal ion with multiple coordination sites, has
The functional group of chelate effect is not particularly limited, can enumerate carboxyl, phosphonic acid base, sulfonic group, phosphate, sulfate, nitrato and
The acidic groups such as boronate, the functional group except the acidic groups such as alcoholic extract hydroxyl group, phenolic hydroxyl group, itrile group, mercapto and amino.Preferably phosphate.
The combined amount of chelate modified epoxy resin (B2) is relative to 100 mass parts of crystallinity acid modified polyolefin (A), preferably
More than 1 mass parts, it is more than more preferably 2 mass parts, it is more than further preferably 3 mass parts, particularly preferably 4 mass parts with
On, it is more than most preferably 5 mass parts.Furthermore it is preferred that below the mass for 20, more preferably 18 below the mass, it is further excellent
It is selected as 16 below the mass, particularly preferably 14 below the mass, and most preferably 12 below the mass.By making it described
In range, it can express excellent adhesiveness and chemical-resistant.
One kind can be only used alone in chelate modified epoxy resin (B2) used in the present invention, can also be used together by more than one.Specifically
The commercially available products such as the EP-49-10 series of ADEKA corporation can be used in ground.
In the present invention, which is characterized in that by the glycidyl amine type epoxy resin (B1) and the chelate modified epoxy
Resin (B2) both epoxy resin are used in combination as essential component.By and with glycidyl amine type epoxy resin (B1) and chela
It closes modified epoxy (B2), can express excellent adhesiveness, chemical-resistant.That is, glycidyl amine type epoxy resin
(B1) have react crystallinity acid modified polyolefin (A) with chelate modified epoxy resin (B2), cured effect.Further
Ground makes crystallinity acid modified polyolefin (A) and glycidyl amine epoxy since glycidyl amine type epoxy resin (B1) has
Between resin (B1), glycidyl amine type epoxy resin (B1), between chelate modified epoxy resin (B2), glycidyl amine type ring
Oxygen resin (B1) reacts with chelate modified epoxy resin (B2), cured catalytic action, therefore passes through mixing glycidic amine type
Epoxy resin (B1), can be improved in 80 DEG C of bondings below, aging and the adhesiveness and chemical-resistant of metal base.
Relative to 100 mass parts of crystallinity acid modified polyolefin (A), glycidyl amine type epoxy resin (B1) changes with chelating
The total combined amount of property epoxy resin (B2) is preferably 2~40 mass parts, more preferably 5~20 mass parts, most preferably 10~
16 mass parts.If if it is less than the range, presence cannot obtain sufficient solidification effect, adhesiveness and chemical-resistant
Low situation reduces, in terms of cost if it is greater than the range for working life property and with the adhesiveness of alkene substrate
Angle is without preferred.
The combined amount of glycidyl amine type epoxy resin (B1) is preferably 1~50 mass % of epoxy resin total amount, more excellent
It is selected as 2~30 mass %, most preferably 3~10 mass %.If combined amount is lower than described value, make in the presence of catalysis cannot be shown
With the situation that adhesiveness and chemical-resistant reduce when low-temperature adhesion, aging tends to cross-linking reaction mistake if being higher than described value
Degree carries out, and rigidity improves, and adhesiveness reduces.In addition, tend to adhesive composition solution save in be easy to carry out cross-linking reaction,
Working life reduces.
Epoxy resin used in the present invention can be used in combination with other epoxy resin.It can enumerate for example, shrinking sweet
Oily ether type epoxy, the glycidyl ester types such as hexahydrophthalic acid ethylene oxidic ester, dimer acid glycidyl ester, isocyanide urea
Sour three-glycidyl ester, 3,4- epoxycyclohexyl-methyl carboxylate, epoxidized polybutadiene or epoxidised soybean oil etc. are alicyclic
Or aliphatic epoxide etc., it is sub concrete example as diglycidyl ether type epoxy resin, it is not particularly limited, but benzene can be enumerated
Phenol phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, these resins be used alone it is a kind of or and with two kinds with
On.
