JPWO2013084953A1 - Method for manufacturing translucent hard substrate laminate - Google Patents

Abstract

A light-transmitting hard substrate laminate can be produced with high production efficiency while reducing the risk of cracking. In the method for producing a light-transmitting hard substrate laminate according to the present invention, the bonding surfaces of the light-transmitting hard substrates are opposed to each other in parallel, and both hard substrates are brought close to each other while maintaining a parallel state. Preliminarily laminating using a photo-curable sticking agent, this is repeated a desired number of times to form a laminate, and the laminate is cured by pressure treatment and light irradiation treatment.

Description

  The present invention relates to a method for producing a translucent hard substrate laminate, and more particularly to a method for producing a plate glass laminate for producing protective glass for a display element.

  Display devices of various electronic devices such as TVs, notebook computers, car navigation systems, calculators, mobile phones, electronic notebooks, and PDAs (Personal Digital Assistants) include liquid crystal displays (LCD), organic EL displays (OELD), electroluminescent displays ( Display elements such as ELD), field emission displays (FED), and plasma displays (PDP) are used. And in order to protect a display element, it is common to install the plate glass product for protection facing a display element.

  This flat glass product is obtained by processing a flat glass into a size and shape suitable for each display device. In order to meet the price level required in the market, it is possible to process a large amount of flat glass products with high production efficiency. Desired.

  Patent Documents 1 and 2 disclose a technique for realizing a high production rate by laminating and processing sheet glass products in which circuits and the like are built. At the time of this lamination, it is necessary to closely superimpose the circuit parts built in each plate glass product, so that a high degree of positioning is required, and further, it is necessary to prevent the occurrence of displacement after superposition.

  Therefore, in Patent Document 1, when each sheet glass product is overlaid, after performing a temporary light irradiation (temporary fastening) along the outer periphery of the sheet glass product, a certain number of sheet glass products are overlaid to form a laminate, A technique is described in which main irradiation of light (main bonding) is performed on the laminate to obtain a laminate.

  In addition, Patent Document 2 describes a technique for obtaining a laminated body by performing main bonding every time sheet glass products are stacked one by one, and repeating this until reaching a certain number of sheets, instead of performing temporary bonding. .

International Publication No. 2011/089963 International Publication No. 2011/089964

  By the way, from the viewpoint of increasing the production rate, it is desired that the glass sheet products are laminated and processed together. However, some glass sheet products do not require a high degree of positioning when laminating the cover glass. For such a device, advanced positioning and temporary fastening are performed as in the technique described in Patent Document 1, or one after another, after advanced positioning as in the technique described in Patent Document 2. There is no need to perform sheet stacking.

  Flat glass products that do not require advanced positioning are also desired to be collectively processed as a laminate from the viewpoint of improving the production rate. On the other hand, there is a possibility that production efficiency may be improved by not going through complicated procedures such as advanced positioning as described in Patent Documents 1 and 2, and it is desired to reduce unnecessary processes. By reducing unnecessary processes in this way, the manufacturing cost can be reduced.

  The present inventor has intensively studied to solve the above-mentioned problems. From the viewpoint of realizing both improvement in productivity of plate glass and further improvement in production efficiency, the composition of the fixed substance and the fixed substance of the composition are used. The present invention has been completed by finding that there is room for improvement in the processing-peeling procedure when using.

The present invention completed on the basis of the above knowledge, in one aspect,
1) preparing a first translucent hard substrate;
2) preparing a second translucent hard substrate;
3) A step of applying a photocurable sticking agent to the first surface of the first translucent hard substrate and / or the first surface of the second translucent hard substrate;
4) The process of making the 1st surface of a 1st translucent hard substrate and the 1st surface of a 2nd translucent hard substrate oppose so that both surfaces may become parallel,
5) Applying pressure to the first surface of the first translucent hard substrate and the first surface of the second translucent hard substrate while maintaining the parallel state to form a laminate And a process of
6) Considering the light-transmitting hard substrate laminate as a first light-transmitting hard substrate, the steps 2) to 5) are repeated at least once, and at least three light-transmitting hard substrates are bonded together. Forming an optical hard substrate laminate; and
7) A process for producing a light-transmitting hard substrate laminate, comprising a step of simultaneously performing a pressure treatment from one or both outermost surfaces of the laminate and a light irradiation treatment to the fixing agent of the laminate for at least a predetermined time. It is.

In one embodiment of the method for producing a translucent hard substrate laminate according to the present invention,
After forming the laminate in step (5), or at least one timing between step (6) and step (7),
5 ′) Light is applied to a part of the fixing agent spread between the light-transmitting hard substrates, or the entire fixing agent is irradiated with light having a lower energy than in the step (7). Then, a step of forming the temporarily fixed translucent hard substrate laminate is performed.

  In still another embodiment of the method for producing a light-transmitting hard substrate laminate according to the present invention, step (7) is performed by irradiating light toward the surface of the second light-transmitting hard substrate. .

  In another one Embodiment of the manufacturing method of the translucent hard board | substrate laminated body which concerns on this invention, the said fixing agent contains a granular material.

In yet another embodiment of the method for producing a light-transmitting hard substrate laminate according to the present invention, the amount of light irradiated in the step (7) is measured by an integrating illuminometer using a 365 nm light receiver, it is in the range of ^{100mJ / cm 2 ~5000mJ / cm 2} .

  In still another embodiment of the method for producing a light-transmitting hard substrate laminate according to the present invention, before repeating steps (2) to (5) in step (6), the obtained laminate is obtained. Roll press.

  In another embodiment of the manufacturing method of the translucent hard board | substrate laminated body which concerns on this invention, a translucent hard board | substrate is plate glass for cover glass uses.

In another aspect of the present invention,
8) Divide the translucent hard substrate laminate obtained using the above-described method for producing a translucent hard substrate laminate in the thickness direction to form a desired number of divided translucent hard substrate laminates. And a process of
9) A step of performing a desired shape processing on each of the divided translucent hard substrate laminates;
10) A step of peeling the light-transmitting hard substrates bonded together by heating the light-transmitting hard substrate laminate after shape processing to form a plurality of plate-shaped products;
Is a method of manufacturing a plate-like product.

  In one embodiment of the method for producing a plate-like product according to the present invention, an uncured adhesive agent is provided between the step (8) and the step (10) toward the side surface of the divided translucent hard substrate laminate. Irradiation with light for curing.

  In another embodiment of the method for producing a plate-like product according to the present invention, in the step (10), the translucent hard substrate laminate after shape processing is immersed in warm water to soften the adhesive in a film shape. Including that.

In another embodiment of the method for producing a plate-like product according to the present invention, the step (10) further includes the step of immersing the translucent hard substrate laminate after shape processing in warm water before the surface of the laminate is immersed. And / or irradiating light from the side.
In still another aspect, the present invention includes a translucent hard substrate laminate produced by a method for producing a translucent hard substrate laminate.

In yet another aspect of the present invention, when producing this light-transmitting hard substrate laminate, it is used to bond each light-transmitting hard substrate,
(A) polyfunctional (meth) acrylate;
(B) monofunctional (meth) acrylate;
(C) a photopolymerization initiator;
Including
(A) As a compounding ratio of polyfunctional (meth) acrylate and (B) monofunctional (meth) acrylate, (A) :( B) = 5: 95 to 95: 5 (parts by mass) photocurable fixing Provide the agent.

In one embodiment of the photocurable fixing agent according to the present invention, in addition to (A) to (C), (D) a particulate material is further contained.
In still another embodiment of the photocurable fixing agent according to the present invention, (E) a thermally expandable microcapsule is further contained.
In still another embodiment of the photocurable fixing agent according to the present invention, (F) an organic peroxide and (G) a decomposition accelerator are further contained.

  In still another embodiment of the photocurable fixing agent according to the present invention, the content of (B) monofunctional (meth) acrylate is 40 to 40 parts in 100 parts by mass of the total amount of (A) and (B). 80 parts by mass.

  In still another embodiment of the photocurable fixing agent according to the present invention, the content of (C) the photopolymerization initiator is 0. 0 parts by mass relative to 100 parts by mass of the total amount of (A) and (B). 1 to 20 parts by mass.

In yet another aspect of the present invention, when producing the light-transmitting hard substrate laminate, the light-transmitting hard substrates are bonded to each other.
(A) polyfunctional (meth) acrylate;
(B) monofunctional (meth) acrylate;
(F) organic peroxides;
(G) a decomposition accelerator;
Including
(A) As a compounding ratio of polyfunctional (meth) acrylate and (B) monofunctional (meth) acrylate, (A) :( B) = 5: 95 to 95: 5 (parts by mass) photocurable fixing Provide the agent.

In one Embodiment of the photocurable sticking agent which concerns on this invention, (D) granular material is further contained.
In still another embodiment of the photocurable fixing agent according to the present invention, (E) a thermally expandable microcapsule is further contained.

  In still another embodiment of the photocurable fixing agent according to the present invention, the content of (B) monofunctional (meth) acrylate is 40 to 40 parts in 100 parts by mass of the total amount of (A) and (B). 80 parts by mass.

  According to the present invention, a translucent hard substrate laminate can be manufactured with high productivity and high production efficiency. The present invention can be suitably used, for example, in a method for mass-producing protective glass for display elements.

