JPH0733502B2 - Method for producing film-bonded steel sheet and adhesive composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a plastic film laminated steel sheet by an electron beam curing method and an adhesive composition thereof.

2. Description of the Related Art Conventionally, various methods have been considered as a method for laminating a plastic film to a metal plate, but one typical method currently practiced is to apply a solvent-based adhesive to the metal plate. There is a method in which the solvent is scattered by a heating method such as hot air, far infrared rays, and near infrared rays, and at the same time, a crosslinking reaction is caused in the adhesive resin, and the films are laminated while the adhesive resin is in a heated state and is tacky.

It is well known that high quality laminated products are produced by utilizing the heat curing method. However, in this case, the line speed during production is restricted by the length of the heating furnace in the case of coil products, and because solvents are used and combustion exhaust gas from the hot air drying furnace, pollution control measures are required. There are problems such as having to do it strictly.

On the other hand, in the resin curing method, the electron beam curing method has been noted since the early 1965's. The features of this method are high-speed curing (10 ^-1 to 10 ^-2 seconds), no waste gas from the oven, etc. Also, 100% non-volatile resin system can be adopted to reduce pollution, line cost is low, For example, there is no thermal aging of the metal plate because it is not heated.

However, these characteristics may be a defect when adopted as a method for curing an adhesive in the production of a laminated metal plate.

That is, in the electron beam curing method, since the curing reaction proceeds in a very short time at room temperature, the internal shrinkage stress of the adhesive layer is very large, and the effect of wetting due to heat fusion in the heat curing method is obtained. Can not be expected. For this reason, it is expected that it will be difficult to obtain a resin system having good adhesion and workability particularly to metals and the like, and having a nonvolatile content of 100%.

The present inventors diligently studied electron beam curable resin systems, and firstly, polyurethane (meth) acrylate having two or more (meth) acryloyl groups and oligo (meth) acrylate having 2 to 6 functional groups. And improving the above-mentioned drawbacks composed of (meth) acrylate monomer, and capable of fast curing,
An adhesive composition with good product quality was developed and filed (Japanese Patent Application Laid-Open No. 59-86676).

However, the adhesive composition of JP-A-59-86676 is
The film adhesion (peel) strength is up to 5kg / 20mm,
The adhesive strength was not yet sufficient.

DISCLOSURE OF THE INVENTION Problems to be Solved by the InventionTherefore, the present inventors further studied the electron beam curable adhesive having good adhesiveness to both the plastic film and the metal, and the non-volatile content is about 100%. The present invention invents a method for producing a film-bonded steel sheet by an electron beam curing method, which is capable of high-speed curing (60 m / min or more) and has good product quality such as processing adhesion, and an adhesive composition thereof.

Means for Solving the Problems That is, the present invention provides (A) an isocyanate forming a chemical structure terminal of a compound having a weight average molecular weight of 3,000 or more, which is synthesized mainly from a hydroxyl-containing bifunctional compound having bromine and an organic diisocyanate. Polyurethane (meth) acrylate having two or more (meth) acryloyl groups obtained by reacting a hydroxyl group-containing (meth) acrylate with (B) having two or more (meth) acryloyl groups in one molecule, and (meth) (Meth) acrylate having a number average molecular weight of 600 or less per acryloyl group (C) A non-volatile (meth) having one (meth) acryloyl group in one molecule and having a number average molecular weight of 120 to 500 A metal plate and a plastic film are attached together with an adhesive containing acrylate as an essential component and (D) an organic metal-containing monomer if necessary. After allowed, there is provided a production method and the adhesive film lamination metal plate by irradiating an electron beam through the film layer, characterized in that of curing the adhesive.

Specific Description of the Invention First, the adhesive composition of the present invention will be described.

Component A is a chemical structure of a compound having a weight average molecular weight of 3000 or more synthesized by using a difunctional bromine-containing difunctional compound and an organic diisocyanate as a main component, and reacting a hydroxyl group-containing (meth) acrylate with an isocyanate 2 A polyurethane (meth) acrylate having at least one (meth) acryloyl group, for example, the general formula It is shown by.

