KR830001728B1 - Peelable Adhesive Structure - Google Patents

Abstract

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Description

Peelable Adhesive Structure

1 is an enlarged cross-sectional view of a painted metal plate used to form an adhesive structure.

2 is a side cross-sectional view of the adhesive structure in the form of a packing crown.

3 is a side cross-sectional view of the adhesive structure in the form of a packing cap.

TECHNICAL FIELD The present invention relates to an adhesive structure that can be peeled off, and more specifically, a plurality of components, at least one of which is a metal, is joined with a coating layer having a multilayer structure interposed therebetween. An adhesive structure is coupled so that a plurality of parts can be peeled off at an interface of a newly assembled coating film.

Conventionally, adhesive adhesive structures are often necessary in packaging fields such as containers, container lids, sealing materials, etc., so that many kinds of parts can be peeled off from each other.

For example, as a sealing material for crowns and other container lids, those obtained by applying a surface protective coating on a metal sheet to a shape such as a crown cap seal are widely used. have. And in the sale of developing parts, such as bottled beverages, when a number of kinds of parts of a bottled product are adhered to each other so that the adhesive structure, etc., which are in close contact with each other, mails a small number of pieces or a packing that is obviously won, In general, a system for sending goods in exchange is adopted.

Such manufacturing of crowns or caps for the sale of developing parts requires the packing to be easily peeled off from the crown chamber or cap, but at the same time, the manufacturing process of the crowns or caps is carried out during the transport, or the wiring of bottled products. In the process of hitting a stopper, the packing should be adhered to the crown or cap thread so as not to be released, and the crown or cap has sufficient corrosion resistance to a corrosive content beverage and a crimping. It is necessary to withstand processing such as rollon.

Also, from the hygienic point of view, printing on the packing surface to which the beverage is directly contacted is impossible, and at the same time, the packing itself is generally flowable and placed in the crown or inside the cap. In view of the above, it is preferable that the inky layer provided on the inner surface of the crown chamber or the cap is transferred to the attached state of the packing when the packing is peeled off.

An adhesive structure in which such peelability is required is required in the case of a can product having an opening mechanism such as a so-called easy open mechanism. For example, as such an easy-open end, one or more openings necessary for drinking the contents are provided in a can end member made of a metal material provided with a surface protective coating film. It is known to adhere | attach the peeling piece which became an organic resin coating metal foil or sheet | seat to cover. Also in the easy-open end, when the content beverage is stored, excellent adhesion and sealing property are required between the can end member and the peeling piece, and during opening, the peeling piece is easily removed from the can end member without breaking. It must be possible.

Conventionally, a plurality of coating layers are provided on the metal sheet constituting the container lid shell, and the packing of the synthetic resin is adhered on the coating layers so that the shell and the packing can be separated between the coating layers. It is already known, and it is already proposed by the inventors that a hydrocarbon resin, such as a petroleum resin, be contained in at least one coating layer for peelability to this coating layer. However, the hydrocarbon resin is one of various resins which is relatively inactive and less reactive. The paint layer containing the hydrocarbon resin is generally poor in wettability and overlaps the paint layer with other paint layers. There is a drawback that it is difficult to do.

In addition, the hydrocarbon resin shows little adhesiveness to the coating layer made of another resin, and the hydrocarbon resin is also insufficient in the dispersibility to the coating film forming base resin. This separation is not detached, but it is difficult to always provide reproducible so-called peelable adhesion so that peeling between coating films occurs without causing packing or coating agglomeration breakage.

In general, paints which tend to form easy-to-peel interfaces, in particular those containing soft resinous hydrocarbon resins, are used in the processing of painted metal materials, for example in presses or drawing or crowning into crowns or caps. During transportation of the yarn or cap, or by wires or rolls by a crimper, the coating film is broken into small pieces during operation, which is very likely to generate so-called dust, which is fatal in terms of hygiene and commodity value. It becomes a defect.

In this way, as far as the present inventors know, a coating material excellent in the wettability between the coating films and the peelable adhesive strength and the duct resistance is not known yet.

MEANS TO SOLVE THE PROBLEM The present inventors make the peelable interface of this adhesive structure at least one made from metal as a modified hydrocarbon resin or modified hydrocarbon resin composition which has a certain range of acid value, when adhering many parts which are metals. When forming between 1st layer and the 2nd layer containing epoxy occasions, it discovered that the said fault point was effectively eliminated.

