JPH066632B2 - Method for producing film having ultraviolet curable coating film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention is an ultraviolet ray that can be used as a base film for various kinds of printing, a base film for functional parts (film printed circuit boards, transparent switches, etc.) and a protective film for various containers. The present invention relates to a method for producing a non-adhesive film having a curable coating film.

<Prior art and its problems> Generally, a film obtained by applying an ultraviolet curable resin and drying it is difficult to carry out a secondary process such as printing because it has tackiness after irradiation with ultraviolet light. On the other hand, after UV irradiation, the surface is hard and inactive, so that the printing ink does not adhere well and the film itself shrinks.

Further, those containing a monomer as a main component have a bad odor or poor film-forming property, or cause cissing, pinholes, unevenness and the like during application, making it difficult to obtain a uniform thin coating film.

Further, when the low boiling point crosslinking monomer or the sensitizer tends to evaporate during the work, insufficient curing is likely to occur.

In addition, there is a disadvantage that homopolymerization of the monomer used for dilution is likely to occur and desired coating film performance is difficult to uniformly develop. Further, after curing, internal residual strain occurs, resulting in poor adhesion and dimensional stability. When a solventless type oligomer of 100% curing component is used, it is very difficult to apply a thin film, and use of a diluting solvent has a weakness that it is difficult to obtain a coating film having a uniform thickness due to resin aggregation caused by scattering of the solvent. .

For example, when a non-adhesive base film is prepared by using a solid epoxy acrylate prepolymer or urethane acrylate prepolymer at room temperature having a melting point of 50 ° C. or higher and a sensitizer (for example, JP-A-59-202).
No. 229), the resins that can be used are limited, and it was extremely difficult to satisfy the physical properties required for various products.

Therefore, an object of the present invention is to produce a film having an ultraviolet-curable coating film that can be easily processed such as printing on the surface before irradiation with ultraviolet rays and can satisfy the physical properties required for various products after irradiation with ultraviolet rays. To provide a method.

<Means and Actions for Solving Problems> Here, the present inventors have earnestly continued research for improving the above-mentioned various drawbacks of the conventional method, and have finally completed the present invention. That is, an oligomer or polymer having a solid melting point of 50 ° C. or higher at room temperature and having an ester bond, a cross-linking agent having a weight of 60% or less of the oligomer or polymer and having a double bond for ester polymerization and photopolymerization, Since a method for producing a film having an ultraviolet-curable coating film was invented, which was characterized in that a non-adhesive coating film was formed by applying a mixed solution containing a sensitizer as a main component to the film and then drying it. is there.

The present invention will be described in more detail below.

An oligomer or polymer having an ester bond having a solid melting point of 50 ° C. or higher at room temperature is poly (meth)
Acrylic acid resins, poly (meth) acrylic acid ester resins, polymethyl (meth) acrylic acid ester resins, and other acrylic acid resins, and acrylic polyols, polyester polyols, and other ester-bonded polyol resins and polyester resins, alkyd resins, allyl Resins, polyester resins such as polycarbonate resins, vinyl chloride acetate copolymer resins, vinyl chloride acetate vinyl resins such as vinyl chloride acetate maleic acid copolymer resins, and acrylate oligomers. Acrylate oligomers are epoxy (meth) An acrylate monomer such as acrylate, urethane (meth) acrylate, polyester (meth) acrylate, or (meth) acrylic (meth) acrylate is used as an oligomer.

60% by weight of the above oligomer or polymer
The following is a cross-linking agent having an ester bond and a double bond for performing photopolymerization, and a di (meth) compound prepared from a diol, triol, tetraol or polyol compound as a raw material.
There are acrylate, tri (meth) acrylate, tetra (meth) acrylate, poly (meth) acrylate,
For example, spiroglycol di (meth) acrylate, bisphenol A di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate. , Dipentaerythritol hexaacrylate, 2-hydroxy-1,3-dimethacryloxypropane and the like are often used.

Generally, many cross-linking agents are liquid or adhesive at room temperature, but those that become non-adhesive when the mixture is dried due to the interaction with the oligomer or polymer due to ester bond etc. It is preferred in the invention. The amount of the cross-linking agent used is 60% or less of the weight of the oligomer or polymer used, which guarantees non-adhesiveness during drying.

Further, the photosensitizer means a photosensitizer or a photopolymerization initiator. Examples of these include carboxylic acid compounds, azo compounds, sulfur compounds, halogen compounds, peroxides. , Active inorganic compounds and others. Among these, carboxylic acid compounds include benzyl compounds, benzoin alkyl ether compounds, diacetyl compounds, benzophenone compounds, substituted alkylphenyl ketone compounds, benzoin silyl ether compounds, and the like, and azo compounds include azobisisobutyronitrile compounds. , Azodibenzoyl-based, azo-
There are 2,4-dimethyl-4-methoxyvaleronitrile-based compounds, diazotium salt-based compounds, and the like, and as the sulfur compounds, there are dibenzothiazolyl sulfildo-based, decylphenyl sulfildo-based, disulfide xizanthate-based, and the like, and halogen. Compounds include carbon tetrachloride, peroxides include hydrogen peroxide, di-t-butyl peroxide, dibenzoyl peroxide, and the like, and active inorganic compounds include silver compounds. There are various redox-based compounds in addition to the compounds, iron compounds, pentamine cobalt-based compounds.

In addition, various dyes belonging to fuchsin type, floresene type, eosin type, and porphyrin type are used as photosensitizers.

Further, in order to further improve hardness and the like, waxes such as paraffin wax, polyethylene wax and montan wax and inorganic substances such as silica, alumina and calcium carbonate can be added. When transparency is required, it is advisable to add micronized particles of methyl methacrylate resin powder or the like.

