JP2601832B2 - Manufacturing method of patterned board - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a patterned board, particularly a patterned board composed of a cloudy portion and a transparent portion, which is produced by photocuring.

[Conventional technology]

Conventionally, as a plate material having a clouded portion and a transparent portion, a plate glass partially formed of frosted glass, a template glass, an organic glass in which a transparent resin and a clouded resin are laminated, and the like are generally used.

[Problems to be solved by the invention]

However, those having irregularities on the surface, such as frosted glass, have a drawback that dirt easily adheres. Furthermore, when a liquid such as water or oil adheres to the surface, the parallel light transmittance increases and the haze decreases. The difference between the transparent part and the cloudy part of the template glass is not clear, and multi-product small-quantity production cannot be performed. The method of laminating a transparent resin and a cloudy resin involves complicated steps and low mass productivity.

As a result of various studies on ultraviolet curing of a resin, the present inventors have found an efficient method for producing a plate having a cloudy portion and a transparent portion.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a patterned plate composed of a cloudy part and a transparent part.

[Means for solving the problem]

The present inventor uses a photomask to irradiate a composition containing at least two or more types of photopolymerizable monomers or oligomers having different refractive indexes with a high haze portion and a low haze portion. It has been found that it is possible to produce a patterned board composed.

That is, the present invention maintains a composition containing at least two types of photopolymerizable monomers or oligomers having a difference in refractive index in the form of a film, divides the surface of the film into a plurality of regions, Curing by irradiating at least one area of the area with light or parallel light from a point light source and curing at least one other area with light or scattered light from a surface light source or by heating A method for producing a patterned plate having a cloudy part and a transparent part.

Hereinafter, the patterned board of the present invention and the method for producing the same will be described more specifically.

The patterned plate of the present invention is obtained by applying a composition containing at least two kinds of photopolymerizable monomers or oligomers having different refractive indices of a homopolymer onto a substrate together with a photopolymerization initiator or enclosing in a cell. Then, after attaching a photomask to it and irradiating it with the first ultraviolet ray, it cures.
It is obtained by removing the photomask and performing the second UV irradiation by a method different from the first irradiation to cure the uncured portion.

Of the two ultraviolet irradiation methods used in the present invention, 1
One is a method for obtaining a high haze ratio, and the other is a method for obtaining a low haze ratio or no haze. That is, as a method for obtaining a high haze ratio, when the length of the major axis of the ultraviolet lamp is d and the distance between the lamp and the irradiation object is 1, d / 1 <0.2 is used. Good to cure.
The length of the long axis of the lamp is the effective emission length actually used for curing, and can be adjusted by a slit or the like. In other words, the irradiation light source for obtaining a high haze ratio used in the present invention emits ultraviolet light or other light that contributes to photopolymerization, and the light source is a point when viewed from the irradiation position (film surface). It is a light source having a shape of a circle or capable of emitting parallel light. In the present invention, a point light source
It is defined that the size of the light source viewed from the irradiated position is such that the viewing angle of the light source is at most 10 °. As a method of obtaining a low haze ratio, irradiation with diffused light may be performed from a surface light source, or from a plurality of directions (preferably from multiple directions). In order to efficiently perform irradiation from multiple directions, a large number of reflectors or irregularly-reflected plates may be provided around the ultraviolet lamp, or frosted glass or the like may be inserted between the lamp and the resin sample to increase the amount of light. It may be scattered or diffused in the direction. In some cases, instead of obtaining a low haze ratio, the film can be cured by heating. However, in the case of heating, it is generally difficult to harden a desired place with high accuracy, and it is suitable for hardening a portion having a high haze ratio and then hardening the rest.

Above the unpolymerized film placed horizontally, for example, a point light source such as an ultra-high pressure mercury lamp is placed about 40 cm above and irradiated with ultraviolet light to cause a curing reaction of the film.
When viewed from a cross section of the film, it is observed that a layer having a microstructure is formed inside the film near the irradiated surface. The thickness of this layer is about 10-2000 microns, and the depth of the layer from the film surface is 0-500 microns. Where the film thickness is usually 1
0-5000 microns. It is considered that light incident on the film is strongly scattered by the microstructure layer, and when the other side is seen through the film, it becomes cloudy and obstructs the view. When the size of the irradiation light source gradually increases, the haze ratio (white turbidity) decreases, and when the size of the irradiation light source is represented by the aforementioned viewing angle, and the viewing angle in the short axis direction becomes larger than 100 °, irradiation is performed. The polymerized film is transparent in any direction and does not show light scattering. As such a light source,
A surface light source or a diffusion light source disposed relatively close to the film to be polymerized can be mentioned. Also, when the film is polymerized by heating, it becomes transparent.