It is a schematic diagram which shows the 1st example of the board | substrate bonding apparatus for producing the laminated body of a translucent hard board | substrate. It is a schematic diagram which shows the example of the lower surface of an upper stage. It is a schematic diagram which shows an example which provided the contact jig | tool with respect to the upper surface of a lower stage. It is a figure which shows the state which mounted the 1st board | substrate on the lower stage. It is a figure which shows the state which conveyed the 1st board | substrate mounted in the lower stage just under the upper stage. It is a figure which shows the state which descends the upper stage and vacuum-sucks the 1st board | substrate. It is a figure which shows the state which raised the upper stage, hold | maintaining the adsorbed 1st board | substrate. It is a figure which shows the state which mounted the 2nd board | substrate on the lower stage. It is a figure which shows the state which has apply | coated the adhesive on the upper surface of the 2nd board | substrate. It is a figure which shows the state which has apply | coated the adhesive on the lower surface of the 1st board | substrate hold | maintained at the upper stage. It is a figure which shows the state which lowered | hung the upper stage, bonded two board | substrates, and UV-irradiated the outer peripheral part of the board | substrate. It is a figure which shows the state which raised the upper stage after UV irradiation. It is a figure which shows the state which the board | substrate bonded together was conveyed by the lower stage, and returned to the original position. It is a schematic diagram which shows the principle of a roll press.

In one embodiment of the method for producing a translucent hard substrate laminate according to the present invention,
1) preparing a first translucent hard substrate;
2) preparing a second translucent hard substrate;
3) A step of applying a photocurable sticking agent to the first surface of the first translucent hard substrate and / or the first surface of the second translucent hard substrate;
4) The process of making the 1st surface of a 1st translucent hard substrate and the 1st surface of a 2nd translucent hard substrate oppose so that both surfaces may become parallel,
5) Applying pressure to the first surface of the first translucent hard substrate and the first surface of the second translucent hard substrate while maintaining the parallel state to form a laminate And a process of
6) Considering the light-transmitting hard substrate laminate as a first light-transmitting hard substrate, the steps 2) to 5) are repeated at least once, and at least three light-transmitting hard substrates are bonded together. Forming an optical hard substrate laminate; and
7) A step of simultaneously performing a pressure treatment from one or both of the outermost surfaces of the laminate and a light irradiation treatment to the fixing agent of the laminate for at least a predetermined time is executed.

In step (1) and step (2), a translucent hard substrate to be processed is prepared. There are no particular restrictions on the light-transmitting hard substrate, but plate glass (tempered plate glass, material plate glass, especially cover glass on which no electrode or circuit is formed), sapphire substrate, quartz substrate, plastic substrate, magnesium fluoride substrate, etc. Can be mentioned. Examples of the glass include tempered glass. Although there is no restriction | limiting in particular in the magnitude | size of a translucent hard board | substrate, it typically has an area of about 10,000-250,000 mm < ² >, and has a thickness of about 0.1-2 mm. Each translucent hard substrate is generally the same size.

  In the step (3), a photocurable fixing agent is applied to the first surface of the first light-transmitting hard substrate and / or the first surface of the second light-transmitting hard substrate. A photo-curable sticking agent is a sticking agent that hardens when irradiated with light such as visible light or ultraviolet light, and softens when heated to a high temperature. The photo-curable sticking agent may be applied to the bonding surface of either one of the light-transmitting hard substrates, but from the viewpoint of improving adhesiveness, it should be applied to the bonding surfaces of both of the light-transmitting hard substrates. Is preferred.

  As the photo-curable fixing agent suitably used in the present invention, (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C) an adhesive containing a photopolymerization initiator. A composition.

(A) As a polyfunctional (meth) acrylate, two or more (meth) acryloylated polyfunctional (meth) acrylate oligomer / polymer or two or more (meth) acryloyl groups at the oligomer / polymer terminal or side chain Polyfunctional (meth) acrylate monomers having can be used. For example, as a polyfunctional (meth) acrylate oligomer / polymer, 1,2-polybutadiene-terminated urethane (meth) acrylate (for example, “TE-2000”, “TEA-1000” manufactured by Nippon Soda Co., Ltd.), hydrogenated product ( For example, “TEAI-1000” manufactured by Nippon Soda Co., Ltd.), 1,4-polybutadiene-terminated urethane (meth) acrylate (for example, “BAC-45” manufactured by Osaka Organic Chemical Co., Ltd.), polyisoprene-terminated (meth) acrylate, polyester-based urethane (Meth) acrylate (for example, “UV-2000B”, “UV-3000B”, “UV-7000B” manufactured by Nippon Synthetic Chemical Co., Ltd., “KHP-11”, “KHP-17” manufactured by Negami Kogyo Co., Ltd.), polyether type Urethane (meth) acrylate (for example, “UV-3700B”, “UV” manufactured by Nippon Synthetic Chemical Co., Ltd. 6100B "), or bisphenol A type epoxy (meth) acrylate, and the like. In these, polyester-type urethane (meth) acrylate and / or polyether-type urethane (meth) acrylate are preferable, and polyester-type urethane (meth) acrylate is more preferable.
Here, the urethane (meth) acrylate is a reaction between a polyol compound (hereinafter represented by X), an organic polyisocyanate compound (hereinafter represented by Y), and a hydroxy (meth) acrylate (hereinafter represented by Z). The urethane (meth) acrylate obtained by this.
Examples of the polyol compound (X) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,4-butanediol, polybutylene glycol, 1, 5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2-butylethyl-1,3-propanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, poly At least polyhydric alcohols such as limethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polytetramethylene glycol, block or random copolymerization of polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide Polyether polyol having one type of structure, a polycondensate of the polyhydric alcohol or polyether polyol and a polybasic acid such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, and isophthalic acid Polyester polyols, caprolactone-modified polytetramethylene polyols and other caprolactone-modified polyols, polyolefin-based polyols, polycarbonate-based poly Lumpur, polybutadiene polyols, polyisoprene polyols, hydrogenated polybutadiene polyols, polydiene polyols such as hydrogenated polyisoprene polyol, silicone polyol, such as polydimethylsiloxane polyols and the like. In these, polyether polyol and / or polyester polyol are more preferable.
The organic polyisocyanate compound (Y) is not particularly limited. For example, aromatic, aliphatic, cycloaliphatic, and alicyclic polyisocyanates can be used. Isocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), hydrogenated xylylene diisocyanate (H-XDI) ), Xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), tetramethylxylylene diisocyanate (m-TMXDI), isophorone diisocyanate Polyisocyanates such as nate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), trimer compounds of these polyisocyanates, reaction products of these polyisocyanates and polyols, etc. Preferably used. In these, hydrogenated xylylene diisocyanate (H-XDI) and / or isophorone diisocyanate (IPDI) are preferable.
Examples of the hydroxy (meth) acrylate (Z) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl acryloyl phosphate, and 4-butyl. Hydroxy (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) Examples include acrylate, dipentaerythritol penta (meth) acrylate, and caprolactone-modified 2-hydroxyethyl (meth) acrylate. In these, 1 or more types in the group which consists of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate is preferable.
The weight average molecular weight of the polyfunctional (meth) acrylate oligomer / polymer is preferably from 7000 to 60000, and more preferably from 13000 to 40000. In Examples, the weight average molecular weight was determined by preparing a calibration curve with commercially available standard polystyrene using tetrahydrofuran as a solvent under the following conditions, using a GPC system (SC-8010 manufactured by Tosoh Corporation).
Flow rate: 1.0 ml / min
Set temperature: 40 ° C
Column configuration: “TSK guardcolumn MP (× L)” manufactured by Tosoh Corporation 6.0 mmID × 4.0 cm1 and “TSK-GEL MULTIPOREHXL-M” manufactured by Tosoh Corporation 7.8 mmID × 30.0 cm (16,000 theoretical plates) ) 2, 3 in total (32,000 theoretical plates as a whole)
Sample injection volume: 100 μl (sample solution concentration 1 mg / ml)
Liquid feeding pressure: 39 kg / cm ²
Detector: RI detector

  Examples of the bifunctional (meth) acrylate monomer include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9- Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, neopentyl glycol modified trimethylolpropane Di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acrylo Shi propoxyphenyl) propane or 2,2-bis (4- (meth) acryloxy-tetra-ethoxyphenyl) propane. Examples of the trifunctional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate and tris [(meth) acryloxyethyl] isocyanurate. Examples of the tetrafunctional or higher (meth) acrylate monomer include dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipenta Examples include erythritol hexa (meth) acrylate. Of these, dicyclopentanyl di (meth) acrylate is preferred.

  In (A), 1 or more types in the group which consists of a polyfunctional (meth) acrylate oligomer / polymer and a bifunctional (meth) acrylate monomer are preferable, and a polyfunctional (meth) acrylate oligomer / polymer and a bifunctional (meta) It is more preferable to use an acrylate monomer in combination. When a polyfunctional (meth) acrylate oligomer / polymer and a bifunctional (meth) acrylate monomer are used in combination, the mixing ratio is 100 parts by mass in total of the polyfunctional (meth) acrylate oligomer / polymer and the bifunctional (meth) acrylate monomer. In terms of mass ratio, polyfunctional (meth) acrylate oligomer / polymer: bifunctional (meth) acrylate monomer = 10 to 90:90 to 10 is preferable, and 30 to 70:70 to 30 is more preferable.