That is, an object of the present invention is to provide an adhesive structure in which a plurality of parts made of at least one metal are bonded to each other with a paint layer interposed between the coating layers, which has excellent wettability, peelable adhesive strength and dust resistance.

Another object of the present invention is to provide an adhesive structure having peelability between coating layers in which wettability, peeling adhesion and dust resistance between paints are improved by acid modification of hydrocarbon resin.

Another object of the present invention is to provide a peelable packing part container lid which is excellent in peelability and dust resistance of the packing.

According to the present invention, in a bonded structure in which a plurality of components in which at least one part is bonded are interposed between coating layers, the peelable interface of the coating layer has a modified hydrocarbon having an acid value of 0.1 to 20. A peelable adhesive structure is provided which is formed between a first layer made of a resin or a modified hydrocarbon resin composition and a second layer containing an epoxy resin.

It demonstrates in detail based on the specific example shown by an accompanying drawing of this invention.

In Fig. 1 showing the cross-sectional structure of a coated metal plate to form a container lid shell, the outer surface of the metal base 1 such as tin plated steel sheet and tin presteel (electrolytic chromic acid treated steel plate) is known per se. Protective paint layer (2). (2) is given. The modified hydrocarbon resin or modified hydrocarbon resin composition has a shape and dimension such that the liner of the coated metal plate is to be provided inside the outer periphery of the top plate of the container lid body or inside the outer periphery of the liner to be provided. The first layer 3 as is partially given. On this 1st (3), the 2nd layer 4 containing an epoxy resin is given over the whole surface, and on this epoxy resin layer 4 in the position corresponding to the said partial coating layer 3, A printing ink layer 5 displaying marks such as shapes is provided, and an adhesive coating layer 6 is provided thereon.

In FIG. 2 showing a crown-shaped adhesive structure, the above-described painted metal plate is roll punched with a skirt plate 8 having a circular plate plate 7 and a corrugated gate.

In the present invention, it is preferable to position the inner portion of the partial coating layer 7 made of the modified hydrocarbon resin or the modified hydrocarbon resin composition inward in order to completely prevent dust generation. In the top plate portion 7 of the crown shell body, the packing 9 made of synthetic resin may have a thick portion 10 suitable for sealing to a container (bottle) bend (not shown).

An important feature of the present invention is a paint layer for forming a peelable adhesive interface between the paint layer 4 containing the epoxy resin and having an acid value of 0.1-20, in particular in the range of 1.0-10.0. When the carbohydrate or acid-modified hydrocarbon resin composition is used, the wetting characteristics of the coating layer are remarkably improved, and excellent paint workability can be obtained without special consideration, and the adhesive strength between the coating layers is at the level of so-called easy adhesion for peeling. It is based on the knowledge that it is possible to adjust and to completely prevent the generation of dust at the time of shaping | molding of a coating metal plate to the container lid shell body, conveyance of this shell body, and sealing and opening of a container lid.

In the present specification, the easy-adhesive interface for peeling means that the two resin layers are not peeled off during normal handling, and when peeled off, they are bonded to the extent that they can be easily peeled off with a finger without using a special mechanism. In general, such an interface is expressed in terms of peel strength, and is in the range of 20-2000 g / cm, especially 50-1500 g / cm.

In the present invention, the critical feature of using an acid-modified hydrocarbon or a resin composition will be apparent by referring to Examples described later.

That is, referring to the first table described later, the coating layer made of the unmodified hydrocarbon resin is poor in wettability, and it is difficult to apply the paint containing the epoxy resin as it is because the paint is splashed. In order to make it possible, wetting agent, such as saturated polyester resin, must be added to epoxy resin paint. However, even with such improvement of the wettability, extremely weak bonds such as 0.01 kg / cm or less are still formed between the paint layers. In addition, as shown in the fourth and fifth tables to be described later, such composite paints have a large amount of dust generated in the coated metal sheet. In contrast, according to the present invention, an acid-modified hydrocarbon resin or resin composition is used. In addition, the wettability of the epoxy resin-containing paint is not only remarkably improved, but the adhesion strength of the coating layer is also in the range of 50-2000 g / cm, and the amount of dust generated during the processing of the coated metal sheet is also remarkable. It can be reduced easily.