The monomer or oligomer used in the present invention is
Any material can be used as long as it can be photocopolymerized, but it is determined in consideration of the chemical and physical properties of the resin as required. As the photopolymerizable monomer or oligomer, those having an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or the like in the molecule are preferable.

For example, polyester acrylate, polyol polyacrylate, modified polyol polyacrylate, polyacrylate with isocyanuric acid skeleton, melamine acrylate, polyacrylate with hydantoin skeleton, polybutadiene acrylate, epoxy acrylate, urethane acrylate, or bisphenol A diacrylate, 2,2- Polyfunctional acrylates such as bis (4-acryloxyethoxy-3,5-dibromophenyl) propane or methacrylates corresponding to these acrylates, or methyl acrylate, tetrahydrofurfuryl acrylate, ethyl carbitol acrylate,
Dicyclopentenyloxyethyl acrylate, isobornyl acrylate, phenyl carbitol acrylate, nonylphenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, ω-hydroxyhexanoyloxyethyl acrylate, acryloyloxyethyl succi Acrylate, acryloyloxyethyl phthalate, phenyl acrylate, tribromophenyl acrylate, phenoxyethyl acrylate, tribromophenoxyethyl acrylate, benzyl acrylate, p-bromobenzyl acrylate,
-Ethylhexyl acrylate, lauryl acrylate, 2,2,3,3-tetrafluoropropyl acrylate and methacrylates corresponding to these monofunctional acrylates, or styrene, p-chlorostyrene,
Vinyl compounds such as divinylbenzene, vinyl acetate, acrylonitrile, N-vinylpyrrolidone, and vinylnaphthalene, or allyl compounds such as diethylene glycol bisallyl carbonate, dialylidenepentaerythritol, triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate. can give.

These compounds can be used either as monomers or after being made into oligomers.

In the present invention, at least two or more selected from these monomers or oligomers are used as a mixture. However, the refractive indices of the homopolymers must be different from each other. The resulting resin has a high haze ratio. Preferably, the at least two monomers or oligomers have a refractive index difference of at least 0.01, more preferably at least 0.05. The mixing ratio of at least two monomers or oligomers having a refractive index difference of 0.01 is 10: 90-90: 10 by weight.
Is preferably within the range. Further, it is preferable that the compatibility of these resins is somewhat poor. If the compatibility is good, the homogeneity of the obtained resin is increased, and a structure causing haze is hardly formed. Further, in a combination having extremely poor compatibility, phase separation occurs before photo-curing, so that the haze ratio of the obtained resin decreases.

The patterned board of the present invention can be obtained by irradiating a mixture of the above monomers or oligomers with ultraviolet light in the presence of a photopolymerization initiator, but the photopolymerization initiator used here is not particularly limited, Any material used in ordinary photopolymerization may be used. For example,
Benzophenone, benzyl, Michler's ketone, 2-chlorothioxanthone, benzoin ethyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, and the like. These may vary depending on the type and reactivity of the monomer or oligomer used, but are generally 0.1 part to 10 parts, preferably 0.5 part to 100 parts of the mixture of the above monomer or oligomer.
It can be used in an amount in the range of 8 parts.

The patterned board of the present invention is produced by applying a mixture containing the above-mentioned monomer or oligomer and a photopolymerization initiator as main components on a substrate or enclosing the mixture in a cell, and then curing the mixture with ultraviolet rays. The substrate used here may be any substrate as long as the surface of the applied film can be smoothed. For example, a flat plate or template of glass, plastic, metal or the like can be used. When a cell is used, at least one surface of the cell must transmit ultraviolet rays necessary for starting photopolymerization, and transparent glass, plastic, and the like are preferable.

The ultraviolet lamp used in the production of the patterned plate of the present invention is not particularly limited as long as it generates ultraviolet light, but usually a mercury lamp or a metal halide lamp is preferable in consideration of ease of handling. is there.

〔The invention's effect〕

According to the plate manufacturing method provided by the present invention, the resin can be freely set and cured into a portion having a high haze ratio and a portion having a low haze ratio (or transparent) by ultraviolet irradiation. Plates with various patterns can be manufactured by an easy method. In addition, the patterned board of the present invention can be manufactured from a flexible one to a hard one by appropriately selecting a resin as a raw material.

