JP2001026749A - Overcoat composition and laminated film for bonding using the composition - Google Patents

Abstract

(57) [Problem] To provide an overcoat layer which is excellent in scratch resistance, blocking resistance at the time of film winding, and which can form an overcoat layer having excellent adhesiveness by heat sealing. SOLUTION: At least one selected from (A) 70 to 99 parts by weight of a hydroxyl group-containing organic resin and (B) an amino resin and a polyisocyanate compound which may be blocked.
An overcoat composition for a laminated film of a packaging material, comprising (C) 0.01 to 5 parts by weight of a modified silicone, based on 100 parts by weight of a total of 1 to 30 parts by weight of a kind of curing agent. An adhesive laminated film in which a coating film of an overcoat composition is formed on one surface of a plastic film, and an adhesive layer is formed on the other surface of the film via a printing ink layer as necessary. And a method for producing a laminated film-covered packaging material in which the laminated film is thermocompressed to the surface of the packaging material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an overcoat composition for a laminated film for covering a packaging material such as a can, an adhesive laminated film having an overcoat formed from the composition, and a laminated film for the adhesive. The present invention relates to a method for producing a laminated film-covered packaging material used.

[0002]

2. Description of the Related Art In recent years,
As a method of coating a packaging material such as a can, a method of bonding and laminating a plastic film such as a polyethylene terephthalate film to the surface of the can has been frequently used in addition to a method of coating a paint.

[0003] In the case of manufacturing a two-piece can laminated with a plastic film, the film is usually laminated after being formed into a can. In general, plastic films are coated with an overcoat in order to impart scratch resistance, and this overcoat is scratch-resistant and is resistant to blocking during film winding. It is a low surface tension coating film that is usually slippery.

When a plastic film is laminated on a packaging material such as a can, the plastic film is laminated on the can by heat sealing via an adhesive, but a lap portion where the film overlaps occurs. At this wrap, the overcoated surface and the adhesive are heat-sealed and the adhesive strength is so low that good lamination cannot be performed. Adhesives are used to bond an unpainted film portion to be a portion and an adhesive.

[0005] However, when an overcoat having an unpainted portion (margin portion) is formed on a plastic film, the overcoat is coated with a roll with the margin cut off. When the coat adheres, there is a problem that poor adhesion of the lap portion occurs, and there is also a problem that printing misalignment is likely to occur due to misalignment of the coating position, resulting in poor production efficiency.

SUMMARY OF THE INVENTION An object of the present invention is to provide an overcoat which is excellent in scratch resistance, blocking resistance upon film winding, and which does not require a margin portion on a film and which has excellent adhesiveness to an adhesive by heat sealing. The present invention is to provide an overcoat composition capable of forming a film, a laminated film for adhesion having an overcoat and excellent adhesion by heat sealing, and a method for producing a laminated film-covered packaging material using the laminated film.

[0007]

Means for Solving the Problems The overcoat is required to have scratch resistance and blocking resistance at the time of film winding, and these performances and the adhesiveness with an adhesive are generally contradictory performances. An overcoat that can be compatible has not been found so far.

The present inventors have found that the above object can be achieved by mixing and using reactive silicon as an additive of an overcoat containing a hydroxyl group-containing organic resin and a curing agent as resin components. It was completed.

That is, the present invention relates to (A) 70 to 99 parts by weight of a hydroxyl group-containing organic resin and (B) 1 to 30 parts by weight of at least one curing agent selected from an amino resin and a polyisocyanate compound which may be blocked. A total of 10
An object of the present invention is to provide an overcoat composition for a laminated film of a packaging material, characterized by containing 0.01 to 5 parts by weight of (C) modified silicon with respect to 0 parts by weight.

[0010] The present invention also provides a plastic film in which an overcoat from the above-mentioned overcoat composition is formed on one surface (first surface) and the other surface (second surface) of the film is required. Depending on the printing ink layer,
An object of the present invention is to provide an adhesive laminated film having an adhesive layer formed thereon.

Further, the present invention provides a method for producing a laminated film-covered packaging material, wherein the laminated film is thermocompression-bonded to the surface of the packaging material such that the adhesive layer of the laminated film faces the surface of the packaging material. Is provided. Hereinafter, the present invention will be described in detail.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the overcoat composition of the present invention will be described in detail below. The overcoat composition of the present invention contains the following hydroxyl-containing organic resin (A), curing agent (B) and modified silicone (C) as essential components.

Hydroxyl-containing organic resin (A) The hydroxyl-containing organic resin (A) is not particularly limited as long as it is an organic resin containing a hydroxyl group. And at least one type of hydroxyl group-containing resin selected from acrylic resins and acrylic resins.

The hydroxyl group-containing organic resin (A) has a hydroxyl value of 1 to 200 mgKOH / g, preferably 5 to 150 mgKOH / g.
KOH / g is preferred in terms of curability and the like, and the number average molecular weight is 1,000 to 40,0.
00, preferably in the range of 10,000 to 30,000 and the glass transition temperature in the range of 40 to 130 ° C, preferably 60 to 130 ° C. It is suitable in terms of properties and the like.