< organic solvent (C) >
Organic solvent used in the present invention (C) is if dissolvable crystallinity acid modified polyolefin (A), glycidyl amine epoxy
If the organic solvent of resin (B1) and chelate modified epoxy resin (B2), then it is not particularly limited.Specifically, example can be used
Such as, the aromatic hydrocarbons such as benzene,toluene,xylene, the fatty families hydrocarbon such as hexane, heptane, octane, decane, hexamethylene, cyclohexene, first
The clicyclic hydrocarbons such as butylcyclohexane, ethyl cyclohexane, the halogenated hydrocarbons such as trichloro ethylene, dichloroethylene, chlorobenzene, chloroform, methanol, ethyl alcohol,
The alcohol series solvents such as isopropanol, butanol, amylalcohol, hexanol, propylene glycol, phenol, acetone, methyl iso-butyl ketone (MIBK), methyl ethyl ketone, oneself
The ketone series solvents such as ketone, cyclohexanone, isophorone, acetophenone, the dioxanes such as methyl cellosolve, ethyl cellosolve, methyl acetate,
The ester series solvents such as ethyl acetate, butyl acetate, methyl propionate, butyl formate, ethylene glycol mono-n-butyl ether, ethylene glycol list isobutyl ether,
Ethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol list isobutyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol
Glycol ether series solvent such as mono-n-butyl ether etc., these can be used a kind or be two kinds or more.
Relative to 100 mass parts of crystallinity acid modified polyolefin (A), organic solvent (C) is preferably 80 mass parts or more, more
More than preferably 90 mass parts, more than further preferably 100 mass parts, more than particularly preferably 110 mass parts.If it is lower than
The range, then solution state and working life property can reduce.Furthermore it is preferred that below the mass for 1000, more preferably 900 mass
Part hereinafter, further preferably 800 below the mass, particularly preferably 700 below the mass.If if being higher than the range,
Then there are unfavorable in terms of manufacturing cost, transportation cost.
From the angle of the solution state of adhesive composition and working life property, organic solvent (C) is preferably selected from by virtue
The solvent (C1) of one or more of the group that fragrant race's hydrocarbon, aliphatic hydrocarbon, clicyclic hydrocarbon and halogenated hydrocarbons are constituted, it is molten by alcohol system with being selected from
The mixed liquor of the solvent (C2) of one or more of the group that agent, ketone series solvent, ether series solvent and glycol ether series solvent are constituted.As
Mixing ratio, preferably solvent (C1)/solvent (C2)=50~97/50~3 (mass ratio), more preferably 55~95/45~5 (matter
Measure ratio), further preferably 60~90/40~10 (mass ratioes), particularly preferably 70~80/30~20 (mass ratioes).If no
Within the above range, the solution state of adhesive composition and working life property can reduce.In addition, particularly preferred solvent (C1)
For aromatic hydrocarbon or clicyclic hydrocarbon, solvent (C2) is ketone series solvent.
< adhesive composition >
Adhesive composition of the present invention is the crystallinity acid modified polyolefin (A), glycidyl amine type epoxy resin
(B1), the mixture of chelate modified epoxy resin (B2) and organic solvent (C).Crystallinity acid modified polyolefin (A), glycidol
Amine type epoxy resin (B1) and chelate modified epoxy resin (B2) can dissolve or is scattered in organic solvent (C).From laundering period property
Angle set out, preferably dissolve.