Therefore, the patterned plate of the present invention can be used alone, but may be laminated with glass or plastic or coated on glass or plastic. And by using these, window materials for construction, window materials for vehicles,
It can be expected to be applied to interior materials, display boards, furniture, etc.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

In addition, the measurement of the light transmittance and the haze rate of each of the plates obtained in the examples was performed as follows.

<Measurement of parallel light transmittance and haze> The total light transmittance and the scattered light transmittance were measured by an integrating sphere light transmittance measurement device according to JISK-6714, and the parallel light transmittance and haze (haze) were determined. .

Example 1 100 parts of N-vinylpyrrolidone (refractive index: 1.509) and 100 parts of benzyl based on 100 parts of polyether urethane acrylate (refractive index: 1.481) obtained by reaction of polypropylene glycol having an average molecular weight of 2,000 with toluene diisocyanate and 2-hydroxyethyl acrylate As shown in FIG. 1, a resin composition obtained by adding and mixing 6 parts of dimethyl ketal was injected between two 20 cm × 20 cm glass plates 5 and 5 sandwiching a 1 mm thick spacer 7 to form a film-like resin composition. The object 6 was covered with a photomask 8 in which the character A was outlined on the glass plate 5, and the ultra-high pressure mercury lamp 1 (2k
w, emission length 2 cm × 2 cm, manufactured by Ushio Inc.) for 1 minute. Next, the photomask 8 was removed, and the same ultraviolet rays were irradiated through the ground glass plate 4 for 1 minute as shown in FIG. The cured product obtained had a character A having a haze ratio of 68% and a surrounding portion having a haze ratio of 0.6%.
It looked white and the surroundings were transparent.

Example 2 A resin composition obtained by adding and mixing 100 parts of tribromophenoxyethyl acrylate and 6 parts of benzyldimethyl ketal to 100 parts of the same polyether urethane acrylate used in Example 1 as shown in FIG. , 200
A resin composition 6 in the form of a film is injected between glass plates 5 and 5 with a spacer 7 having a thickness of .mu.m therebetween. A photomask 8 in which the character A is outlined is covered, and ultra-high pressure mercury is applied from a distance of 50 cm. Lamp 1 (2kw, emission length 2cmx2cm, Ushio Electric)
Was irradiated for 1 minute through the ground glass plate 4. Next, the photomask 8 was removed, and as shown in FIG. 4, ultraviolet rays from an ultra-high pressure mercury lamp were irradiated for 2 minutes from a distance of 50 cm.
The resulting cured product has a haze ratio of the letter A of 0.5%,
The haze ratio of the surrounding portion was 88%, and the letter A was visible through the ground glass plate.

Example 3 The resin composition used in Example 1 to which 2 parts of benzyl peroxide, which is a heat polymerization initiator, was further added was used to form a film, as shown in FIG. Irradiated. Next, the film-shaped resin composition was cured by heating for about 60 minutes in a heating furnace maintained at 150 ° C. In the obtained cured product, the haze ratio of the portion of the character A was 68%, the haze ratio of the surrounding portion was 0.5%, and the character A was cloudy.
Its surroundings were transparent.

[Brief description of the drawings]

1 to 4 are side views each showing an embodiment of the present invention. 1, 2, ultra-high pressure mercury lamp, 4, frosted glass plate 5, glass plate, 6, resin film 7, spacer

Continued on the front page (72) Inventor Tetsu Shiiki 4-8-8 Doshomachi, Higashi-ku, Osaka-shi, Osaka Inside Nippon Sheet Glass Co., Ltd. (72) Inventor Motoaki Yoshida 4-8, Doshomachi, Higashi-ku, Osaka-shi, Osaka Inside Nippon Sheet Glass Co., Ltd. (72) Inventor Shinichiro Kitayama 3-1-1, Kasuganaka, Konohana-ku, Osaka, Osaka Sumitomo Chemical Incorporated (72) Inventor Teruho Adachi 3-1-1, Kasuganaka, Konohana-ku, Osaka-shi Sumitomo Chemical Co., Ltd. (72) Inventor Masahiro Ueda 3-1-1 Kasuganaka, Konohana-ku, Osaka, Osaka No. 98 Sumitomo Chemical Co., Ltd. (56) Reference JP-A-64-40903 (JP, A)

Claims (1)

(57) [Claims] A composition containing at least two types of photopolymerizable monomers or oligomers having different refractive indices is maintained in the form of a film, and the surface of the film is divided into a plurality of regions. At least one region is cured by irradiating with light from a point light source or parallel light, and at least one other region is cured by irradiating with light or scattered light from a surface light source or by heating. A method for producing a patterned plate having a cloudy part and a transparent part, characterized by the above-mentioned.