JPH0780281B2 - Plastic laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention has excellent surface hardness, abrasion resistance, scratch resistance, flexibility, and water resistance, especially boiling water resistance, and further excellent weather resistance. It relates to a plastic laminate.

[Conventional technology]

Conventionally, a method of applying a cured layer of a radiation curable composition is known as a method of hardening the surface of a plastic,
Even if these layers are directly applied to a plastic film or sheet-like molded article requiring flexibility, especially a polyethylene terephthalate film or sheet, the adhesiveness between the cured layer and polyethylene terephthalate is extremely poor, and the cured layer peels off, There was a serious problem that wear resistance was reduced in a short period of time.

In order to overcome this problem, as a method of improving the adhesion between the hardness-enhancing film and polyethylene terephthalate, an acrylic resin, polyester resin, polyurethane resin, etc. dissolved, emulsified or suspended in water and / or an organic solvent is used. An undercoating method is being tried. For example, JP-A-60-166453 is known as a laminate in which a cured product layer of a radiation curable composition is applied to an undercoated polyethylene terephthalate film.

However, in most of the treatment agents dissolved, emulsified or suspended in water and / or an organic solvent, after the application, the medium is simply evaporated by drying, and these are cold water or an organic solvent. When it is immersed in or exposed to the above, the hardened layer is peeled off due to delamination between the adhesive layer and the polyethylene terephthalate film, swelling or dissolution of the easily adhesive layer, and wear resistance is reduced. That is, the water resistance and chemical resistance were insufficient.

Moreover, when these are pasted on a glass window or used outdoors, weather resistance deterioration, which is considered to be mainly caused by the action of ultraviolet rays, is caused, cracking occurs in the hardened layer, or the hardened layer peels off. Then, there are serious problems such as deterioration of abrasion resistance and remarkable deterioration of aesthetics.

[Problems to be solved by the invention]

The object of the present invention is to improve such problems, surface hardness, abrasion resistance, scratch resistance, excellent flexibility, and water resistance,
In particular, it is intended to provide a plastic laminate having excellent boiling water resistance.

[Means for solving problems]

MEANS TO SOLVE THE PROBLEM This invention has the following structure in order to achieve the said objective, namely, (1) Polyethylene terephthalate layer (I), Polyester resin layer (II) whose heat of crystal fusion is 0.2 cal / g or more and 5 cal / g or less, and radiation curability A radiation-curable layer (III) comprising a layer (III) laminated in this order, wherein the radiation-curable layer (III) has a monomer (A) having two or more (meth) acryloyloxy groups in one molecule. ) A radiation-curable composition comprising at least one of the following, wherein the composition is a polymerizable monomer comprising a substituted or unsubstituted N-vinylpyrrolidone compound represented by the following general formula (1). (B)
Is 0-40 with respect to the total amount of polymerizable monomers in the composition.
A layered product of a plastic, which is a layer of a radiation-cured reaction product of a composition which is contained in an amount of 1% by weight.

(However, in the formula, R ¹ , R ² and R ³ independently represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms.) The polyethylene terephthalate of the polyethylene terephthalate layer (I) in the present invention includes homopolyethylene terephthalate (Normally, the heat of crystal fusion is about 10 cal / g) is generally used, but if the heat of crystal fusion is 8 cal / g or more,
For example, it may include a copolymerized polyethylene terephthalate in which about 5% of another polyester-forming component is copolymerized, or a polyester blend in which about 5% of another polyester is blended.

An ultraviolet absorber can be added to the polyethylene terephthalate layer (I).

An ultraviolet absorber that can be added to the polyethylene terephthalate layer (I) is added in a polymer polycondensation step, before melt extrusion, or during melt extrusion, and can be uniformly dispersed with good compatibility and can reduce the polymerization degree of the polymer. The ones that have little impact are selected. Specific examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-.
Carboxybenzophenone, 2,4-di-tert-butylbutylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-hydroxy-4-n-octoxybenzophenone, p- Ta-sialybutyl phenyl salicylate, resorcinol monobenzoate, methylene bis (2-hydroxy-4-alkoxybenzophenone), 2- (3 ', 5'-di-sialyamyl-2'-hydroxyphenyl) benzotriazole , 2- (2'-
Hydroxy-3 '-, 5'-di-tert-sialybutylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and the like are preferable, but not limited thereto. Not a thing.