In the acid-modified hydrocarbon resin or hydrocarbon resin composition used in the present invention, it is also extremely important to have an acid value in the range of 0.1-20, especially 1.0-10. That is, as shown in the second table described later, when a modified hydrocarbon resin having an acid value less than the above range is used, the improvement of the wettability and the adhesive strength is unsatisfactory, while when the acid value is larger than the above range, the adhesive strength is too high. The object of the present invention, which forms a heteroadhesive interface for peeling, becomes difficult to achieve. In the present invention, as the acid-modified hydrocarbon resin, a partially ester-modified hydrocarbon resin obtained by partially reacting an acid-modified hydrocarbon resin or an acid-modified hydrocarbon resin obtained by reacting a hydrocarbon paper with an unsaturated carboxylic acid or its anhydride can be suitably used. have. As the hydrocarbon resin as a raw material, a petroleum resin, a macron indene resin, a terpene resin, etc. are suitably used, and in particular, a hydrocarbon resin or a natural resin having a softening point (circulation method) of 180 ° C or lower, particularly 120 ° C or lower, is suitably used. Used.

As the stone resin, it is known that petroleum unsaturated hydrocarbons such as cyclopentadiene or higher olefin crab hydrocarbons (generally C ₅ to C ₁₁ ) are obtained by heating and polymerizing them in the presence of a catalyst. It is particularly suitable as. The coumarone indene resin is known to have a relatively low degree of polymerization obtained by polymerizing a tar oil (usually 160-180 ° C) mainly composed of coumarone, indene, etc. in the presence of heat or a catalyst. Can be used. As the terpene resin, a resin obtained by polymerizing a terpene hydrocarbon or a natural polymer, in particular terepine oil or nobinene oil, in the presence of a catalyst is used.

As ethylenic unsaturated carboxylic acid or its anhydride reacted with these hydrocarbon resins, acrylic acid, methacrylic acid, maleic acid, maleic acid monomethyl ester, fmaric acid, monoethyl acetate, crotonic acid, citracon, 5-sannor Acid monomers, such as bornen-2 and 3-dicarboxylic acid, and acidic products, such as maleic anhydride, a citraconic acid anhydride, suitaconic acid, 5-norbornene-2, 3-dicarboxylic acid anhydride, and a tetrahydro phthalic anhydride The monomers are used alone or in two or more kinds of combinations. As the acid monomer, it is also possible to use unsaturated fatty acids such as oleic acid, linoleic acid, linoleic acid or dry oil such as cottonseed oil, linseed oil, safflower oil, soybean oil, skim castor oil, and tol oil. . These acid to acid anhydride monomers may include other monomers such as ethyl acrylate, methyl methacrylate, 2-ethylnuclear acrylate, mono or diethyl maleate, vinyl acetate, vinyl propionate, acrylamide, methacrylamide, maleide, Acrolein, methacrolein, vinyl methylcatone, acrylonitrile, methacrylonitrile, γ-hydroxy methacrylate propyl, β-hydroxy ethyl acrylate, vinyl methyl ether, vinyl ethyl ether, acryl ethyl ether, glycidyl It can also be used in the combination with an acrylate, glycidyl methacrylate, glycidyl vinyl ether.

What is necessary is just to provide the acid value of the said range finally in hydrocarbon resin in the quantity of the acid or acid anhydride monomer to be used.

These monomers and the hydrocarbon resin can be reacted as a melt system, a solution system, or a solid-liquid heterogeneous system.

Both addition reactions or graft reactions can be initiated by heating, and for example, it can be seen that the reaction proceeds sufficiently even without a catalyst in the reaction of the melting agent. Of course, a radical initiator or other radical initiation means can also be used. Examples of the initiator include organic peroxides such as dichmilperperoxide, t-butylhydroperoxide, dibenzoylperoxide and dilauroyl peroxide, and azonitriles such as azobis isobitrionitrile and azobis isopropionitrile. This is used in the amount of catalyst known per se. As the radical initiation means, ionizing radiation ultraviolet rays such as X-rays, γ-rays, and electron beams, or mechanical radical initiation means such as interweaving kneading of ultraviolet rays with a sensitizer or ultrasonic irradiation.