Examples of the epoxy resin usable as the hydroxyl-containing organic resin (A) include bisphenol-type epoxy resins and novolak-type epoxy resins; modified epoxy resins obtained by reacting various types of modifiers with epoxy groups or hydroxyl groups in these epoxy resins. Can be mentioned.

The bisphenol type epoxy resin is, for example, a resin obtained by condensing epichlorohydrin and bisphenol to a high molecular weight in the presence of a catalyst such as an alkali catalyst, if necessary. Any resin obtained by condensing in the presence of a catalyst such as a catalyst into a low molecular weight epoxy resin and subjecting the low molecular weight epoxy resin to a bisphenol to undergo a polyaddition reaction may be used.

As the bisphenol, bis (4-
Hydroxyphenyl) methane [bisphenol F],
1,1-bis (4-hydroxyphenyl) ethane, 2,
2-bis (4-hydroxyphenyl) propane [bisphenol A], 2,2-bis (4-hydroxyphenyl) butane [bisphenol B], bis (4-hydroxyphenyl) -1,1-isobutane, bis (4- (Hydroxy-tert-butyl-phenyl) -2,2-propane, p- (4-hydroxyphenyl) phenol, oxybis (4-hydroxyphenyl), sulfonylbis (4-hydroxyphenyl), 4,4′-dihydroxybenzophenone, Bis (2-hydroxynaphthyl) methane and the like can be mentioned, and among them, bisphenol A and bisphenol F are preferably used. The above bisphenols can be used alone or as a mixture of two or more.

Commercially available bisphenol epoxy resins include, for example, Epicoat 1001, 1004, 1007, and 100 manufactured by Yuka Shell Epoxy Co., Ltd.
9, 1010: Araldite AER6 manufactured by Asahi Ciba
097, 6099; and Epomic R-309 manufactured by Mitsui Chemicals, Inc.

Examples of the novolak type epoxy resin usable as the epoxy resin include various novolak types such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, and phenol glyoxal type epoxy resin having a large number of epoxy groups in the molecule. Type epoxy resin.

The modified epoxy resin includes, for example, an epoxy ester resin obtained by reacting a drying oil fatty acid with the bisphenol type epoxy resin or the novolak type epoxy resin; a polymerizable unsaturated monomer component containing acrylic acid or methacrylic acid. An epoxy acrylate resin reacted with an isocyanate compound; a urethane-modified epoxy resin reacted with an isocyanate compound; an amine compound reacted with an epoxy group in the above-mentioned bisphenol-type epoxy resin, novolak-type epoxy resin or the above-mentioned various types of modified epoxy resins to form an amino group or An amine-modified epoxy resin into which a quaternary ammonium salt is introduced can be used.

The polyester resin which can be used as the hydroxyl group-containing organic resin (A) comprises an esterified product of a polybasic acid component and a polyhydric alcohol component. As the polybasic acid component, for example, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, maleic anhydride ,
Itaconic acid, one or more dibasic acids selected from dimer acids and the like and lower alkyl esterified products of these acids are mainly used, and benzoic acid, crotonic acid,
Monobasic acids such as pt-butylbenzoic acid, and tribasic or higher polybasic acids such as trimellitic anhydride, methylcyclohexentricarboxylic acid, and pyromellitic anhydride are used in combination. Examples of the polyhydric alcohol component include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, 1,4-hexanediol, 1,6-hexanediol, and cyclohexanedimethanol. , Hydrogenated bisphenol A, bisphenol A
And dihydric alcohols such as ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A, and if necessary, trihydric or higher polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. Can be used in combination. These polyhydric alcohols can be used alone or in combination of two or more. Esterification or transesterification of both components can be performed by a method known per se, for example, obtained by polycondensing the polybasic acid component and the polyhydric alcohol component at a temperature of about 180 to 250 ° C. be able to.

Further, after obtaining a polyester having a hydroxyl group from the polybasic acid component and the polyhydric alcohol component, the hydroxyl group of the polyester is added to the hydroxyl group of maleic acid, maleic anhydride, phthalic anhydride, trimellitic anhydride and the like. A polyester resin having a carboxyl group introduced into the resin by reacting with a basic acid may be used.

The acrylic resin that can be used as the hydroxyl-containing organic resin (A) may be a monomer mixture of a hydroxyl-containing monomer and another monomer copolymerizable with the monomer by a solution polymerization method in the presence of a radical polymerization initiator. It can be obtained by copolymerization according to a conventional method.

Examples of the hydroxyl-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl vinyl. Ether, 2-hydroxypropylvinyl ether, 2-hydroxyethylallyl ether and the like can be mentioned.

Other monomers copolymerizable with the above-mentioned hydroxyl-containing monomer include, for example, vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and α-chlorostyrene; methyl (meth) acrylate, Ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (n-,
i-, t-) butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n
-The number of carbon atoms of acrylic acid or methacrylic acid such as octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate; 1 to 24
Alkyl esters or cycloalkyl esters of vinyl acetate, vinyl chloride, vinyl ether, acrylonitrile, methacrylonitrile, and the like. In addition, a polymer of one or more of these monomers and / or A so-called macromonomer having a polymerizable unsaturated group at a terminal can also be mentioned as a copolymerizable monomer. In the present invention, "(meth) acrylate"
Means "acrylate or methacrylate".

