JP3094311B2 - Fluorine resin coated metal laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-based resin-coated metal laminate, and more particularly to a fluorine-based resin-coated metal laminate in which a metal substrate and a fluorine-based resin are integrally bonded via an adhesive resin layer. is there.

[0002]

2. Description of the Related Art Fluororesins have excellent properties as coating materials because of their excellent chemical resistance, solvent resistance and weather resistance, and are widely used.

[0003] However, the fluorine resin has poor adhesion to various substrates, and has a drawback that even if the surface of the various substrates is coated with the fluorine resin, the formed coating film is easily peeled off.

Various attempts have been made to improve the adhesion of fluororesins to, for example, metal substrates. For example, a method in which a composition comprising an epoxy acrylate resin, a vinylidene fluoride resin, a methacrylic resin and the like is used as a primer (Japanese Patent Laid-Open No. 1-149880), a method comprising an epoxy and / or epoxyphenol resin and a thermoplastic methacrylic resin Method for utilizing the composition as a primer (Japanese Patent Laid-Open No. 2-47176)
Publication) and the like.

[0005]

However, the technique of coating a metal substrate with a fluororesin is not yet sufficient, and there is still a defect that the formed coating film is easily peeled off. The present invention relates to bonding and integration of a metal substrate and a fluororesin, and a laminate having no disadvantages in the related art, that is,
An object of the present invention is to provide a fluorine-based resin-coated metal laminate having high interlayer adhesive strength and sufficiently good adhesive strength durability.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the metal base and the vinylidene fluoride resin layer were combined with a carboxyl group-containing modified polyolefin resin layer. It has been found that the above-mentioned object is achieved by laminating via an adhesive resin layer made of a specific copolymerization product, and the present invention has been completed.

That is, the present invention is characterized in that a metal base layer, a carboxyl group-containing modified polyolefin resin layer, an adhesive resin layer made of the following copolymerization product, and a vinylidene fluoride resin layer are laminated in this order. This is a fluorine-based resin-coated metal laminate.

The above-mentioned copolymerization product comprises (A) an olefin polymer (a) having at least one functional group in one molecule and a functional group having reactivity with the functional group of the olefin polymer. Radical polymerizable olefin polymer 90 obtained by reacting a radical polymerizable monomer (b)
10 to 90% by weight of (B) a monomer containing an alkyl acrylate, an alkyl methacrylate and / or a fluorine-containing unsaturated monomer, which is copolymerizable with the radically polymerizable olefin polymer, as an essential component. % Of the copolymerized product.

The fluorine-based resin-coated metal laminate of the present invention may further comprise a polyolefin resin layer between the carboxyl group-containing modified polyolefin-based resin layer and an adhesive resin layer comprising the following copolymerization product, if necessary. .

[I] Structure of laminated body (1) Metal substrate layer Iron and its alloy, aluminum and its alloy, copper and its alloy, stainless steel and the like.

(2) Carboxyl group-containing modified polyolefin resin layer: ethylene, propylene, butene-1,4-methylpentene-
1, a carboxyl group (an acid anhydride group) is added to a homopolymer, a plurality of copolymers of α-olefins such as hexene-1, octene-1, or a copolymer with other monomers containing these as a main component. ) Are introduced by the reaction. Compounds that introduce a carboxyl group include (meth) acrylic acid,
There are maleic acid, itaconic acid, hymic acid and acid anhydrides thereof, among which (meth) acrylic acid and maleic anhydride are preferred in view of adhesiveness.

Here, the denaturation reaction includes graft, random,
Although the form of the block, oxidation, etc., does not matter, the amount of the carboxyl group introduced is 1 × 10 ^{−3 to} 0.3 mol / 100 g, preferably
5 × 10 ^{−3 to} 0.2 mol / 100 g, particularly preferably 1 × 10 ⁻² to
0.1 mol / 100g. If it is within this range, the olefin resin in which the carboxyl group is directly introduced is diluted with the same or different olefin resin that has not been introduced, and other components such as a rubber-like polymer and an inorganic filler are added to the effect of the present invention. May be used as the modified olefin-based resin in a range not significantly impairing the above.

(3) Adhesive resin layer The adhesive resin layer is formed of a radically polymerizable olefin polymer (A).
And a copolymerizable monomer containing an alkyl acrylate, an alkyl methacrylate and / or a fluorine-containing unsaturated monomer as an essential component.