For example, in the reaction of a homogeneous solution system, petroleum resins, monomers, and initiators are dissolved in an aromatic solvent such as toluene, xylene, and tetratrine to be grafted, and the resulting modified hydrocarbons are recovered as precipitates. In the heterogeneous reaction, the powder of the hydrocarbon resin and the diluent of the monomer or the monomer are brought into contact with the ionizing radiation under irradiation to perform grafting. In addition, in the reaction of a homogeneous melting system, the mixture of the initiators is melt-kneaded in a stirring vessel, an extruder, a kneader, or the like, if desired, to form a modified hydrocarbon. In any of these cases, the resultant modified hydrocarbon paper may be attached to washing, extraction, or the like in order to remove unpolymerized monomers, homopolymers, or initiator residues.

The acid-modified hydrocarbon resin thus obtained is partially reacted with alcohols to be a partial ester-modified hydrocarbon resin having an acid value in the above-described range, and can be used in this form for the purpose of the present invention. In this case, as the alcohols, monohydric alcohols such as methanol, ethanol and propanol, and polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin can be used. The conditions for esterification are known per se and may be esterified by such a known means.

Another example of the acid-modified hydrocarbon resin is one in which the hydrocarbon resin is oxidized to oxygenated gas such as oxygen or air. Oxidation of the hydrocarbon resin can be easily performed by blowing the above-mentioned gas into the solution or the solution of the resin.

In the present invention, the acid-modified or partially-modified hydrocarbon resin obtained by the above-described method can be mixed with the unmodified hydrocarbon resin, if desired, as long as the acid value of the final mixture is within the range specified in the present invention. In the form according to the present invention, the acid-modified resin is mixed with the unmodified hydrocarbon resin so that the acid value of the final mixture is in the above-described range, and used for forming the first coating film.

As the acid-modified olefin resin, a resin modified by adding a graft reaction of an acid or an acid anhydride monomer described above to an olefin resin such as high density polyethylene and isotactic polypropylene is used. As a raw material olefin resin, although the above-mentioned thing is suitable, medium to low density polyethylene and crystalline ethylene propylene copolymer can also be used as needed. Since the conditions of the addition to graft reaction are the same as in the case of the modified hydrocarbon resin, they are not particularly described here. Instead of using a modified olefin resin as an acid or an acid anhydride, an acid group-containing polyethylene obtained by oxidizing polyethylene oxide, that is, polyethylene with a molecular oxygen or the like in a molten state or a solution state can be used.

These acid-modified olefin resins or polyethylene oxides (B) are preferably mixed with the hydrocarbon resin (A) in a weight ratio of A: B = 99.5: 0.5 to 40:60, particularly 98: 2 to 50:50. .

In the present invention, the modified hydrocarbon resin or modified hydrocarbon resin composition described above can be used as the first coating layer alone, but if desired, the film-forming base which is not more than 20% by weight per total is known per se. It can be used as a 1st coating layer by combining with resin, for example, a phenol resin, an amino resin, an epoxy resin, an alkyd resin, rosin, an oleoresin, a polyamide resin, a polyester resin, a vinyl resin.

The coating material of the modified hydrocarbon resin or modified hydrocarbon resin composition used in the present invention has many advantages in the production of a container lid in addition to the above characteristics.

That is, the composite resin layer which generally forms a peelable adhesive interface has already had a considerable amount of dust generation in processing, handling, etc. to a container lid, as mentioned above.

In view of this, in the case of the peelable packing part container lid, the part providing the above-mentioned composite resin layers 3 and 4 should be in the outer circumference of the top plate part or inward of the outer circumference of the liner being formed, that is, the container lid. In the shaping of the shell, it is hardly processed or is subjected to the processing. It is hardly limited to the lowest plated part, and there is no dust at the time of press forming or draw processing, and the lid of the container Also in the transportation of the sieve, the portion where the composite coating films 3 and 4 are positioned is protected by the skirt portion 8 of the shell, and the liner at the time of sealing the container mouth of the container lid. It is greatly preferred to be completely protected by (9), and as a result to completely prevent the occurrence of dust. The modified hydrocarbon resin used in the present invention has an appropriate adhesiveness suitable for printing by flat plates, iron plates, intaglios, screens, etc., and thus has the advantage that partial coating by printing is easily performed. The modified hydrocarbon resin can be given in the form of liquid ink or paint, or in hot melt ink or paint.