In the range of not damaging performance of the invention, adhesive composition of the present invention changes in the crystallinity acid
Property polyolefin (A), glycidyl amine type epoxy resin (B1), except chelate modified epoxy resin (B2) and organic solvent (C), also
Can mix various curing accelerators carry out using.As curing accelerator, be not particularly limited, can enumerate carboxylic metallic salt,
Tertiary amines, quaternary ammonium salt, organic peroxide, hydrazine compound, metal chelate compound, Thiourea, phosphorus-containing compound, alkalinity vulcanization
Agent class etc..As the carboxylic metallic salt, the metal salt of the carboxylic acid of carbon atom number 1~30 can be enumerated.It is golden as the carboxylic acid is constituted
Belong to salt carboxylic acid, can enumerate for example acetic acid, butyric acid, octanoic acid, capric acid, lauric acid, myristic acid, palmitinic acid, stearic acid, oleic acid,
Behenic acid, octenoic acid, erucic acid, elaidic acid, adipic acid, malonic acid, succinic acid, glutaric acid, citric acid, tartaric acid, malic acid, two
The aliphatic carboxylic acids such as Glycolic acid；Benzoic acid, chlorobenzoic acid, anisic acid, aminobenzoic acid, phthalic acid, terephthalic acid (TPA), naphthalene
The aromatic carboxylic acids such as formic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid；Aphthenic acids；Pyruvic acid etc..In addition, as carboxylic metallic salt is constituted
Metal can be enumerated for example, Li, Na, K, Mg, Ca, Zn, Al, Cu, Pb, Co, Fe, Mn, Sn, Ti etc..As the carboxylic metallic salt,
Specifically, can enumerate lithium acetate, sodium acetate, magnesium acetate, aluminium acetate, potassium butyrate, calcium butyrate, zinc butyrate, Sodium Caprylate, calcium octoate,
Capric acid potassium salt, capric acid magnesium, capric acid zinc, lithium laurate, sodium laurate, calcium laurate, Aluminum trilaurate, potassium myristate, myristic acid
Sodium, aluminium myristate, sodium palmitate, zinc palmitate, magnesium palmitate, odium stearate, potassium stearate, calcium stearate, zinc stearate,
Enuatrol, sodium behenate, sodium benzoate, zinc benzoate, sodium phthalate, phthalic acid aluminium, terephthalic acid (TPA) magnesium, naphthalene two
Calcium carboxylates, dibutyl tin laurate, tributyl tin laurate, dioctyltin laurate, tributyltin acetate, oxalic acid dibutyl
Tin, dioctyl tin diacetate, 2 ethyl hexanoic acid dibutyl tin, butyl titanate, tetrabutyl titanate, four -2- ethyl hexyl of metatitanic acid
Ester, cobalt naphthenate, copper naphthenate, magnesium naphthenate, acetoacetate cobalt etc..Among these, it is preferable that lithium laurate, the moon can be enumerated
Sodium metasilicate, calcium laurate, Aluminum trilaurate, potassium myristate, Sodium myristate, aluminium myristate, sodium palmitate, zinc palmitate,
Magnesium palmitate, odium stearate, potassium stearate, calcium stearate, zinc stearate, enuatrol.In addition, the metal salt as carboxylic acid,
The polymer with carboxylic metallic salt structure can be used.It as such a polymer, can enumerate: there is ethylene and radical polymerization
The conjunction property IA race of carboxylic acid, Group IIA, Group IIB, IIIB race metal (such as Li, Na, K, Mg, Ca, Zn, Al etc.) salt be copolymerized
Structure polymer；Metal salt and other free-radical polymerised carboxylic acids with ethylene and free-radical polymerised carboxylic acid and/or
Its derivative carries out the polymer etc. of structure made of multi-component copolymer.In addition, can enumerate as the tertiary amines for example, diformazan
Base aniline, triethanolamine, dimethyl-p-toluidine etc..In addition, can enumerate as the hydrazine compound for example, 1- acetyl group -2-
Phenyl hydrazine etc..In addition, can enumerate as the metal chelate compound for example, vanadium acetylacetonate etc..In addition, as the sulphur
Ureas can be enumerated for example, dimethyl phosphine, triphenylphosphine etc..In addition, can enumerate as the phosphorus-containing compound for example, dimethyl
Phosphine, triphenylphosphine etc..In addition, can enumerate as the alkaline vulcanizing agent class for example, hexa, n-butanal-aniline contracting
Close object etc..
In the range of not damaging performance of the invention, adhesive composition of the present invention changes in the crystallinity acid
Property polyolefin (A), glycidyl amine type epoxy resin (B1), except chelate modified epoxy resin (B2) and organic solvent (C), also
Can mix various additives carry out using.It is not particularly limited as additive, it is preferable to use fire retardant, pigment, resist blocking and that
Agent etc..
< laminated body >
Laminated body of the invention be fold polyolefin resin substrate and metal base with adhesive composition layer of the present invention and
At laminated body.
As the method for stacking, conventionally known lamination manufacturing technology can be used.Although for example, be not particularly limited,
The suitable coating apparatus such as roll coater or bar coater can be used in the surface coating adhesive composition of metal base, and done
It is dry., can be when the adhesive phase that metallic substrate surface is formed be in molten state after drying, laminate adhesive is poly- on the coated face
Olefin resin substrate obtains laminate structures.
The thickness of the adhesive phase formed by described adhesive composition is not particularly limited, but preferably 0.5~10 μm, more
Preferably 0.8~9.5 μm, further preferably 1~9 μm.