Here, R ₁ is a hydrogen atom or a methyl group, R ₂ is a substituted or unsubstituted hydrocarbon group or a group in which the same or different hydrocarbon groups are linked to each other by an ether bond or an ester bond, and has at least one hydroxyl group. It represents an a-valent group and may be substituted with a halogen atom or the like. a is an integer of 1 to 3.

R ₃ may be the same or different and represent a residue of an organic diisocyanate.

R _{4 s} may be the same or different and each represents a residue of a hydroxyl group-containing bifunctional compound having bromine. n represents an integer of 1 or more.

In the present specification, the (meth) acryloyl group means a methacryloyl group or an acryloyl group, and the polyurethane (meth) acrylate means a polyurethane methacrylate or a polyurethane acrylate. Other similar descriptions have similar meanings.

The role of the component A is mainly to give flexibility and adhesion when the adhesive layer is processed, and the adhesiveness is particularly improved by containing bromine.

As the component A, for example, a hydroxyl-containing bifunctional compound having bromine and an organic diisocyanate are first reacted to synthesize a high-molecular weight prepolymer having an isocyanate group at the terminal chain-extended by a urethane bond. It is obtained by subjecting a terminal isocyanate group to an addition reaction with a hydroxyl group-containing (meth) acrylate.

The weight average molecular weight of polyurethane (meth) acrylate is 3,000 or more, preferably 5,000 or more. The higher the weight average molecular weight, the better the physical properties obtained. Due to the above restrictions, 100,000 or less is preferable.

Examples of the hydroxyl-containing bifunctional compound having bromine used for constituting the urethane (meth) acrylate include: However, the present invention is not limited to these.

Among these, a bromine compound having an aromatic ring is preferable from the viewpoint of improving adhesion to metals and plastics.

These may be used alone or in combination of two or more.

The required amount of bromine contained in the polyurethane (meth) acrylate molecular skeleton is such that the molecular weight of the polyurethane (meth) acrylate per bromine atom is 300 to 20000, preferably 300 to 7000 for the purpose of the present invention. It is a thing. If this value is greater than 20,000, the adhesion to metal and film will be poor, and if it is less than 300, the flexibility will be significantly lost.

Further, in order to adjust the viscosity, adhesiveness, flexibility of the cured product, etc. of the polyurethane (meth) acrylate as necessary, if the bromine content is within the range of the present invention, the active hydrogen group-containing diamine containing no bromine is used. A part of the functional compound may be used together.

Examples of such combinations include alkylene diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol.

Oxyacid esters of alkylene diols such as lactic acid propylene glycol ester and hydroxypivalic acid neopentyl glycol ester.

Diethylene glycol, triethylene glycol, 2,2
-Bis [4- (2-hydroxypropoxy) phenyl]
Polyether diols such as propane, polypropylene glycol and polytetramethylene glycol.

3,9-bis (1,1-dimethyl-2-hydroxyethyl)-
A heterocyclic diol containing an ether bond such as 2,4,8,10-tetraoxyspiro [5,5] undecane.

Dihydric alcohols such as polycaprolactone diol, ethylene glycol, propylene glycol and tetramethylene glycol and maleic acid, fumaric acid, adipic acid,
Polyester diol obtained by polycondensation reaction with dibasic acids such as sebacic acid, azelaic acid and phthalic acid.

Thioether glycols such as diethylene thioether glycol.

Dithiols such as ethylenedithiol, trimethylenedithiol and tetramethylenedithiol may be mentioned.

Examples of the organic diisocyanate used in the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hexanemethylene diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, 1,3-bis (α , Α-dimethylisocyanatomethyl) benzene and the like.

When the plastic substrate to be laminated is transparent and the yellowing of the adhesive is disliked, so-called non-yellowing type diisocyanate is preferably used.

As the hydroxyl group-containing (meth) acrylate, it is necessary to have at least one hydroxyl group and a (meth) acryloyl group at the same time, but in order to impart physical properties, particularly elasticity, of the cured adhesive, (meth) acryloyl Radix is 1
A range of 3 is preferred.