(B) Monofunctional (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate , Isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo Pentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate , Caprolactone-modified tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t-butyl Aminoethyl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, phenol (ethylene oxide 2 mol modified) (meth) Chryrate, phenol (ethylene oxide 4 mol modified) (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol (ethylene oxide 4 mol modified) (meth) acrylate, nonylphenol ( Ethylene oxide 8 mol modified) (meth) acrylate, nonylphenol (propylene oxide 2.5 mol modified) (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid ( (Meth) acrylate, trifluoroethyl (meth) acrylate, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (Meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, (meth) acrylic acid dimer, β- (meth) acryloyloxyethyl hydrogen succinate, n- (meth) acryloyloxyalkyl hexahydrophthalimide, 2 -(1,2-cyclohexacarboximido) ethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate and the like. Moreover, maleic acid and fumaric acid can be used.
Among (B), phenol (ethylene oxide 2 mol modified) (meth) acrylate, 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate One or more members selected from the group consisting of phenol (ethylene oxide 2 mol modified) (meth) acrylate, 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate and / or 2-hydroxy- It is more preferable to use together with 3-phenoxypropyl (meth) acrylate. When using phenol (ethylene oxide 2 mol modified) (meth) acrylate and 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate and / or 2-hydroxy-3-phenoxypropyl (meth) acrylate in combination The mixing ratio is phenol (ethylene oxide 2 mol modified) (meth) acrylate and 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate and / or 2-hydroxy-3-phenoxypropyl (meth). Phenol (ethylene oxide 2 mol modified) (meth) acrylate: 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate and / or 2-hydroxy-3 in a mass ratio in a total of 100 parts by mass of acrylate -Phenoxypropyl (meth) acryl Over preparative = 10-90: 90-10 is preferred, 30 to 45: 70 to 55 is more preferable.

  The blending ratio of (A) polyfunctional (meth) acrylate and (B) monofunctional (meth) acrylate is preferably (A) :( B) = 5: 95 to 95: 5 (parts by mass). (A) If the polyfunctional (meth) acrylate is 5 parts by mass or more, there is no fear that the initial adhesiveness is lowered, and if it is 95 parts by mass or less, peelability can be secured. The cured fixing agent is peeled off into a film by being immersed in warm water. (B) As for content of monofunctional (meth) acrylate, 40-80 mass parts is further more preferable in 100 mass parts of total amounts of (A) and (B).

  (C) The photopolymerization initiator is blended for sensitization with visible light or ultraviolet active light to promote photocuring of the resin composition, and various known photopolymerization initiators can be used. . Specifically, benzophenone or a derivative thereof; benzyl or a derivative thereof; anthraquinone or a derivative thereof; benzoin; a benzoin derivative such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, or benzyl dimethyl ketal; diethoxyacetophenone, 4 Acetophenone derivatives such as t-butyltrichloroacetophenone; 2-dimethylaminoethyl benzoate; p-dimethylaminoethyl benzoate; diphenyl disulfide; thioxanthone or derivatives thereof; camphorquinone; 7,7-dimethyl-2,3-dioxobicyclo [ 2.2.1] Heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2 Bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2 2.1] Camphorquinone derivatives such as heptane-1-carboxylic acid chloride; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Α-aminoalkylphenone derivatives such as amino-1- (4-morpholinophenyl) -butanone-1; benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, 2,4 , 6-Trimethylbenzoyldimethoxyphenylphosphine oxide, 2 Acylphosphine oxide derivatives such as 1,4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetate And tic acid 2- [2-hydroxy-ethoxy] -ethyl ester. A photoinitiator can be used 1 type or in combination of 2 or more types. Among these, benzyldimethyl ketal, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- One or more of the group consisting of [2-hydroxy-ethoxy] -ethyl ester are preferred.

  (C) The content of the photopolymerization initiator is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of (A) and (B). .5 to 15 parts by mass is most preferable, and 1 to 8 parts by mass is more preferable. If it is 0.1 mass part or more, the effect of hardening acceleration | stimulation will be acquired reliably, and sufficient curing rate can be obtained if it is 20 mass parts or less. Addition of 1 part by mass or more of component (C) makes it possible to cure without depending on the amount of light irradiation, further increases the degree of crosslinking of the cured product of the composition, and does not cause misalignment or the like during cutting. Is more preferable in that

  The photocurable sticking agent preferably contains a particulate substance (D) that does not dissolve in the components (A), (B), and (C) of the sticking agent. Thereby, since the composition after hardening can hold | maintain fixed thickness, a processing precision improves. Furthermore, since the linear expansion coefficient of the cured product of the adhesive composition and the granular material (D) are different, the peelability when peeling after bonding the light-transmitting hard substrate using the adhesive composition is improved. To do.

  As a material of the particulate substance (D), either generally used organic particles or inorganic particles may be used. Specifically, examples of the organic particles include polyethylene particles, polypropylene particles, crosslinked polymethyl methacrylate particles, and crosslinked polystyrene particles. Inorganic particles include ceramic particles such as glass, silica, alumina, and titanium. In these, an organic particle is preferable and 1 or more types in the group which consists of bridge | crosslinking polymethyl methacrylate particle | grains and bridge | crosslinking polystyrene particle | grains are more preferable.

  The granular material (D) is preferably spherical from the viewpoint of improving processing accuracy, that is, controlling the thickness of the adhesive. It is preferable that the average particle diameter by the laser method of a granular material (D) exists in the range of 20-200 micrometers. When the average particle size of the granular material is 20 μm or more, the peelability is excellent, and when it is 200 μm or less, the temporarily fixed member is not easily displaced and excellent in dimensional accuracy. A more preferable average particle diameter (D50) is 35 to 150 μm, more preferably 50 to 120 μm, from the viewpoint of peelability and dimensional accuracy. The particle size distribution is measured by a laser diffraction type particle size distribution measuring device.

  The amount of the particulate material (D) used is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B) from the viewpoints of adhesiveness, processing accuracy, and peelability. 0.1 to 10 parts by mass is more preferable, and 0.2 to 6 parts by mass is most preferable.

  The photocurable fixing agent preferably further contains (E) a thermally expandable microcapsule. The thermally expandable microcapsules are organic thermally expandable particles in which an organic solvent is encapsulated with an organic material (polymer). Specific examples of the organic solvent for the inner shell include organic solvents such as isobutane, pentane, petroleum ether, hexane, octane, and isooctane, and the organic material (polymer) for the outer shell includes vinylidene chloride, acrylonitrile, and acrylate. And thermoplastic resins made of methacrylic acid esters and the like. In such a heat-expandable microcapsule, the organic material (polymer) of the outer shell is softened by heating and the organic solvent of the inner shell is gasified, the volume expands, for example, 5 to 250 times, and peelability is expressed. Thereby, peeling of the substrates fixed with the photocuring fixing agent can be promoted.

  (E) The use amount of the thermally expandable microcapsule is 0 with respect to the total amount of 100 parts by mass of (A) and (B) from the viewpoint of the balance between the above-described peeling promotion effect and sufficient adhesive force. 0.1 to 29.9 parts by mass, preferably 1 to 15 parts by mass, and more preferably 1.5 to 10 parts by mass.

(E) The average particle diameter of the thermally expandable microcapsule is 5 to 100 μm, preferably 5 to 50 μm, and more preferably 8 to 20 μm. If the average particle size is too small, the releasability may be reduced. On the other hand, if the average particle size is too large, the adhesive strength of the composition before peeling may be reduced. Excellent balance.
Moreover, 70 to 130 degreeC is preferable and the foaming start temperature has more preferable 75 to 100 degreeC. If the foaming start temperature is too low, the heat-expandable microcapsule expands due to processing heat during processing of the member, making it difficult to obtain dimensional accuracy. On the other hand, if the temperature is too high, the peelability after processing is poor. By setting the foaming start temperature within this range, the balance between dimensional accuracy and peelability is excellent.
The photocurable fixing agent may contain (F) an organic peroxide and (G) a decomposition accelerator. Thereby, sclerosis | hardenability is obtained reliably.

  (F) Examples of organic peroxides include diacyl peroxides such as lauroyl peroxide and benzoyl peroxide, t-butylperoxy-3,5,5-trimethylhexanoate, cumylperoxyneodecanoate, and hexyl. Alkyl such as peroxybivalate, t-butyl peroxyisobutyrate, t-butyl peroxybivalate, t-butyl peroxyacetate, t-butyl peroxybenzoate, tertiary butyl peroxy-2-ethylhexanate Peroxyesters, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, dinormalpropyl peroxydicarbonate, bis (4-tertiarybutylcyclohexyl) peroxydicarbonate, di-2-eth Peroxydicarbonates such as diethylperoxydicarbonate, dimethoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate and diallylperoxydicarbonate, t-butylperoxyisopropyl carbonate Peroxycarbonates such as di-t-butylperoxycyclohexane, peroxyketals such as di- (t-butylperoxy) butane, dicumyl peroxide, t-butylcumyl peroxide, di-t -Dialkyl peroxides such as butyl peroxide, hydroperoxides such as cumene hydroperoxide, tetramethylbutyl hydroperoxide, ketone peroxides such as cyclohexanone peroxide, etc. It is below. Among these, alkyl peroxyesters and / or hydroperoxides are preferable, hydroperoxides are more preferable, and cumene hydroperoxide is most preferable.

