JP2685106B2 - Method of manufacturing light control laminated resin plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a method for producing a resin plate by photocuring a photopolymerizable composition.

<Prior Art> The present inventors have studied a method for producing a resin plate having various characteristics by using a photopolymerizable composition containing a compound having a polymerizable carbon-carbon bond in the molecule. It was For example, application by the present inventors, Japanese Patent Application No. 62-316460
(S62.12.14 application) "Light control plate and its manufacturing method", Japanese Patent Application No. 62-197836 (S62.8.7. Application) "Light scattering resin plate and its manufacturing method", Japanese patent application No. 62-197838 (S62.8.7) .application)
A “method for producing a transparent resin body” can be mentioned.

This resin plate can be used alone, but it is also preferably used as a laminate which is attached to the surface of the transparent plate or is interposed between a plurality of transparent plates. Examples of this laminate include Japanese Patent Application No. 62-10714 (application S.62.7.13) “Wind glass window” Japanese Application No. 62-107143 (application S62.7.13). The method of applying the resin plate to a transparent plate such as a transparent plastic plate or a glass plate is not limited, and a known method can be used. For example, using an adhesive synthetic resin film such as polyvinyl butyral or ethylene / vinyl acetate copolymer, the transparent plate / synthetic resin film / resin plate (light control plate) / synthetic resin film / transparent plate are laminated in this order. It is possible to obtain an integrated laminate by heating and pressurizing by a known method.

<Problems to be Solved by the Invention> In the case where the above-mentioned resin plate is adhered using an adhesive synthetic resin film, the adhesive strength at the interface between the resin plate and the synthetic resin film is the light used in producing the resin plate. Since it depends on the composition of the polymerizable composition and the composition of the synthetic resin film, it is necessary to appropriately combine the two in order to obtain sufficient adhesive strength depending on the intended use of the laminate.

In the method for producing a resin plate, as a means for molding the resin into a plate shape, two plate-like bodies, which are transparent to the irradiation light for photopolymerization, of the photopolymerizable composition are provided at predetermined intervals. A method is employed in which a film is maintained by enclosing it in a cell or coating it on a substrate and performing predetermined light irradiation. In the method using the cell, a plate-like body which is opaque to the irradiation light for photopolymerization cannot be used, or a plate-like body having a large area whose one side length exceeds several tens of cm is provided with a predetermined interval. Since there are many restrictions such as difficulty in maintaining, it is more practical to apply the photopolymerizable composition onto a substrate to form a film.

A resin plate obtained by applying a photopolymer composition onto a substrate to form a film and then irradiating the film with light to cure the resin plate has a surface in contact with the substrate and a surface not in contact with the substrate. Here, the surface that is in contact with the substrate is referred to as a “substrate surface”, and the surface that is not in contact with the substrate and is in contact with the surrounding atmosphere is referred to as an “atmosphere surface”. Depending on the synthetic resin film used to form the laminate, the adhesive strength of the atmosphere surface of the resin plate may be significantly lower than the adhesive strength of the substrate surface. For example, when an ethylene / vinyl acetate copolymer film is used as the synthetic resin film, this tendency is remarkable. When a light control plate having a surface with a small adhesive strength is used to form a laminated body, there is a problem that the surface with a small adhesive strength of the light control plate is gradually peeled from the end portion of the laminated body.

<Means for Solving the Problem> An object of the present invention is to provide a method for manufacturing a resin plate having excellent adhesiveness by solving such a problem. The inventors of the present invention have found that the adhesive strength of the atmosphere surface of the resin plate becomes low depending on the synthetic resin film used in forming such a laminated body because the film-like body that was in contact with the atmosphere air at the time of light irradiation. As oxygen in the air dissolves on the surface, radical polymerization initiated by light irradiation is prohibited, and it is thought that this may occur because the cured state of this part is on the substrate surface. The present invention has been completed.

That is, in the present invention, in each molecule, a polymerizable carbon-
A photopolymerizable composition having at least two kinds of compounds having carbon bonds and different in refractive index from each other is maintained in a film form on a substrate, and the film form is formed from a predetermined direction by using a linear light source. Light control that has a function of scattering incident light in a predetermined angle range by irradiating light on the surface of the film and polymerizing and curing it, and adhering a synthetic resin film to one of the two surfaces of the polymerized and cured film that is not in contact with the substrate In the method for manufacturing a laminated resin plate, the film-like body is irradiated with the light while being held in an inert gas atmosphere, thereby preventing a decrease in adhesive strength between the synthetic resin film and the polymerized cured film. And a method for producing a light control laminated resin plate.

The compound having a polymerizable carbon-carbon bond in the molecule used in the present invention is preferably a compound having an acryloyl group, a methacryloyl group, a vinyl group, an allyl group or the like in the molecule.

