JP2017206398A - Method for producing light transmissive hard substrate laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of producing a light transmissive hard substrate laminated body at high production efficiency while reducing the risk of cracks.PROBLEM TO BE SOLVED: To provide a method for producing a light transmissive hard substrate laminated body comprising a process where pressurization is performed to a part of either or both of the outermost face of a pasted laminated body to provide the laminated body with a pressurized recessed part and a non-pressurized flat part, the area projected on the face perpendicular to the directional axis at which the laminated body is laminated in the recessed part is smaller than the area projected on the face perpendicular to the directional axis at which the laminated body is laminated in the flat part, and also, the shortest distance from the edge face parallel to the directional axis at which the laminated body is laminated in the pressurized part for providing the recessed part is 5% or lower than the length of the whole circumference of the contour projected on the face perpendicular to the directional axis at which the laminated body is laminated.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for manufacturing a light-transmitting hard substrate laminate, and more particularly to a method for manufacturing a laminate using a thin light-transmitting hard substrate (particularly a light-transmitting hard substrate such as thin glass having a thickness of 0.2 mm or less). .

  Regarding portable electronic devices having a touch panel function typified by a mobile phone, a smartphone, a portable music player, a tablet terminal, and a notebook computer, a protective film made of a resin is widely used as a protective material for those displays. However, glass has excellent transmittance compared to resin, slipperiness when touching and operating the display with fingertips, display protection performance, ease of bonding (bubbles are difficult to enter during bonding), scratch resistance, etc. In recent years, the demand for glass as a protective material for displays has increased due to its characteristics. Furthermore, the demand for protective materials using thin glass (thin glass) with a thickness of 0.2 mm or less is increasing due to the demand for light weight and thinning of mobile devices.

  In addition, such a thin glass is composed of an optically transparent adhesive (OCA: Optical Clear Adhesive) formed of a cover glass and a sensor glass (a glass substrate on which a sensor is formed) on the display of the portable electronic device described above. It is used as a sensor glass on a touch panel with a laminated structure.

  Furthermore, thin glass has high flexibility and durability, and it can be used as a cover glass for foldable liquid crystal displays (LCDs) and organic EL displays (OLEDs) used in electronic paper, wearable terminals, foldable terminals, etc. The demand for is increasing.

  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 techniques for realizing high production efficiency 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 provisional light irradiation (temporary fastening) along the outer peripheral portion 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 laminated body to obtain the laminated body.

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

  Patent Document 3 relates to a technique for laminating and processing sheet glass products that do not require a high degree of positioning, and a technique for laminating sheet glass products one by one and performing a final adhesion after reaching a certain number of sheets to obtain a laminate. Have been described.

  Patent Document 4 describes a method of dividing and processing a material glass block formed by integrally fixing a plurality of material sheet glasses with a fixing agent interposed therebetween.

  Patent Document 5 describes a method of obtaining a plate glass product by dividing and chamfering a glass laminate formed by bonding a plurality of plate glasses having substantially the same shape and size in plan view. ing.

  In Patent Document 6, two translucent hard substrates are arranged in parallel with a fixing agent sandwiched between them, and the outer peripheral portion of the fixing agent is irradiated with light for curing the fixing agent and temporarily fixed. A method for obtaining a laminate by performing main fastening to cure the entire surface of the fixing agent is described.

  In Patent Document 7, two light-transmitting hard substrates are arranged in parallel with a fixing agent interposed therebetween, and light is applied to cure the entire surface of the fixing agent spread by applying pressure. The method of obtaining is described.

  In Patent Document 8, a glass plate is laminated through an adhesive layer, the adhesive layer is cured to obtain a laminate, cut into small pieces with a glass cutter, subjected to shape processing, and the adhesive layer is peeled off to form a glass. A processing method for separating the plates is described.

  In Patent Document 9, a temporary fixing adhesive is applied to a fixing member or a workpiece, the workpiece or the fixing member is mounted, irradiated with visible light or ultraviolet light, and fixed simultaneously with the irradiation for at least a fixed time. A temporary fixing method in which pressure is applied from one or both of the member and the workpiece is described.

International Publication No. 2011/089963 International Publication No. 2011/089964 International Publication No. 2013/084953 JP 2009-256125 A JP 2000-169166 A International Publication No. 2013/011969 International Publication No. 2013/011970 JP 2014-129197 A International Publication No. 2010/010900

  By the way, from the viewpoint of increasing production efficiency, it is desired to laminate and process a sheet glass product in a lump. However, some sheet glass products do not require advanced positioning when laminating a cover glass or the like. As for things, advanced positioning and temporary fixing are performed as in the techniques described in Patent Documents 1, 6, 7, and 9, or after advanced positioning as in the technique described in Patent Document 2, one by one. It is not necessary to perform sheet stacking where the sheets are bonded.