  (F) The amount of the organic peroxide used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B). 1-3 parts by mass are most preferred. If it is 0.01 mass part or more, sclerosis | hardenability will be obtained reliably, and if it is 10 mass parts or less, sufficient storage stability will be obtained and skin irritation will become low.

(G) As the decomposition accelerator, a decomposition accelerator that accelerates the decomposition of the organic peroxide is preferable.
(G) The following is mentioned as a decomposition accelerator which accelerates | stimulates decomposition | disassembly of an organic peroxide.
When organic peroxides such as hydroperoxides and ketone peroxides are used, examples of the decomposition accelerator include organic acid metal salts and organic metal chelates. Examples of organic acid metal salts and organic metal chelates include cobalt naphthenate, copper naphthenate, manganese naphthenate, cobalt octenoate, copper octenoate, manganese octenoate, cobalt octylate, copper acetylacetonate, and titanium acetylacetonate. Manganese acetylacetonate, chromium acetylacetonate, iron acetylacetonate, vanadyl acetylacetonate, cobalt acetylacetonate and the like. Among these, cobalt octylate and / or vanadyl acetylacetonate are preferable, and cobalt octylate is most preferable. Other decomposition accelerators include thiourea derivatives, mercaptobenzimidazoles, amines and the like. These (G) decomposition accelerators can use 1 type (s) or 2 or more types.

(G) The use amount of the decomposition accelerator is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass in total of (A) and (B). Most preferred is 3 to 3 parts by mass. If it is 0.01 mass part or more, sclerosis | hardenability will be obtained reliably, and if it is 10 mass parts or less, sufficient storage stability will be obtained.

The photocurable adhesive containing (F) an organic peroxide and (G) a decomposition accelerator is typically provided as a two-component composition. Regarding the two-component type, it is preferable that all the essential components of the photocurable adhesive are not mixed during storage, and the photocurable adhesive is stored separately in the first agent and the second agent. In this case, it can be used as a two-part photocurable adhesive by applying both agents simultaneously or separately to a member and contacting and curing. When used as a two-component photocurable adhesive, it is preferable that the first agent contains at least (F) an organic peroxide and the second agent contains at least (G) a decomposition accelerator. (C) The photopolymerization initiator may be contained in one or both of the first agent and the second agent. In the present invention, the composition can be cured only by mixing two agents.
For example, (F) an organic peroxide and (G) a decomposition accelerator may be used in combination for the lamination of the hard substrate 11 having no light transmissivity, instead of (C) the photopolymerization initiator.

  Furthermore, a small amount of a polymerization inhibitor can be used in the photocurable fixing agent preferably used in the present invention in order to improve the storage stability. Polymerization inhibitors include methyl hydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol), catechol, hydroquinone monomethyl ether, monotertiary butyl hydroquinone, 2,5-ditertiary butyl hydroquinone. P-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butylcatechol, 2-butyl-4-hydroxyanisole and 2 , 6-ditertiary butyl-p-cresol and the like.

  The amount of these polymerization inhibitors used is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B). When the amount used is within this range, storage stability is ensured, and good adhesiveness is obtained without becoming uncured.

Further, in the photocurable fixing agent, a polar organic solvent may be used together.
In addition, the photo-curing fixing agent has various types of elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, plasticizers, antioxidants, and the like that are generally used within a range that does not impair the object of the present invention. Additives such as inorganic fillers, solvents, fillers, reinforcing materials, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.

  In the step (4), the first surface of the first light-transmitting hard substrate and the first surface of the second light-transmitting hard substrate are opposed to each other so that both surfaces are parallel to each other. In general, the light-transmitting hard substrates are opposed so that the light-transmitting hard substrates are exactly overlapped in the surface direction, for example, so that the light-transmitting hard substrates have a predetermined positional relationship in the surface direction. As a means for implementing this, it is conceivable to use a guide rail, a batting bar or a frame for restricting the moving direction of the translucent hard substrate and moving it to a certain position.

  In the step (5), the first surface of the first translucent hard substrate and the first surface of the second translucent hard substrate are subjected to pressure while maintaining the parallel state determined in the step (4). Is applied to form a laminate. Since a photo-curing fixing agent is used, both substrates are not completely bonded only by applying pressure. In this pressure treatment process, a substrate with a uniform thickness can be obtained by laminating the substrates in parallel. By roll pressing, the thickness accuracy after roll pressing is improved. To do. When the thickness accuracy is improved, troubles during shape processing are reduced. When only the roll press is performed without the pressure treatment, unevenness in the adhesive thickness is likely to occur.

  Further, if pressure is not applied when the light-transmitting hard substrates are bonded together, the substrate may be greatly displaced during roll press, or the adhesive may not spread over the entire surface depending on the application pattern of the fixing agent. Not only does the glass come into contact with each other at the part where the fixing agent does not spread, but also a part that is not bonded is generated. The part that is not bonded also causes chipping or cracking during shape processing, which causes a decrease in productivity. However, when pressure is applied at the time of bonding, the sticking agent easily spreads over the entire bonding surface at the time of roll pressing regardless of the application pattern of the sticking agent, and this problem can be reduced.

  From the viewpoint of stacking accuracy, it is preferable that the fixing agent spreads over the bonding surface with a certain thickness. If the amount of the applied sticking agent is too small, the sticking agent does not spread over the entire bonding surface, which causes bubbles to be generated on the bonding surface. When bubbles are generated, the positional accuracy is lowered. If the amount of the applied sticking agent is too large, the sticking agent leaks from the gap between the bonding surfaces. Even if the sticking agent leaks to some extent, it may be wiped off, and this is not a big problem, but if the amount is large, the sticking agent is wasted.

  The pressure at the time of bonding is also related to the spread of the fixing agent. Therefore, it is desired to appropriately adjust the bonding pressure in addition to the amount of the fixing agent. As a means for realizing this, a method of using a bonding apparatus having a function of controlling a pressure when the light-transmitting hard substrates are bonded to each other can be considered.

The specific pressure and time for bonding may be appropriately set in consideration of the above. For example, the pressure is 10 g / cm ^{2 to} 800 g / cm ² , typically 100 g / cm ^{2 to} 700 g / cm ^2. The time is 10 seconds to 5 minutes, typically 1 to 4 minutes. At this time, heating may be performed. However, since heating may cause the substrate to warp due to internal stress, heating is preferably not performed.

  In order to increase the lamination accuracy, it is also conceivable to control the thickness of the fixing agent itself. As described above, as a method for controlling the thickness, there is a method of mixing a granular material into the fixing agent, as well as a function of controlling the height of the light-transmitting hard substrates when the light-transmitting hard substrates are bonded together. A method using a bonding apparatus is conceivable.

  In step (6), steps (2) to (5) are repeated at least once, assuming that the translucent hard substrate laminate obtained in step (5) is the first translucent hard substrate. Thereby, the translucent hard board | substrate laminated body by which the at least 3 translucent hard board | substrate was bonded together is obtained. From the viewpoint of improving the production efficiency of the plate-like product, a translucent hard substrate laminate in which 10 or more translucent hard substrates, typically 10 to 30 translucent hard substrates are laminated, is manufactured. It is desirable. Also, when laminating each translucent hard substrate laminate in order, after forming the laminate in step (5), light is fixed to the adhesive spread between both translucent hard substrates. Irradiating a part of the agent or irradiating the entire fixing agent with light having energy lower than that in the step (7), and performing the step (5 ′) of forming the temporarily fixed translucent hard substrate laminate. May be. In addition, also when repeating process (2)-(5) in process (6), it is preferable to roll-press the obtained laminated body before that.

  Including the case where the steps (2) to (5) are repeated in the step (6), in the step (5), as described above, it is preferable to roll press the light-transmitting light-transmitting hard substrate. The principle of the roll press is shown in FIG. The roll press has at least a pair of rolls 41 installed in the vertical direction, and the substrate 42 sandwiched between the rolls 41 is fed forward by the rotation of the rolls. During this time, the substrate 42 receives pressure in the vertical direction. Since the substrates are brought into close contact with each other by the pressure treatment, the risk of misalignment while passing through the roll press is reduced, and when the temporary fixing of the step (5 ′) is further performed, Misalignment that may occur can be reduced more reliably, while the fluidity is maintained because the fixing agent is not cured. For this reason, by passing the light-transmitting light-transmitting hard substrate through a roll press, the fixing agent flows appropriately and the thickness uniformity is improved. Since the substrates are bonded in parallel at the time of the pressure treatment, the uniformity of the thickness of the fixing agent is higher than that of roll pressing without pressure treatment. Excess adhesive will flow out of the perimeter of the substrate. Even when bubbles are generated between the substrates during the pressure treatment, the substrates can be removed while passing through the press.

  Even in the case of temporary fixing in the step (5 ′), the adhesive is weak because the hardened adhesive is controlled so as to be only at the outer periphery, and the roll press in the step (5) The hardened part can be broken. If breakage does not occur well, the light irradiation process in step (5 ') may not be performed uniformly on the entire outer periphery of the substrate, but light irradiation on the outer periphery may be performed intermittently. As a result, the fixing agent on the outer periphery of the substrate is divided into an uncured portion and a cured portion, and the cured portion is easily broken from the uncured portion as a starting point.