Examples of such a hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy-3-.
Chloropropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate. , 1,4-butylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, tetramethylolmethane tri (meth) acrylate, triethylene glycol mono ( Examples thereof include (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polycaprolactone glycol mono (meth) acrylate. These may be used alone or in combination of two or more.

The component B mainly imparts high-speed curing property,
Having two or more (meth) acryloyl groups in one molecule,
A (meth) acrylate having a number average molecular weight per one (meth) acryloyl group, that is, a (meth) acryloyl group equivalent of 90 or more and 600 or less is a (meth) acrylate of the following polyhydric alcohol.

The (meth) acrylate of this polyhydric alcohol refers to one in which a (meth) acrylic acid group is introduced by reacting (meth) acrylic acid with the hydroxyl group at the end of the polyhydric alcohol, and combined with urethane (meth) acrylate to achieve a high degree of crosslinking density. It plays a role to obtain. For that purpose, one molecule contains two or more (meth) acryloyl groups,
The (meth) acryloyl group equivalent is 90 or more and 600 or less, preferably 150 or less, more preferably about 130 or less. still,
In this case, a mixture of polyhydric alcohol (meth) acrylate may be used. The polyhydric alcohol mentioned here means the following.

That is, as the dihydric alcohol, ethylene glycol, propylene glycol, chloropropylene glycol, butanediol (1,2
3-or 1,4- or 2,3-), 3-methylpentanediol, 2,2-diethylpropanediol, pentamethylene glycol, 1,6-hexanediol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol , Neopentyl glycol, hexamethylene diol, etc., alicyclic glycol type, 14-cyclohexanediol, cyclohexane-1,4-dimethanol, hydrogenated bisphenol A, etc., polyalkylene glycol type, diethylene glycol, triethylene glycol, polyethylene Glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, polybutadiene diol, etc., and as an aromatic glycol type, 2,2'-bis (4-hydroxyphenyl) propane ( Addition of alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) to phenols such as bisphenol A), bis (4-hydroxyphenyl) methane (also known as bisphenol F), 4,4'-dihydroxyphenyl, hydroquinone and resorcin. Examples thereof include glycols obtained by the above.

As the trihydric or higher alcohol, as an alkanetriol type, glycerin, trimethylolmethane, triemerolethane, trimethylolpropane, 1,2,6-hexanetriol, 1,2,3-butanetriol, alkanetetraol , Erythritol, pentaerythritol, dipentaerythritol and the like.

By using the component B, the urethane (meth) acrylate is reactively crosslinked, and is rapidly cured. Also, B
Various properties of the adhesive layer by being crosslinked by the components,
That is, chemical resistance, heat resistance, boiling water resistance, solvent resistance, durability such as corrosion resistance and weather resistance are improved.

Here, the quantitative relationship between the A component and the B component is as follows:
The number of C = C bonds in the B component is 0.05 to 30 per one unsaturated carbon double bond (hereinafter abbreviated as C = C bond) of the (meth) acrylate group contained in the molecule of the A component. The range of 0.1 to 3 is desirable.

If the number of C = C bonds in the B component is smaller than the range of the present invention, there arises such disadvantages that the crosslink density is low, or the various performances of the above-mentioned products are not sufficient. On the other hand, when the number of C = C bonds of the B component is larger than the range of the present invention, crosslinking proceeds too much, the flexibility of the adhesive layer is lost, or the internal stress increases due to large shrinkage. Due to such reasons, it becomes inconvenient in terms of adhesion, workability and the like. The amount of B component is about 0.1 to 50 relative to 100 parts by weight of A component.
Parts by weight.

Component C is a non-volatile (meth) acrylate monomer having one (meth) acryloyl group in one molecule and a molecular weight of 120 to 500.

Examples thereof include esters of (meth) acrylic acid with alkyl alcohol, cyclic ether alcohol, glycidyl alcohol and the like.

As a specific example, n-butyl (meth) acrylate, t-
There are butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate and the like.

Other examples include alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate, polyol mono (meth) such as ethylene glycol mono (meth) acrylate and propylene glycol mono (meth) acrylate. Acrylate, phenyl glycidyl ether, butyl glycidyl ether, bisphenol A mono (meth)
Examples thereof include epoxy (meth) acrylates such as glycidyl ether.