(A) Production of radically polymerizable olefin polymer (A) (a) Olefin polymer (a component) One molecule used as a raw material of the copolymerization product of the present invention has at least one functional group in one molecule. The olefin polymer (component (a)) preferably has a weight average molecular weight of about 1,0.
00 to 200,000, particularly preferably about 10,000 to 100,000. If the molecular weight of the component (a) is too low, the adhesion of the obtained copolymerization product to the substrate becomes insufficient, and if it is too high, it tends to gel during copolymerization with the monomer (B) described below. Tend.

The olefin polymer having at least one functional group in one molecule of the component (a) is produced by reacting an existing polyolefin with an unsaturated compound having a desired functional group.

(A) Polyolefin Examples of the polyolefin as a precursor of the component a include polyethylene, polypropylene, polybutene-1, ethylene.
Α-olefins such as propylene copolymers and ethylene-butene copolymers or copolymers of these copolymers, α-olefins such as ethylene-propylene-diene copolymers and isobutene-isoprene copolymers with conjugated dienes Coalescing,
Polybutadiene, conjugated diene polymers such as polyisoprene, styrene / butadiene copolymer, styrene / butadiene / styrene block copolymer or hydrogenated product thereof, styrene / isoprene copolymer, styrene / isoprene / styrene block copolymer or Examples thereof include copolymers of an aromatic vinyl compound such as a hydrogenated product thereof and a conjugated diene, and chlorinated products of these polyolefins. Among these polyolefins, ethylene polymer, propylene polymer,
Most preferred are α-olefin polymers such as styrene polymers, styrene elastomers such as styrene / butadiene / styrene block copolymers or hydrogenated products thereof, and modified chlorinated polyolefins.

(B) Unsaturated Compound Having a Functional Group As the functional group of the component a, various types can be considered in relation to the reaction with the monomer of the component b. For example, carboxylic acid or its anhydride, Examples of the unsaturated compound having an epoxy group, a hydroxyl group, and an isocyanate group and having these functional groups to be reacted with the precursor polyolefin include the following compounds.

(Carboxylic acid or anhydride group-containing unsaturated compound) When the carboxylic acid or its anhydride group is introduced into the precursor polyolefin, the compound may be (meth) acrylic acid, fumaric acid, maleic acid or its anhydride. And unsaturated carboxylic acids such as itaconic acid and its anhydride, crotonic acid and its anhydride, citraconic acid and its anhydride, and their anhydrides.

(Epoxy Group-Containing Unsaturated Compound) When an epoxy group is introduced, glycidyl (meth) acrylate,
Mono- and di-glycidyl esters of maleic acid, mono- and di-glycidyl esters of itaconic acid, glycidyl esters of unsaturated carboxylic acids such as mono- and di-glycidyl esters of allylsuccinic acid, glycidyl esters of p-styrene carboxylic acid, Allyl glycidyl ether,
Glycidyl ethers such as 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, p-glycidylstyrene, 3,4-epoxy-1-butene, 3,4-epoxy-
Epoxy olefins such as 3-methyl-1-butene, vinylcyclohexene monoxide and the like can be mentioned.

(Hydroxy group-containing unsaturated compound) When a hydroxyl group is introduced, 2-hydroxyethyl (meth) acrylate,
Hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxyethyl acrylate-6-hexanolide addition polymer, 2-propene Examples thereof include alkenyl alcohols such as 1-ol, alkynyl alcohols such as 2-propyn-1-ol, and hydroxyvinyl ether.

(Isocyanate Group-Containing Unsaturated Compound) When isocyanate is introduced, 2-isocyanateethyl (meth) acrylate, methacryloyl isocyanate and the like can be mentioned.

The reaction between the precursor polyolefin and the unsaturated compound having a functional group is carried out by a conventional method, usually using a radical initiator.

(B) Radical-Polymerizable Monomer (Component (b)) The radical-polymerizable olefin polymer (A) used in the production of the copolymerization product has a functional group of the olefin polymer (component (a)) It is obtained by reacting a radical polymerizable monomer (component b) having a functional group having reactivity with the functional group. Therefore, depending on the functional group of component a, b
The functional groups of the components are selected as follows.