When adding an ultraviolet absorber, the addition amount is 0.
1-5% by weight is preferred, more preferably 0.3-4% by weight
Is. If the amount added is less than the above range, the effect of improving weather resistance cannot be expected, and if the amount added is too large, the degree of polymerization of the polyester during melt extrusion decreases significantly, which is not preferable.

The polyester resin having a heat of crystal fusion of 0.2 cal / g or more and 5 cal / g or less in the present invention (hereinafter abbreviated as D-crystalline polyester resin) means that at least 70 mol% or more of the dibasic acid component is a terephthalic acid residue. , Other dibasic acid components are isophthalic acid, aromatic dicarboxylic acids such as orthophthalic acid, succinic acid, adipic acid, azelaic acid, aliphatic dicarboxylic acids such as sebacic acid, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, One or more dibasic acid residues selected from alicyclic dicarboxylic acids such as hexahydrophthalic acid, wherein at least 60 mol% or more of the glycol component is an ethylene glycol residue,
Other glycol components include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, alkylene glycols such as neopentyl glycol, polyalkylene glycols such as diethylene glycol and triethylene glycol, 1,4- Examples thereof include low crystalline copolymer polyesters having one or more glycol residues selected from cyclohexanediol, ethylene oxide and propylene oxide adducts of bisphenol A, and 1,4-cyclohexanedimethanol.

Among these, a copolymerized polyester consisting of 75 mol% to 95 mol% of terephthalic acid, 25 mol% to 5 mol% of a dibasic acid other than terephthalic acid and ethylene glycol is preferable, and 80 mol% to 90 mol% of terephthalic acid is preferable. A copolymerized polyester composed of 20 mol% to 10 mol% of a dibasic acid other than terephthalic acid and ethylene glycol is particularly desirable.

From the viewpoints of easiness of synthesis of the copolyester and formation of the laminated film, a copolyester in which the dibasic acid is terephthalic acid and isophthalic acid and the glycol is ethylene glycol is preferable, and in this case, terephthalic acid is
82 to 93 mol% and isophthalic acid of 18 to 7 mol% are preferable in terms of adhesiveness and boiling water resistance.

Examples of the monomer (A) having two or more (meth) acryloyloxy groups (acryloyloxy group or methacryloyloxy group) in one molecule in the present invention include the following (meth) acrylates. it can.

The first group is a group of monomers (A ₁ ) having two (meth) acryloyloxy groups in one molecule, and specific examples thereof include (meth) acrylates of (a) to (f) below. Can be mentioned.

(A) (Meth) of alkylene glycol having 2 to 12 carbon atoms
Acrylic acid diesters: ethylene glycol di (meth) acrylate propylene glycol di (meth) acrylate 1,4-butanediol di (meth) acrylate neopentyl glycol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, etc. (B) (meth) acrylate diesters of polyoxyalkylene glycol: diethylene glycol di (meth) acrylate triethylene glycol di (meth) acrylate tetraethylene glycol di (meth) acrylate dipropylene recall di (meth) acrylate polyethylene glycol di (Meth) acrylate polypropylene glycol di (meth) acrylate etc. (c) (meth) acrylic acid diesters of polyhydric alcohol: pentaerythritol di (Meth) acrylate (d) (meth) acrylic acid diesters of bisphenol A or hydrogenated bisphenol A ethylene oxide and propylene oxide: 2,2'-bis (4-acryloxyethoxyphenyl) propane 2, 2'-bis (4-acryloxypropoxyphenyl)
Propane or the like (e) A diisocyanate compound (e) and two or more alcoholic hydroxyl group-containing compounds are reacted in advance with a terminal isocyanate group-containing compound to be further reacted with an alcoholic hydroxyl group-containing (meth) acrylate Urethane (meth) acrylates having one or more (meth) acryloyloxy groups: (f) Two in the molecule obtained by reacting a compound having two or more epoxy groups in the molecule with acrylic acid or methacrylic acid Epoxy (meth) acrylates having the above (meth) acryloyloxy group: Among these monomers having two (meth) acryloyloxy groups in one molecule, 1,4-butanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate is a balun for the hardness and flexibility of the hardened layer. It is preferable because it has good moisture resistance, a large effect of improving the adhesiveness, and good water resistance. Especially when the monomer (B) is not used, it is desirable to use these.