Here, to explain the term non-volatile, if left in the open system in the air for 24 hours (for example, on a Petri dish), or even if heated at 100 ℃ for 10 seconds, The weight change rate is within 5%.

Component C is mainly to adjust the viscosity of the adhesive system by mixing it with components A and B. If the amount of component C is 250 parts or more per 100 parts by weight of component A, the curing reaction will be delayed. In some cases, it may become uncured,
The viscosity of the adhesive is remarkably reduced, which impairs workability during application. When it is 10 parts or less, the role of the viscosity adjusting agent in the component A and B blending system is not often fulfilled.

Component D is an organic metal-containing monomer. By using the D component, the adhesion of the processed portion to the metal plate is improved.
Examples thereof include 2-acid phosphoxyethyl (meth) acrylate and 3-chloro-2- (meth) acrylate.
Examples of phosphorus-containing compounds such as acid phosphoxypropyl, (meth) acryloxyethyl phosphate, bis (meth) acryloxyethyl phosphate, and tris (meth) acryloxyethyl phosphate, as well as those containing titanium and silicon There is.

The component D is used in an amount of 10 parts by weight or less per 100 parts by weight of the component A.

The composition of the present invention comprises the above-mentioned components (A), (B) and (C) as essential components, and optionally contains the above-mentioned component (D). The composition may optionally contain a thermal polymerization inhibitor, a colorant (pigment or dye), and a low boiling point (preferably
It does not matter if a small amount of organic solvent (180 ℃ or less) is included.

The composition of the present invention is a combination of the components A, B and C, or the addition of the component D, but the purpose can be achieved only by combining them.

Next, a method for producing a film-bonded steel sheet by the electron beam curing method of the present invention will be described.

The plastic film used in the present invention is not particularly limited, and polyvinyl chloride, polyacrylic, polyester, polyethylene, polypropylene, polycarbonate, fluoropolymer, synthetic rubber and other films can be used. The film thickness is usually about 10 to 500 μ.

Further, as the metal plate, hot-rolled plate, cold-rolled plate, zinc iron plate, electrogalvanized steel plate, tin plate, tin-free steel, other alloy-plated steel plate, stainless steel, aluminum plate, steel plate and other metal plates, and those If necessary, a chemical conversion treatment, for example, a treatment such as a phosphate treatment, a chromate treatment, an organic phosphate treatment, or an organic chromate treatment can be used.

An example of how to use this adhesive is as follows. (Surface treatment) A steel sheet is coated with the electron beam curable adhesive of the present invention with a roll coater, and immediately a plastic film is laminated with a roll and electron beam irradiation is performed on the plastic film to cure the adhesive and laminate. Manufacture steel sheet.

The roll coater method is most suitable as the coating method, but the method is not limited to this, and may be a gravure method, an offset method, a knife coater, a spray, or a flow coater method.

The viscosity of the adhesive is about 100,000 cp, considering the heating application.
Can be applied up to s position. An appropriate thickness of the adhesive is in the range of 1 to 30 μm.

As the electron beam irradiation device, a known electron beam accelerating device such as a scanning type or non-scanning type can be used.
The irradiation dose required for curing the adhesive is about 0.1 to 20 Mrad, preferably 0.5 to 10 Mrad as a substantial dose that passes through the film.

Post-heating may be performed after the electron beam irradiation. Achievable plate temperature is around 40-300 ℃.

The laminated metal plate using the electron beam curable adhesive of the present invention is used for outdoor applications such as roofs, walls, doors, etc., or indoor applications such as TV cabinets, room air conditioners, stereo decorative boards, and steel desks. It is also applicable to many uses such as the current thermosetting laminated metal plate.

Example 1 (a) 1 mol of polyester diol consisting of phthalic acid and ethylene glycol, (b) 3 mol of ethylene oxide adduct of bisphenol A, (c) tetrabromobisphenol A bis which is a hydroxyl-containing bifunctional compound containing bromine. After mixing 1 mol of (2-hydroxyethyl ether), 10 mol of (d) tolylene diisocyanate was added dropwise to carry out an addition reaction to obtain a polymer having a molecular weight of 3000.