(I) Monomer having a functional group reactive with carboxylic acid or its anhydride group The functional group reactive with carboxylic acid or its anhydride group of the olefin monomer (a) is , A hydroxyl group, an epoxy group and an isocyanate group, and the radical polymerizable monomers having these functional groups include the following.

(Radical polymerizable monomer having hydroxyl group)
As the radical polymerizable monomer having a hydroxyl group, for example,
Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxyethyl acrylate-6 -Hexanolide addition polymers, alkenyl alcohols such as 2-propen-1-ol, alkynyl alcohols such as 2-propyn-1-ol, and hydroxyvinyl ethers.

(Radical Polymerizable Monomer Having Epoxy Group) Examples of the radical polymerizable monomer having an epoxy group include glycidyl (meth) acrylate, mono- and diglycidyl esters of maleic acid, and mono- and di-glycidyl esters of itaconic acid.
And di-glycidyl esters, allyl succinic acid mono-
And glycidyl esters of unsaturated carboxylic acids such as di-glycidyl esters, glycidyl esters of p-styrene carboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-glycidyl ethers such as p-glycidyl ether, p-glycidyl styrene, 3,
Examples thereof include epoxy olefins such as 4-epoxy-1-butene and 3,4-epoxy-3-methyl-1-butene, and vinylcyclohexene monoxide.

(Radical Polymerizable Monomer Having Isocyanate Group) Examples of the radical polymerizable monomer having an isocyanate group include 2-isocyanatoethyl (meth) acrylate and methacryloyl isocyanate.

Of these monomers, the radical polymerizable monomer having a hydroxyl group is most preferable as the radical polymerizable monomer for the component a having a carboxylic acid or its anhydride group.

(Ii) Monomers Having Functional Groups Reactive with Epoxy Groups Functional groups which react with the epoxy groups of the olefin polymer (a) include carboxyl groups and hydroxyl groups, and radical polymerization having these functional groups The following are examples of the reactive monomer.

(Radical polymerizable monomer having a carboxyl group) Examples of the radical polymerizable monomer having a carboxyl group include unsaturated acid carboxyethyl vinyl ether such as (meth) acrylic acid and carboxyalkyl vinyl ether such as carboxypropyl vinyl ether. And the like.

(Radical polymerizable monomer having hydroxyl group)
Examples of the radical polymerizable monomer having a hydroxyl group include those exemplified as the radical polysynthetic monomer (b) having reactivity with the carboxylic acid or the anhydride group of the olefin polymer (a). Can be.

Among these monomers, a radical polymerizable monomer having a carboxyl group is most preferable as the radical polymerizable monomer for the component a having an epoxy group.

(Iii) Monomers Having Functional Groups Reactive with Hydroxyl Groups Functional groups that react with the hydroxyl groups of the olefin polymer (a) include isocyanate groups, carboxyl groups, and epoxy groups. Examples of the monomer having the following are:

(Radical Polymerizable Monomer Having Isocyanate Group, Carboxyl Group or Epoxy Group) The radical polymerizable monomer having an isocyanate group and the radical polymerizable monomer having an epoxy group include the olefin polymer ( Each monomer having an epoxy group or an isocyanate group exemplified as the monomer (b) having a reactivity with the carboxylic acid group or its anhydride group of the a) is also a radical polymerizable having a carboxyl group. Examples of the monomer include monomers having a carboxyl group exemplified as the monomer (b) having reactivity with the epoxy group of the olefin polymer (a).

Among these monomers, the radical polymerizable monomer for the component a having a hydroxyl group is most preferably a radical polymerizable monomer having an isocyanate group.

(Iv) Monomers Having Functional Groups Reactive with Isocyanate Groups The functional groups which react with the isocyanate groups of the olefin polymer (a) include a hydroxyl group and a carboxyl group. Examples of the monomer include the following.

(Radical polymerizable monomer having a hydroxyl group or a carboxyl group) Examples of the radical polymerizable monomer having a hydroxyl group or a carboxyl group include the carboxylic acid of the olefin polymer (a), an anhydride group thereof, and an epoxy group. The radical monomer having a carboxyl group and the radical polymerizable monomer having a hydroxyl group, which are exemplified as the monomer (b) having a functional group having reactivity with OH, can be exemplified.

Among these monomers, the radical polymerizable monomers for the component a having an isocyanate group include:
A radical polymerizable monomer having a hydroxyl group is most preferred.

