JP5916620B2 - Method for peeling translucent hard substrate laminate and method for producing plate product using the same - Google Patents

Description

  The present invention relates to a method for peeling a light-transmitting hard substrate laminate. Moreover, this invention relates to the manufacturing method of the plate-shaped product which uses the peeling method of a translucent hard board | substrate laminated body.

  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.

  Therefore, Japanese Patent Laid-Open No. 2009-256125 (Patent Document 1) proposes a method for increasing the production efficiency of plate glass products. Specifically, “a large number of material glass sheets (1) are stacked, and each material glass sheet (1) is integrally fixed by a peelable fixing material (2) interposed between each material glass sheet (1). Forming the material glass block (A), dividing the material glass block (A) in the plane direction to form a small-area divided glass block (B), and processing at least the outer periphery of the divided glass block (B) A product glass block (C) having a product shape in plan view is formed, and after the end face processing of the product glass block (C), the product glass block (C) is individually separated. "Processing method" is proposed (claim 1). Thereby, “division, outer shape processing, and end face processing are performed in a state in which a large number of material sheet glasses are stacked, so that a large number of sheet glass products can be obtained with a small number of steps, and productivity is high” (paragraph 0007). ) Is described.

  Further, Patent Document 1 states that “the fixing material (2) interposed between the respective material glass plates (1) is cured when irradiated with ultraviolet rays, and is cured by softening the cured state when heated. It is described that “the material is used” (claim 4). As a result, "When a photocurable liquid sticking agent is interposed between the upper and lower material plate glasses and pressed in the vertical direction, the liquid sticking agent spreads in the form of a film with a uniform thickness over the entire surface between the upper and lower material plate glasses. In this state, when the infrared rays are irradiated, the liquid sticking agent spread in the form of a film is cured and the upper and lower plate glasses are fixed together, so that a large number of material plate glasses are stacked quickly and accurately. In addition, after final processing (end face processing), when the product glass block is accommodated in hot water or the like and heated, the fixing agent hardened between the plate glasses is softened, Therefore, it is easy to collect and process the fixing agent without causing environmental pollution "(paragraph 0007). Specifically, it is described that "when heated to 80 to 90 degrees with warm water, the cured state is softened and peeled off from the object" (paragraph 0010).

  On the other hand, JP 2010-95627 A (Patent Document 2) contains (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C) a photopolymerization initiator. The temperature of hot water when peeling a member temporarily fixed using a photocurable temporary fixing adhesive composition having a glass transition temperature of −50 ° C. to 40 ° C. is preferably 90 ° C. or less, and 30 ° C. It is described that -90 degreeC is more preferable and 40-90 degreeC is the most preferable (paragraph 0042).

JP 2009-256125 A JP 2010-95627 A

  According to the processing method of the plate glass described in Patent Document 1, it is possible to manufacture a plate glass product having a predetermined shape with high production efficiency. However, in the peeling method described in Patent Document 1, there is a case in which a so-called adhesive residue in which a part of the adhesive remains on the surface of the glass product after separation occurs, which is a factor for reducing the production efficiency. Patent document 2 has no description about peeling a translucent hard board | substrate laminated body without adhesive residue.

  Then, this invention makes it a subject to provide the method of peeling a translucent hard board | substrate laminated body, such as a glass block, without adhesive residue. Moreover, this invention makes it another subject to provide the manufacturing method of the plate-shaped product which uses the said peeling method.

The present invention provides the following means for solving the above problems.
In one aspect, the present invention provides a step 1 of preparing a light-transmitting hard substrate laminate in which two or more light-transmitting hard substrates are bonded together with a photocurable fixing agent, and a light-transmitting hard substrate laminate. A step of peeling the light-transmitting hard substrates laminated together by heating, and a step 2 of forming a plurality of light-transmitting hard substrates separated from each other, In step 2, the laminate is first contacted with water that is 40 to 90 ° C. higher than the glass transition temperature of the cured product of the photocurable fixing agent, and then the second water is 5 to 25 ° C. higher than the glass transition temperature. It is the peeling method including making it contact.