An isocyanate group at both ends of 1 mol of this polymer (e) and 2 mol of 2-hydroxyethyl acrylate were subjected to an addition reaction to produce a component having a molecular weight of 3200A.

50 parts of this A component and 3.1 parts of ethylene glycol dimethacrylate as the B component (one double bond of the B component is used for each double bond in the A component), C
An adhesive consisting of 50 parts of methoxydiethylene glycol methacrylate as a component was applied onto a nickel displacement-plated zinc steel plate (plate thickness 0.5 mm) so as to have a film thickness of 6 μ after hardening, and a soft vinyl chloride sheet (band- CR19533 manufactured by Kagaku Co., Ltd. was pressure-bonded with a roll, and then an electron beam was irradiated at an acceleration voltage of 300 Kv so that the irradiation dose was 7.5 Mrad. Then, it was immersed in boiling water for 5 seconds and post-heated to obtain a vinyl chloride resin metal laminated steel sheet. The adhesive performance of the obtained vinyl chloride resin metal laminated steel sheet is shown in Table 1.

Example 2 (a), (b), (c), (d) is the same as Example 1.
The molecular weight of (e) is 4800, and the molecular weight of component A is 5000.
Manufactured to be. 50 parts of this A component and 2.0 parts of ethylene glycol dimethacrylate as the B component (one double bond in the A component was made to have one double bond), and tetrahydrofurfuryl as the C component. An adhesive containing 50 parts of acrylate and 5 parts of phosphorus-containing ester (PM2, manufactured by Nippon Kayaku Co., Ltd.) as component D was blended in the same manner as in Example 1.

Using this adhesive, a vinyl chloride resin metal laminated steel sheet was obtained by the same production method as in Example 1. The adhesive performance of the obtained vinyl chloride resin metal laminated steel sheet is shown in Table 1.

Example 3 (a), (b), (c), (d) is the same as Example 1.
The molecular weight of (e) is 9800, and the molecular weight of component A is 1000.
It was manufactured to be 0. 50 parts of this A component and bismethacryloxypolyethoxyphenylpropane as the B component
An adhesive containing 2.7 parts, 50 parts of tetrahydrofurfuryl acrylate as the C component, and 5 parts of phosphorus-containing ester (PM1 manufactured by Nippon Kayaku Co., Ltd.) as the D component was blended in the same manner as in Example 1.

Using this adhesive, a vinyl chloride resin metal laminated steel sheet was obtained by the same production method as in Example 1. The adhesive performance of the obtained vinyl chloride resin metal laminated steel sheet is shown in Table 1.

Example 4 An adhesive was manufactured by using the same composition as in Example 3 with the components A, B, C, and D. This adhesive was applied to an aluminum plate (plate thickness 1.0 mm) coated with a chromate treatment solution so that the film thickness would be 6 μ after curing, and a sheet containing polyethylene terephthalate having a thickness of 100 μ as a main component (Toray Lumirror) was roll-pressed and irradiated with an electron beam at an accelerating voltage of 300 KV and an irradiation dose of 8.0 Mrad to obtain a polyethylene terephthalate resin metal laminated steel sheet. The adhesive performance of the obtained product is shown in Table 1.

Example 5 A sheet was prepared by using the adhesive and the metal plate shown in Example 4.
A product in which μ of polyethylene (F101-1 manufactured by Tokyo Sankei Industry Co., Ltd.) was used was obtained by the same manufacturing method as in Example 4. The adhesive performance of the obtained product is shown in Table 1.

Comparative Example 1 A urethane acrylate having a molecular weight of 10,000 and excluding (c) in the component A shown in the claims of Example 1 was produced. The B component, C component, D
An adhesive was obtained by blending the components in the same manner as in Example 3. Using this adhesive, a vinyl chloride resin metal laminated steel sheet was obtained by the same production method as in Example 1. The adhesive performance of the obtained vinyl chloride resin metal laminated steel sheet is shown in Table 1.

EFFECTS OF THE INVENTION As described above, according to the present invention, since the polyurethane (meth) acrylate containing bromine in the molecular skeleton is used as the component A, the adhesion between the film and the metal plate is significantly improved, and a high quality product is obtained. It has the effect that it can be produced at high speed and with a reduced pollution process.