(C) Reaction In order to obtain the above-mentioned radical polymer olefin polymer (component A), the olefin polymer (a) and the radical polymerizable monomer (b) are reacted with a functional group in the olefin polymer (a). The functional group in the radical polymerizable monomer (b) is 0.1 to 10 per equivalent of the group.
Equivalent, preferably 0.2 to 5 equivalents,
Let both react. When the amount is less than the above equivalent, the content of the polymer of the component (B) increases when the monomer (B), which is copolymerizable with the radically polymerizable olefin polymer (A), is copolymerized. If the amount exceeds the above equivalent range, gelation tends to occur.

The reaction temperature is usually 20 to 150 ° C., preferably
50-120 ° C.

In order to accelerate the reaction, an acid or a basic compound such as sulfuric acid, paratoluenesulfonic acid, zinc chloride, pyridine, triethylamine, dimethylbenzylamine or the like is used as a catalyst in the esterification reaction, and dibutyltin is used in the urethanization reaction. Dilaurate or the like may be used.

In the reaction, in order to prevent the formation of a homopolymer of a vinyl monomer, the reaction is carried out under an atmosphere of oxygen or air, and an appropriate amount of a polymerization inhibitor such as hydroquinone, vitroquinone monomethyl ether or phenothiazine is added to the reaction system. Is preferably added.

The reaction is preferably performed in a suitable organic solvent, and examples of the organic solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, cellosolve acetate and the like.

(B) Copolymerizable Monomer (B) A monomer copolymerizable with the radically polymerizable olefin polymer (A) used for producing the polymerization product of the adhesive layer of the present invention ( B) contains one or both of an alkyl (meth) acrylate and a fluorine-containing unsaturated monomer as essential components.

(Alkyl (meth) acrylate component) Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate,
Examples thereof include butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, and among them, methyl (meth) acrylate is most preferred.

(Fluorine-containing unsaturated monomer component) Examples of the fluorine-containing unsaturated monomer include trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluorobutyl (meth) acrylate, and octafluoro Fluoroalkyl (meth) acrylates such as pentyl (meth) acrylate, heptadecafluorononyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tetrafluoroethylene,
Trifluoroethylene, vinylidene fluoride, vinyl fluoride,
Monochlorotrifluoroethylene, 1-chloro-2,2-difluoroethylene, 1,1-dichloro-2,2-difluoroethylene, vinylidene chlorofluoride, hexafluoropropene, 3,3,3,2-tetrafluoropropene, Trifluoromethylethylene, 2-fluoropropene, 2-chloro-1,
1,3,3,3-pentafluoropropene, 1,1,2-trichloro-
3-trifluoropropene, perfluoro-1-butene,
Including perfluoro-1-pentene, perfluorobutylethylene, perfluoro-1-heptene, perfluoro-1-nonene, 8-H-perfluoro-1-octene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, perfluorododecylethylene, etc. Fluorinated olefins and the like can be mentioned, and among these, fluoroalkyl (meth) acrylate is most preferred.

(Other Copolymerizable Monomer) In the present invention, the monomer (B) copolymerizable with the radically polymerizable olefin polymer (A) may contain other monomers in addition to the above-mentioned essential monomer components. A copolymerizable monomer is added as an optional component. Examples of such a monomer include α-, β-unsaturated carboxylic acids such as (meth) acrylic acid and monoalkyl maleate, 2-hydroxyethyl (meth) acrylate,
Polymerizable monomers having an oxirane group such as hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate, and glycidyl (meth) acrylate, and non-polymerizable monomers such as (meth) acrylamide (Meth) of polyhydric alcohols such as saturated amide, (meth) acrylonitrile, epoxy acrylate, alkylene oxide adduct (meth) acrylate, ethylene glycol-di (meth) acrylate, and propylene glycol (meth) acrylate
Acrylates, urethane-modified polyvalent acrylates having a (meth) acryloyl group in one molecule, vinyl ethers such as vinyl acetate, vinyl chloride, ethyl vinyl ether, butyl vinyl ether and hexyl vinyl ether;
Examples thereof include aromatic compounds having a vinyl group such as vinyl toluene, styrene and α-methylstyrene, and olefins such as ethylene, propylene, butene and isoprene.

(Quantity ratio) The mixing ratio of the above-mentioned essential components (meth) acrylate and / or fluorine-containing unsaturated monomer is as follows:
30% by weight or more based on the whole copolymerizable monomer (B),
Preferably, 50% by weight or more is required. If it is less than the above range, the adhesion to the fluorine resin is insufficient.