One of these monomers (A ₁ ) may be used, or 2
You may use it in mixture of 2 or more types.

The proportion of these monomers (A ₁ ) used is preferably 0 to 80% by weight, more preferably 10 to 10% by weight based on the total amount of the polymerizable monomers.
80% by weight, most preferably 15-70% by weight.

If the amount of the monomer (A ₁ ) exceeds 80% by weight, a cured film having sufficient abrasion resistance cannot be obtained, which is not preferable.
When the amount of the monomer (A ₁ ) used is small, the flexibility of the cured film tends to decrease and the adhesiveness with the layer (II) tends to decrease. Has no such problems at all.

The second group is a group of monomers (A ₂ ) having three or more (meth) acroyloxy groups in one molecule, and
Examples thereof include compounds in which the polyhydric alcohol having 3 or more alcoholic hydroxyl groups in the molecule is an esterified product of 3 or more (meth) acrylic acid.

Specific examples include pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate dipentaerythritol tri (meth) acrylate dipentaerythritol tetra (meth) acrylate dipentaerythritol penta (meth) acrylate dipentaerythritol hexa (meth) ) Acrylate Trimethylolpropane tri (meth) acrylate These monomers (A ₂ ) may be used alone or in combination of two or more.

The proportion of these monomers (A ₂ ) used is preferably 20 to 90% by weight, more preferably 30 to 80% by weight, based on the total amount of polymer monomers.

When the amount of the monomer (A ₂ ) is less than 20% by weight, a cured film having sufficient abrasion resistance cannot be obtained, and when the amount exceeds 90% by weight, shrinkage due to polymerization is large, It is not preferable because distortion remains in the cured film and flexibility of the film is reduced.

The polymerizable monomer (B) is a substituted or unsubstituted N-vinylpyrrolidone compound represented by the following general formula (1).

(However, in the formula, R ¹ , R ² and R ³ independently represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms).

Specific examples of the polymerizable monomer (B) include N-vinylpyrrolidone N-vinyl-3-methylpyrrolidone N-vinyl-5-methylpyrrolidone.

In particular, N-vinylpyrrolidone is industrially easily available and easy to use.

The proportion of these monomers (B) used is preferably in the range of 0 to 40% by weight, based on the total amount of polymerizable monomers, and is preferably 1 to 30.
% Is more preferable, and 5 to 30% is particularly preferable.

When the proportion of the monomer (B) used exceeds 40% by weight, the water resistance is lowered and the hardened layer may be easily peeled off, which is not preferable.

The radiation-curable composition used in the present invention contains a monomer having one (meth) acryloyloxy group in one molecule or another polymerizable vinyl monomer for the purpose of adjusting the properties of the laminate. , Can be added within a range that does not impair the object of the present invention.

For example, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth)
Acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, isobornyl (meth) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-hydroxy-3-phenylpropyl (meth) acrylate and the like can be mentioned.

One method of curing the radiation curable composition in the present invention is a method of irradiating with ultraviolet rays. In this case, it is desirable to add a photopolymerization initiator to the composition. Specific examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p
-Dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin isopropyl ether,
Methyl benzoyl formate, p-isopropyl-α-
Carbonyl compounds such as hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, Examples thereof include sulfur compounds such as 2-methylthioxanthone, and peroxide compounds such as benzoyl peroxide and di-t-butyl peroxide. These photopolymerization initiators may be used alone or in combination of two or more. The amount of the photopolymerization initiator used is 100 times the polymerizable monomer composition.
0.01 to 10 parts by weight is suitable with respect to parts by weight. When electron rays or gamma rays are used as the curing means, it is not always necessary to add a photopolymerization initiator.

The radiation curable composition used in the present invention contains hydroquinone in order to prevent thermal polymerization during production or a dark reaction during storage.
It is desirable to add known thermal polymerization inhibitors such as hydroquinone monomethyl ether and 2,5, t-butyl hydroquinone. The amount added is 0.005 based on the total weight of the polymerizable compound.
~ 0.05 wt% is preferred.

The radiation-curable composition used in the present invention may contain an organic solvent within the range that does not impair the object of the present invention for the purpose of improving workability during coating and controlling the coating film thickness. .