  In one embodiment, the method for peeling a light-transmitting hard substrate laminate according to the present invention has a first contact time of 1 to 120 minutes and a second contact time of 1 minute or more.

  In another embodiment of the method for peeling a light-transmitting hard substrate laminate according to the present invention, the glass transition temperature of the cured body of the photocurable fixing agent is 0 to 40 ° C.

  In still another embodiment of the method for peeling a translucent hard substrate laminate according to the present invention, the transition time from the end of the first contact to the start of the second contact is 0.1 to 120 seconds.

  The peeling method of the translucent hard board | substrate laminated body which concerns on this invention is another one Embodiment. WHEREIN: After the process 1, before the contact to the water in the process 2, a fixing agent is hardened with respect to the translucent hard board | substrate laminated body. To light.

  In another embodiment of the method for peeling a light-transmitting hard substrate laminate according to the present invention, the light-transmitting hard substrate is a plate glass.

  In still another embodiment of the method for peeling a translucent hard substrate laminate according to the present invention, the fixing agent is (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, and (C ) Contains a photopolymerization initiator.

  In another aspect, the present invention is a method for manufacturing a plate-like product using the method for peeling a translucent hard substrate laminate according to the present invention.

  According to this invention, a translucent hard board | substrate laminated body is peeled without adhesive residue. For this reason, it can contribute to the improvement of the production efficiency of plate-shaped products.

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

<Step 1. Preparation of translucent hard substrate laminate>
Although there is no restriction | limiting in particular as a translucent hard board | substrate which comprises a translucent hard board | substrate laminated body, Plate glass (Tempered plate glass, raw material glass plate, glass substrate with a transparent conductive film, a glass substrate with which the electrode and the circuit were formed, etc.) , Sapphire substrate, quartz substrate, plastic substrate, magnesium fluoride substrate and the like. Although there is no restriction | limiting in particular in the magnitude | size of one translucent hard board | substrate, Typically, it has an area of about 10,000-250,000 mm < ² >, and has a thickness of about 0.1-2 mm. In general, the light-transmitting hard substrates to be laminated have the same size. The translucent hard substrate laminate is formed by laminating two or more translucent hard substrates. From the viewpoint of production efficiency, preferably 5 or more, more preferably about 10 to 30 translucent hard substrates are light. Laminated via a curable adhesive.

  Although not limited, the surface of each translucent hard board | substrate can be attached | subjected with the predetermined printing pattern and plating pattern for showing one of the functions of a plate-shaped product. Examples of the print pattern include a mobile phone display screen design, and examples of the plating pattern include a metal wiring pattern such as Al or AlNd, and a rotary encoder provided with a chromium plating pattern.

  The photocurable sticking agent has a property of being cured by irradiation with light such as ultraviolet rays and softening when heated to a high temperature. The irradiation light is generally ultraviolet rays, but is not limited thereto, and may be appropriately changed according to the characteristics of the fixing agent used. For example, microwaves, infrared rays, visible light, ultraviolet rays, X-rays, γ rays, electron beams and the like can be irradiated. Thus, in the present invention, light refers to not only visible light but also electromagnetic waves (energy rays) including a wide wavelength region.

  Lamination of the translucent hard substrate is performed by, for example, sandwiching each translucent hard substrate having a photocurable adhesive applied to one or both bonded surfaces, and then sandwiching the translucent hard substrate. It can be carried out by irradiating light for curing the spreading adhesive. By repeating this a desired number of times, a translucent hard substrate laminate in which a desired number of translucent hard substrates are laminated can be produced.

  As the photocurable fixing agent, any known one can be used and is not particularly limited. For example, (A) polyfunctional (meth) acrylate and (B) monofunctional as described in JP-A-10-95627. An adhesive composition containing (meth) acrylate and (C) a photopolymerization initiator is preferred.

  (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 the 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- 6100B "), or bisphenol A type epoxy (meth) acrylate.

  Among these, polyester-based urethane (meth) acrylate and / or polyether-based urethane (meth) acrylate are preferable, and polyester-based urethane (meth) acrylate is more preferable because of its great effect.