Curing Agent (B) The curing agent (B) is selected from an amino resin and a polyisocyanate compound which may be blocked, and functions as a curing agent for the hydroxyl-containing organic resin (A).

Examples of the amino resin include a methylolated amino resin obtained by reacting an amino component such as melamine, urea, benzoguanamine, acetoguanamine, steroganamin, spiroguanamine, dicyandiamide and an aldehyde with an aldehyde. Aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like. Further, those obtained by etherifying the methylolated amino resin with an appropriate alcohol can also be used. Examples of the alcohol used for the etherification include methyl alcohol, ethyl alcohol, and the like.
n-propyl alcohol, i-propyl alcohol, n
-Butyl alcohol, i-butyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like. As the amino resin, a methylolated melamine resin in which at least a part of a methylol group is alkyl-etherified is preferable.

The optionally blocked polyisocyanate compound used as the curing agent (B) includes both unblocked and blocked polyisocyanate compounds.

Examples of the non-blocked polyisocyanate compound include hexamethylene diisocyanate,
Aliphatic diisocyanates such as trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as hydrogenated xylylene diisocyanate and isophorone diisocyanate; tolylene diisocyanate;
Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate; triphenylmethane-4,4 ',
4 "-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4,4'-dimethyldiphenylmethane-2,2 ',
An organic polyisocyanate itself such as a polyisocyanate compound having three or more isocyanate groups such as 5,5'-tetraisocyanate, or each of these organic polyisocyanates and a polyhydric alcohol, a low molecular weight polyester resin or water, etc. And cyclized polymers of the above-mentioned organic polyisocyanates, and isocyanate-biuret compounds. Of these, isocyanurate obtained by cyclopolymerization of hexamethylene diisocyanate is preferably used.

The blocked polyisocyanate compound is obtained by blocking the isocyanate group of the non-blocked polyisocyanate compound with a blocking agent, and the blocking agent may be a phenolic compound such as phenol, cresol or xylenol; ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-
Lactams such as propiolactam; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol,
alcohols such as tert-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol; formamidoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime;
Oxime-based blocking agents such as diacetyl monooxime, benzophenone oxime, and cyclohexane oxime; and active methylene-based blocking agents such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone. Among them, oxime-based blocking agents are preferably used.

Modified Silicon (C) Modified silicon (C) is obtained by modifying dimethylpolysiloxane to introduce a modifying group into the terminal and / or side chain of the dimethylpolysiloxane chain. As this modifying group,
Organic groups having functional groups such as epoxy group, amino group, carboxyl group, hydroxyalkyl group and polymerizable unsaturated group (vinyl group, acryloyl group, methacryloyl group, etc.); hydrogen atom (forms SiH group together with Si), hydroxyl group (Forming a silanol group with Si), an alkoxyl group (forming an alkoxysilyl group with Si), a polyether group, a fluorine atom-containing hydrocarbon group, a mercapto group, and an alkylaralkyl group. In the modified silicon (C), these modifying groups may be used alone or in combination of two or more. Modified silicon has various viscosities, and the viscosity can be changed, for example, by changing the molecular weight.

The viscosity at room temperature (25 ° C.) is 1000 mm ²
/ S (centistokes), preferably 10-90
As a commercially available modified silicon (hereinafter sometimes abbreviated as “low-viscosity modified silicon”) in the range of 0 mm ² / s, for example, Silwet L-3720 (manufactured by Nippon Unicar, epoxy group-containing, viscosity 700 mm ² / s), KF
865 (manufactured by Shin-Etsu Chemical Co., Ltd., containing amino group, viscosity 90 mm ²
/ S), Silwet FZ-3705 (manufactured by Nippon Unicar, containing amino group, viscosity 220 mm ² / s), Silwet FZ-3722 (manufactured by Nippon Unicar, containing hydroxyalkyl group, viscosity 40 mm ² / s), sill Wet F
Z-3702 (manufactured by Nippon Unicar, containing SiH group, viscosity 90 mm ² / s), Silwet L-9000 (10
0) (manufactured by Nippon Unicar, containing silanol groups, viscosity 10)
0 mm ² / s), Silwet FZ-3701 (manufactured by Nippon Unicar Company Limited, alkoxysilyl group-containing, 18 mm ² /
s), SH3746 (manufactured by Dow Corning Toray Silicone Co., Ltd., containing a polyether group, viscosity 120 mm ² /
s), X-22-820 (manufactured by Shin-Etsu Chemical Co., Ltd., containing a fluorine atom-containing hydrocarbon group, viscosity 100 mm ² / s), BY16
-838 (manufactured by Dow Corning Toray Silicone Co., Ltd., containing a mercapto group, viscosity 300 mm ² / s), KF-20
01 (manufactured by Shin-Etsu Chemical Co., Ltd., containing mercapto group, viscosity 150m
m ² / s).