As the organic solvent, those having a boiling point of about 50 ° C. to 150 ° C. are easy to use from the viewpoint of workability during coating and drying properties before and after curing. Specific examples include methanol, ethanol,
Examples include alcohol solvents such as isopropyl alcohol, acetic ester solvents such as methyl acetate and ethyl acetate, ketone solvents such as acetone and methyl ethyl ketone, aromatic solvents such as toluene, and cyclic ether solvents such as dioxane. . These solvents may be used alone or in combination of two or more.

The composition of the present invention, if necessary, a dye, a pigment, a lubricant,
A leveling agent, an antistatic agent, a surfactant and the like may be added.

The thickness of the cured layer (III) is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less. When the thickness of the hardened layer (III) is less than 0.5 μm, abrasion resistance is insufficient and it is easily scratched, and when it exceeds 10 μm, the hardened film tends to be brittle, and when the laminate is bent, It is not preferable because the cured film is easily cracked.

〔Production method〕

The three-layer plastic laminate of the present invention as described above comprises a step of forming a two-layer laminated film or sheet comprising a polyethylene terephthalate layer (I) and a low crystalline polyester resin layer (II), and a layer (II) It is manufactured by a two-step process of coating and curing the radiation-curable resin composition on the above.

The method of laminating the low crystalline polyester resin is not particularly limited, but the method of coextrusion film formation described in British Patent No. 1465973 is desirable, and the layer thickness of the low crystalline polyester resin to be laminated is 1 μm or more. 10 μm or less is desirable.

When it is less than 1 μm, the adhesion performance with the abrasion resistant layer tends to be nonuniform, and when it exceeds 10 μm, workability in the processing step such as curling and blocking is deteriorated, which is not preferable.

The radiation curable composition of the present invention can be applied by brush coating, dip coating, knife coating, roll coating, spray coating, flow coating, spin coating (spinner, whaler, etc.).
A commonly used coating method such as the above can be easily applied. Each method has its own characteristics, and the coating method is appropriately selected depending on the required performance of the laminate or the intended use.

Examples of the method of curing the radiation curable composition of the present invention include a method of irradiating with active energy rays such as ultraviolet rays, electron rays or gamma rays.

Practically, the method of irradiating with ultraviolet rays is simple and preferable. UV sources include UV fluorescent lamps, low pressure mercury lamps,
There are high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps, etc.

The excellent effect of the present invention is that the specific low crystalline polyester layer (II) is laminated on the polyethylene terephthalate layer, and the monomer (A) and (B) are further laminated on the layer (II). It is caused by using a composition mixed in a specific ratio as a paint. Monomer (B)
Has a property of penetrating into the layer (II) and swelling it by itself. When it is blended in a specific ratio as in the present invention, it is considered that after the coating material is applied, it appropriately interacts with the layer (II) and contributes to the improvement of the adhesiveness. However, the homopolymer of the monomer (B) has remarkably poor water resistance, and particularly the homopolymer of N-vinylpyrrolidone is soluble in water. As a result of blending the monomers (A) and (B) in a specific ratio as in the present invention, there is a remarkable effect that the adhesiveness is high as described above and the adhesiveness is not impaired even when immersed in boiling water. Occurs. When the monomer (B) is not used, the monomer (A ₁ )
As the layer (II), a layer having permeability may be selected, and it is considered that devising a solvent during coating promotes these effects. Further, it is considered that the result of the interaction between the layer (II) and the coating material greatly contributes to the improvement of the weather resistance. When ultraviolet rays are applied to a film having a hardened layer on the existing surface, the adhesiveness at the interface between the hardened layer and the underlayer is reduced, and the hardened layer is likely to peel off. It is presumed that, in the laminate, as a result of the above action, the decrease in adhesiveness was remarkably reduced, and the weather resistance was improved.

Furthermore, in the present invention, when the polyethylene terephthalate layer (I) contains an ultraviolet absorber, when the laminated body is used by being stuck to a transparent body such as window glass, ultraviolet rays are emitted from the polyethylene terephthalate layer side on the back surface. It becomes possible to almost prevent the deterioration by passing through.
When it is used as a protective sheet or sheet by sticking to a material that reflects ultraviolet rays, such as metal,
Since it is possible to prevent the once transmitted ultraviolet rays from being reflected and again passing through the laminate, it is considered that the weather resistance of the laminate itself is further improved in combination with the above-mentioned effect.

The laminate of the present invention has excellent surface hardness and wear resistance, and each layer is closely adhered to the hardness, and is excellent in water resistance, especially boiling water resistance and weather resistance, so that it can be used in a wide range of applications. To be done.