  The apparatus for roll pressing is known per se and is considered not to require detailed explanation. In the present invention, however, it is desirable to determine the operating conditions in consideration of the following points. First, it is desirable that the roll is longer than the width of the translucent hard substrate. This is because when a plurality of short rolls are arranged in the axial direction, a gap is generated between the rolls, and it becomes difficult to apply a uniform pressure across the width direction of the substrate. In addition, the rolls are arranged in pairs so as to sandwich the bonded substrates from above and below, but if there is only one pair of rolls, the substrate is likely to warp, so two or more pairs (for example, two pairs, (3 pairs or 4 pairs) is preferably installed in the plate passing direction. From the viewpoint of preventing the substrate from warping, the roll is preferably not heated.

  If the roll pressure is too high, the substrate will be cracked or the particulate matter in the adhesive will be crushed. As a result, the desired thickness cannot be obtained. On the other hand, if the roll pressure is too low, the thickness cannot be obtained, and bubbles are removed. I can't do that either. It is desirable to appropriately adjust the roll pressure so as to remove bubbles and obtain a desired thickness. For example, the roll press can be operated such that the linear pressure of the roll is 0.1 kN / m to 10 kN / m, typically 0.2 kN / m to 5 kN / m. The clearance between the upper and lower rollers may be changed according to the number of bonded sheets.

  If the feed rate of the translucent hard substrate is too high, not only the bubbles cannot be removed but also the desired thickness cannot be obtained. On the other hand, if the feed rate is too slow, the productivity is inferior. desirable. For example, the roll press machine can be operated at a feed rate of 100 to 800 mm / min, typically 150 to 700 mm / min.

  The material of the roll is not particularly limited, but silicone, urethane rubber, and the like are preferable because they do not damage the substrate, do not dissolve by the overflowing adhesive, and can obtain a desired thickness.

  When there is a waiting time before the transition from the step (6) to the step (7), or when the step (7) is performed at a place away from the place where the step (6) is performed, the translucent rigid substrate is It is conceivable to store it in a storage place or transport it to an irradiation device. In such a case, it is desired to prevent the displacement of the substrate during transportation and the leakage of the sticking agent during storage. Therefore, between the step (6) and the step (7), a part of the fixing agent is irradiated with light between the light-transmitting hard substrates and spread, or lower than the step (7). You may implement the process (6 ') which forms the temporarily fixed translucent hard board | substrate laminated body by irradiating the light of energy to the whole fixing agent. By irradiating light to a part of the adhesive spread between both substrates, for example, the outer peripheral part, only the part is cured, and both light-transmitting hard substrates are attached with a relatively weak force. Can be matched. Temporary fastening is also useful for preventing positional displacement of the substrate during roll press. The temporary fixing in the step (5 ') and the step (6') may be performed at at least one timing, and the light irradiation for temporary fixing may be performed from the side direction of the laminate to be irradiated.

  Since the light energy required for temporary fixing is much smaller than the light required to cure the entire fixing agent, a simple lighting device such as a black light is sufficient. Thereby, the stacking accuracy can be increased while considering the safety of the operator. In light of the purpose that the bonded light-transmitting hard substrate does not easily shift in position, the outer periphery should be a region with a certain amount of width, but it does not shift when exposed to the inside excessively. The purpose of temporary fixing is reduced, and the irradiation time is lengthened, so that the production efficiency is lowered. Typically, the outer peripheral portion irradiated for temporary fastening has a width of about 5 to 25 mm, more typically about 7 to 17 mm. Moreover, it is preferable that the outer peripheral part which irradiates light exists in the margin area | region which does not form a part of plate-shaped product. When irradiating the whole fixing agent, the light irradiation history of the part which forms a plate-shaped product can be made uniform, and distortion of the fixing agent is suppressed. As a result, it is possible to suppress distortion of the substrate of the portion.

  The wavelength of light irradiated for temporary fixing may be appropriately changed according to the characteristics of the fixing agent to be used. For example, irradiation with microwaves, infrared rays, visible light, ultraviolet rays, X-rays, γ rays, electron beams, etc. Can do. In general, the irradiation light is ultraviolet light because it can be used easily and has relatively high energy. Thus, in the present invention, light refers to not only visible light but also electromagnetic waves (energy rays) including a wide wavelength region.

The light to be irradiated for temporary fixing may be an irradiation amount necessary to temporarily fix the translucent hard substrate, and is generally 1 to 500 mJ / cm ^{2 as} measured by an integrating illuminometer using a 365 nm light receiver. , Typically 3 to 300 mJ / cm ² , more typically 5 to 500 mJ / cm ² . The irradiation time is generally 1 to 120 seconds, typically about 2 to 60 seconds, and preferably about 2.5 to 20 seconds.

  In step (7), after the final roll press in step (6), pressure treatment from one or both of the outermost surfaces of the obtained laminate, that is, the exposed surfaces of the translucent hard substrate laminated on the outermost portion. And a light irradiation treatment for curing the entire fixing agent sandwiched between the light-transmitting hard substrates of the laminate. In addition, the pressurizing process and the light irradiation process are simultaneously performed for at least a predetermined time.

  In the pressure treatment in the step (7), it is preferable to apply pressure from one or both so as to make the intervals between the respective light-transmitting hard substrates of the laminate obtained in the step (6) uniform. The pressure application is not particularly limited as long as it is a known method, but a method of applying pressure using, for example, a vacuum press or a pressure press is preferable.

  Here, “uniform” means that the difference obtained by subtracting the smallest place from the place where the distance between the light-transmitting hard substrates in the laminate is the largest is in the range of 40 μm or less. If it exists in this range, when processing each translucent hard board | substrate, favorable dimensional accuracy will be obtained. From the viewpoint of dimensional accuracy, it is preferable that the difference obtained by subtracting the smallest place from the place where the distance between the light-transmitting hard substrates in the laminate is within the range of 20 μm or less, and more preferably within the range of 10 μm or less. Preferably, it is still more preferable that it exists in the range of 5 micrometers or less.

The pressure treatment in step (7) is 1 g / cm ² or more and 1000 kg / cm ² or less, preferably 3 g / cm ² or more and 800 kg / cm ² or less, more preferably from one or both outermost surfaces of the laminate. 5 g / cm ² or more and 500 kg / cm ² or less, still more preferably 10 g / cm ² or more and 300 kg / cm ² or less. If the distance between the light-transmitting hard substrates in the laminate is uniform, there is no problem even if pressure is locally applied to the light-transmitting hard substrate, but it is better to apply pressure to the entire surface. This is preferable from the viewpoint of maintaining a uniform spacing. In addition, by making the applied pressure within the above range, it is possible to maintain a uniform interval between the translucent hard substrates, while the applied pressure is such that each translucent hard substrate is damaged. Absent.

Further, in the step (7), a light irradiation process is required to irradiate the fixing agent with at least one of visible light or ultraviolet light to increase the adhesive strength of the fixing agent. The wavelength of light to be irradiated may be appropriately changed according to the characteristics of the fixing agent to be used. For example, microwaves, infrared rays, visible light, ultraviolet rays, X-rays, γ rays, electron beams and the like can be irradiated. In general, the irradiation light is ultraviolet light because it can be used easily and has relatively high energy. Thus, in the present invention, light refers to not only visible light but also electromagnetic waves (energy rays) including a wide wavelength region. As the light source, for example, a black light, a high-pressure mercury lamp, an LED light, or a metal halide lamp can be used.
The irradiation amount of the irradiated light is usually 100 mJ / cm ² or more, preferably 200 mJ / cm ² or more, more preferably 400 mJ / cm ² or more, most preferably, as measured with an integrating illuminometer using a 365 nm light receiver. is a 500 mJ / cm ² or more, and usually, 5000 mJ / cm ² or less, preferably 4500mJ / cm ² or less, more preferably 4000 mJ / cm ² or less, more preferably 3800mJ / cm ² or less, even more preferably 3600mJ / Cm ² or less, most preferably 3500 mJ / cm ² or less.

  In the step (7), the pressure treatment and the light irradiation treatment are simultaneously performed for at least a predetermined time. Thus, by performing both processes simultaneously for a certain period of time, the distance between the light-transmitting hard substrates in the laminate becomes uniform, and a remarkable effect is obtained in terms of dimensional accuracy when processing the light-transmitting hard substrate. The term “processing” as used herein refers to each processing described in step (9) described later. The certain time here is not particularly limited as long as it includes a period during which curing is performed. In addition, it is preferable to perform the subsequent pressure treatment and the light irradiation treatment at the same time after the pressure treatment is performed in advance, because the intervals between the light-transmitting hard substrates can be made uniform.

<Manufacture of plate products>
A plate-like product can be produced from the translucent hard substrate laminate obtained by the above-described method for producing a translucent hard substrate laminate.

  First, in step (8), the translucent hard substrate laminate is divided in the thickness direction to form a desired number of divided translucent hard substrate laminates. The dividing method is not particularly limited, but a disk cutter (diamond disc, cemented carbide disc), fixed abrasive type or loose abrasive type wire saw, laser beam, etching (eg, chemical etching using hydrofluoric acid, sulfuric acid, etc.) And electrolytic etching), red tropics (nichrome wire), and water jet, each alone or in combination, and divided into rectangular parallelepiped shapes of the same size. Etching can also be used for surface treatment of the cut surfaces after division.

  Next, in step (9), desired shape processing is performed on each of the divided light-transmitting hard substrate laminates. This process has the advantage that the production speed of the plate-like product can be greatly increased because the divided light-transmitting hard substrate laminate can be integrally processed into the desired plate-like product shape. is there. Shape processing may be performed by any known means. For example, grinding with a rotating grindstone, drilling with an ultrasonic vibration drill, end surface processing with a rotating brush, drilling with etching, end surface processing with etching, outer shape processing with etching, burner Flame processing using The processing methods can be used alone or in combination. Etching can also be used for surface treatment after shape processing.

