JPH06286073A - Manufacture of hard coating film - Google Patents

Abstract

PURPOSE:To provide a method for efficiently obtaining a hard coating film having excellent properties such as weather resistance, mar-proofness, etc. CONSTITUTION:A method for manufacturing a hard coating film comprises the steps of forming an ionizing radiation curable resin layer of mixed resin of weather-resistant resin and ionizing radiation curable resin on one or both side surfaces of a plastic film base material, then laminating a coating plastic film on the curable resin layer, then curing the curable resin layer by emitting an ionizing radioactive ray, then peeling and removing the plastic film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hard coat film used as an exterior material for buildings, for example.

[0002]

2. Description of the Related Art A hard coat film having excellent properties such as weather resistance and scratch resistance is formed by forming a curable resin layer containing an ultraviolet absorber on one or both sides of a plastic film substrate and curing it. It is manufactured by

[0003]

In the conventional method for producing a hard coat film described above, an ultraviolet absorber is added to the cured resin layer, and the curing treatment is performed in an atmosphere containing oxygen. Therefore, it has a drawback that the curing speed of the resin layer is extremely slow.

On the other hand, the present invention provides a method by which a hard coat film having excellent properties such as weather resistance and scratch resistance can be efficiently obtained.

[0005]

According to the present invention, an ionizing radiation curable resin layer made of a mixed resin of a weather resistant resin and an ionizing radiation curable resin is formed on one surface or both surfaces of a plastic film substrate, and then the ionized radiation curable resin layer is formed. Laminating a coating plastic film on the radiation-curable resin layer surface, then curing the mixed resin layer by irradiating with ionizing radiation, followed by peeling the coating plastic film, removing from the method for producing a hard coat film Become.

In the present invention, an ionizing radiation curable resin layer containing an ultraviolet absorber is formed on one side or both sides of a plastic film substrate, and then a plastic film for coating is laminated on the surface of the ionizing radiation curable resin layer. Then
Then, the resin layer is cured by irradiating it with ionizing radiation, and subsequently, the method for producing a hard coat film comprises peeling and removing the coating plastic film.

Further, the present invention comprises a method for producing a hard coat film, wherein a plastic film having irregularities is used as the covering plastic film, and the plastic film is laminated so that the irregular surface of the plastic film is in contact with the surface of the ionizing radiation curable resin layer. .

In the method of producing a hard coat film of the present invention having the above-mentioned constitution, the plastic film substrate is made of AAS resin, ABS resin, ACS resin, amino resin, cellulose resin such as cellulose acetate, cellulose acetate butyrate, ethyl cellulose, ethylene. -Α-olefin copolymer resin, ionomer resin, methacryl-styrene copolymer resin, nitrile resin, phenol resin, polyamide resin, polyacrylate resin, polycarbonate resin, polybutadiene resin, polybutylene terephthalate resin, polyethylene resin, polyethylene terephthalate resin , Polymethylmethacrylate resin, polypropylene resin, polyphenylene oxide resin, polystyrene resin, AS resin, polyurethane resin, polyvinyl chloride resin, acrylic modified resin Vinyl chloride resin, a film according to the unsaturated polyester resin or the like is utilized.

When forming a mixed resin layer of a weather resistant resin and an ionizing radiation curable resin on a plastic film substrate, the weather resistant resin may be polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene.・ Fluorine resin such as polytetrafluoroethylene copolymer, acrylic resin such as methyl polymethacrylate, ethyl polymethacrylate, ethyl polyacrylate and butyl polyacrylate, polycarbonate resin, silicone-acrylic resin The mixed resin of the above-mentioned fluorine-based resin and acrylic resin is used.

Further, as the ultraviolet absorber when forming the ionizing radiation curable resin layer containing the ultraviolet absorber on the plastic film substrate, for example, 2- (2'-hydroxy-3 ', 5'- Di-tert-butylphenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl- 5'-isobutylphenyl) -5-chlorobenzotriazole, 2-
(2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-
2 ′ such as (2′-hydroxy-3′-isobutyl-5′-propylphenyl) -5-chlorobenzotriazole
-Hydroxyphenyl-5-chlorobenzotriazole type ultraviolet absorbers,

2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2
2'-hydroxyphenyl benzotriazole type ultraviolet absorbers such as-(2'-hydroxy-5'-methylphenyl) benzotriazole,

2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, etc. Dihydroxybenzophenone type ultraviolet absorbers,

2-Hydroxybenzophenone type ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone, salicylate type ultraviolet absorbers such as phenyl salicylate, etc. may be used.