  In addition, flat glass products that do not require advanced positioning are also subjected to complicated procedures such as advanced positioning as described in Patent Document 2 as a technique for batch processing as a laminate from the viewpoint of improving production efficiency. There is a possibility of improving the production efficiency by not having it, and it is desired to reduce unnecessary processes. By reducing unnecessary processes in this way, the manufacturing cost can be reduced.

  Further, in Patent Documents 3 to 5 and 8, there is a problem that production efficiency is poor because a main body is bonded after a sticking agent is spread and bonded between a certain number of glasses and bonded together. On the other hand, it is desired to further improve production efficiency and reduce manufacturing cost by reducing unnecessary processes.

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

[1]
1) preparing a first translucent hard substrate;
2) preparing a second translucent hard substrate;
3) A step of applying a photocurable adhesive to the first surface of the first translucent hard substrate and / or the first surface of the second translucent hard substrate;
4) a step of causing the first surface of the first translucent hard substrate and the first surface of the second translucent hard substrate to face each other;
5) bonding the first surface of the first translucent hard substrate and the first surface of the second translucent hard substrate to produce a laminate;
6) By applying pressure to one or both of the outermost surfaces of the laminated body bonded together, the laminated body is provided with a pressurized concave portion and a non-pressurized flat portion, The area projected on the surface perpendicular to the direction axis of the laminate of the laminate is smaller than the area projected on the surface of the flat portion perpendicular to the direction axis of the laminate, and the recess The shortest distance from the end face parallel to the stacking direction axis of the laminate is the length of the entire circumference of the contour projected onto the plane perpendicular to the stacking direction axis of the stack. A step of 5% or less;
7) At least a part of the pressed recess is subjected to light irradiation treatment, and the first light-transmitting hard substrate and the second light-transmitting hard substrate are locally locked by the cured recess. A step of producing a temporary translucent hard substrate laminate,
8) Apply pressure from the end to the other end using the roll press so that the end on the side where the temporarily fixed translucent hard substrate laminate is locked is the starting side of the roll press. And a step of pressurizing the flat portion to form a laminate on which the translucent hard substrate is bonded, and a method for manufacturing the translucent hard substrate laminate.

[2]
5 ′) Considering the laminate produced in step (5) as the first light-transmitting hard substrate, steps (2) to (5) are repeated at least once, and at least three light-transmitting hard substrates are attached. The manufacturing method of the translucent hard board | substrate laminated body of [1] description including the process of forming the match | combined laminated body.

[3]
7 ′) Steps (2) to (7) are repeated at least once, assuming that the temporarily fixed light-transmitting hard substrate laminate produced in step (7) is the first light-transmitting hard substrate, and at least three sheets The manufacturing method of the translucent hard board | substrate laminated body of [1] or [2] including the process of forming the laminated body on which the translucent hard board | substrate was bonded together.

[4]
The penetration according to any one of [1] to [3], wherein a depth from the outermost surface at the pressurizing portion of the concave portion pressed by the step (6) is in a range of 0.5 to 50 mm. Manufacturing method of optical hard board | substrate laminated body.

[5]
The manufacturing method of the translucent hard board | substrate laminated body as described in any one of [1]-[4] which forms a some recessed part by repeating a process (6) in multiple times.

[6]
The manufacturing method of the translucent hard board | substrate laminated body as described in any one of [1]-[5] whose area of the said recessed part pressurized by process (6) is 1 mm < ² > or more.

[7]
Of the recesses obtained by pressurization in step (6), the portion where the depth from the outermost surface is the maximum is a distance of 0 to 50 mm from the end surface parallel to the axis in the stacking direction of the laminate. The manufacturing method of the translucent hard board | substrate laminated body as described in any one of [1]-[6] which is settled in a field.

[8]
Translucent hard board | substrate lamination | stacking as described in any one of [1]-[7] whose shape of the said recessed part obtained by pressing by a process (6) is dot shape, substantially circular shape, or rod shape. Body manufacturing method.

[9]
The thickness according to any one of [1] to [8], wherein the thickness of the concave portion obtained by pressing in the step (6) is substantially equal to the thickness of the laminate obtained in the step (8). Manufacturing method of optical hard board | substrate laminated body.

[10]
The thickness of the said recessed part obtained by pressurizing by a process (6) is the range of 0.5-50 mm, The translucent hard board | substrate laminated body as described in any one of [1]-[9]. Production method.