On the other hand, the viscosity at room temperature (25 ° C.) is 1000
mm ² / s (centistokes) or more, preferably 10
Commercially available modified silicon in the range of 00 to 10000 mm ² / s (hereinafter sometimes abbreviated as “high-viscosity modified silicon”) includes, for example, SF8411 (Toray
Dow Corning Silicone, epoxy group-containing, viscosity 8000 mm ² / s), Silwet L-9300
(Nippon Unicar, epoxy group-containing, viscosity 6000m
m ² / s), SF8417 (manufactured by Dow Corning Toray Silicone Co., Ltd., containing amino group, viscosity 1200 mm ² /
s), Silwet FZ-319 (manufactured by Nippon Unicar,
Amino group-containing, viscosity 2000 mm ² / s), Silwet L-9000 (8000) (Nippon Unicar Co., Ltd., a silanol group-containing, viscosity 8000mm ² / s), SF841
8 (manufactured by Dow Corning Silicone Toray Co., Ltd., containing carboxyl group, viscosity 2500 mm ² / s), Silwet FZ-3703 (manufactured by Nippon Unicar, containing carboxyl group, viscosity 3000 mm ² / s), KF-8003 (Shin-Etsu Chemical Company, amino group-containing, viscosity 1850 mm ² / s),
SF8421EG (manufactured by Dow Corning Toray Silicone Co., Ltd., containing epoxy group and polyether group, viscosity 350
0 mm ² / s).

As the modified silicon (C), these low-viscosity modified silicon and high-viscosity modified silicon can be used alone or in combination of two or more. Above all, by mixing and using the above-mentioned low-viscosity modified silicone and high-viscosity modified silicon, the resulting overcoat can have excellent heat sealing properties, blocking resistance and scratch resistance. In this case, modified silicon (C)
The types of modifying groups in the low-viscosity modified silicon and the high-viscosity modified silicon used as a mixture may be the same or different.

In the overcoat composition used in the method of the present invention, the mixing ratio of the hydroxyl group-containing organic resin (A) and the curing agent (B) is based on 100 parts by weight of the total (solid content) of both. , Resin (A) is 70 to 99
Parts by weight, preferably 75 to 95 parts by weight, and the curing agent (B) within the range of 1 to 30 parts by weight, preferably 5 to 25 parts by weight, the curability, blocking resistance and scratch resistance of the coating film. It is suitable in terms of properties and the like. Also, modified silicon (C)
Is 0.01 to 5.0 parts by weight, preferably 0.05 to 3.0 parts by weight, based on 100 parts by weight of the total (solid content) of the resin (A) and the curing agent (B). It is preferable from the viewpoints of blocking resistance, scratch resistance, and the like. When the modified silicon (C) is used in combination with low-viscosity modified silicon and high-viscosity modified silicon,
Each of the low-viscosity modified silicone and the high-viscosity modified silicon is 0.01 part by weight or more, preferably 0.05 part by weight or more, and the total amount is 5.0 parts by weight or less, preferably 3.0 parts by weight.
It is excellent in heat sealability with the adhesive layer of the overcoat, blocking resistance, scratch resistance, and the like when it is within the range of not more than part by weight.

The overcoat composition contains the hydroxyl group-containing organic resin (A), the curing agent (B) and the modified silicon (C) as essential components, and contains a curing catalyst, an organic solvent, and the like, if necessary. be able to.

When the curing agent (B) is an amino resin, in particular, a low molecular weight alkyl etherified amino resin, a sulfonic acid compound or an amine neutralized sulfonic acid compound is suitably used as the curing catalyst. . Representative examples of the sulfonic acid compound include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and dinonylnaphthalenedisulfonic acid. The amine in the amine-neutralized sulfonic acid compound may be any of a primary amine, a secondary amine and a tertiary amine. When the curing agent (B) is a blocked polyisocyanate compound, it is preferable to use a curing catalyst that promotes the dissociation of the blocking agent of the blocked polyisocyanate compound. For example, tin octylate, dibutyl Tin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate),
Organometallic catalysts such as dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide, and lead 2-ethylhexanoate can be suitably used.

Next, the adhesive used for forming the adhesive layer in the adhesive laminated film of the present invention will be described. Adhesive As the adhesive used to form the adhesive layer in the present invention, those containing 1 to 50 parts by weight of a non-blocked or blocked polyisocyanate compound in 100 parts by weight of the resin component are preferably used. be able to. As the resin component constituting the adhesive together with the unblocked or blocked polyisocyanate compound, an organic resin containing a hydroxyl group can be suitably used. Examples of the organic resin include a polyester resin, an acrylic resin, and an epoxy resin. These can be used alone or in combination of two or more. Among the above organic resins, a hydroxyl group-containing polyester resin can be suitably used.

The above-mentioned hydroxyl group-containing polyester resin has a number average molecular weight of 1,000 to 40,000, preferably 10,
000-30,000, glass transition temperature 0-100 ° C,
It preferably has a temperature of 35 to 90 ° C and a hydroxyl value of 0.1 to 3
0 mgKOH / g, preferably 1 to 20 mgKOH / g
And the acid value is preferably 50 mgKOH / g or less, more preferably 1 to 25 mgKOH / g.

The above-mentioned hydroxyl group-containing polyester resin is, for example, so as to have the property value of the above-mentioned hydroxyl group-containing polyester resin according to the production method when the hydroxyl group-containing organic resin (A) in the overcoat composition is a polyester resin. It can be adjusted and manufactured.