  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, caprolactone modified 2-hydroxyethyl (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, etc. . 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 is obtained by using a GPC system (SC-8010, manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent under the following conditions, and creating a calibration curve using commercially available standard polystyrene. It was.
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. Among these, 1,6-hexadiol di (meth) acrylate and / or dicyclopentanyl di (meth) acrylate is preferable and dicyclopentanyl di (meth) acrylate is more preferable because of its great effect.

  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.

Among the polyfunctional (meth) acrylates, one or more members selected from the group consisting of polyfunctional (meth) acrylate oligomers / polymers, bifunctional (meth) acrylate monomers, and trifunctional (meth) acrylate monomers are effective. The polyfunctional (meth) acrylate oligomer / polymer is preferably used in combination with a bifunctional (meth) acrylate monomer and / or a trifunctional (meth) acrylate monomer. It is most preferable to use a polymer and a bifunctional (meth) acrylate monomer in combination.
When the polyfunctional (meth) acrylate oligomer / polymer is used in combination with a bifunctional (meth) acrylate monomer and / or a trifunctional (meth) acrylate monomer, the content ratio of the polyfunctional (meth) acrylate oligomer / polymer and bifunctional ( Multifunctional (meth) acrylate oligomer / polymer: bifunctional (meth) acrylate monomer and / or trifunctional (meth) acrylate monomer in a mass ratio in a total of 100 parts by mass of meth) acrylate monomer and trifunctional (meth) acrylate monomer = 10-90: 90-10 are preferable, 25-75: 75-25 are more preferable, and 40-65: 60-35 are the most preferable.

  (A) The polyfunctional (meth) acrylate is preferably hydrophobic. Hydrophobic polyfunctional (meth) acrylate refers to (meth) acrylate having no hydroxyl group. In the case of water-solubility, the cured product of the composition swells at the time of cutting, which causes positional displacement, which may be inferior in processing accuracy. Even if it is hydrophilic, it can be used as long as the cured product of the composition does not swell or partially dissolve in water.

(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, maleic acid, fumaric acid, ω-carboxy -Polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, (meth) acrylic acid dimer, β- (meth) acryloyloxyethyl hydrogen succinate, n- (meth) acryloyloxyalkylhexahydro Examples include phthalimide, 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, and benzyl (meth) acrylate.

  Among monofunctional (meth) acrylates, phenolethylene oxide 2 mol-modified (meth) acrylate, 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate and 2-hydroxy-3 are effective. -One or more members selected from the group consisting of phenoxypropyl (meth) acrylate are preferred. Phenolethylene oxide 2 mol modified (meth) acrylate and 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate and / or 2-hydroxy-3-phenoxypropyl (meth) acrylate may be used in combination. More preferred.

  When using phenol ethylene oxide 2 mol modified (meth) acrylate in combination with 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate and / or 2-hydroxy-3-phenoxypropyl (meth) acrylate The content ratio is a total of 100 parts by mass of phenol ethylene oxide 2 mol modified (meth) acrylate, 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate. In a mass ratio, phenol ethylene oxide 2 mol modified (meth) acrylate: 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate and / or 2-hydroxy-3-phenoxypropyl (meth) acrylate = 5-80: 9 20 is preferably 15 to 60: 85 to 40 is more preferable, and 20 to 40: 80 to 60 being most preferred.

(B) Monofunctional (meth) acrylate is more preferably hydrophobic as in (A). Hydrophobic polyfunctional (meth) acrylate refers to (meth) acrylate having no hydroxyl group. In the case of water-solubility, the cured product of the composition swells at the time of cutting, which causes positional displacement, which may be inferior in processing accuracy. Even if it is hydrophilic, it can be used if the cured product of the composition does not swell or partially dissolve with water.

  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, releasability 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 4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and / or oxy-phenyl- And acetic 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) 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of (A) and (B), and, as for content of a photoinitiator, 0.5-10 mass parts 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 total mass of the components (A), (B) and (C) preferably accounts for 90% by mass or more of the photocurable fixing agent from the viewpoint of releasability, and typically accounts for 95% by mass or more. And can occupy 98% by mass or more.