< polyolefin resin substrate >
As polyolefin resin substrate, carry out suitably selecting from conventionally known polyolefin resin.For example, without special
Limitation, but polyethylene, polypropylene, ethylene-propylene copolymer can be used etc..Wherein, it is preferable to use polyacrylic unstretching film (under
Wen Zhong, also referred to as CPP.).Its thickness is not particularly limited, but preferably 20~100 μm, more preferably 25~95 μm, further
Preferably 30~90 μm.In addition, can in polyolefin resin substrate hybrid pigment as needed and various additives.
< metal base >
It as metal base, is not particularly limited, but such as aluminium, copper, steel, zinc, duralumin, die casting (die can be used
Cast) various metals and its alloy such as.In addition, metal foil, rolled plate, panel, pipe, tank, lid etc. can be used as its shape
Arbitrary shape.In general, for the preferred aluminium foil of angle of processability etc..Though logical in addition, can be different according to using purpose different
Often carried out in the form of the sheet material of 0.01~10mm of thickness, preferably 0.02~5mm using.
In addition, can surface treatment be implemented in the surface to these metal bases in advance, untreated state can also be maintained.Two kinds of situations
Same effect can be played down.
Hereinafter, embodiment can be enumerated the present invention is described in more detail.However, the present invention is not limited by embodiment
It is fixed.The part recorded in embodiment and in comparative example indicates mass parts.
The Production Example > of < crystallinity acid modified polyolefin (A)
Production Example 1
Into 1L autoclave, propene-1-butene copolymer (Mitsui Chemicals society system " TAFMER (registered trademark) XM7080 ") 100 is added
25 mass parts of mass parts, 150 mass parts of toluene and maleic anhydride, 6 mass parts of di-tert-butyl peroxide, after being warming up to 140 DEG C,
It futher stirs 3 hours.Then, it after cooling resulting reaction solution, is poured into the container added with a large amount of methyl ethyl ketone,
Resin is precipitated.Then, by the way that the liquid containing the resin is centrifuged, the acid for the maleic anhydride that is graft-polymerized is modified
Propene-1-butene copolymer is separated with (poly-) maleic anhydride and low molecular weight substance, is purified.Then, by under reduced pressure at 70 DEG C
It is 5 hours dry, obtain maleic anhydride modified propene-1-butene copolymer (PO-1, acid value 48mgKOH/g resin, weight average molecular weight
50,000,75 DEG C of Tm, Δ H 25J/g).
Production Example 2
In addition to the inventory of maleic anhydride is changed to 20 mass parts, equally carries out with Production Example 1, change thus to obtain maleic anhydride
Property propene-1-butene copolymer (PO-2, acid value 25mgKOH/g resin, weight average molecular weight 80,000,75 DEG C of Tm, Δ H 30J/g).
Production Example 3
In addition to the inventory of maleic anhydride being changed to 3 mass parts, di-tert-butyl peroxide is changed to 0.5 mass parts, with manufacture
Example 1 equally carries out, and (PO-3, acid value 5mgKOH/g resin, again divides equally thus to obtain maleic anhydride modified propene-1-butene copolymer
Son amount 180,000,80 DEG C of Tm, Δ H 25J/g).
Production Example 4
In addition to the inventory of maleic anhydride is changed to 30 mass parts, equally carries out with Production Example 1, change thus to obtain maleic anhydride
Property propene-1-butene copolymer (PO-4, acid value 55mgKOH/g resin, weight average molecular weight 40,000,70 DEG C of Tm, Δ H 25J/g).
Production Example 5
In addition to the inventory of maleic anhydride being changed to 2 mass parts, di-tert-butyl peroxide is changed to 0.5 mass parts, with manufacture
Example 1 equally carries out, and (PO-5, acid value 3mgKOH/g resin, again divides equally thus to obtain maleic anhydride modified propene-1-butene copolymer
Son amount 200,000,80 DEG C of Tm, Δ H 25J/g).
(production of host agent 1)
Into the 500ml four-hole boiling flask equipped with water-cooled reflux condenser and blender, the maleic anhydride obtained in Production Example 1 is added
100 mass parts of modified propylene-butylene copolymer (PO-1), 120 mass parts of 280 mass parts of hexahydrotoluene and methyl ethyl ketone,
It is warming up to 80 DEG C while agitating, persistently stirs 1 hour, thus to obtain host agent 1.Solution state is as shown in table 1.