(C) Production of Copolymerization Product The copolymerization product is obtained by copolymerizing the radically polymerizable olefin polymer component (A) and the monomer component (B).

(Copolymerization conditions) The copolymerization reaction between the above components (A) and (B) is carried out by toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate,
Organic solvents such as cellosolve acetate, ethanol, butanol, and propanol are used as reaction solvents.

As the copolymerization catalyst, benzoyl peroxide,
Peroxides such as di-tert.butyl peroxide and cumene hydroperoxide, and azobis compounds such as azobisisobutyronitrile are contained in the component (B) in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight. Used in amounts. The copolymerization reaction
The reaction can be carried out by heating and reacting at a temperature of 50 to 200 ° C, preferably 70 to 120 ° C for 1 to 20 hours.

The amount of the reaction solvent is adjusted so that the total amount of each of the copolymer components (A) and (B) is 5 to 50% by weight in the reaction mixture, and the reaction is carried out in an atmosphere of an inert gas such as nitrogen gas or the like. It is preferable to carry out under air current. To reduce unreacted residual monomers, an azobis compound and a peroxide may be used in combination as a polymerization initiator.

(Copolymerization Product) After completion of the copolymerization reaction, the copolymerization product obtained by separation and washing contains 10 to 90% by weight, preferably 30 to 70% by weight of the monomer component (B). % Of a radically polymerizable olefin polymer component (A)
It contains 10% by weight, preferably 70 to 30% by weight.

(Adhesive Resin) As the adhesive resin used in the adhesive resin layer in the present invention, in addition to the copolymerization product obtained above, this is further diluted with an olefin polymer, an acrylic polymer or a fluorine-based resin. Can be used. However, the above range of the content of the monomer component (B) also applies to the adhesive resin when the copolymerization product is further diluted with the above resin, and the monomer component (B) If the content is out of this range, the adhesiveness becomes poor.

(4) Vinylidene Fluoride Resin Layer The vinylidene fluoride resin layer constituting one layer of the fluorine-based resin laminate of the present invention is composed of vinylidene fluoride as a main component in addition to a homopolymer of vinylidene fluoride. And a copolymer resin of other fluorine vinyl monomers such as vinyl fluoride, ethylene tetrafluoride, and propylene hexafluoride.

The vinylidene fluoride resin may contain an inorganic filler, a coloring agent, various stabilizers and the like in a quantitative range that does not significantly impair the effects of the present invention. In particular, the addition of a small amount of pigment is preferable because the effect of design can be improved in the case of a laminated molded article in which a vinylidene fluoride resin is formed on the surface layer. Further, an acrylic ester resin such as polymethyl methacrylate having extremely good compatibility with the vinylidene fluoride resin may be blended.

(5) Other Constituent Layers The fluorine-based resin laminate of the present invention is basically composed of the essential layers composed of the above-mentioned constitutional layers. It can be done. For example,
A polyolefin resin layer may be provided between the carboxyl group-containing modified polyolefin resin (2) and the copolymerization product layer (3). Such an intermediate resin layer has an effect of increasing the film thickness of the laminate and preventing the rust of the metal base material from progressing due to penetration of moisture from the damaged portion when the surface layer is damaged.

Examples of such polyolefin resins include homopolymers or copolymers of α-olefins such as ethylene, propylene and butene-1, and vinyl esters (such as vinyl acetate) containing these α-olefins as main components. , Unsaturated carboxylic acids (such as acrylic acid and maleic anhydride) or esters thereof (such as acrylic esters and methacrylic esters), aromatic vinyl monomers (such as styrene), vinyl silanes, and γ-methacryloyloxypropyl methoxy silanes Block, random or graft copolymers with other unsaturated monomers.

(6) Order of Layer Construction The fluorine-based resin-coated metal laminate of the present invention basically has a vinylidene fluoride resin layer formed as the outermost layer, and the above-mentioned metal laminate is formed adjacent to the vinylidene fluoride resin layer. A modified polyolefin-based resin layer containing a carboxy group is formed adjacent to an adhesive resin layer made of a polymerization product, and a metal substrate is formed adjacent to the modified polyolefin resin layer.