On the other hand, the epoxy resin constituting the second layer 4 may be a polymer compound containing two or more epoxy groups in a molecule, an initial reaction product thereof, or a low molecular weight polymer compound reactive with these epoxy groups (curing agent) Component), etc. are used.

Generally, epoxy resins obtained by condensation of epichlorohydrin excess with phenol are suitable.

Such epoxy resin is the following formula

Is a zero or positive integer, in particular 12 or less, and the silver polyhydric phenol is a hydrocarbon residue.

It has a molecular structure represented by. As bivalent phenol (HO-R_OH), 2. 2-bis (4-hydroxyphenyl) propane [bisphenol A] and 2, 2-bis (4-hydroxyphenyl) butane [bisphenol B]. 1, 1-bis (4-hydroxyphenyl) ethane.

Although polycyclic phenols, such as bis (4-hydroxyphenyl) methane [bisphenol F], especially bisphenol A, are suitable, the initial condensation product of a phenol and formaldehyde can also be used as a polyhydric phenol.

For the purpose of the present invention, it is preferable to use an epoxy resin in the range of 140 to 4000, particularly in the range of 200 to 2500, as the resin component.

As the curing agent to be used in combination with these epoxy resin components, polyfunctional compounds such as polybasic acids, acid anhydrides, polyamines, polyamides, and the like are used for epoxy groups. Suitable examples thereof include ethylenediamine, diethylenetriamine, triethylene tetramine, metaphenylenediamine, 4, 4-diaminodiphenylmethane, 4, -4'-diaminodiphenylsulfone, and 4'-dia. Mino diphenyl ether, dimer acid polyamide, adipic acid hydrazide, oxalic acid, phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, cyclopentadiene ethylmaleic anhydride, dodecyl zucchin anhydride, dichloromaleic acid Anhydride, chloredic acid anhydride and the like.

These curing agents are preferably used in an amount of 2 to 150 parts by weight (hereinafter% and parts are based on weight unless otherwise specified) per 100 parts by weight of the epoxy resin component, particularly in an amount of 20 to parts by weight.

In a suitable aspect of the present invention, the above-mentioned epoxy resin component and at least one thermosetting resin selected from the group consisting of resol type phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins are combined to form a coating film. Used as layer (4). The ratio of the two can be varied within a wide range, but it is generally preferable to use them in a weight ratio of 5:95 to 95: 5, especially 40:60 to 90:10. This epoxy resin component and the said thermosetting resin can be used for formation of the coating film layer 4 in the state which mixed, or can be used for formation of the coating film 4 in the state which precondensed.

As the protective coating layer 2, from the viewpoint of workability and corrosion resistance, vinyl resins, in particular (a) vinyl chloride, (b) vinyl acetate, vinyl alcohol, vinyl acetal, acrylic acid, methacrylic acid, maleic acid, fmaric acid, ita Copolymers with at least one of other ethylenically unsaturated monomers such as cholic acid, alkyl acrylates, alkyl methacrylates and vinylidene chloride are suitably used. The composition of vinyl chloride (a) with other ethylenically unsaturated monomers (b) can vary in various ways, but generally at a mole ratio of a / b = 95/5 to 60/40, especially 90/10 to 70/30. It is preferable to exist, and the molecular weight of this vinyl resin should just be in the molecular weight range which can form a film generally.

Examples of suitable vinyl-based resins include vinyl chloride / vinyl acetate copolymer, vinyl chloride / vinyl acetate copolymer partial saponification, vinyl chloride / vinyl acetate copolymer partial saponification part acetalide, vinyl chloride / vinylidene chloride / acrylic acid copolymer And so on.

Other epoxy resins, amino resins, acrylic resins, vinyl butyral resins, etc. are also used alone or in combination with the above-mentioned vinyl resins.

As the packing 9, synthetic resins having suitable cushioning properties and sealing properties, for example, olefin resins such as polyethylene, ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, soft vinyl chloride resins, and the like are suitably used. As the coating layer 6, for the olefin resin packing, a paint containing an acid-modified olefin resin or polyethylene oxide, and for the vinyl chloride resin packing, the above-mentioned vinyl resin and acrylic crab resin paint are used. The molding of the packing 9 is a method of extruding a thermoplastic resin in a container lid shell from the viewpoint of workability, and simultaneously performs molding and thermal bonding of a packing shape by pressing, or a fluid composition such as a plastic sol in the shell body. By supplying, the method of oil field and centrifugal molding by centrifugal force can be employ | adopted. Alternatively, the disk packing of the thermoplastic resin may be formed from outside, and the shell may be adhered to the platen portion.