(production of host agent 2~12)
Change crystallinity acid modified polyolefin and organic solvent as shown in table 1, makes host agent 2 with method identical with host agent 1
~12.Combined amount, solution state are as shown in table 1.
[table 1]
Embodiment 1
Mix the ADEKA RESIN of 500 mass parts host agents 1,2 mass parts as the chelate modified epoxy resin (B2) of curing agent
TETRAD (the registrar of (registered trademark) EP-49-10P, 0.2 mass parts as glycidyl amine type epoxy resin (B1)
Mark)-X, obtain adhesive composition.The evaluation result of working life property, adhesiveness and chemical-resistant is as shown in table 2.
Embodiment 2~21, comparative example 1~7
As shown in Table 2,3, change host agent 1~12 and each curing agent, with method same as Example 1 carry out embodiment 2~
21, comparative example 1~7.Combined amount, working life property, adhesiveness and chemical-resistant are as shown in Table 2,3.
[table 2]
[table 3]
Curing agent used in table 2,3 is following substance.
< glycidyl amine type epoxy resin (B1) >
N, N, N ', N '-four glycidyl group m-xylene diamine: TETRAD (registered trademark)-X (Mitsubishi's gas chemistry strain formula meeting
Society's system)
The chelate modified epoxy resin of < (B2) >
Chelate modified epoxy resin: ADEKA RESIN (registered trademark) EP-49-10P (ADEKA corporation)
Phosphoric acid modification epoxy resin: Uradil DD-79 (DSM CoatingResins corporation)
< diglycidyl ether type epoxy resin >
Phenol novolak type epoxy resin: jER (registered trademark) 152 (Mitsubishi chemical Co., Ltd's system)
Other curing agent of < >
Polyisocyanate: DURANATE (registered trademark) TPA-100 (Asahi Kasei Corporation's system)
Silane coupling agent: KBM-403 (SHIN-ETSU HANTOTAI's organosilicon Co. Ltd. system)
Each crystallinity acid modified polyolefin, host agent and the adhesive composition obtained for as described above, based on following
Method carries out analysis measurement and evaluation.
The measurement of acid value
< crystallinity acid modified polyolefin (A) >
The acid value (mgKOH/g resin) of crystallinity acid modified polyolefin (A) in the present invention is to neutralize 1g acid modified polyolefin (A)
Necessary KOH amount, the test method based on JIS K0070 (1992) are measured.Specifically by acid modified polyolefin 1g
After being dissolved in the dimethylbenzene 100g that temperature is adjusted to 100 DEG C, using phenolphthalein as indicator under synthermal, with 0.1mol/L hydrogen-oxygen
Change potassium ethanol solution [trade name " the alcohol repellency potassium hydroxide solution of 0.1mol/L ", He Guangchun medicine (strain) system] to be titrated.At this point,
Potassium hydroxide amount needed for titration is scaled mg, calculates acid value (mgKOH/g resin).
The measurement of weight average molecular weight (Mw)
Weight average molecular weight in the present invention be using Japanese water generation corporation gel permeation chromatography Alliancee 2695 (under
Referred to herein as GPC, standard substance: polystyrene resin, mobile phase: tetrahydrofuran, chromatographic column: Shodex KF-806+KF-
803, column temperature: 40 DEG C, flow velocity: 1.0ml/ points, detector: photodiode array detector (wavelength 254nm=ultraviolet light)) and
The value of measurement.
The measurement of fusing point, heat of fusion
Fusing point, heat of fusion in the present invention are to use differential scanning type calorimeter (hereinafter referred to DSC, TA instrument Japan system, Q-
2000) heating melting, cooling resinification, the summit based on melting peakss when heating melts again, are carried out with 20 DEG C/minute of speed
Temperature and area and the value measured.
The evaluation of host agent solution state
For the solution state of host agent 1~13, fly type viscosimeter TVB-10M by using the rich Le of Toki Sangyo Co., Ltd.
(hereinafter also referred to as Brookfield viscometer) measures 25 DEG C of solution viscosity and is evaluated.