If the order of forming these layers is different, the adhesiveness between these layers will be remarkably reduced, and the antifouling property and the weather resistance will be inferior.

The thickness of each layer is not particularly limited. Generally, except for the metal base material, the carboxyl group-containing modified polyolefin resin layer and the polyolefin resin layer each have a thickness of 0.05 to 5 mm, preferably 0.5 to 3 mm. Adhesive resin layer 1
The thickness of the vinylidene fluoride resin layer is about 0.01 to 2 mm, preferably about 0.05 to 2 mm, and preferably about 0.05 to 1 mm.

[II] Production of Laminated Body The fluororesin-coated metal laminated body of the present invention basically comprising four or five layers can be produced by applying a usual laminating method. A method of laminating a film or sheet of the raw material components to be applied, and laminating them by hot pressing in a state where they are stacked, applying a solution or emulsion of an adhesive resin to a film of vinylidene fluoride resin, drying the film, and then drying the film. And a method in which the raw material components of each constituent layer are melt-laminated on a metal substrate by co-extrusion molding, and a method in which the film and the co-extrusion molding are used in combination.

[0063]

【Example】

Example 1 (Production of adhesive resin) A glass flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with a hydrogenated styrene / butadiene / styrene block copolymer (Clayton G-1652, manufactured by Shell Chemical Company). 100g and xylene 1,000g
And the system was purged with nitrogen and heated to 125 ° C.

Next, a solution prepared by dissolving 4.0 g of maleic anhydride and 0.6 g of dicumyl peroxide in 80 g of xylene was dropped into the above system over 6 hours. The reaction was continued at the same temperature for 1 hour.

After the completion of the reaction, the inside of the reaction system was cooled to around room temperature, poured into 3,000 g of acetone, and the maleated hydrogenated styrene / butadiene / styrene block copolymer was reprecipitated, separated by filtration, and dried. As a result, an olefin copolymer (a) was obtained. The content of maleic anhydride in the produced olefin copolymer was determined by infrared absorption spectrometry and neutralization titration, and was 1.5% by weight.

Next, 20 g of the olefin copolymer (a) obtained above and 150 g of toluene were placed in a glass flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
Was dissolved in the mixture by heating to 70 ° C. in an air stream.

To this, 2-hydroxyethyl acrylate
A solution of a radical polymerizable monomer (b) obtained by dissolving 0.36 g, 1 g of dimethylbenzylamine and 0.06 g of hydroquinone monomethyl ether in 30 g of toluene was added, and the solution was added at the same temperature.
The reaction was carried out for a time to obtain a radically polymerizable olefin polymer (A).

Subsequently, under a nitrogen stream, the monomer (B) is
A solution of a monomer (B) containing methyl methacrylate obtained by dissolving 20 g of methyl methacrylate and 0.12 g of azobisisobutyronitrile in 80 g of toluene was added, and reacted for 2 hours. Then, 0.12 g of azobisisobutyronitrile was added. Then 2
The operation of reacting for hours was repeated four times, and finally, the reaction was further conducted for 2 hours, and then cooled to obtain an adhesive resin.

(Production of Laminated Body) Next, a vinylidene fluoride resin (PVDF: KYNAR-720, manufactured by Atochem North America) was used.
The adhesive resin obtained above was applied to one side of a 100 μm thick film to a thickness of 5 μm.

A carboxyl group-containing modified polypropylene (Modic P311F) 100 μm film is superimposed on the adhesive resin-coated surface of the film, and a metal base is further contacted with the carboxyl group-containing modified polypropylene film. As a material, a 1.0 mm-thick aluminum plate (A1050P, manufactured by Taiyo Kiki Co., Ltd.) was stacked, and heated and pressed by a hot press molding machine to obtain a laminate. Heat press conditions are 200
° C, 15 kg / cm ² , time 3 minutes.

(Evaluation of Adhesive Strength) Next, the adhesive strength between the carboxyl group-containing modified polypropylene film layer having a width of 20 mm and the aluminum plate was measured at a tensile speed of 50 mm / min using an Instron type tensile tester. However, 5.0kg / 20
Material destruction occurred at mm width or more.