In this aspect of the present invention, when the packing 9 is peeled off, the partial coating layer 3 and the epoxy of the modified hydrocarbon resin, for example, are pressed by pressing the peripheral part of the packing 9 with a nail or a mechanism. Peeling with the resin layer 4 advances first in a press part, and then breaking of the coating layers 4 and 6 in this part is performed. Next, peeling proceeds easily at the interface between the layer 3 and the layer 4, and the packing 9 is easily carried out at the shell top plate part 7 with the printing ink layer 5 thereon. Come off

The adhesive structure of the present invention may be in the form of a so-called packing part cap. In this case, as shown in FIG. 3, the packing 9 is comprised as the thick sealing part 10 and the thin center part 11, and the weakening line 12 which can be fully cut or broken is provided in this boundary. Thus, only the packing center portion 11 can be peeled off and the lid sealability can be maintained even after peeling off the packing.

In this aspect of the present invention, the partial coating layer 3 such as a modified hydrocarbon resin may be provided so as to correspond to the entire surface of the packing. Or it may provide in the peeling start part of a packing.

The adhesive structure of the present invention is particularly useful for the use of the peelable packing container lid as described above, but other uses, for example, temporary sealing between a plurality of parts, peelable protective coatings on articles, and the like. It is also widely available.

For example, metals, steel, copper, aluminum, zinc inert steel, bronze, cupronickel, duralumin, diecasting, and other metals or alloys may be used. Or steel plated with aluminum or the like, or phosphoric acid treated or chromic acid treated or electrochromic chromium treated steel. The shape of the metal gas can be any shape such as metal foil, rolled sheet metal, sheet metal, sheet, pipe, rod, beam, beam, twisted wire, can or other container, building structure, vehicle structure, and the like. have. On the other hand, as the second component to be adhered to the metal substrate, in addition to the above metal substrate, film sheets or other molded articles made of various plastics or rubbers, various papers or composites thereof can be used.

The outstanding effects of the present invention are illustrated in the following examples.

Example 1

Aliphatic hydrocarbon resin (trade name, Tacky roll 1000 Sumidomo Chemical Co., Ltd., softening point 100 ° C, average molecular weight 1200, color 7 (guider) acid value 0.04) 500 g at 190 ° C 3 g of maleic anhydride was added to the mixture, followed by stirring for 90 minutes, and the resulting resin had a softening point of 100 ° C. and a colorant 7. An acid value of 5.0, 50 wt% of the obtained acid-modified hydrocarbon resin using kerosene as a solvent. To prepare a paint.

500 g of an alicyclic hydrocarbon resin [trade name ECR-4 Eso Chemical Co., Ltd., softening point 120 degreeC, acid value 0.3] are melt | dissolved at 200 degreeC, Then, 2 g of acrylic acid is added stirring, and it is made to react for 2 hours, maintaining temperature. The acid-modified hydrocarbon resin of the softening point 121 degreeC and acid value 4.3 obtained by this reaction was dissolved in kerosene (50 wt% concentration), and it was set as the coating material B.

500 g of hydrogenated hydrocarbon resin [trade name Ekoretsu 5100 Eso Chemical Co., Ltd., softening point 105 degreeC, acid value 0.01] and 6 g of maleic anhydride are heated at 190 degreeC for 2 hours in presence of 1 g of methyl ethyl ketone peroxides. Next, the excess maleic anhydride is removed by washing, and the resulting acid-modified hydrocarbon resin (softening point 105 ° C., acid value 4.6) is dissolved at 200 ° C., and 6 g of ethylene glycol is added to proceed the esterification reaction at 200 ° C. for 2 hours. .