The unblocked or blocked polyisocyanate compound in the adhesive acts as a curing agent for the above-mentioned hydroxyl-containing organic resin, and also reacts with the plastic film surface, the packaging material and, if necessary, the ink layer to form an adhesive. Contribute to the improvement of As the non-blocked or blocked polyisocyanate compound, those mentioned as the optionally blocked polyisocyanate compound which can be used as the curing agent (B) in the overcoat composition can be used.

The amount of the unblocked or blocked polyisocyanate compound in the adhesive is in the range of 1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the resin component. It is suitable from the viewpoints of blocking properties, water resistance, adhesion at the initial stage and after retort treatment, and the like.

The adhesive may contain a curing catalyst, a pigment, an organic solvent, and the like, if necessary, in addition to the resin component.

As the above curing catalyst, when the curing agent (B) is a blocked polyisocyanate compound in the overcoat composition, an organometallic catalyst which is a curing catalyst that can be used as needed is appropriately used. Can be.

Examples of the pigments include inorganic color pigments such as titanium white, zinc white, titanium yellow, red iron oxide, carbon black and various calcined pigments;
Organic coloring pigments such as cyanine green, organic red pigment and organic yellow pigment; metallic luster pigments such as aluminum powder and glittering mica powder; precipitated barium sulfate, calcium carbonate,
Extenders such as talc, clay, silica, mica, and alumina; Although the amount of the pigment is not particularly limited, it is usually preferable that the amount is within a range of 140 parts by weight or less based on 100 parts by weight of the total amount of the polyester resin (A) and the curing agent (B). is there. As a pigment,
By using a white pigment such as titanium white, it is possible to double as a white coat.

Next, the adhesive laminated film of the present invention using the overcoat composition and the adhesive will be described. Adhesive laminated film The adhesive laminated film of the present invention has a plastic film on which one side (first side) is coated with the overcoat composition to form an overcoat, and the other side of the film ( On the second surface), an adhesive layer of the above adhesive is formed via a printing ink layer as necessary.

As the plastic film, any plastic film having heat resistance and strength can be used, but a polyester film, in particular, a film in which 75 to 100% of ester repeating units are composed of ethylene terephthalate units is preferable. It is. Examples of the ester unit other than the ethylene terephthalate unit include ester units such as phthalic acid, isophthalic acid, succinic acid, and adipic acid. The surface of the plastic film is preferably subjected to a surface treatment such as a corona discharge treatment in order to improve the adhesion to the overcoat, the adhesive and the ink. The thickness of the plastic film is not particularly limited, but usually a thickness of about 5 to 30 μm can be suitably used.

One side of the plastic film (first side)
Surface) with a coating machine such as a roll coater, so that the dry film thickness is usually about 0.5 to 10 μm. By heating and drying for about 60 seconds, an overcoat layer can be formed.

The ink used for forming the ink layer which may be interposed on the other side (second side) of the plastic film as required is a known printing technique used for printing packaging films. The ink can be used without any particular limitation, and the printing ink can be applied by the same method as the printing of the packaging film. Preferably, the type of printing ink is a cross-linkable heat-resistant ink,
For example, polyester resin-based, acrylic resin-based, and alkyd resin-based resins can be used.

On the second surface (ink layer surface) of the plastic film on which the printing ink layer is formed as required,
The adhesive is a roll coater method, a gravure method, a gravure offset method, a spray coating method, or the like, and is usually a dry film thickness of 0.3 to 15 μm by a known coating means.
m, and dried at a temperature of, for example, 50 to 180 ° C. until a tack-free state is obtained, if necessary. Thereby, a laminated film for adhesion can be obtained.

The obtained laminated film for bonding can be laminated to a packaging material immediately after production. Usually, the laminated film for bonding is wound up in a coil shape and stored until use when laminating to the packaging material. Is done. During this storage, the overcoat layer and the adhesive layer overlap, so that blocking resistance between these layers is required. If the blocking resistance is poor, there arises a problem that the coil cannot be unwound, and even if the coil is unwound, a part of the adhesive adheres to the surface of the overcoat layer.

Production of Laminated Film-Coated Packaging Material A laminated film-coated packaging material can be produced by laminating the above-mentioned adhesive laminated film to a packaging material. Examples of the packaging material include a metal packaging material such as a metal plate and a metal foil, a plastic packaging material and a paper packaging material, and a composite packaging material combining two or more of these.

As the metal plate used for the above-mentioned packaging material,
For example, hot-rolled steel sheet, cold-rolled steel sheet, hot-dip galvanized steel sheet, electro-galvanized steel sheet, iron-zinc alloy-plated steel sheet, zinc-aluminum alloy-plated steel sheet, nickel-zinc alloy-plated steel sheet, nickel-tin alloy-plated steel sheet, tinplate, Metal plate materials such as chromium-plated steel plate, aluminum-plated steel plate, turn-plated steel plate, nickel-plated steel plate, stainless steel, tin-free steel, aluminum plate, copper plate, titanium plate, etc .; Metal plates that have been subjected to treatment, chromate treatment, composite oxide film treatment, etc .; coated metal plates such as these coated metal plates or primer coated metal plates with a primer layer such as white coat formed on the surface of the chemically converted metal plate Can be mentioned. In the present invention, the term “metal sheet” also includes a processed metal sheet obtained by molding a flat metal sheet such as the above-described metal sheet material, a chemical conversion-treated metal sheet or a primer-coated metal sheet into, for example, a can body. It shall be.