< evaluation criteria >
Zero (practical excellent): less than 500mPas
△ (can be practical): 500mPas or more, it is less than 1000mPas
× (can not be practical): 1000mPas or more, or viscosity cannot be measured due to gelation
The evaluation of working life property
Working life property refers to mixed cross-linker or curing agent in crystallinity acid modified polyolefin, even after its mixing when by
The stability of the solution after a certain period of time.It is few that the good situation of working life property refers to that the viscosity of solution rises, can long-term preservation；
The bad situation of working life property refers to that the viscosity of solution rises (thickening), gel phenomenon occurs when serious, it is difficult on substrate
Coating, is unable to long-term preservation.
The working life property of the adhesive composition obtained in embodiment 1~18 and comparative example 1~8 is by 25 DEG C and 40 DEG C of atmosphere
After enclosing lower storage 24 hours, 25 DEG C of solution viscosity is measured using Brookfield viscometer to be evaluated.Evaluation result such as 2,3 institute of table
Show.
< evaluation criteria >
Zero (practical excellent): less than 500mPas
△ (can be practical): 500mPas or more, it is less than 1000mPas
× (can not be practical): 1000mPas or more, or viscosity cannot be measured due to gelation
The production of laminated body between metal base and polyolefin resin substrate
As metal base, use aluminium foil (firmly light aluminium foil Co. Ltd. system, 8079-0,40 μm of thickness)；As polyolefin resin
Substrate, using un-stretched polypropylene film (Japan spin Co. Ltd. system PYLEN (registered trademark) Film-CT, 40 μm of thickness) (under
CPP is also referred to as in text.).
On metal base, the adhesive composition obtained in Examples 1 to 32 and comparative example 1~15 is carried out using bar coater
Adjustment and coating, 3 μm of film thickness of the adhesive phase after making drying.Use air drier under 100 DEG C of atmosphere coated face
It is 1 minute dry, obtain 3 μm of film thickness of adhesive phase.Polyolefin resin substrate is overlapped in described adhesive layer surface, by making
Laminating machine (SA-1010-S) is tested with the small desk of TESTER SANGYO CO.LTD, with 0.3MPa, 1m/ at 80 DEG C
Divide and be bonded, at 40 DEG C, 50%RH, solidify within 120 hours, obtain laminated body.
For the laminated body of acquisition as described above, evaluated using following methods.
The evaluation of adhesiveness
The laminated body is cut to 100mm × 15mm size, the evaluation of adhesiveness is carried out by T-type disbonded test.Evaluation knot
Fruit is as shown in table 3~6.
< T-type disbonded test >
According to the test method of ASTM-D1876-61, using the Tensilon RTM-100 of ORIENTEC Corporation,
Peel strength under 25 DEG C of environment, under tensile speed 50mm/ points of measurement.Removing between metal base/polyolefin resin substrate
Intensity (N/cm) uses the average value of 5 test values.
< evaluation criteria >
☆ (extremely excellent on practical): 8.0N/cm or more or CPP generating material is damaged (hereinafter referred to as " material is broken ".) material
Breakage, which refers to, does not generate removing on the interface metal base/CPP, metal base or CPP are destroyed.
◎ (practical upper especially excellent): 7.5N/cm or more, it is less than 8.0N/cm
Zero (practical excellent): 7.0N/cm or more is less than 7.5N/cm
△ (can be practical): 6.0N/cm or more, it is less than 7.0N/cm
× (can not be practical): less than 6.0N/cm
The evaluation of chemical-resistant
In order to one of the usage mode of laminated body to aluminium foil and CPP the packaging material as lithium ion battery usability into
Row research carries out the evaluation of the chemical-resistant (hereinafter also referred to as electrolyte resistance) using electrolyte test.By the layer
Stack is cut to the size of 100mm × 15mm, by its electrolyte [to ethylene carbonate/diethyl carbonate/dimethyl carbonate=
Electrolyte made of the lithium lithium phosphate of addition in 1/1/1 (volume ratio)] in, it is impregnated 1 day at 85 DEG C.Then, stacking is taken out
Body is cleaned with ion exchange water, is wiped water with blotting paper (paper wiper), is fully dried moisture, be cut to
The size of 100mm × 15mm carries out the evaluation of chemical-resistant by T-type disbonded test.