  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 fixing agent after hardening can hold | maintain fixed thickness, a processing precision improves. Furthermore, since the linear expansion coefficient of the hardened | cured material of a sticking agent and a granular material (D) differs, the peelability at the time of peeling after bonding a translucent hard board | substrate using a sticking agent improves.

  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.

The granular material (D) is preferably spherical from the viewpoint of improving the processing accuracy, that is, controlling the film thickness of the photocurable fixing agent. The average particle diameter (D50) of the particulate material (D) is preferably in the range of 20 to 200 μm. When the average particle diameter (D50) 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 hardly displaced during processing, and the dimensional accuracy is excellent. 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 average particle diameter (D50) is measured by a laser diffraction 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. 0.05 to 10 parts by mass is more preferable, and 0.1 to 6 parts by mass is most preferable. If it is 0.01 mass part or more, the film thickness of the composition after hardening will be substantially constant, and if it is 20 mass parts or less, there is no possibility that initial adhesiveness will fall.

  A polymerization inhibitor (E) can be added to the photocurable fixing agent to improve 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 the polymerization inhibitor (E) used is preferably 0.001 to 3 parts by mass and more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B). If it is 0.001 mass part or more, storage stability will be ensured, and if it is 3 mass parts or less, favorable adhesiveness will be obtained and it will not become uncured.

  For the photo-curable adhesive, various elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, inorganic fillers, solvents, fillers, reinforcements, etc., which are generally used within the range that does not impair the object of the present invention. Additives such as materials, plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents, polar organic solvents and surfactants may be added.

  The glass transition temperature of the cured product after photocuring the fixing agent is preferably 0 ° C to 40 ° C. 5 to 35 degreeC is preferable from a viewpoint of peelability and dimensional accuracy, and 10 to 30 degreeC is more preferable. When the glass transition temperature of the cured body is within this range, when the transparent rigid substrate laminate is immersed in water to peel off, the cured body of the fixing agent itself undergoes a large thermal expansion, resulting in a bonding area. Decreases and the adhesive strength decreases. Therefore, the hardened body of the fixing agent is easily peeled off from the translucent hard substrate laminate in the form of a film. If the glass transition temperature of the hardened body of the fixing agent is 0 ° C. or higher, deviation is unlikely to occur during processing of the temporarily fixed member, and the dimensional accuracy is excellent. If it is 40 degrees C or less, peelability will improve.

  The glass transition temperature of the cured product can be adjusted, for example, by the following method. In order to increase the glass transition temperature, (A) increase the content of polyfunctional (meth) acrylate, (C) decrease the content of photopolymerization initiator, (A) polyfunctional (meta) ) Acrylate is selected, and (A) polyfunctional (meth) acrylate and (B) monofunctional (meth) acrylate having a high glass transition temperature of the cured product are selected. Conversely, in order to lower the glass transition temperature, (A) reduce the content of polyfunctional (meth) acrylate, select (A) polyfunctional (meth) acrylate with a small number of functional groups, (C) start photopolymerization There are methods of increasing the content of the agent and selecting (A) polyfunctional (meth) acrylate or (B) monofunctional (meth) acrylate having a low glass transition temperature of the cured product. In the present invention, the glass transition temperature refers to a value measured by the DMA method (dynamic viscoelasticity measurement method).

<Step 2. Peeling of translucent hard substrate laminate>
The translucent hard substrate laminate is subjected to shape processing as necessary, and then peeled and separated into each translucent hard substrate. It is possible to completely finish the necessary shape processing before peeling so that the separated light-transmitting hard substrate can be shipped as a plate-like product as it is. You can also. In the present invention, when peeling off the translucent hard substrate laminate, it is characterized in that it is brought into two-stage contact with water having different temperatures. Specifically, first, from the glass transition temperature of the cured product of the photocurable fixing agent. First, the laminate is brought into contact with water that is 40 to 90 ° C higher, and then is contacted with water that is 5 to 25 ° C higher than the glass transition temperature. Although there is no restriction | limiting in particular in the method to contact, Since the fixing agent softens in a film form and isolate | separates into each translucent hard board | substrate well, the method immersed in water is preferable. In addition, when the water temperature reaches 100 ° C., it boils and is inconvenient, so the water temperature used in the first contact and the second contact is preferably less than 100 ° C.