Examples of the film include polyester, polyolefin, polyhalogenoolefin, polyamide, and polyether sulfone. When the product is used as a transfer foil or the like, it goes without saying that these films may be subjected to a release treatment or provided with a release layer in advance.

As a drying method, there is a method of drying at room temperature, hot air, or far infrared rays.

A solid solution having a melting point of 50 ° C. or higher at room temperature and having a ester bond as an oligomer or polymer, and a cross-linking agent having a double bond for photopolymerization with an ester bond and a photosensitizer as a main component are applied on a film. Examples of the method include reverse coating, gravure coating, gravure printing, screen printing, dipping and spraying. After coating by these methods, it is dried to prepare a film having a non-adhesive UV-curable coating film.
Next, the film can be further processed by screen printing, gravure printing, offset printing, vapor deposition and the like. The product of the present invention is produced as described above, and as it is,
Alternatively, after transferring and removing the film, it is irradiated with ultraviolet rays to sequentially react the unreacted and remaining photopolymerizable double bonds to improve various physical properties of the obtained cured surface and also to improve hardness. To improve.

Hereinafter, the technical contents of the embodiments of the present invention will be described in more detail.

<Example 1> A release-treated polyester film was coated with a coating solution having the following composition to a film thickness of about 10 µm by a reverse coating method, and then dried at 140 ° C for 30 seconds to have a non-adhesive UV-curable coating film. A film was made.

1-Hydroxycyclohexyl phenyl ketone 3g Olestar Q176 (Mitsui Toatsu Chemicals, Inc.) 70g Pentaerythritol triacrylate 30g MP-1000 (Soken Chemicals) 10g Ethyl acetate / methyl ethyl ketone = 3/2 50g For transfer After printing on it, transfer it to an acrylic plate and irradiate it with ultraviolet light (80 w / cm, 5 m / mi
n, 10 seconds) and then a pencil scratching test (JISK54
00), the hardness was 5H. For comparison, when the same test was conducted without the UV-cured coating, the hardness was 1
It was H.

<Example 2> A release-treated polyester film was coated with a coating solution having the following composition by a gravure coating method so as to have a thickness of 6 µm, and then left at room temperature and dried to prepare a film having a non-adhesive coating film. .

2-Hydroxy-2-methyl-1-phenyl-1-propan-1-one 3g DIANAR BR-83 (Mitsubishi Rayon Co., Ltd.) 70g Orestar Q176 (Mitsui Toatsu Chemicals, Inc.) 30g Pentaerythritol trimethacrylate 50 g Ethyl acetate 300 g Hardness was 4H in the pencil scratching test when used for transfer as in Example 1.

<Example 3> A release-treated polyamide film was coated with a coating solution having the following composition in a film thickness of about 10 µm by a reverse coating method, and then dried at 160 ° C for 30 seconds to form a film having a non-adhesive coating film. It was made.

Azobisisobutyronitrile 1 g 1-Hydroxycyclohexyl phenyl ketone 3 g Hitaloid 3083 (Hitachi Chemical Co., Ltd.) 80 g Dipentaerythritol hexaacrylate 45 g Mitsui Hiwak 210M (Mitsui Petrochemical Co., Ltd.) 9 g Ethyl acetate / toluene = 3 / 2 200 g When used for transfer as in Example 1, the hardness was 5H in the pencil scratch test.

<Example 4> A release-treated polyether sulfone was coated with a coating solution having the following composition to a film thickness of about 7 µm by a reverse coating method, and then dried at 80 ° C for 90 seconds to have a non-adhesive coating film. A film was made.

2-Hydroxy-2-methyl-1-phenyl-1-propan-1-one 2 g Dipentaerythritol hexaacrylate 40 g Byron 200 (Toyobo Co., Ltd.) 80 g Ethyl acetate 200 g For transfer as in Example 1. The pencil scratch test showed a hardness of 4H.

<Example 5> A polyester film was coated with a coating solution having the same composition as in Example 4 by a gravure coating method, and then heated at 100 ° C for 40 seconds to prepare a film having a non-adhesive coating film.

After that, a circuit pattern is printed on the coated surface with a conductive ink, and then UV irradiation (8
(0 w / cm, 5 m / min, 20 seconds) and cured to obtain a printed circuit board film having excellent physical properties.

<Effects of the Invention> The present invention relates to a method for producing a film having a novel UV-curable coating film, and the product has the following advantages. That is, since the coating film before UV irradiation is non-adhesive, it is possible to easily perform secondary processing such as stacking the film immediately after forming the coating film, winding it, and printing on the coating film surface. In addition, a wide range of resins can be selected for the coating liquid that forms a non-adhesive coating film, and the cured coating film after UV irradiation can satisfy the physical properties required for various products. . This means that, when the present invention is applied to a transfer base film, it has appropriate flexibility and can be freely transferred to a flat surface, a curved surface or a three-dimensional surface until it is irradiated with ultraviolet rays, and after the transfer, the ultraviolet rays are transferred. By irradiating, it can be converted into a hard protective layer to obtain a beautiful and strong painted product or the like.

INDUSTRIAL APPLICABILITY The present invention can be applied to base films for various kinds of printing, printed circuit boards and base films for various other functional parts. In particular, the novel ultraviolet curable film for transfer produced by the method has a wide range of applications to industrial products, electrical products and daily necessities, and the effect of the present invention is great.

Claims (1)

[Claims] 1. An oligomer or polymer having a solid melting point of 50 ° C. or higher at room temperature and having an ester bond, and a cross-linking having a weight of 60% or less of the oligomer or polymer and having a double bond for ester polymerization and photopolymerization. Of a film having a UV-curable coating film, characterized in that a non-adhesive coating film is formed by applying a mixed solution containing a photosensitizer and a photosensitizer as main components to the film and then drying it. .