< evaluation criteria >
☆ (extremely excellent on practical): 8.0N/cm or more or material it is broken
◎ (practical upper especially excellent): 7.5N/cm or more, it is less than 8.0N/cm
Zero (practical excellent): 7.0N/cm or more is less than 7.5N/cm
△ (can be practical): 6.0N/cm or more, it is less than 7.0N/cm
× (can not be practical): less than 6.0N/cm
Industrial utilizability
Adhesive composition of the present invention contains crystallinity acid modified polyolefin, epoxy resin and organic solvent, i.e.,
Make long-term preservation that will not generate thickening and gelation, good working life property can be maintained, and metal base and polyene can be taken into account
Good adhesiveness between hydrocarbon resin substrate.Therefore, the polyolefin resin substrate formed by adhesive composition of the invention with
The laminate structure of metal base, not only in household electrical appliances external application plate, furniture raw material, building in the fields such as dress component, also
The packaging material (Soft Roll form) that can be used as the lithium battery for personal computer, mobile phone, video camera etc. is utilized extensively.
Claims (8)
1. a kind of adhesive composition containing the crystallinity acid modified polyolefin A that acid value is 5~50mgKOH/g resin, shrinks
Glyceramine type ring oxygen resin B 1, chelate modified epoxy resin B2 and organic solvent C.
2. adhesive composition as described in claim 1, the glycidyl amine type epoxy resin B1 is to have 2 in 1 molecule
The epoxy resin of a above glycidyl.
3. adhesive composition as claimed in claim 1 or 2, the glycidyl amine type epoxy resin B1 is general formula (1) institute
The compound shown；
[changing 1]
In general formula (1), R is the aryl that can have substituent group, and X1 and X2 are each independently the carbon atom number 1 that can have substituent group
~5 alkylidene, m are 1 or 2, and n is 1 or 2.
4. the adhesive composition as described in any one of claims 1 to 3, the chelate modified epoxy resin B2 is 1 point
Glycidyl with 2 or more in son, the functional group with chelate effect with 1 or more and not nitrogen atom
Epoxy resin.
5. the adhesive composition as described in any one of Claims 1 to 4 changes relative to 100 mass parts crystallinity acid
Property polyolefin A, the chelate modified ring of glycidyl amine type epoxy resin B1,1~20 mass parts containing 0.01~20 mass parts
The organic solvent C of oxygen resin B 2,80~1000 mass parts.
6. the adhesive composition as described in any one of Claims 1 to 5, organic solvent C is solvent C 1 and solvent C 2
Mixed liquor；Solvent C 1 is selected from one or more of the group being made of aromatic hydrocarbon, aliphatic hydrocarbon, clicyclic hydrocarbon and halogenated hydrocarbons
Solvent, solvent C 2 be in the group being made of alcohol series solvent, ketone series solvent, ester series solvent and glycol ether series solvent 1
Kind or more solvent；By quality ratio, 1/ solvent C 2=50~97/50~3 of solvent C.
7. the adhesive composition as described in any one of claim 1~6 is used for polyolefin resin substrate and Metal Substrate
The bonding of material.
8. a kind of laminated body of polyolefin resin substrate and metal base, uses described in any one of claim 1~7
Adhesive composition is bonded.
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| JP2016-157784 | 2016-08-10 | ||
| PCT/JP2017/026074 WO2018030086A1 (en) | 2016-08-10 | 2017-07-19 | Polyolefin adhesive composition |
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| CN113025127A (en) * | 2019-12-25 | 2021-06-25 | Dic株式会社 | Coating agent, laminate, molded body, and packaging material |
| CN114630877A (en) * | 2019-09-26 | 2022-06-14 | 东亚合成株式会社 | Adhesive composition and bonding method |
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| JP7215091B2 (en) * | 2017-12-22 | 2023-01-31 | 東洋紡株式会社 | Polyolefin adhesive composition |
| WO2021045125A1 (en) * | 2019-09-06 | 2021-03-11 | 東洋紡株式会社 | Polyolefin-based adhesive composition |
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2017
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| JP2009292853A (en) * | 2008-06-02 | 2009-12-17 | Yokohama Rubber Co Ltd:The | Metal-olefinic resin adhesive composition excellent in salt water-resistant adhesion |
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| CN113025127A (en) * | 2019-12-25 | 2021-06-25 | Dic株式会社 | Coating agent, laminate, molded body, and packaging material |
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| WO2018030086A1 (en) | 2018-02-15 |
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