Examples of plastic packaging materials include cellophane, nylon, polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride, polystyrene, polyvinyl alcohol, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polycarbonate, polytetrafluoroethylene, and ethylene. And packaging materials such as films made of acrylic acid copolymers, polysulfones, and composites of these plastics.

The conditions for bonding the adhesive layer surface of the adhesive laminated film to the surface of the packaging material are such that the adhesive laminated film is not deteriorated, the plastic film and the packaging material are sufficiently adhered, and a laminate having a good appearance is obtained. There is no particular limitation as long as a film-coated packaging material can be obtained. As an example of the bonding condition, for example, the temperature of the surface of the packaging material at the time of thermocompression bonding is set to about 120 to 200 ° C. by a method using a heating roll or a method of preheating a metal plate, for a short time (usually about 2 seconds or less). Then, a method of laminating the packaging material and the laminated film for bonding by heat and pressure can be mentioned.

The adhesive layer of the laminated film-covered packaging material obtained as described above can be separately heated and thermoset. However, when the packaging material is a can, the adhesive layer in the can manufacturing process after lamination is used. Thermal curing can also be performed by baking the repair paint film on the welded portion or by heating when baking the paint film on the inner surface of the can. In the case of a two-piece can, it is possible to utilize heat curing by heating when baking the paint film on the inner surface of the can after lamination on the outer surface of the can body.

The laminated film-covered packaging material can also be manufactured by thermocompression bonding the laminated film obtained by removing the adhesive layer from the adhesive laminated film to the packaging material having the adhesive layer formed thereon. The laminated film-covered packaging material obtained by the present invention is used for metal, plastic or paper beverage cans, food cans, art cans, 5 gallon cans and other metal cans, caps and other metal lids, laminate tubes, magic bottles ,
The present invention can also be applied to the exterior of household appliances such as the exterior of a refrigerator.

[0058]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. In the following, “parts” and “%” are used unless otherwise specified.
Are based on weight.

Preparation of Overcoat Composition Example 1 90 parts of "Epicoat 1009" (manufactured by Yuka Shell Epoxy Co., Ltd., hydroxyl value about 180 mgKOH / g), "Cymel 3"
03 "(Mitsui Cytec Co., Ltd., low molecular weight methyl etherified melamine resin) 10 parts," Silwet L-9000
(100) "(manufactured by Nippon Unicar, silanol group-containing modified dimethylpolysiloxane, silanol group equivalent of about 2,0
0.5 parts of 00, a viscosity of 100 mm ² / s at 25 ° C.) and 0.5 parts of dodecylbenzenesulfonic acid were dissolved in a mixed solvent (methyl ethyl ketone / toluene = 50/50 (weight ratio)) to obtain a nonvolatile content of 30%. Overcoat composition A
Was prepared.

Examples 2 to 19 and Comparative Examples 1 and 2 The procedure of Example 1 was repeated, except that the composition was changed as shown in Table 1 below.
Of each overcoat composition was prepared. The blending amount in Table 1 is indicated by the solid content.

(Note) in Table 1 has the following meanings.

(* 1) UE3200: manufactured by Unitika Ltd., trade name “Elitel UE3200”, polyester resin,
Number average molecular weight 16,000, Tg 65 ° C, hydroxyl value 6m
gKOH / g. (* 2) LR1503: manufactured by Mitsubishi Rayon Co., Ltd., trade name "Dianal LR1503", an acrylic resin solution having a solid content of 50%, and a resin solid content having a weight average molecular weight of about 23,000.
It has a number average molecular weight of about 9,000, a Tg of 81 ° C., a hydroxyl value of 32 mg KOH / g and an acid value of 3 mg KOH / g. (* 3) BL-3175: manufactured by Sumitomo Bayer Urethane Co., Ltd.
Trade name "Desmodur BL-3175", hexamethylene diisocyanate triisocyanurate blocked solution, solid content about 75%. (* 4) TPA-B80E: trade name “Duranate TPA-B80E” manufactured by Asahi Kasei Corporation, a block compound solution of triisocyanurate of hexamethylene diisocyanate having a solid content of about 80%.

(* 5) FZ-3705: trade name “Silwet FZ-3705” manufactured by Nippon Unicar, amino-containing modified dimethylpolysiloxane, amino group equivalent of about 4,
000, viscosity 220 mm ² / s at 25 ° C. (* 6) FZ-3720: manufactured by Nippon Unicar, trade name "Silwet FZ-3720", modified dimethylpolysiloxane containing an epoxy group, epoxy group equivalent of about 1,20
Viscosity at 0, 25 ° C. 700 mm ² / s. (* 7) FZ-3703: manufactured by Nippon Unicar, trade name "Silwet FZ-3703", carboxyl group-containing modified dimethylpolysiloxane, carboxyl group equivalent of about 3,600, viscosity at 25 ° C of 3,000 mm ² / s . (* 8) L-9300: manufactured by Nippon Unicar, trade name "Silwet L-9300", modified dimethylpolysiloxane containing epoxy group, epoxy group equivalent about 4,000, 25
Viscosity at ℃ 6,000mm ² / s.