Separately, an adhesive resin was applied to one side of a 0.5 mm thick sheet of vinylidene fluoride resin (PVDF: KYNAR-720, manufactured by Atochem North Co., Ltd.) so as to have a thickness of 5 μm, and the adhesive resin coated surface of this sheet was applied. So that it can be contacted with a carboxyl group-modified polypropylene (Mitsubishi Yuka, Modick P
311F) 0.5mm thick sheets are stacked and 5kg /
and 3 minutes thermocompression bonding in cm ^2, 200 ° C. to form a laminated body, likewise using an Instron type tensile tester, the adhesive strength between the vinylidene fluoride resin layer and a carboxyl group-containing modified polypropylene layer at 20mm width When measured at a tensile speed of 50 mm / min, the width was 6 kg / 20 mm, and it was confirmed that practically sufficient adhesive strength was obtained between the vinylidene fluoride resin layer and the carboxyl group-modified polypropylene layer by using an adhesive resin. Was done.

Examples 2 to 7 In the same manner as in Example 1, except that the methyl methacrylate used as the monomer (B) for producing the adhesive resin was changed to the monomers shown in Table 1. This was carried out to produce an adhesive resin, and a laminate was obtained in the same manner as in Example 1. The adhesive strength was evaluated in the same manner as in Example 1. Table 1 shows the obtained results.

[0074]

[Table 1]

Example 10 (Polymethyl methacrylate graft-modified polypropylene) In a glass flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 100 g of polypropylene (MA-2P, manufactured by Mitsubishi Yuka Co., Ltd.) and 1,000 g of chlorobenzene were added. And the system was purged with nitrogen and heated to 130 ° C.
A solution of 20 g and 1 g of dicumyl peroxide in 80 g of chlorobenzene was added dropwise over 6 hours. After an aging reaction at the same temperature for 1 hour, the mixture was poured into 3,000 g of acetone to precipitate maleated polypropylene, followed by filtration and drying to obtain a white powdery modified resin. As a result of infrared absorption spectrum measurement and neutralization titration of this modified resin, the content of maleic anhydride was 8.0% by weight.

In a glass flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 20 g of the maleated polypropylene obtained above, 180 g of xylene, 1.92 g of 2-hydroxyethyl acrylate and 1 g of dimethylbenzylamine were added.
And 0.06 g of hydroquinone monomethyl ether, and reacted at 120 ° C. for 5 hours in an air stream.

Subsequently, methyl methacrylate was added under a nitrogen stream.
20 g, azobisisobutyronitrile 0.12 g and xylene
After adding 80 g and reacting for 2 hours, 0.12 g of azobisisobutyronitrile was added 4 times every 2 hours, and finally 2
A time-aging reaction was performed.

This reaction solution was added to a mixed solvent consisting of 900 g of methanol and 180 g of water to precipitate polymethyl methacrylate graph-modified polypropylene, which was then filtered and dried to obtain a white powdery modified resin.

Using the resulting modified resin as an intermediate layer, vinylidene fluoride resin (KYNAR-72, manufactured by Atochem North America)
0), a modified carboxyl group-containing polypropylene (Madeik P311F, manufactured by Mitsubishi Yuka Co., Ltd.) was extruded by a three-layer co-extrusion molding method, and the carboxyl group-containing modified polypropylene layer was 1.
Extrusion lamination was performed so as to be in contact with a 0 mm thick aluminum plate. The thickness structure of the obtained laminate is such that the vinylidene fluoride resin layer is 50 μm.
Thickness, the modified resin layer was 50 μm thick, and the carboxyl group-containing modified polypropylene layer was 100 μm.

(Evaluation of Adhesive Strength) The adhesive strength between the carboxyl group-containing modified polypropylene film layer and the aluminum plate in a width of 20 mm was measured at a tensile speed of 50 mm / min using an Instron type tensile tester. kg / 20mm
It was width.

Example 11 Vinylidene fluoride resin (KYC manufactured by Atochem North America, KY
The adhesive resin obtained in Example 1 was applied on one side of a 100 μm thick film of NAR-720) so as to have a thickness of 5 μm.

A 100 μm-thick polypropylene film (FY6C, manufactured by Mitsubishi Yuka Co., Ltd.) is laminated so as to be in contact with the adhesive resin coated surface of this film, and a carboxyl group-containing modified polypropylene (Mitsubishi Yuka Modic) is further brought into contact with the polypropylene film. : P311F) Laminate 100μm of film and add 1.0mm thick aluminum plate (Tayo Aki: A105
0P) were stacked and heated and pressed by a hot press molding machine to obtain a laminate. The conditions of the hot press were 200 ° C., 15 kg / cm ² , and the time was 3 minutes.