  In the present invention, the purity of “water” is not important, and industrial water or tap water is sufficient. Of course, pure water such as distilled water or deionized water may be used. Further, water to which a drug is added can also be used. Examples of the drug include surfactants, and any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used. By adding the surfactant, an effect of improving the peelability can be obtained.

  Although it is not intended that the present invention be limited by theory, the peeling mechanism of the present invention is as follows.

In the first stage, by bringing the laminate into contact with water that is 40 to 90 ° C. higher than the glass transition temperature of the cured product of the photocurable fixing agent, the cured product of the fixing agent thermally expands in a short time, and the fixing agent The internal stress generated when the is cured is released. At this time, a wavy or three-dimensional deformation occurs at the interface between the translucent hard substrate and the fixing agent, the reduction of the adhesion area is achieved, the adhesion strength is reduced, and cracks are formed on each bonding surface of the laminate. Entering naturally begins to separate the sticking agent from the translucent hard substrate. If the temperature in the first stage is too high, the translucent hard substrate may be deteriorated, and if the temperature in the first stage is too low, sufficient cracks are not formed on each bonded surface, which is not preferable. The preferable water temperature in the first stage is 45 to 87 ° C. higher than the glass transition temperature, and the more preferable water temperature is 50 to 85 ° C. higher than the glass transition temperature.
Further, if the contact time of the laminate in the first stage with water is too short, the separation of the fixing agent becomes insufficient. On the other hand, if it is too long, the translucent hard substrate may be deteriorated. Minutes are preferred, 2 to 80 minutes are more preferred, and 5 to 65 minutes are even more preferred.

In the first stage, the fixing agent is not completely separated from the translucent hard substrate, and in general, the fixing agent is still adhered to one of the translucent hard substrates. While maintaining the first-stage temperature conditions, it is possible to apply an external force to advance the peeling of the adhesive, causing adhesive residue and often being harsh as a manual work environment. Workability is bad.
Therefore, following the first stage, each translucent hard substrate separated into water having a temperature higher by 5 to 25 ° C. than the glass transition temperature in the second stage is brought into contact, and then the fixing agent is peeled off in this temperature environment. Thus, the adhesive can be easily and completely peeled off from the translucent hard substrate without any adhesive residue. Further, the water temperature of the second contact is lower than the water temperature of the first contact, which is advantageous as a work environment. As a method for separating the cured product of the photocurable fixing agent and each translucent hard substrate, it is desirable to perform the method while immersing in the water used for the second contact. It is permissible to temporarily lift it from the water during the work. If the water temperature in the second stage is too high, it is not preferable in terms of adhesive residue and workability in the separation of the cured product of the photocurable fixing agent and each light-transmitting hard substrate, and light if the water temperature in the second stage is too low. This is not preferable because the cured curable adhesive film becomes hard, the film and glass are difficult to separate, and the translucent hard substrate is damaged. A preferable water temperature in the second stage is a temperature 7 to 23 ° C. higher than the glass transition temperature, and a more preferable water temperature is a temperature 10 to 20 ° C. higher than the glass transition temperature.
In addition, if the contact time of the laminate in water in the second stage is too short, it is not preferable from the viewpoint of workability, but there is no harmful effect on the long time. Therefore, the contact time of the laminated body with water in the second stage can be set to an arbitrary time of 1 minute or longer, for example, one week or one month. However, from the viewpoint of production efficiency, 1 to 120 minutes are preferable, 2 to 100 minutes are more preferable, and 3 to 30 minutes are even more preferable.