It can be used as a shatterproof film by adhering it to a window glass, or it can be used as a light control film by adhering it to a window glass after dyeing or forming a metal thin film on the exposed surface of the layer (I). In addition, applications such as labels and stamping foils, applications such as decorations and displays attached to glass and metal plates, and various surface protection materials such as lenses,
It can also be used for watches, calculators and instrument covers, touch panels, etc.

The laminate of the present invention is preferably used for laminated safety glass. Here, the laminated glass has at least one inorganic glass layer and at least one synthetic resin layer, and one outermost layer is an inorganic glass and the other outermost layer is a synthetic resin layer. Say.

The laminate of the present invention is suitable for use as the outermost synthetic resin layer, and it is preferable that the radiation-curable layer (III) is the exposed surface at that time in order to prevent the surface from being scratched.

Examples of the structure of the laminated safety glass include a laminated body of the present invention, a thermoplastic synthetic resin layer, and a glass layer laminated in this order. However, the glass layer may be composed of one layer or a plurality of glass layers. It may be a laminated glass formed by laminating a layer and a plurality of thermoplastic synthetic resins.

Examples of the thermoplastic synthetic resin used between the laminate and the glass of the present invention include polyurethane-based thermoplastic resins, polyvinyl butyral resins, polybutadiene resins, ethylene-vinyl acetate copolymer-based resins, polyolefin-based elastomers, and other thermoplastic resins and Elastomers are suitable.

From the viewpoint of transparency, impact resistance, penetration resistance, and other aspects, a polyurethane-based thermoplastic resin is preferable.

The thickness of the thermoplastic synthetic resin layer is not particularly limited, but it is preferably 0.2 mm or more, particularly preferably 0.4 to 10 mm.

The thickness of the glass layer is not particularly limited, but when it is only one layer, it is 2 mm or more, particularly 3.5 to 5 mm is suitable, and when it is laminated glass, 4 mm or more, especially
4.2-10mm is suitable.

As a use of this laminated safety glass, window glass for automobiles is particularly suitable. For example, it can be used as a window material for automobiles such as a windshield and a rear glass, a side glass and a sunroof. Especially, it is most suitable as a windshield from the viewpoint of safety.

[Characteristic test method, evaluation criteria]

The measuring method of the characteristics and the evaluation criteria in the present invention are as follows.

Crystal fusion heat DSC (Differential Scanning Calor) manufactured by PERKIN-LEMER
10 mg of the sample was melted by using a imeter) -2 type, quenched with liquid nitrogen, and then heated at a heating rate of 10 ° C./min.
The calorific value is obtained from the exothermic peak associated with crystallization.

Abrasion resistance Rub the surface of the hardened layer with steel wool # 0000 to check the scratch resistance. The judgment was performed as follows.

S-3: Almost no scratches even with strong rubbing.

S-2; Slightly scratched when rubbed considerably.

S-1: Scratch is caused even by weak friction.

Polyethylene terephthalate without any abrasion resistant coating (III) is S-1 rank.

Adhesiveness A cross-cut (100 squares of 1 mm ² ) is made on the cured layer, Nichiban cellophane tape (24 mm width) is pasted on it, and the peeling area is rapidly peeled off at a peeling angle of 180 ° C. The rankings are as follows.

Adhesion index A5; peeling area 10% or less A4; 〃 20% or less A3; 〃 30% or less A2; 〃 40% or less A1; when 〃 40% or more Strips 1 cm wide and 5 cm long from the flexible laminate The test piece was cut out and wound on a stainless steel rod with the hardened layer on the outside, and the minimum diameter at which cracks did not occur was examined.

Water resistance to boiling After immersing the laminated body in boiling water for 1 hour, the presence or absence of abnormalities in appearance such as cracks were observed, and the same adhesion test was performed.

Ultraviolet irradiation tester (FM-1 type manufactured by Suga Test Instruments Co., Ltd.)
UV irradiation test with a mercury lamp (mercury lamp 400W,
After the distance between the light source and the sample was 30 cm), changes in appearance such as cracks were observed, and the above abrasion resistance test and adhesion test were performed.

〔Example〕

Example 1 A low crystalline polyester resin having the following composition was synthesized by a conventional method.