(* 9) L-9000 (8000): manufactured by Nippon Unicar, trade name "Silwet L-9000 (8)
000) ", a modified dimethylpolysiloxane containing a silanol group, a silanol group equivalent of about 30,000, and a viscosity at 25 ° C of 8,000 mm ² / s. (* 10) FZ-319: manufactured by Nippon Unicar Co., Ltd., trade name “Silwet FZ-319”, amino group-containing modified dimethylpolysiloxane, amino group equivalent of about 4000, 25 ° C.
Viscosity at 2,000mm ² / s. (* 11) L-45: manufactured by Nippon Unicar, trade name "Silwet L-45", unmodified dimethylpolysiloxane,
Viscosity at 25 ° C. 100 mm ² / s.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

Production of Adhesive Production Example 1 85 parts of “Elitel UE3200”, “Duranate T”
PA-B80E "12.5 parts (10 parts by solid content),
"Duranate TPA100" (Hexamethylene diisocyanate polyisocyanate compound manufactured by Asahi Kasei Corporation)
5 parts and 0.5 parts of dibutyltin dilaurate were mixed and dispersed in a mixed solvent (methyl ethyl ketone / toluene = 50/50) to prepare an adhesive solution a having a nonvolatile content of about 30%.

Production Example 2 85 parts of “Elitel UE3200”, “Titanium White JR6”
03 "(manufactured by Teica, titanium white), 200 parts," Duranate TPA-B80E "12.5 parts (solid content: 10 parts)
Parts), 5 parts of "Duranate TPA100" (manufactured by Asahi Kasei Corporation, hexamethylene diisocyanate-based polyisocyanate compound) and 0.5 parts of dibutyltin dilaurate in a mixed solvent (methyl ethyl ketone / toluene = 50/50).
The mixture was mixed and dispersed therein to prepare an adhesive solution b having a nonvolatile content of about 45%.

Example 20 One side of a polyethylene terephthalate film (PET film) having a thickness of 12 μm and having both surfaces subjected to corona discharge treatment,
The dry thickness of the overcoat composition A obtained in Example 1 was 2
μm, and dry in a dryer at an ambient temperature of 135
Dry at 6 ° C. for 6 seconds. Then, the adhesive solution a obtained in Production Example 1 was coated on the other surface of the PET film with a dry film thickness of 5%.
μm, and dry in a dryer at an ambient temperature of 120
The resultant was dried at a temperature of 1 ° C. for 1 minute to obtain an adhesive laminated film.

Next, the obtained laminated film for bonding was
The adhesive layer is faced on a bright aluminum plate set on a laminator set at 170 ° C., and pressure-bonded at a laminating pressure of 5 kg / cm and a laminating speed of 2 m / min to obtain a laminated film-coated metal plate. Was.

Examples 21 to 39 and Comparative Examples 1 and 2 The procedure of Example 20 was repeated, except that the types of overcoat composition and adhesive solution used were as shown in Table 1 below. Each laminated film for adhesion and each laminated film-coated metal plate were obtained.

Example 40 In Example 20, an adhesive solution a was used in place of the adhesive solution b, and a polyester-based ink was applied to the surface of the PET film to which the adhesive solution was applied before forming the adhesive layer. The same procedure as in Example 20 was carried out except that the entire surface was printed and dried at 100 ° C. for 1 second, and then the adhesive solution a was applied on the ink layer, to obtain an adhesive laminated film and a laminated film-coated metal plate.

Various tests were carried out on the laminated films for adhesion or the metal plates coated with the laminated films obtained in Examples 20 to 40 and Comparative Examples 1 and 2 based on the following test methods.
The test results are shown in Table 2 below.

The tests of dynamic friction coefficient, scratch resistance and adhesion were carried out on a laminated film-coated metal plate which had been subjected to the following three conditions (a), (b) and (c). (A) the laminated film-coated metal plate itself obtained in each example,
(B) the laminated film-coated metal sheet obtained in each example was baked for 120 seconds at an ambient temperature of 210 ° C., and the post-baked laminated film-coated metal sheet was removed. 30 at 125 ° C in ionic water
Laminated film-coated metal plate treated with hot water for 10 minutes.

Test method : Blocking resistance: the surface (overcoat surface) and the back surface (adhesive layer surface) of the adhesive laminated film were superimposed and 10
kg / cm ² pressure, temperature 25 ℃, humidity 60%
Stored in RH room for 3 days. The laminated film after storage is cut into a width of 30 mm and a tensile speed of 50 mm.
Peeling strength (g / 30) at 180 ° peeling at 0 mm / min
mm) was measured and evaluated according to the following criteria. ◎: Peel strength is less than 10 g / 30 mm, ：: Peel strength is 10 g / 30 mm or more and 20 g / 30 m
m, Δ: 50 g / 30 m when the peel strength is 20 g / 30 mm or more.
m: ×: Peel strength is 50 g / 30 mm or more.