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-bis Polyfunctional acrylates such as (4-acryloxyethoxy-3,5-dibromophenyl) propane or methacrylates corresponding to these acrylates, or methyl acrylate, tetrahydrofurfuryl acrylate, ethyl carbitol acrylate,
Dicyclopentenyloxyethyl acrylate, isobornyl acrylate, phenylcarbitol acrylate, nonylphenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, ω-hydroxyhexanoyloxyethyl acrylate, acryloyloxyethyl succinate, acryloyloxyethyl Phthalate, phenyl acrylate, tribromophenyl acrylate, phenoxyethyl acrylate, tribromophenoxyethyl acrylate, benzyl acrylate, p-bromobenzyl acrylate, 2
-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, a mixture of at least two kinds selected from these compounds is used as the photopolymerizable composition, and the combination and the mixing ratio in the case of the mixture are selected according to the kind of the desired resin plate.

In the present invention, the resin plate is a compound or a mixture thereof and a photopolymerizable composition containing a photopolymerization initiator if necessary to maintain a film on the substrate, from the light source necessary for the desired resin plate production It is obtained by irradiating with light, preferably ultraviolet light. The photopolymerization initiator used here is not particularly limited, and any photopolymerization initiator used in ordinary photopolymerization may be used. For example, benzophenone, benzyl Michler's ketone, 2-chlorothioxanthone, benzoin ethyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 2-hydroxy-
Examples include 2-methylpropiophenone and 1-hydroxycyclohexyl phenyl ketone.

In the present invention, the film-like body is maintained by applying the photopolymerizable composition onto the surface of the substrate. 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. However, if the polymerization light is to be irradiated from the back side of the substrate, it is necessary to use a substrate that can transmit this light.

In the present invention, as an example of a method for holding a film of the photopolymerization composition in an inert gas atmosphere, for example, a plate whose surface facing a light source for photopolymerization is transparent to irradiation light for photopolymerization It may be carried out by using a closed container having a window of a shape and having an inlet and an outlet for an inert gas.
After arranging the substrate so that the surface coated with the photopolymerizable composition faces the transparent body in this container, the oxygen in the container is reduced by introducing an inert gas from the inert gas inlet. Maintain an inert gas atmosphere. The inert gas referred to here is not particularly limited, but it does not inhibit the radical polymerization reaction of the photopolymerizable composition and does not react with the photopolymerizable composition. For example, a gas such as nitrogen gas, helium or argon can be used. Further, the oxygen remaining in the closed container needs to be at most 5% by volume fraction, more preferably 1%.
The following is preferred. If it is higher than 5%, the radical polymerization that should be initiated by the light irradiation is inhibited because oxygen in the atmosphere is dissolved on the surface of the film-like body which is in contact with the atmosphere during the light irradiation. The cured state of the portion is different from that of the substrate surface, and as a result, the adhesive strength on the atmosphere surface of the resin plate becomes low. After the oxygen concentration in the closed container is sufficiently lowered by the introduction of the inert gas, light from a light source suitable for producing a desired resin plate is irradiated to cure the composition in the form of a film. The inert gas inlet and outlet of the hermetic container do not have to be closed during the light irradiation, and the inert gas may be continuously circulated in the container.

In addition, an application by the present inventors, Japanese Patent Application No. 63-219144 (S.
63.9.1-day application) a method of irradiating a continuous strip-shaped film with light, that is, maintaining a predetermined photopolymerizable composition in a film having a predetermined length and width, A light source is arranged so as to face the film-like body so that the long axis direction of the light source extends across the lengthwise direction, and from the light source at an angle predetermined by the width direction position of the film-like body. An irradiation angle limiting means for irradiating a part of the film-like body with the light is disposed between the light source and the film-like body, and the film-like body is provided with respect to the light source and the limiting means. The method of irradiating light from the light source at a predetermined irradiation angle over the entire length of the film-like body while relatively moving the film-like body to cure the film-like body is also inactive in the same manner as the above method. An atmosphere can be created. For example, the closed container can be arranged on the membrane moving means. At this time, it is preferable to prevent the inflow of outside air and keep the inside of the container in an inert atmosphere by constantly circulating the inside of the container to keep the inside of the container at a pressure slightly higher than the atmosphere.

<Effects of the Invention> The resin plate produced by the present invention is adhered to the transparent plate surface by using an adhesive synthetic resin film, or in the case of a laminate inserted between a plurality of transparent plates. Since the adhesive strength with the synthetic resin film is high and the adhesive strength is the same on any surface of the resin plate, the laminated body of the light control plate does not gradually peel off from its end.

<Examples> Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples.