Composition of low crystalline polyester resin Acid component terephthalic acid 82.5 mol% Isophthalic acid 17.5 mol% Alcohol component ethylene glycol 100 mol% The heat of crystalline fusion of this resin was 1.3 cal / g. Next, this resin was laminated on polyethylene terephthalate by a coextrusion method to form an unstretched film. Then, this was biaxially stretched in the longitudinal and transverse directions and heat-treated to obtain a laminated film having a total thickness of 25 μm with a thickness ratio of the low crystalline polyester resin layer and the polyethylene terephthalate layer of 2: 8.

Next, on the low crystalline polyester layer of this laminated film, 70 parts by weight of pentaerythritol triacrylate,
30 parts by weight of N-vinylpyrrolidone, 1-hydroxycyclohexyl phenyl ketone (Ciba Geigy: “IRUGACUR
The composition obtained by stirring and mixing 4 parts by weight of E "184) was uniformly applied using a bar coater so that the film thickness after curing would be 3 μm. This was set at a height of 12 cm from the coating surface. did
It was passed under a 5.6 kw high pressure mercury lamp (manufactured by Toshiba) having an intensity of 80 W / cm at a speed of 3 m / min. The coating film was completely cured.

The surface of this laminate is smooth and has no fog, and the abrasion resistance is S-
3, the flexibility was 2.0 mmφ, the adhesiveness was rank A5, and the boiling water resistance was rank A5.

Example 2 On top of the low crystalline polyester layer of the laminated film used in Example 1, 80 parts by weight of 1,6-hexanediol diacrylate, 20 parts by weight of N-vinylpyrrolidone, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone. Using a bar coater, the composition obtained by stirring and mixing
Was applied. Apply this to the coated surface under N ₂ atmosphere.
Cured from a height of 30 cm with a 2 kw high pressure mercury lamp for 30 seconds.
The coating film was completely cured.

The surface of this laminate is smooth and has no fog, and the abrasion resistance is S-
3, the flexibility was 2.0 mmφ, the adhesiveness was rank A5, and the boiling water resistance was rank A5.

Example 3 The composition ratio of the polymerizable monomer of the radiation curable composition was 60 parts by weight of pentaerythritol triacrylate, 10 parts by weight of 2,2'-bis (4-acryloxydiethoxyphenyl) propane, N-vinyl. A laminate was obtained in the same manner as in Example 1 except that 30 parts by weight of pyrrolidone and 4 parts by weight of 1-hydroxycyclohexylphenyl ketone were used.

The surface of this laminate is smooth and has no fog, and the abrasion resistance is S-
2. Flexibility was 2.0 mmφ, and both adhesiveness and boiling water resistance were rank A5.

Example 4 On the low crystalline polyester layer of the laminated film used in Example 1, 30 parts by weight of pentaerythritol triacrylate, 70 parts by weight of 1,6-hexanediol diacrylate, and 4 parts by weight of 1-hydroxycyclohexylphenylketone were used. , Ethyl acetate 20 parts by weight, isopropyl alcohol 5
The composition prepared by mixing and dissolving parts by weight was applied using a bar coater so that the film thickness after curing would be 3 μm. This is N ₂
In the atmosphere, it was passed under a high pressure mercury lamp with a strength of 80 W / cm set at a height of 12 cm above the coated surface at a speed of 3 m / min, and then dried at 80 ° C for 1 minute. Hardened.

The surface of this laminate is smooth and has no fog, the ranks of abrasion resistance and adhesiveness are S-3 and A5, respectively, and the flexibility is 2.0 m.
It was mφ.

When the boiling water resistance of this laminate was examined, cracking was not observed at all, and there was no decrease in the adhesiveness of the cured layer, which was ranked A5.
Met.

After the weather resistance test was carried out for 300 hours, the characteristics were examined and no abnormalities in appearance were observed, and neither abrasion resistance nor adhesiveness of the cured film was decreased.

Comparative Example 1 The radiation curable coating composition used in Example 1 was used as a film Meli of ICI Co.
It was applied to nex-505 and similarly UV cured. The properties of the cured film at the initial stage were good, but when immersed in boiling water for 1 hour, the coating film was completely peeled off with cellophane tape, and the adhesion rank was A1.

Comparative Example 2 Same as Example 1 except that the composition ratio of the polymerizable monomer of the radiation curable composition used in Example 1 was 55 parts by weight of pentaerythritol triacrylate and 45 parts by weight of N-vinylpyrrolidone. To form a laminated body. After curing, the coated surface became cloudy and the transparency was significantly reduced.