The ionizing radiation curable resin is, for example, a mixed resin composition containing a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule.

Specific examples of the prepolymers and oligomers include unsaturated polyesters formed by condensation products of unsaturated dicarboxylic acids and polyhydric alcohols, polyester methacrylates, polyether methacrylates, polyol methacrylates, melamine methacrylates, etc. Acrylates such as methacrylates, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polyol acrylates, and melamine acrylates are used.

Further, specific examples of the monomer include styrene, a styrene-based monomer such as α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate,
Acrylic esters such as butyl acrylate, methoxybutyl acrylate, phenyl acrylate, etc.,

Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, etc.,

2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dibenzylamino) ethyl acrylate, methacrylic acid Substituted amino alcohol esters of unsaturated acids with 2- (N, N-dimethylamino) methyl, 2- (N, N-diethylamino) propyl acrylate, etc.

Unsaturated carboxylic acid amides such as acrylamide and methacrylamide,

Diacrylate compounds such as ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate and triethylene glycol diacrylate,

Dipropylene glycol diacrylate,
Polyfunctional compounds such as ethylene glycol acrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate,

Trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate,
A polythiol compound having two or more thiol groups in the molecule such as pentaerythritol tetrathioglycol is used.

The ionizing radiation-curable resin is usually 5 to 95% by weight of the above-mentioned prepolymer or oligomer,
95-5% by weight of monomer and / or polythiol compound
And a mixed composition thereof is used.

In the ionizing radiation curable resin, when the ionizing radiation curable resin is cured by irradiation with ultraviolet rays, for example, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester are used. , Tetramethylmeuram monosulfide,
Needless to say, it contains a photopolymerization initiator such as thioxanthone and a photosensitizer added as necessary, for example, a photosensitizer such as n-butylamine, triethylamine, and tri-n-butylphosphine. is there.

In the ionizing radiation-curable resin, for the purpose of adjusting physical properties such as flexibility and surface hardness of the resulting ionizing radiation-curable resin layer, a non-ionizing radiation-curable resin such as polyurethane-based or cellulose-based resin is used. , Polyester-based, polyacrylic-based, polybutyral, polyvinyl chloride, polyvinyl acetate, and other thermoplastic resins, 1 to 70% by weight, preferably 5
˜50 wt% can be added.

The ionizing radiation-curable resin layer is applied to a plastic film substrate by, for example, roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating.・ Dry thickness is 0.1 due to smooth coat and comma coat.
It is formed to have a thickness of 100 μm.

As the covering plastic film laminated on the surface of the ionizing radiation-curable resin layer formed on the plastic film substrate, polypropylene film, polyethylene terephthalate film and the like are preferably used.

As the covering plastic film having irregularities, for example, a plastic film obtained by embossing, a plastic film coated with a matting agent, a plastic film mixed with a matting agent, and the like can be used.

Irradiation of ionizing radiation is performed by, for example, ultraviolet irradiation of a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, a metal halide lamp, or a Cockloft-Walton type, a Handegraph type, a resonance transformer. 100 to 1000 KeV, preferably 100 to 30 by various electron beam accelerators such as reactor type, insulated core transformer type, linear type, dynamitron type, high frequency type, etc.
0.5-30 Mra with an electron beam of 0 KeV energy
Irradiation of d is performed.

[0030]

According to the method of the present invention, the surface of the ionizing radiation-curable resin layer is laminated with a coating plastic film to cure the ionizing radiation-curable resin layer in an oxygen-free atmosphere. It is possible to extremely efficiently produce a hard coat film having excellent properties and scratch resistance.

Further, by using a plastic film having irregularities as the coating plastic film, a hard coat film having antiglare properties can be obtained extremely efficiently.

[0032]

EXAMPLES The specific constitution of the method for producing a hard coat film of the present invention will be described below based on examples.

Example 1 A 75 μ thick acrylic film (Mitsubishi Rayon Co., Ltd.)
) Is coated on one side with a weather resistant hard coat paint (Dainichiseika Co., Ltd.) that uses a mixed resin of weather resistant resin and ionizing radiation curable resin as a vehicle, and the solvent is removed. To form a dry coating film having a thickness of 5 μm.