Example 1 Polyether urethane acrylate (refractive index 1.490) composed of polytetramethylene ether glycol, toluene diisocyanate and bidroxyethyl acrylate 1
A photopolymerized resin composition consisting of 00 parts, 100 parts of tribromophenoxyethyl acrylate (refractive index 1.567), and 6 parts of benzylmethyl ketal was poured onto a glass plate having a length of 500 mm and a width of 300 mm to form a film having a thickness of 300 μm. Form the body. As shown in FIG. 1, the film-coated glass plate 2 is placed horizontally inside a closed container 8 having a transparent glass plate 3 capable of transmitting irradiation light for polymerization on the upper surface thereof, and a nitrogen gas is introduced through an inert gas inlet 4. Introduce gas. The mixed gas of the air and the introduced nitrogen gas in the closed container is discharged from the discharge port 4. After the introduction of nitrogen gas was continued, the oxygen concentration in the container decreased sufficiently and the volume fraction became about 0.5%. Then, a rod-shaped ultraviolet ray was emitted upward at a distance of 60 cm from the center of the glass plate 2 in the perpendicular direction. Lamp 1 (80W /
cm, 2 KW, lamp length 25 cm) is installed horizontally so that the length direction thereof is perpendicular to one side ab of the glass plate, and ultraviolet rays are irradiated from the front transparent glass plate 2 side. The annular body composition on the glass plate 2 is polymerized and cured to obtain a light control plate. This light control plate and two 0.25 mm thick ethylene-vinyl acetate copolymer films (Dumilan, Takeda Pharmaceutical Co., Ltd.) and two 1 mm thick polytetrafluoroethylene sheets (Teflon, manufactured by Dipon) By using Teflon sheet / Dumilan / Light control plate / Dumilan / Teflon sheet in this order, put this laminate in a rubber bag, evacuate the inside of the rubber bag, vacuum and then heat to 95 ° C and hold for 10 minutes. Then, the laminate was thermocompression bonded. After that, by taking out the laminated body that has been thermocompression bonded, by peeling the Teflon sheet on both sides,
A light control laminate of Dumiran / light control plate / Dumilan was obtained.

When this light control laminated body is observed from the front with the one side ab facing downward, the entire laminated body is opaque,
The entire surface of the laminated body became transparent when the laminated body was inclined by 20 degrees or more on each side. The adhesive strength between the Dumiran / light control plate of this light control laminate was measured by the 180-degree peeling method described in JIS Z0237. Both the atmosphere surface and the substrate surface of the light control laminate show the same adhesive strength, and the values are shown in Table 1.

Comparative Example 1 The same resin composition as in Example 1 is poured onto a glass plate having a length of 500 mm and a width of 300 mm to form a film-like body having a thickness of 300 μm. Here, a light control plate was obtained by curing by irradiating light from a rod-shaped ultraviolet lamp in the same manner as in Example 1 except that the closed container was not used. The adhesive strength of the Dumiran / light control plate was measured in the same manner as in Example 1. As shown in Table 1, the adhesive strength was as high as 1.0 kg / 25 mm on the substrate surface of the light control plate, but was as low as 0.2 kg / 25 mm on the atmosphere surface.

[Brief description of the drawings]

FIG. 1 is a side view showing one embodiment of the present invention, and FIG. 2 is a sectional view showing a schematic section of a laminated body. 1 ... Light source, 2 ... Membrane 3 ... Transparent glass plate, 4 ... Inert gas inlet 5 ... Gas outlet, 6 ... Adhesive synthetic resin film 7 ... Resin plate

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshifumi Tsujino 3-5-11 Doshumachi, Chuo-ku, Osaka-shi, Osaka Prefecture Nippon Sheet Glass Co., Ltd. (72) Hiroaki Yamamoto 3-chome, Dosho-cho, Chuo-ku, Osaka-shi, Osaka No. 5-11 within Nippon Sheet Glass Co., Ltd. (56) Reference JP-A-50-56425 (JP, A) JP-A-64-77001 (JP, A)

Claims (1)

(57) [Claims] 1. A photopolymerizable composition containing at least two kinds of compounds each having a polymerizable carbon-carbon bond in the molecule and different in refractive index from each other, is maintained in a film form on a substrate,
Using a linear light source, the film is irradiated with light from a predetermined direction to polymerize and cure, and out of both surfaces of the polymerized and cured film,
In a method for producing a light control laminated resin plate having a function of scattering an incident light in a predetermined angle range by adhering a synthetic resin film to a surface not in contact with the substrate, the film-like body is held in an inert gas atmosphere. The method for producing a light control laminated resin plate, characterized in that the adhesive strength between the synthetic resin film and the polymerized and cured film is prevented from being lowered by irradiating the light while simultaneously performing the light irradiation.