  Photocuring attached to each translucent hard substrate when the transition time from the first contact to the second contact, that is, the time from the stop of the first contact of water to the laminate until the start of the second contact is too long Since it becomes impossible to isolate | separate the hardened | cured material of an adhesive agent and each translucent hard board | substrate, it is not preferable. Therefore, the transition time from the first contact to the second contact is preferably 0.1 to 120 seconds, more preferably 0.5 to 60 seconds, and even more preferably 1 to 20 seconds. .

Although there is no restriction | limiting in particular as shape processing, it illustrates below.
First, there is a shape process in which a light-transmitting hard substrate laminate is divided in the thickness direction to form a desired number of divided light-transmitting 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), water jet, and red tropics (nichrome wire), each of which is used alone or in combination, and is divided into rectangular parallelepiped shapes of the same size. Etching can also be used for surface treatment of the cut surfaces after division.

  Moreover, there exists a shape process performed with respect to each divided | segmented translucent hard board | substrate laminated body. 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. The shape processing here 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 by etching, end surface processing by etching, outer shape by etching Processing, flame processing using a burner, etc. are mentioned. The processing methods can be used alone or in combination. Etching can also be used for surface treatment after shape processing.

In the step 2, for the purpose of restoring the internal stress before the contact with water, the light transmissive hard substrate laminate may be irradiated with light to cure the fixing agent. Thereby, for example, the peelability which has been lowered due to exposure to high temperature during transportation or storage is recovered. At this time, if the light irradiation amount is too weak, the internal stress will not be restored, and the peelability will not be recovered. On the other hand, if the light irradiation amount is too strong, the translucent hard substrate may be deteriorated. it is preferable that the 2000~12000mJ / cm ² irradiation amount of, more preferably, to 2500~10000mJ / cm ^2, it is even more preferred that the 3000~9000mJ / cm ^2.

  The following examples are provided for a better understanding of the invention and its advantages, but the invention is not limited to these examples.

<Example 1>
1. Preparation of photocurable adhesive The following components (A) to (D) were mixed to prepare a photocurable adhesive.
(A) As a polyfunctional (meth) acrylate, “UV-3000B” (abbreviated as “UV-3000B” hereinafter referred to as “urethane acrylate”) manufactured by Nippon Gosei Co., Ltd., a polyol compound is a polyester polyol, and an organic polyisocyanate compound is isophorone diisocyanate. , 20 parts by mass of hydroxy (meth) acrylate is 2-hydroxyethyl acrylate), 15 parts by mass of 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; 15 parts by mass of phenol ethylene oxide 2 mol modified acrylate (“Aronix M-101A” manufactured by Toa Gosei Co., Ltd.)
(C) 10 parts by mass of benzyldimethyl ketal (“IRGACURE651” manufactured by BASF), hereinafter abbreviated as “BDK”) as a photopolymerization initiator,
(D) 1 part by weight of spherical crosslinked polystyrene particles having an average particle size of 100 μm (“GS-100S” manufactured by Ganz Kasei Co., Ltd.)
(E) 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S” manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as “MDP”) as a polymerization inhibitor

2. Production of Sheet Glass Laminate Two plate glasses (width 530 mm × length 420 mm × thickness 0.7 mm) were prepared as light-transmitting hard substrates, and bonded together via the photocurable adhesive agent to produce a sheet glass laminate. Specifically, after 40 g of the above-mentioned photocurable fixing agent is applied on the first sheet glass, the second sheet glass is pasted on the first sheet glass, and the surface of the second sheet glass is started. The photocurable fixing agent was cured by UV irradiation. The UV irradiation amount was 3000 mJ / cm ² (measured by an integrating illuminometer with a 365 nm light receiver), and the UV irradiation time was 20 seconds. By repeating this procedure, a sheet glass laminate composed of 12 sheet glasses was produced. Then, the plate glass laminated body was cut | disconnected in the thickness direction with the disc cutter, and many plate glass laminated bodies divided | segmented by width 100mm x length 50mm x thickness 8mm were obtained.