(Evaluation of Adhesive Strength) The adhesive strength between the carboxyl group-containing modified polypropylene film layer and the aluminum plate with a width of 20 mm was measured at a tensile speed of 50 mm / min using an Instron type tensile tester. kg / 20mm
Material was destroyed at the width or more.

Comparative Example 1 A 100 μm thick film of a carboxyl group-containing modified polypropylene (Modic P311F) was superposed on one side of a 100 μm thick film of a vinylidene fluoride resin (KYNAR-720), and further the carboxyl group-containing modified polypropylene film was An aluminum plate having a thickness of 1.0 mm was stacked as a metal substrate so as to be in contact with the aluminum plate, and was heat-pressed with a hot press molding machine to obtain a laminate. The conditions of the heat press were 200 ° C., 15 kg / cm ² , and 3 minutes.

(Evaluation of Adhesive Property) Using an Instron-type tensile tester, the adhesive strength between the carboxyl group-containing modified polypropylene film layer and the aluminum plate in a width of 20 mm was measured at a tensile speed.
When measured at 50 mm / min, the adhesive strength was 5.0 kg / 20 mm width or more and the material was broken, but using the same tensile tester,
When the adhesive strength between the vinylidene fluoride film layer and the carboxyl group-containing modified polypropylene film layer with a width of 20 mm was measured at a tensile speed of 50 mm / min, interfacial peeling occurred at a width of 0.1 kg / 20 mm.

Comparative Example 2 An acrylic / epoxy adhesive (Sony Chemical Co., Sony Bond SC-462) was applied to one side of a 100 μm thick film of vinylidene fluoride resin (KYNAR-720) to a thickness of 5 μm. . The carboxyl-containing modified polypropylene (Modick P311F)
A film having a thickness of 100 μm was stacked, and an aluminum plate having a thickness of 1.0 mm was further stacked as a metal substrate so as to be in contact with the modified polypropylene film containing a carboxyl group, followed by thermocompression bonding using a hot press molding machine to obtain a laminate. Heat press conditions are 200
° C, 15 kg / cm ² , 3 minutes.

(Evaluation of Adhesive Property) Using an Instron-type tensile tester, the adhesive strength between the carboxyl group-containing modified polypropylene film layer and the aluminum plate with a width of 20 mm was measured at a tensile speed.
When measured at 50 mm / min, the adhesive strength was 5.0 kg / 20 mm width or more and the material was broken, but using the same tensile tester,
When the adhesive strength between the vinylidene fluoride film layer and the carboxyl group-containing modified polypropylene film layer at a width of 20 mm was measured at a tensile speed of 50 mm / min, the adhesive strength was 0.2 kg / min.
It was 20 mm wide.

[0088]

Industrial Applicability The fluorine-coated metal laminate of the present invention is a multi-layer laminate having improved antifouling properties and weather resistance and having high adhesive strength and suitable for practical use. Can be used.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kazuyuki Hata 1 Tohocho, Yokkaichi City, Mie Prefecture Mitsubishi Yuka Co., Ltd. Yokkaichi Research Institute (56) References JP 3-65794 (JP, B2) (58) ) Surveyed field (Int.Cl. ⁷ , DB name) B32B 15/08

Claims (2)

(57) [Claims] 1. A fluorine-based material comprising a metal substrate layer, a carboxyl group-containing modified polyolefin-based resin layer, an adhesive resin layer made of a copolymerized product described below, and a vinylidene fluoride resin layer laminated in this order. Resin-coated metal laminate. Copolymerization product: (A) an olefin polymer (a) having at least one functional group in one molecule, and a radical polymerizable monomer having a functional group reactive with the functional group of the olefin polymer (B) an alkyl acrylate, alkyl methacrylate and / or fluorine-containing copolymerizable with 90 to 10% by weight of a radically polymerizable olefin polymer obtained by reacting the polymer (b) with the radically polymerizable olefin polymer. A copolymerized product obtained by copolymerizing 10 to 90% by weight of a monomer containing an unsaturated monomer as an essential component. 2. The fluorine-based resin-coated metal according to claim 1, wherein a polyolefin-based resin layer is provided between the carboxyl group-containing modified polyolefin-based resin layer and an adhesive resin layer made of a copolymerized product. Laminate.