Front Page Continuation (72) Inventor Oka Zenji 1 Kimitsu, Kimitsu-shi, Chiba Shin Nippon Steel Co., Ltd. Inside the Kimitsu Steel Works (72) Inventor, Shinichi Enomoto Kimitsu 1, Kimitsu-shi, Chiba Nippon Steel Construction Material Co., Ltd. Inside the Kimitsu Works (72) Inventor Rishi Onuma 1 Kimitsu, Kimitsu-shi, Chiba Nippon Steel Construction Materials Co., Ltd. Inside the Kimitsu Works (72) Inventor Kiyomi Kato 1-6-18-807 Kichijoji Minami-cho, Musashino City, Tokyo ( 72) Inventor Koichi Hagiwara, Nakanosho-cho, Negami-cho, Nomi-gun, Ishikawa-142-3

Claims (4)

[Claims] 1. A compound having a weight average molecular weight of 3000 or more (A) a compound having a bromine-containing bifunctional compound and an organic diisocyanate as a main component, and having a hydroxyl group-containing (meth) acrylate in the isocyanate forming the chemical structure terminal. Polyurethane (meth) acrylate having two or more reacted (meth) acryloyl groups, (B) Number of two or more (meth) acryloyl groups in one molecule, and number per (meth) acryloyl group An essential component is a (meth) acrylate having an average molecular weight of 600 or less, and (C) a non-volatile (meth) acrylate having one (meth) acryloyl group in one molecule and having a number average molecular weight of 120 to 500. After laminating the metal plate and the plastic film via the adhesive contained as, the electron beam is irradiated through the film layer to cure the adhesive. A method for producing a film-bonded metal plate, comprising: 2. A hydroxyl group-containing (meth) acrylate is added to the isocyanate forming the chemical structure of a compound (A) having a weight average molecular weight of 3000 or more, which is synthesized mainly from a bifunctional compound having a bromine group and an organic diisocyanate. Polyurethane (meth) acrylate having two or more reacted (meth) acryloyl groups, (B) Number of two or more (meth) acryloyl groups in one molecule, and number per (meth) acryloyl group An essential component is a (meth) acrylate having an average molecular weight of 600 or less, and (C) a non-volatile (meth) acrylate having one (meth) acryloyl group in one molecule and having a number average molecular weight of 120 to 500. Further, (D) the metal plate and the plastic film are bonded together via an adhesive containing an organic metal-containing monomer, and then an electric charge is passed through the film layer. Film lamination manufacturing method of combined metal plate, characterized in that of curing the adhesive by irradiating the line. 3. A compound having a weight average molecular weight of 3000 or more (A) a compound having a bromine-containing difunctional hydroxyl group-containing compound and an organic diisocyanate as a main component and having a hydroxyl group-containing (meth) acrylate in the isocyanate forming the chemical structure terminal. Polyurethane (meth) acrylate having two or more reacted (meth) acryloyl groups, (B) Number of two or more (meth) acryloyl groups in one molecule, and number per (meth) acryloyl group An essential component is a (meth) acrylate having an average molecular weight of 600 or less, and (C) a non-volatile (meth) acrylate having one (meth) acryloyl group in one molecule and having a number average molecular weight of 120 to 500. An electron beam curable adhesive composition for adhering a metal and a plastic film containing the above. 4. (A) A hydroxyl group-containing (meth) acrylate is added to an isocyanate having a chemical structure terminal of a compound having a weight average molecular weight of 3000 or more synthesized by using a difunctional compound having a bromine group having a hydroxyl group and an organic diisocyanate as main components. Polyurethane (meth) acrylate having two or more reacted (meth) acryloyl groups, (B) Number of two or more (meth) acryloyl groups in one molecule, and number per (meth) acryloyl group An essential component is a (meth) acrylate having an average molecular weight of 600 or less, and (C) a non-volatile (meth) acrylate having one (meth) acryloyl group in one molecule and having a number average molecular weight of 120 to 500. And (D) an electron beam curable adhesive composition for adhering a metal containing an organic metal-containing monomer to a plastic film.