3. Evaluation of peelability of sheet glass laminate Each of the thus obtained divided sheet glass laminates was immersed in warm water under the temperature and time conditions shown in Table 1 to evaluate the peelability. The transition time from the first contact to the second contact was 10 seconds. The peelability is determined by examining the adhesive residue on the surface of each sheet glass after peeling. For the 12 glasses constituting each laminate, no adhesive residue was found at all, and 1 or 2 adhesive residues. Δ was observed on the surface of the glass plate, and × was observed when 3 or more adhesive residues were observed. The results are shown in Table 1.

4). Measurement of glass transition temperature A sticking agent is sandwiched between PET films using a 1 mm thick silicon sheet as a mold, and a fusion device using an electrodeless discharge lamp is used under the condition of an integrated light quantity of 2000 mJ / cm ² at a wavelength of 365 nm. After curing from the top surface, the bottom was further cured under the condition of an integrated light quantity of 2000 mJ / cm ² with a wavelength of 365 nm to produce a 1 mm-thick adhesive cured body. The produced cured body was cut into a length of 50 mm and a width of 5 mm with a cutter to obtain a cured body for measuring a glass transition temperature. The obtained cured body was subjected to stress and strain in a tensile direction of 1 Hz to the cured body in a nitrogen atmosphere by a dynamic viscoelasticity measuring device “DMS210” manufactured by Seiko Electronics Industry Co., Ltd. Tan δ was measured while the temperature was raised at a rate of, and the temperature at the peak top of the tan δ was taken as the glass transition temperature.
As a result, the glass transition temperature was 26 ° C.

5. Re-UV Irradiation Test A divided plate glass laminate was produced by the same method as described above, and then kept at 25 ° C. for 4 weeks. This laminate was not peeled off in a peeling test by hot water immersion in which the first stage was 90 ° C. × 10 minutes and the second stage was 40 ° C. × 15 minutes. However, the UV irradiation amount: 3000 mJ / cm ² (365 nm light receiver) When the same peeling test was performed again after performing UV irradiation again with measurement using an integrating illuminometer, UV irradiation time 94 seconds), peeling was performed without any adhesive residue.

<Example 2>
Other than using a photocurable sticking agent having the following components, as in Example 1, preparation of a divided sheet glass laminate, appearance and peelability evaluation after temperature control of the sheet glass laminate, and further, glass transition temperature Measurements were performed. The results are shown in Table 2. The glass transition temperature of the cured product of this fixing agent was 16 ° C.

Composition of the photocurable sticker of Example 2:
(A) As a polyfunctional (meth) acrylate, 20 parts by mass of “UV-3000B” (urethane acrylate, hereinafter abbreviated as “UV-3000B”) manufactured by Nippon Gosei Co., Ltd., 1,6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) "Light acrylate 1,6-HX-A", hereinafter abbreviated as "1,6-HX-A") 10 parts by mass,
(B) As monofunctional (meth) acrylate, 40 parts by mass of 2- (1,2-cyclohexacarboximide) ethyl acrylate (“Aronix M-140” manufactured by Toa Gosei Co., Ltd., hereinafter abbreviated as “M-140”), 30 parts by mass of phenol ethylene oxide 2 mol modified acrylate (“Aronix M-101A” manufactured by Toa Gosei Co., Ltd.)
(C) 10 parts by mass of benzyldimethyl ketal (“IRGACURE651” manufactured by BASF, hereinafter abbreviated as “BDK”) as a photopolymerization initiator,
(D) 1 part by weight of spherical crosslinked polystyrene particles having an average particle size of 100 μm (“GS-100S” manufactured by Ganz Kasei Co., Ltd.)
(E) 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S” manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as “MDP”) as a polymerization inhibitor

<Example 3>
Other than using a photocurable sticking agent having the following components, as in Example 1, preparation of a divided sheet glass laminate, appearance and peelability evaluation after temperature control of the sheet glass laminate, and further, glass transition temperature Measurements were performed. The results are shown in Table 3. The glass transition temperature of the cured product of this fixing agent was 34 ° C.