  In the step (10), the translucent hard substrates bonded together are heated by heating the translucent hard substrate laminate after the shape processing to form a plurality of plate-like products. Although there is no restriction | limiting in particular as a heating method, In order for a sticking agent to soften in a film form and to isolate | separate into each plate-shaped product well, the method of immersing the translucent hard board | substrate laminated body after shape processing in warm water is preferable. A suitable temperature of the hot water varies depending on the fixing agent employed, but is usually about 60 to 95 ° C, preferably 80 to 90 ° C.

Furthermore, in the step (10), when peeling off each light-transmitting hard substrate from the laminate, it is preferable to irradiate the fixing agent with visible light or ultraviolet rays before the hot water immersion treatment, so that the cured for peeling off. The time for immersing the fixing agent in warm water can be shortened. Dose of visible light or UV irradiation at this time, 1000 mJ / cm ² or more at 365nm for each irradiation surface 40000mJ / cm ² or less, more preferably 2000 mJ / cm ² or more 38000mJ / cm ² or less, even more preferably 4000mJ / cm ² or more 36000mJ / cm ₂ is less than or equal to. By setting the irradiation amount within this range, the effect of shortening the time required for the hot water immersion treatment is increased.

  Further, as described above, when the number of laminated light-transmitting hard substrates is increased, the fixing agent in the layer away from the irradiation source is hard to be cured. Therefore, a step of irradiating light for curing the uncured fixing agent toward the side surface of the divided translucent hard substrate laminate can be provided between the step (8) and the step (10). . Since light is irradiated toward the side surface, it is advantageous for curing the fixing agent inside the laminate.

The irradiation amount of the light to be irradiated is generally 1000 to 15000 mJ / cm ^{2 with} respect to one side surface of the translucent hard substrate laminate as measured by an integrating illuminometer using a 365 nm light receiver, typically It is 1500-10000 mJ / cm < ² >, More typically 2000-9000 mJ / cm < ² >, Preferably it is 4000-8000 mJ / cm < ² >. The irradiation time is generally about 0.1 to 120 seconds, typically about 15 to 75 seconds, and more typically about 20 to 60 seconds.
As the light source, for example, a black light, a high-pressure mercury lamp, an LED light, a metal halide lamp, or the like can be used. However, since the irradiation intensity is strong if a high-pressure mercury lamp or a metal halide lamp is used, a further effect can be expected.

<Example of device configuration>
The example of the translucent hard board | substrate bonding apparatus which can be used when producing a translucent hard board | substrate is demonstrated.

FIG. 1 is a schematic view showing a first example of a translucent hard substrate laminating apparatus that can be suitably used in the present invention. The translucent hard substrate laminating apparatus 10 includes a gantry 11, an upper stage 12, a press unit 13, a suction unit 14, a suction hole 15, an LED unit 16, one or more lower stages 17, and a plurality of lower stages. Includes a lower stage moving means 18, a side clamp 19, a lower substrate coating unit 20, and an upper substrate coating unit 21 for each lower stage.
In this embodiment, the LED unit 16 is provided to perform temporary fastening (step (5 ′) or step (6 ′)) by ultraviolet irradiation to the outer periphery of the substrate. The LED unit 16 is not necessary in the embodiment in which temporary fixing is not performed.

  The gantry 11 is a base portion on which each component of the translucent hard substrate laminating apparatus 10 is mounted, and an electrical unit 23 is disposed inside. The electrical unit 23 performs sequence control of each component device by PLC (Programmable Logic Controller).

  The upper stage 12 holds the upper translucent hard substrate 25 by vacuum suction. Therefore, a plurality of suction holes 15 are opened on the lower surface of the upper stage 12, and the suction holes 15 are connected to the suction unit 14 by piping. FIG. 2 is a schematic diagram of the lower surface of the upper stage 12 and shows an example of the arrangement of the suction holes 15. A vacuum pump, a vacuum ejector, or the like can be used as the suction unit 14.

  Connected to the upper part of the upper stage 12 is a press unit 13 for bonding the upper translucent hard substrate 25 while pressing it against the lower translucent hard substrate 24. The press unit 13 has an elevating cylinder (not shown) that can move the upper stage 12 in the Z direction (vertical direction). The pressurizing force, moving speed, pressurizing time, and height are controlled by a servo motor. can do.

  A plurality of LED units 16 for irradiating the lower translucent hard substrate 24 with ultraviolet rays for curing the fixing agent are embedded in the lower surface of the upper stage 12. The LED units 16 may be arranged along the outer periphery of the upper translucent hard substrate 25 adsorbed on the upper stage 12, or may be arranged on the entire surface of the adsorbed substrate 25. FIG. 2 shows an example of the arrangement state of the LED units 16. The LED unit 16 can be arranged not only in one row but also in two or more rows in parallel, so that the width of the outer peripheral portion to be irradiated can be increased. The range of the portion that is not cured can be adjusted by adjusting the arrangement interval of the LED units 16.

  The lower stage 17 holds the lower translucent hard substrate 24 and receives pressure from the upper stage 12 during pressing. The lower stage 17 can be moved in the X axis direction, the Y axis direction, and the θ axis direction by the lower stage moving means 18. The lower stage moving means 18 includes a θ table that enables a horizontal turning movement, and an X table and a Y table that enable a horizontal movement. These tables are driven by a motor. A motor-driven side clamp 19 that is movable in the X-axis direction and the Y-axis direction for positioning the translucent hard substrate placed thereon is provided on the upper surface of the lower stage 17. Instead of the side clamp 19, as shown in FIG. 3, a positioning contact jig 70 for placing the translucent hard substrate at a predetermined position may be provided on the upper surface of the lower stage 17. In this case, the translucent hard substrate is moved by hand in the direction indicated by the arrow and placed at a position fixed by the contact jig 70. Further, in order to prevent the position of the translucent hard substrate from being displaced, similarly to the upper stage 12, the lower translucent hard substrate 24 can also be held by vacuum suction.

  The lower substrate coating unit 20 includes a photo-curing adhesive dispenser 20a and a motor-driven robot 20b connected to the dispenser 20a and movable in the X-axis, Y-axis, and Z-axis directions. The fixing agent can be applied to the upper surface of the optical hard substrate 24 in an arbitrary pattern. The fixing agent is automatically and quantitatively discharged. The coating amount is controlled by a digital pressure gauge and a coating speed.

  The upper substrate coating unit 21 automatically coats the photocurable adhesive toward the lower surface of the upper translucent hard substrate 25 in a state where the upper translucent hard substrate 25 is held by the upper stage 12. To do. The application amount is controlled by a pressure gauge and application time. The upper substrate coating unit 21 is provided with a motor-driven robot 21b having a rotation shaft that can rotate in the horizontal direction beside the upper and lower stages, and the tip rotary nozzle 21a is located near the center of the upper stage 12 during coating. The fixing agent is applied from the tip of the nozzle 21a. When the application is completed, it is stored beside the upper and lower stages so as not to interfere with the bonding of the translucent hard substrate.

  A procedure for laminating a translucent hard substrate using the translucent hard substrate laminating apparatus 10 according to the first example in which the cover glass is laminated will be described with reference to FIGS.

  First, the first translucent hard substrate 26 is placed on the first lower stage 17 and fixed at a predetermined position by a side clamp 19 (not shown) (FIG. 4). Placement of the translucent hard substrate 26 on the first lower stage 17 can be performed manually, but a large number of translucent hard substrates 26 are stored in a dedicated cassette, and the first is automatically made. It may be placed on the lower stage 17. The translucent hard board | substrate 26 mounted is moved just under the upper stage 12 by the lower stage moving means 18 (not shown) (FIG. 5). Next, the upper stage 12 is lowered by the press unit 13. The translucent hard substrate 26 is vacuum-sucked by the suction force from the suction hole 15 (not shown) (FIG. 6). The adsorbed translucent hard substrate 26 rises with the upper stage 12 while being held, and waits for the second substrate (FIG. 7).

  Next, the second translucent hard substrate 27 is placed on the first lower stage 17 and fixed to a predetermined position by a side clamp 19 (not shown) (FIG. 8). On the upper surface of the second light-transmitting hard substrate 27, the fixing agent 28 is applied in a predetermined pattern from the lower substrate coating unit 20 (FIG. 9). After the application is completed, the second translucent hard substrate 27 placed on the first lower stage 17 moves directly below the upper stage 12.

  After the position adjustment, the nozzle 21a attached to the arm tip of the upper substrate coating unit 21 moves to the vicinity of the center of the first substrate 26 held by the upper stage 12, and the fixing agent 29 is transferred from the nozzle 21a. It is applied to the lower surface of the first translucent hard substrate 26 (FIG. 10). After the adhesive (28, 29) is applied to the upper and lower translucent hard substrates (26, 27), the upper stage 12 is lowered by the press unit 13 and the two translucent hard substrates (26, 27) are applied. ) Are pressed and bonded together, the adhesive (28, 29) sandwiched between the upper and lower light-transmitting hard substrates spreads over the entire surface of the light-transmitting hard substrate. While maintaining the pressurized state, ultraviolet light is irradiated from the LED unit 16 to the outer peripheral portion of the translucent hard substrate (FIG. 11). As a result, only the fixing agent on the outer peripheral portion is cured.