Example 5 The composition ratio of the polymerizable monomer of the radiation curable composition used in Example 4 was 70 parts by weight of pentaerythritol triacrylate, 15 parts by weight of 1,4-butanediol diacrylate,
A laminate was obtained in the same manner as in Example 4 except that 15 parts by weight of N-vinylpyrrolidone, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, and 20 parts by weight of ethyl acetate were used.

The surface of this laminate is smooth and has no fog, the ranks of abrasion resistance and adhesiveness are S-3 and A5, respectively, and the flexibility is 2.0 m.
It was mφ.

When the boiling water resistance of this laminate was examined, cracking was not observed at all, and there was no decrease in the adhesiveness of the cured layer, which was ranked A5.
Met.

Even in the weather resistance test (300 hours), no abnormality in appearance was observed, and neither abrasion resistance nor adhesion of the cured film was deteriorated.

Example 6 The composition ratio of the polymerizable monomers of the radiation curable composition used in Example 4 was set to dipentaerythritol hexaacrylate.
70 parts by weight, 1,6-hexanediol diacrylate 20 parts by weight, N-vinylpyrrolidone 10 parts by weight, 1-hydroxycyclohexyl phenyl ketone 4 parts by weight, ethyl acetate 20
A laminate was obtained in the same manner as in Example 4 except that the laminate was composed of parts by weight.

The surface of this laminate was smooth and free from fogging, and the abrasion resistance, adhesiveness, flexibility, boiling water resistance, and properties after the weather resistance test were at the same level as those obtained in Example 4. .

Example 7 The composition ratio of the polymerizable monomer of the radiation curable composition used in Example 4 was 20 parts by weight of pentaerythritol triacrylate, 70 parts by weight of 1,4-butanediol diacrylate,
A laminate was obtained in the same manner as in Example 4 except that 10 parts by weight of N-vinylpyrrolidone, 4 parts by weight of 1-hydroxycyclohexylphenyl ketone, and 20 parts by weight of ethyl acetate were used.

The surface of this laminate is smooth and has no fog, the ranks of abrasion resistance and adhesiveness are S-3 and A5, respectively, and the flexibility is 2.0 m.
It was mφ.

With respect to boiling water resistance, no abnormal appearance such as cracking was observed, and the adhesiveness of the cured layer was not deteriorated at all. Further, even after the weather resistance test, no abnormal appearance, abrasion resistance, and deterioration of the adhesiveness of the cured film were observed.

〔The invention's effect〕

The present invention is a polyethylene terephthalate film, laminated with a polyester resin having a heat of crystal fusion in a specific range, and further curing a radiation-effective composition in which a specific monomer is blended in a specific ratio on the layer. By providing the layer, a laminate having excellent surface hardness, abrasion resistance, scratch resistance, flexibility, water resistance, particularly boiling water resistance, and weather resistance can be obtained.

Claims (3)

[Claims] 1. A polyethylene terephthalate layer (I),
A plastic laminate comprising a polyester resin layer (II) having a heat of crystal fusion of 0.2 cal / g or more and 5 cal / g or less and a radiation curable layer (III) laminated in this order, wherein the radiation curable layer ( III) is at least 1 of the monomer (A) having two or more (meth) acryloyloxy groups in one molecule.
A radiation curable composition comprising a seed, wherein the polymerizable monomer (B) comprising a substituted or unsubstituted N-vinylpyrrolidone compound represented by the following general formula (1) is included in the composition. , With respect to the total amount of polymerizable monomers in the composition,
A plastic laminate, which is a layer of a radiation curing reaction product of a composition containing 0 to 40% by weight. (However, in the formula, R ¹ , R ² and R ³ independently represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms) 2. The monomer (A) comprises at least one kind of the monomer (A ₁ ) having two (meth) acryloyloxy groups in one molecule and three or more (( ₁ ) The plastic laminate according to claim (1), which comprises at least one kind of a monomer (A ₂ ) having a (meth) acryloyloxy group. 3. The mixing ratio of the polymerizable monomer in the composition is as follows: Monomer A ₁ : 0 to 80% by weight Monomer A ₂ : 20 to 90% by weight Monomer B: 0 to 40% by weight %, The plastic laminate according to claim (2).