By this reaction, ester modified hydrocarbon resin (softening point 107 ° C acid value) was obtained. Obtained resin was melt | dissolved in the same kerosene as the said 2 sample, and it was set as the coating material C. A pre-degreased 0.3 mm thick electroplated briquette plate on both sides, with vinyl paint (vinyl chloride acetate copolymer VYHH UCC 25% solution of methyl ethyl catone) as a dry film, rolled onto the surface with a thickness of 2μ. After coating, heating at 180 ° C. for 10 minutes is performed to prepare a double-sided coating plate. Next, the above-mentioned solution of the coating material A-C is apply | coated to the film surface of 4 micrometers, respectively, and it heats 180 degreeC-10 minutes, and forms the 1st coating film layer on one surface of the obtained coating plate. Next, as the first coating layer, an epoxy-phenolic coating (30 wt% solution of xylene and butyl cellosolve equivalent equivalent solvent of epicoat # 1007 / PP-3005 = 80/20) was applied so as to have a dry coating of 5μ. After bonding an aluminum foil having a thickness of 0.1 mm onto the coated surface, heating was performed at 190 ° C. for 15 minutes to form an adhesive structure of the aluminum foil-second coating layer-floor lacquer layer-buriki.

As a comparative example, the composition which does not have a 1st coating layer, and the composition which used unmodified hydrocarbon resin of coating AC as a 2nd coating layer were created, and peeling between aluminum foil and a burriki board is carried out about the 7 types of adhesive structures obtained. The strength was measured by a tensile test with tensirone. The measurement conditions were performed at room temperature (20 degreeC) with the tensile velocity of 50 mm / min, and the peeling angle of 180 degrees. The above result was shown in Table 1.

Table-1

Peeling occurred in any case between a 1st coating film layer and a 2nd coating film layer.

* Due to poor wetting, the second coating layer was used as the measurement by adding 5 parts of saturated polyester in the coating.

Example 2

500 g of the aliphatic hydrocarbon resin used in Example 1 was melted at 200 ° C., and then the amount of maleic anhydride was changed and added to prepare an acid hydrocarbon resin having various acid values, and a solution was prepared using kerosene as a solvent.

By the same operation as in Example 1, an aluminum foil-buriki adhesive structure having an acid-modified hydrocarbon resin having a different amount of modification as the first coating layer was prepared, and the peel strength of the adhesive structure obtained was measured. Marked on.

TABLE 2

Peeling occurred in any case between a 1st coating film layer and a 2nd coating film layer.

* The addition of 5 parts of saturated polyester was used as a wet improvement.

Example 3

Aromatic hydrocarbon resin (trade name Patrodine 120 Mitsui Petrochemical Co., Ltd., softening point 120 ° C. (cyclic method), average molecular weight 870, acid value 0.10) was dissolved in a concentration of 50 wt% using Solveso 100 as a solvent and used as sample solution D. Ready Next, the following 1-4 solutions are prepared as an addition solution.

(1) The polyethylene oxide (density 1.0, softening point 135 degreeC, carbonyl content 35meh / 100g) was melt | dissolved in the heat xylene of 120 degreeC, and it was set as the 20 wt% solution.

(2) Maleic anhydride modified polyolefin was dissolved in hot xylene to make a 20 wt% solution.

(3) 500 g of linseed oil was blown at 120 deg. C, dehydrated, and boiled for 7 hours to obtain linseed oil type 2.9.

(4) A vinyl chloride-vinyl acetate copolymer (VYHH) 100 is dissolved in 400 g of a mixed solvent of cyclohexanone / xylene (80/20).

To solution D, 5 parts of a solution of 1-4 in solid content B were each added and stirred well to prepare various resin-added hydrocarbon resin compositions. A phenol-modified alkyd (trade name Phthacyd x 414 Hidabat Chemical) was applied on the surface-treated steel sheet having a thickness of 0.23 mm so as to have a film thickness of 2 mu, and heated to 180 ° C.-10 minutes. Next, the above-mentioned resin-added hydrocarbon resin composition of 1-4 is roll-coated so as to have a film thickness of 4 mu on the bottom coating layer, and a first coating layer is formed under heating conditions of 180 ° C-10 minutes. Epoxy urea paint (Epicowood 1007 / butylated urea (trade name P-138 Nippon Reich Hould) / polyethylene oxide = 80/20/15 as a second coating film added polyethylene oxide (density 1: 1, softening point 132 ° C) The ethyl cellosol portion and a 30 wt% solution of n-butanol mixed solvent] were roll-coated so that the dry coating was 3 mu m, and the heat treatment was cured at 190 ° C for 10 minutes. A 0.2 mm-thick sheet of low density polyethylene (trade name Sumikasen LK-30) was placed on the second coating layer, and thermally compressed at 140 ° C.-30 seconds using a hot press, and the TFS-coating-first coating layer-second coating layer- The adhesive structure of the composition of polyethylene was prepared.