  After the ultraviolet irradiation, the suction to the upper substrate 26 is released, and only the upper stage 12 is raised (FIG. 12). The bonded light-transmitting hard substrate is conveyed by the lower stage 17 and returned to the original position (FIG. 13). The pressurizing process and temporary fixing of the translucent hard substrate are completed by the above steps.

Thereafter, the temporarily fixed light-transmitting hard substrate laminate is passed through a roll press, and the next light-transmitting hard substrate 26 is mounted using the second lower stage 17 again as shown in FIGS. Are finally held on the upper stage 12 side. Subsequently, as shown in FIGS. 8 to 13, the substrate 26 held on the upper stage 12 is respectively placed on the surface of the upper substrate 26 of the laminate obtained by pasting the substrates 26 and 27 previously produced. Are bonded together in a state where a fixing agent is applied to the surface of the substrate.
The above operation is repeated for the number of substrates to be stacked.
Next, by performing light irradiation for curing the entire fixing agent, it is possible to collectively form a translucent hard substrate laminate.

  Specifically, for example, as described above, a laminate obtained by laminating a plurality of substrates may be subjected to pressure treatment from the upper side, and light irradiation may be performed from the lower side in that state.

  The embodiments of the present invention have been described above with reference to the drawings. However, the present invention is not limited to these embodiments, and various variations are possible.

<Invention Example>
1. Preparation of Fixing Agent The following components (A) to (D) were mixed to prepare an fixing agent. Two types of fixing agents were prepared.
(Fixing agent 1)
(A) As a polyfunctional (meth) acrylate, 20 parts by mass of “UV-3000B” (hereinafter abbreviated as “UV-3000B”) manufactured by Nihon Gosei Co., Ltd., dimethylol-tricyclodecane diacrylate (“Light” manufactured by Kyoeisha Chemical Co., Ltd.) Acrylate DCP-A ", hereinafter abbreviated as" DCP-A "), 25 parts by mass,
(B) As monofunctional (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate ("Aronix M-5700" manufactured by Toa Gosei Co., Ltd., hereinafter abbreviated as "M-5700") 35 parts by mass, phenol ethylene oxide 2 mol 20 parts by mass of modified acrylate (“Aronix M-101A” manufactured by Toa Gosei Co., Ltd.)
(C) 4 parts by mass of BDK: benzyldimethyl ketal (“IRGACURE651” manufactured by BASF) as a photopolymerization initiator,
(D) Monodisperse spherical cross-linked polystyrene particles having an average particle diameter (D50) of 100 μm (“GS-100S” manufactured by Ganz Kasei Co., Ltd.) as a particulate material not dissolved in (A) to (C) 0.3 parts by mass (others) As a polymerization inhibitor, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S (In-D)” manufactured by Sumitomo Chemical Co., Ltd.) 0.1 part by mass

(Fixing agent 2)
(A) As a polyfunctional (meth) acrylate, “UV-3000B” (hereinafter referred to as “UV-3000B”) manufactured by Nippon Gosei Co., Ltd. Weight average molecular weight 18000, polyol compound is polyester polyol, and organic polyisocyanate compound is isophorone diisocyanate. , Hydroxy (meth) acrylate is 2-hydroxyethyl acrylate) 15 parts by mass, dicyclopentanyl diacrylate (manufactured by Nippon Kayaku Co., Ltd., “KAYARAD R-684”, hereinafter abbreviated as “R-684”),
(B) As a monofunctional (meth) acrylate, 2- (1,2-cyclohexacarboximide) ethyl acrylate (“Aronix M-140” manufactured by Toa Gosei Co., Ltd., hereinafter abbreviated as “M-140”), 50 parts by mass; 25 parts by mass of phenol ethylene oxide 2 mol modified acrylate (“Aronix M-101A” manufactured by Toa Gosei Co., Ltd.)
(C) BDK as a photopolymerization initiator: 1.5 parts by mass of benzyldimethyl ketal (“IRGACURE651” manufactured by BASF)
(D) Monodispersed spherical cross-linked polystyrene particles having an average particle size (D50) of 100 μm (“GS-100S” manufactured by Ganz Kasei Co., Ltd.) as granular materials not dissolved in (A) to (C) (parts) As a polymerization inhibitor, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S (In-D)” manufactured by Sumitomo Chemical Co., Ltd.) 0.1 part by mass (others) 3 parts by mass of expandable microcapsules (foaming start temperature: 75 ° C., “F-36D” manufactured by Matsumoto Yushi Seiyaku Co., Ltd.)

(Fixing agent 3)
(A) As a polyfunctional (meth) acrylate, 15 parts by mass of “UV-3000B” manufactured by Nippon Gosei Co., Ltd. (hereinafter abbreviated as “UV-3000B”), dicyclopentanyl diacrylate (“KAYARAD” manufactured by Nippon Kayaku Co., Ltd.) R-684 ", hereinafter abbreviated as" R-684 ") 15 parts by mass,
(B) As a monofunctional (meth) acrylate, 45 parts by mass of 2- (1,2-cyclohexacarboxyimide) ethyl acrylate (“Aronix M-140” manufactured by Toagosei Co., Ltd., hereinafter abbreviated as “M-140”), 25 parts by mass of phenol ethylene oxide 2 mol modified acrylate (“Aronix M-101A” manufactured by Toa Gosei Co., Ltd.)
(C) As a photopolymerization initiator, BDK: benzyl dimethyl ketal (“IRGACURE651” manufactured by BASF) 10 parts by mass,
(D) Monodispersed spherical cross-linked polystyrene particles having an average particle size (D50) of 100 μm (“GS-100S” manufactured by Ganz Kasei Co., Ltd.) as granular materials not dissolved in (A) to (C) (parts) As a polymerization inhibitor, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S (In-D)” manufactured by Sumitomo Chemical Co., Ltd.) 0.1 part by mass

(Fixing agent 4)
<First Agent> (A) As a polyfunctional (meth) acrylate, 15 parts by mass of “UV-3000B” (hereinafter referred to as “UV-3000B”) manufactured by Nippon Gosei Co., Ltd., dicyclopentanyl diacrylate (Nipponization) “KAYARAD R-684” manufactured by Yakuhinsha Co., Ltd., hereinafter abbreviated as “R-684”) 15 parts by mass,
(B) As a monofunctional (meth) acrylate, 45 parts by mass of 2- (1,2-cyclohexacarboxyimide) ethyl acrylate (“Aronix M-140” manufactured by Toagosei Co., Ltd., hereinafter abbreviated as “M-140”), 25 parts by mass of phenol ethylene oxide 2 mol modified acrylate (“Aronix M-101A” manufactured by Toa Gosei Co., Ltd.)
(C) 25 parts by mass of BDK: benzyldimethyl ketal (“IRGACURE651” manufactured by BASF) as a photopolymerization initiator,
(D) 1 part by mass of monodisperse spherical cross-linked polystyrene particles (“GS-100S” manufactured by Ganz Kasei Co., Ltd.) having an average particle size (D50) of 100 μm as a particulate material not dissolved in (A) to (C) 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol) (“Sumilyzer MDP-S (In-D)” manufactured by Sumitomo Chemical Co., Ltd.) 0.1 parts by mass (F) organic peroxide as an agent 2 parts by mass of cumene hydroperoxide (Nippon Yushi Co., Ltd. “Park Mill H”, hereinafter abbreviated as “CHP”) <Second Agent> (A) As a multifunctional (meth) acrylate, “Nippon Gosei Co., Ltd.” UV-3000B (Urethane acrylate, hereinafter abbreviated as “UV-3000B”) 15 parts by mass, dicyclopentanyl diacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd., hereinafter “ -684 "abbreviated) 15 parts by weight,
(B) As a monofunctional (meth) acrylate, 45 parts by mass of 2- (1,2-cyclohexacarboxyimide) ethyl acrylate (“Aronix M-140” manufactured by Toagosei Co., Ltd., hereinafter abbreviated as “M-140”), 25 parts by mass of phenol ethylene oxide 2 mol modified acrylate (“Aronix M-101A” manufactured by Toa Gosei Co., Ltd.)
(C) 25 parts by mass of BDK: benzyldimethyl ketal (“IRGACURE651” manufactured by BASF) as a photopolymerization initiator,
(D) 1 part by mass of monodisperse spherical cross-linked polystyrene particles (“GS-100S” manufactured by Ganz Kasei Co., Ltd.) having an average particle size (D50) of 100 μm as a particulate material not dissolved in (A) to (C) 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S (In-D)” manufactured by Sumitomo Chemical Co., Ltd.) 0.1 part by mass (G) decomposition accelerator 2 parts by mass of cobalt octylate (“Cobalt octylate” manufactured by Shinto Paint Co., Ltd., hereinafter abbreviated as “Oct-Co”)

2. Bonding of light-transmitting hard substrate 12 glass plates are formed using the bonding apparatus having the structure of FIG. 1 described above as a light-transmitting hard substrate with a glass plate (horizontal 530 mm × vertical 420 mm × thickness 0.7 mm). A laminate having an uncured state in which the sticking agent was uncured was prepared by bonding with the sticking agent. The operating conditions of the device are as follows. As the fixing agent 4, the first agent and the second agent were weighed and mixed in equal amounts.
<Operation conditions for bonding equipment>
Bonding pressure: 400 g / cm ²
・ Bonding time: 180 seconds ・ Amount of adhesive applied to upper plate glass: 5 g
-Adhesive amount applied to lower plate glass: 33 g

3. Roll press The produced plate glass was roll-pressed. The operating conditions of the roll press are as follows.
<Roll press operating conditions>
-Number of roll pairs: 2
-Whether the roll is heated: None-Linear pressure: 0.5 kN / m
・ Roll width: 1m
・ Feeding speed: 200mm / min ・ Roll material: Silicone

4). Curing of Fixing Agent UV irradiation was performed on the entire surface of the laminate of sheet glass after roll pressing. Irradiation conditions are as follows.
・ UV irradiation amount: 2000 mJ / cm ² (measured by an integrating illuminometer using a 365 nm light receiver)
・ UV irradiation time: 40 seconds ・ UV light source: Metal halide lamp

<Viscosity of fixing agent>
The viscosity of each fixing agent was measured using an E-type viscometer at a temperature of 25 ° C. The results are shown in Table 1.