Then, a thickness of 25 μm is formed on the dry coating film.
A coating film made of polypropylene film (Toray Co., Ltd.) is laminated and the ultraviolet irradiation device (1
60 w / cm, 10 m / min. ), The coating film was peeled off and removed to obtain the desired hard coat film.

Example 2 One side of a plastic film substrate made of a polyethylene terephthalate film having a thickness of 50 μm (Toray Industries, Inc .: an easily adhering film) was provided on one surface with weather resistance of a mixed resin of a weather resistant resin and an ionizing radiation curable resin. A hard coat paint (Dainichiseika Co., Ltd.) was applied and the solvent was removed to form a dry coating film having a thickness of 5 μm.

Then, a thickness of 25 μm is formed on the dry coating film.
A coating film made of polypropylene film (Toray Co., Ltd.) is laminated and the ultraviolet irradiation device (1
60 w / cm, 10 m / min. ), The coating film was peeled off and removed to obtain the desired hard coat film.

Example 3 A 75 μm thick acrylic film (Mitsubishi Rayon Co., Ltd.)
) Is coated on one side with a weather-resistant hard coat paint (Dainichiseika Co., Ltd.), which is a mixture of weather-resistant resin and ionizing radiation-curable resin, and the thickness is removed by removing the solvent. A 5μ dry coating was formed.

Then, a thickness of 25 μm is formed on the dry coating film.
The coating film made of the matted polyethylene terephthalate film of 1. is laminated so that the matted surface of the coating film and the dry coating film are in contact with each other, and the laminated film is placed in an ultraviolet irradiation device (160 w / cm, 10 m / min.). After passing twice, the coating film was peeled off and removed to obtain a target hard coat film in which the surface of the hard coat layer was matted.

Example 4 On one surface of a plastic film substrate made of a polyethylene terephthalate film (Toray Industries, Inc .: easy-adhesive film) having a thickness of 50 μ, weather resistance by a mixed resin of a weather resistant resin and an ionizing radiation curable resin A hard coat paint (Dainichiseika Co., Ltd.) was applied and the solvent was removed to form a dry coating film having a thickness of 5 μm.

Then, a thickness of 25 μm is formed on the dry coating film.
The coating film made of the matted polyethylene terephthalate film of 1. is laminated so that the matted surface of the coating film and the dry coating film are in contact with each other, and the laminated film is placed in an ultraviolet irradiation device (160 w / cm, 10 m / min.). After passing twice, the coating film was peeled off and removed to obtain a target hard coat film in which the surface of the hard coat layer was matted.

[0041]

INDUSTRIAL APPLICABILITY In the method for producing a hard coat film of the present invention, the ionizing radiation-curable resin layer is cured by irradiating it with ionizing radiation in an atmosphere in which oxygen does not exist, and has weather resistance and scratch resistance. It is possible to efficiently obtain a hard coat film having excellent properties.

In the method for producing a hard coat film of the present invention, a plastic film having irregularities is used as a coating film, and the plastic film is laminated so that the irregular surface of the plastic film is in contact with the ionizing radiation curable resin layer. Thereby, a hard coat film having excellent weather resistance, scratch resistance, and antiglare property can be efficiently obtained.

Claims (3)

[Claims] 1. A plastic film substrate, on one or both sides of which an ionizing radiation curable resin layer made of a mixed resin of a weather resistant resin and an ionizing radiation curable resin is formed, and then the ionizing radiation curable resin layer surface is coated. Laminating a plastic film, then curing the ionizing radiation-curable resin layer by irradiating with ionizing radiation, subsequently,
A method for producing a hard coat film, which comprises peeling and removing a coating plastic film. 2. An ionizing radiation-curable resin layer containing an ultraviolet absorber is formed on one or both sides of a plastic film substrate, and a coating plastic film is laminated on the surface of the ionizing radiation-curable resin layer, and then, A method for producing a hard coat film, which comprises irradiating ionizing radiation to cure the ionizing radiation-curable resin layer, and subsequently peeling and removing the coating plastic film. 3. The method for producing a hard coat film according to claim 1 or 2, wherein a plastic film having unevenness is used as a coating plastic film, and the uneven surface of the plastic film serves as an ionizing radiation curable resin layer surface. A method for producing a hard coat film, which comprises laminating the films so that they are in contact with each other.