Heat sealability: The front and back surfaces of the adhesive laminated film are overlapped and pressed with a laminator set at 170 ° C. under conditions of a laminating pressure of 5 kg / cm and a laminating speed of 2 m / min. It was baked at an ambient temperature of 210 ° C. for 120 seconds. Next, the baked pressure-bonded film is cut into a width of 20 mm, and peel strength (g / 20 mm) when peeled at 180 ° at a pulling speed of 20 mm / min.
Was measured and evaluated according to the following criteria. ◎: The peel strength is large and the film breaks at the time of peeling. 、: The peel strength is 150 g / 20 mm or more, but the film does not break. Δ: The peel strength is 100 g / 20 mm or more and 150 g / 2.
Less than 0 mm, ×: Peel strength is less than 100 g / 20 mm.

Coefficient of dynamic friction: EGAN SLIP at 20 ° C.
Using TESTER (manufactured by Thwing Albert Instrument Co., USA), a weight of 1 kg with a steel ball three-point contact type was placed on the overcoat surface of the laminated film-coated metal plate, and the dynamic friction coefficient at a moving speed of 10 cm / min [ Friction resistance (g) /
1000 (g)] and evaluated according to the following criteria. ：: Dynamic friction coefficient is less than 0.06, ○: Dynamic friction coefficient is 0.06 or more and less than 0.10, Δ: Dynamic friction coefficient is 0.10 or more and less than 0.14, ×: Dynamic friction coefficient is 0.14. that's all.

Scratch resistance: When using a Bowden friction tester (manufactured by Shinko Zoki Co., Ltd., Soda-type adhesion slide tester), a weight with a load of 100 g was placed on the overcoat surface of the laminated film-coated metal plate and rubbed 30 times. Was evaluated according to the following criteria. ◎: almost no scratches on the coated surface, ：: slight scratches on the coated surface, Δ: considerable scratches on the coated surface, ×: recognized on the entire coated surface.

Adhesion: When a cross cut reaching the PET film is made using a knife on the overcoat surface of the laminated film-coated metal plate, and a cellophane adhesive tape is adhered to the cross cut portion, and then the tape is immediately peeled off. Of the overcoat from the PET film was evaluated according to the following criteria. ◎: no overcoat peeling was observed; ○: slight overcoat peeling was observed but within 0.5 mm from the knife scratch; Δ: considerable overcoat peeling was observed; ×: overcoat peeling was observed. Is remarkably recognized.

[0081]

[Table 4]

[0082]

[Table 5]

[0083]

As described above, the laminated film for adhesion formed with the coating film of the overcoat composition according to the present invention has an excellent resistance to scratches in the overcoat layer, and has a high heat resistance to blocking and heat between the overcoat layer and the adhesive layer. It has excellent sealing properties. The overlapping part of the adhesive layer and the overcoat layer where the adhesive laminated film overlaps by applying the adhesive laminated film to the packaging material surface by thermocompression bonding is strengthened by heating (heat sealing). Can be adhered to. Therefore, when forming the overcoat on the plastic film, it is not necessary to provide a margin portion in order to secure the adhesiveness of the overlapping portion, so that it is possible to eliminate the problem of the printing shift due to the shift of the coating position of the overcoat.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 201/00 C09J 201/00 (72) Inventor Keiji Inomata 4-7-17-1 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Seki F-term in Nishi Paint Co., Ltd.

Claims (9)

[Claims] 1. A total of 100 to 99 parts by weight of (A) a hydroxyl group-containing organic resin and 1 to 30 parts by weight of (B) at least one curing agent selected from an amino resin and a polyisocyanate compound which may be blocked. An overcoat composition for a laminated film of a packaging material, comprising (C) 0.01 to 5 parts by weight of modified silicon based on parts by weight. 2. The composition according to claim 1, wherein the hydroxyl group-containing organic resin (A) is at least one hydroxyl group-containing resin selected from an epoxy resin, a polyester resin and an acrylic resin. 3. The composition according to claim 1, wherein the curing agent (B) is a mixture of an amino resin and a polyisocyanate compound which may be blocked. 4. The modified silicon (C) at 25 ° C.
Viscosity is 1000mm ^Two/ S modified silicon and 25 ℃
Viscosity at 1000 mm^Two/ S or more modified silicon
The mixture according to any one of claims 1 to 3, which is a mixture with
Composition. 5. One side (first side) of a plastic film
An overcoat is formed from the overcoat composition according to any one of claims 1 to 4, and a printing ink layer is optionally formed on the other surface (second surface) of the film. An adhesive laminated film having an adhesive layer formed thereon. 6. An adhesive layer comprising an adhesive containing 50 to 99 parts by weight of a hydroxyl group-containing polyester resin and 1 to 50 parts by weight of a blocked or unblocked polyisocyanate compound in 100 parts by weight of a resin component. The laminated film according to claim 5, which is: 7. The laminated film according to claim 5, wherein the adhesive layer is a white adhesive layer containing a white pigment. 8. The laminated film according to claim 5, which is thermocompression-bonded to the surface of the packaging material such that the adhesive layer of the laminated film faces the surface of the packaging material. A method for producing a laminated film-covered packaging material. 9. The method according to claim 8, wherein the packaging material is a metal can.