<Tensile shear bond strength>
The tensile shear bond strength of each fixing agent was measured according to the following. The results are shown in Table 1.
Tensile shear bond strength: measured in accordance with JIS K 6850. Specifically, using the heat-resistant glass (trade name “Heat-resistant Pyrex (registered trademark) glass”, 25 mm × 25 mm × 2.0 mm) as the adherend, the bonded part was made into a circle having a diameter of 8 mm, and the produced adhesive was used. Two sheets of heat-resistant glass are laminated, using a UV irradiator, integrated light quantity 2000 mJ / cm ² (Illuminance at 365 nm: 160 mW / cm ² , “ECS-401GX (UV curing device equipped with metal halide lamp) manufactured by Eye Graphics Co., Ltd.) )) To obtain a tensile shear bond strength test piece. The prepared test piece was measured for tensile shear bond strength at a tensile rate of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.

<Hardness>
The hardness (Shore D) of each fixing agent was measured according to the following. The results are shown in Table 1.
Put PET on the glass plate, adhere the silicon mold (28mmφ × 5mmt or 28mmφ × 1mmt), pour the sticking agent, put PET on it, place the glass plate, use UV irradiation machine, A hardness test piece was prepared by irradiating once each from the front and back under conditions of an integrated light quantity of 2000 mJ / cm ² (“F450-20 (UV curing device equipped with metal halide lamp)” manufactured by Fusion UV Systems Japan). The produced test piece was measured for hardness under an environment of a temperature of 23 ° C. and a humidity of 50% using a digital rubber hardness meter (DD2-D type manufactured by Kobunshi Keiki Co., Ltd.). Note that five test pieces of 28 mmφ × 1 mmt were stacked.
<Peel test>
A peel test of each fixing agent was performed according to the following. The results are shown in Table 1.
After sticking 80 mm square blue plates using a sticking agent, using a UV irradiator, integrated light intensity of 2000 mJ / cm ² (illuminance of 365 nm: 160 mW / cm ² , “ECS-401GX manufactured by Eye Graphics Co., Ltd.) (Metal halide lamp mounted UV curing apparatus) ”)) was cured to prepare a test piece for a peel test. The produced test piece was measured for time (minutes) until it was immersed in 90 ° C. warm water and peeled off.

DESCRIPTION OF SYMBOLS 10 Translucent hard board | substrate bonding apparatus 11 Base 12 Upper stage 13 Press unit 14 Suction unit 15 Suction hole 16 LED unit 17 Lower stage 18 Lower stage moving means 19 Side clamp 20 Lower substrate coating unit 20a Dispenser 20b Robot 21 Upper substrate coating unit 21a Nozzle 21b Robot 23 Electrical unit 24 Lower translucent hard substrate 25 Upper translucent hard substrate 26, 27 Translucent hard substrate 28, 29 Fixing agent 41 Roll 42 Bonded Substrate 70 attachment jig

Claims (22)

1) preparing a first translucent hard substrate;
2) preparing a second translucent hard substrate;
3) A step of applying a photocurable sticking agent to the first surface of the first translucent hard substrate and / or the first surface of the second translucent hard substrate;
4) The process of making the 1st surface of a 1st translucent hard substrate and the 1st surface of a 2nd translucent hard substrate oppose so that both surfaces may become parallel,
5) Applying pressure to the first surface of the first translucent hard substrate and the first surface of the second translucent hard substrate while maintaining the parallel state to form a laminate And a process of
6) Considering the light-transmitting hard substrate laminate as a first light-transmitting hard substrate, the steps 2) to 5) are repeated at least once, and at least three light-transmitting hard substrates are bonded together. Forming an optical hard substrate laminate; and
7) A process for producing a light-transmitting hard substrate laminate, comprising a step of simultaneously performing a pressure treatment from one or both outermost surfaces of the laminate and a light irradiation treatment to the fixing agent of the laminate for at least a predetermined time. . After forming the laminate in step (5), or at least one timing between step (6) and step (7),
5 ′) Light is applied to a part of the fixing agent spread between the light-transmitting hard substrates, or the entire fixing agent is irradiated with light having a lower energy than in the step (7). The method for producing a light-transmitting hard substrate laminate according to claim 1, wherein the step of forming the temporarily fixed light-transmitting hard substrate laminate is performed.   The process (7) is a method for producing a light-transmitting hard substrate laminate according to claim 1 or 2, wherein the step (7) is performed by irradiating light toward the surface of the second light-transmitting hard substrate.   The manufacturing method of the translucent hard board | substrate laminated body as described in any one of Claims 1-3 in which the said sticking agent contains a granular material. A light irradiation amount in the step (7), measured at integrating luminometer using 365nm of the light receiver, 100mJ / cm ² ~5000mJ / cm in the range of ² to any one of claims 1 to 4 Manufacturing method of transparent translucent substrate laminate.   In the said process (6), before repeating process (2)-(5), the laminated body obtained is roll-pressed, The translucent hard board | substrate laminated body as described in any one of Claims 1-5. Production method.   The method for producing a light-transmitting hard substrate laminate according to any one of claims 1 to 6, wherein the light-transmitting hard substrate is a plate glass for cover glass. 8) A translucent hard substrate laminate obtained by using the method for producing a translucent hard substrate laminate according to any one of claims 1 to 7 is divided in a thickness direction, and a desired number of divided substrates are divided. Forming a translucent hard substrate laminate,
9) A step of performing a desired shape processing on each of the divided translucent hard substrate laminates;
10) A step of peeling the light-transmitting hard substrates bonded together by heating the light-transmitting hard substrate laminate after shape processing to form a plurality of plate-shaped products;
A method for producing a plate-like product including   9. The method according to claim 8, further comprising irradiating light for curing the uncured fixing agent toward the side surface of the divided translucent hard substrate laminate between the step (8) and the step (10). A manufacturing method for plate products.   The method for producing a plate-like product according to claim 8 or 9, wherein the step (10) includes immersing the translucent hard substrate laminate after shape processing in warm water and softening the fixing agent in a film form.   The step (10) includes irradiating light from the surface and / or side surface of the laminate before immersing the translucent hard substrate laminate after shape processing in warm water. Production method.   The translucent hard board | substrate laminated body produced by the manufacturing method of the translucent hard board | substrate laminated body as described in any one of Claims 1-7. In producing the light-transmitting hard substrate laminate according to claim 12, it is used for bonding each light-transmitting hard substrate,
(A) polyfunctional (meth) acrylate;
(B) monofunctional (meth) acrylate;
(C) a photopolymerization initiator;
Including
(A) As a compounding ratio of polyfunctional (meth) acrylate and (B) monofunctional (meth) acrylate, (A) :( B) = 5: 95 to 95: 5 (parts by mass) photocurable fixing Agent.   The photocurable sticking agent according to claim 13, further comprising (D) a particulate material in addition to (A) to (C).   The photocurable fixing agent according to claim 13 or 14, further comprising (E) a thermally expandable microcapsule.   The photocurable sticking agent according to any one of claims 13 to 15, further comprising (F) an organic peroxide and (G) a decomposition accelerator.   (B) Content of monofunctional (meth) acrylate is 40-80 mass parts in 100 mass parts of total amounts of (A) and (B), The photocuring as described in any one of Claims 13-16 Adhesive.   (C) Content of a photoinitiator is 0.1-20 mass parts with respect to 100 mass parts of total amounts of (A) and (B), It is any one of Claims 13-17 Photo-curable adhesive. In producing the light-transmitting hard substrate laminate according to claim 12, it is used for bonding each light-transmitting hard substrate,
(A) polyfunctional (meth) acrylate;
(B) monofunctional (meth) acrylate;
(F) organic peroxides;
(G) a decomposition accelerator;
Including
(A) As a compounding ratio of polyfunctional (meth) acrylate and (B) monofunctional (meth) acrylate, (A) :( B) = 5: 95 to 95: 5 (parts by mass) photocurable fixing Agent.   Furthermore, (D) The photocurable sticking agent of Claim 13 containing a granular material.   21. The photocurable adhesive according to claim 19 or 20, further comprising (E) a thermally expandable microcapsule.   (B) Content of monofunctional (meth) acrylate is 40-80 mass parts in 100 mass parts of total amounts of (A) and (B), The photocuring as described in any one of Claims 19-21 Adhesive.

Images