Composition of the photocurable sticker of Example 3:
(A) As a polyfunctional (meth) acrylate, 10 parts by mass of “UV-3000B” (urethane acrylate, hereinafter abbreviated as “UV-3000B”) manufactured by Nippon Gosei Co., Ltd., “light acrylate” manufactured by Kyoeisha Chemical Co., Ltd. TMP-A ”, hereinafter abbreviated as“ TMP-A ”) 20 parts by mass,
(B) As monofunctional (meth) acrylate, 40 parts by mass of 2- (1,2-cyclohexacarboximide) ethyl acrylate (“Aronix M-140” manufactured by Toa Gosei Co., Ltd., hereinafter abbreviated as “M-140”), 30 parts by mass of phenol ethylene oxide 2 mol modified acrylate (“Aronix M-101A” manufactured by Toa Gosei Co., Ltd.)
(C) 5 parts by mass of benzyldimethyl ketal (“IRGACURE651” manufactured by BASF, hereinafter abbreviated as “BDK”) as a photopolymerization initiator,
(D) 1 part by weight of spherical crosslinked polystyrene particles having an average particle size of 100 μm (“GS-100S” manufactured by Ganz Kasei Co., Ltd.)
(E) 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S” manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as “MDP”) as a polymerization inhibitor

<Example 4>
Other than using a photocurable sticking agent having the following components, as in Example 1, preparation of a divided sheet glass laminate, appearance and peelability evaluation after temperature control of the sheet glass laminate, and further, glass transition temperature Measurements were performed. The results are shown in Table 4. The glass transition temperature of the cured product of this fixing agent was 29 ° C.

Composition of the photocurable sticking agent of Example 4:
(A) As a polyfunctional (meth) acrylate, 20 parts by mass of “UV-3000B” (hereinafter abbreviated as “UV-3000B”, urethane acrylate, weight average molecular weight 18000) manufactured by Nippon Gosei Co., Ltd., dicyclopentanyl diacrylate (Nipponization) “KAYARADR-684” manufactured by Yakuhin Co., Ltd., hereinafter abbreviated as “R-684”) 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) 10 parts by mass of benzyldimethyl ketal (“IRGACURE651” manufactured by BASF), hereinafter abbreviated as “BDK”) as a photopolymerization initiator,
(D) 1 part by weight of spherical crosslinked polystyrene particles having an average particle size of 100 μm (“GS-100S” manufactured by Ganz Kasei Co., Ltd.)
(E) 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S” manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as “MDP”) as a polymerization inhibitor

Claims (6)

Step 1 for preparing a light-transmitting hard substrate laminate in which two or more light-transmitting hard substrates are bonded together with a photocurable adhesive, and heating the light-transmitting hard substrate laminate are bonded together. the which was translucent rigid boards peeled, I peeling method der of the translucent rigid substrate laminate and a step 2 of forming a plurality of separate light-transmitting hard substrate, wherein the binder is ( A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C) a photopolymerization initiator, and a glass transition temperature of the cured product of the fixing agent is 0 to 40 ° C. 2, the laminate is first contacted with water that is 40 to 90 ° C. higher than the glass transition temperature of the cured product of the photocurable fixing agent, and then the second contact with water that is 5 to 25 ° C. higher than the glass transition temperature. A peeling method comprising:   The peeling method of the translucent hard board | substrate laminated body of Claim 1 whose time of a 1st contact is 1-120 minutes, and the time of a 2nd contact is 1 minute or more. The peeling method of the translucent hard board | substrate laminated body of Claim 1 or 2 whose transition time from the end of 1st contact to the start of 2nd contact is 0.1 to 120 second. The translucency as described in any one of Claims 1-3 which in order to harden a fixing agent with respect to a translucent hard board | substrate laminated body after the process 1 and before the contact to the water in the process 2. A method for peeling a hard substrate laminate. The translucent hard board | substrate peeling method as described in any one of Claims 1-4 whose translucent hard board | substrate is plate glass. The manufacturing method of the plate-shaped product using the peeling method of the translucent hard board | substrate laminated body as described in any one of Claims 1-5 .