The peel strength of polyethylene-metal was measured about the obtained adhesive structure. The results are shown in Table 3.

Table-3

Peeling occurred in any case between a 1st coating film layer and a 2nd coating film layer.

Example 4

After forming base coat layer (epoxy-amino paint), printing, overcoat layer (epoxy ester paint) on one side (surface of crown) of 0.23mm thickness surface treatment steel, the other side (The surface used as the inner surface of a crown) is given with the film thickness of 3 micrometers for the rust prevention of the vinyl floor coating packer used in Example 1.

Next, the No. used in Example 1 was used. 1 to 3, acid-modified hydrocarbon resin solution of No. 3 and No. Maleic anhydride modified hydrocarbon resin solution of Example 3, No. 1 to No. Resin-added hydrocarbon resin solution 5 was applied on the rustproof lacquer lacquer layers, respectively, and the first coating layer was formed by drying at 150 ° C-10 minutes.

Apply the epoxy-urea paint (epicoat 1009 / superbecamin P-138 = 80/20 xylan, 30et% solution of the same amount of mixed solution of butyl cellosolve) onto the obtained first layer film layer so as to be 3μ as a dry film. Then, heat treatment for 190 ° C.-15 minutes is performed to form a second coating layer.

Next, using a commercial alkyd ink on the second coating layer, development printing of a design in which a design, a text, etc. is written in a circular range of 26m / m in outer diameter is made and dried.

Next, the polyethylene oxide-added epoxy-urea-based paint used in Example 3 as an adhesive was applied onto the second partially coated film layer and roll-coated in a total thickness such that the dry coating was 5 mu, followed by heat treatment at 190 ° C. for 10 minutes. Is done.

By the above operation, the metal coating plate of the multilayer coating structure with which the composition of the 1st coating layer of an inner surface side was different was created. Moreover, the plate of the coating film structure which abbreviate | omitted the 1st coating film layer as a comparative example was also created simultaneously. The resulting coated plate is molded into a crown shell (JIS.S.9017 type 5 crown size) with an inner diameter of 26.6 mm with the center of the developing printing portion at the center of the crown top plate using a crown press. Density 0.92. The low density polyethylene of melt index 7.0 was melt extruded using a conventional extruder (diameter 20 mm. L / D 10), about 0.5 g of the discharged molten polyethylene flowed into the inside of the crown shell, and immediately with a cold metal punch. Punching was performed to obtain a crown shell having a polyethylene liner on the inner surface. Next, the polyethylene liner was peeled off from the obtained polyethylene liner portion crown, and the peel strength at that time was measured with a tensile tester. Again, the same characteristics (processability such as punching bending, liner retention in transporting and wiring processes, dust generation amount) required as crown shells were evaluated at the same time. The results are shown in Table 4.

Table-4

Peeling occurred all between the 1st coating film layer and the 2nd coating film layer, and the image development printing part was transferred to the liner side.

Example 5

In the same manner as in Example 4, a first coating layer, a second coating layer, and development printing were applied to one side (inner side of the crown) of the treated steel sheet, and as an adhesive, a vinyl chloride-vinyl acetate copolymer (VMCH UCC). 1) A solution (methyl ethyl katone 20wt% solution) was co-cured so as to have a dry coating of 5 µ, and heated and dried at 180 ° C for 10 minutes to prepare a metal coating plate having a multilayer coating structure.

The obtained salt line vinyl liner portion crown was evaluated in terms of capry strength and crown performance as in Example 4. The results are shown in Table 5.

With respect to the peeled sample, the peeling interface was between the first coating film and the second coating film, and the developing print portion was transferred to the peeled liner.

Table-5

Claims (1)

In an adhesive structure in which a plurality of parts made of at least one metal are bonded to each other with a coating layer interposed therebetween, the peelable interface of the coating layer is formed of a modified hydrocarbon resin or modified hydrocarbon resin composition having an acid value of 0.1 to 20. A peelable adhesive structure formed between a layer of 1 and a second layer containing an epoxy resin.

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