[11]
The manufacturing method of the translucent hard board | substrate laminated body as described in any one of [1]-[10] whose area of the area which performs light irradiation by a process (7) is 1 mm < ² > or more.

[12]
The method for producing a light-transmitting hard substrate laminate according to any one of [1] to [11], wherein the method of performing light irradiation in the step (7) is light irradiation by a spot irradiator.

[13]
9) Considering the temporarily fixed light-transmitting hard substrate laminate produced in step (8) as the first light-transmitting hard substrate, steps (2) to (8) are repeated at least once, and at least three transparent The manufacturing method of the translucent hard board | substrate laminated body as described in any one of [1]-[12] including the process of forming the translucent hard board | substrate laminated body in which the optical hard board | substrate was bonded together.

[14]
The method for producing a translucent hard substrate laminate according to any one of [1] to [13], wherein the number of laminated translucent hard substrate laminates is in the range of 20 to 300.

[15]
The manufacturing method of the translucent hard board | substrate laminated body as described in any one of [1]-[14] whose translucent hard board | substrate has a polygonal shape.

[16]
10) After forming the translucent hard board | substrate laminated body by process (8) or / and process (9), it further includes the process of leaving still at normal temperature for 1 hour or more and hardening a fixing agent [1]-[15]. The manufacturing method of the translucent hard board | substrate laminated body as described in any one of these.

[17]
The area of one or both translucent hard substrates on the outermost surface of the translucent hard substrate laminate is larger than the translucent hard substrates other than one or both translucent hard substrates on the outermost surface [1] to [ 16] The manufacturing method of the translucent hard board | substrate laminated body as described in any one of [16].

[18]
The amount of light irradiation in the step (7) is measured with an integrating illuminometer using a 365 nm light receiver, and is in the range of 5 to 5000 mJ / cm ² [1] to [17]. Manufacturing method of transparent translucent substrate laminate.

[19]
The manufacturing method of the translucent hard board | substrate laminated body as described in any one of [1]-[18] whose translucent hard board | substrate is plate glass of thickness 0.2mm or less.

[20]
11) A translucent hard substrate laminate obtained by using the method for producing a translucent hard substrate laminate as described in any one of [1] to [19] is divided in a thickness direction, and a desired number Forming a divided transparent translucent substrate laminate,
12) A step of performing a desired shape processing on each of the divided light-transmitting hard substrate laminates;
13) 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-like products;
A method for producing a plate-like product including

[21]
Step (13) is a method for producing a plate-like product according to [20], comprising immersing the light-transmitting hard substrate laminate after shape processing in warm water and softening the fixing agent in the form of a film.

[22]
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 [1]-[19].

[23]
[22] In producing the light-transmitting hard substrate laminate according to [22], used to bond between the light-transmitting hard substrates,
(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.

[24]
The photocurable sticking agent according to [23], which further contains (D) a particulate material in addition to the above (A) to (C).

[25]
The photocurable fixing agent according to [24], wherein the particulate material (D) is a filler.

[26]
Furthermore, (E) The photocurable sticking agent as described in any one of [23]-[25] containing an organic peroxide.

[27]
Furthermore, (F) The photocurable sticking agent as described in [26] containing the decomposition accelerator of the said organic peroxide.

[28]
Furthermore, (G) The photocurable sticking agent as described in any one of [23]-[27] containing a thermally expansible microcapsule.

[29]
(B) Content of monofunctional (meth) acrylate is 30-90 mass parts in total amount of 100 mass parts of (A) and (B), It is any one of [23]-[28]. Photo-curing adhesive.

[30]
(C) Content of a photoinitiator is any one of [23]-[29] which is 0.1-25 mass parts with respect to 100 mass parts of total amounts of (A) and (B). The photocurable sticking agent according to 1.

[31]
A laminate of translucent hard substrates,
A plurality of laminated transparent substrates,
Including a fixing layer made of a fixing agent disposed between the translucent hard substrates,
The laminate has a concave portion and a flat portion,
The recess is for locking a plurality of the translucent hard substrates,
The thickness of the concave portion along the stacking direction of the stacked body is smaller than the thickness of the flat portion along the stacking direction of the stacked body,
The area projected on the surface perpendicular to the direction axis of the laminate of the laminate of the concave portion is smaller than the area projected on the surface of the flat portion perpendicular to the direction axis of the laminate.
5% of the total perimeter of the contour projected on a plane perpendicular to the direction axis of the laminate as viewed from the end surface parallel to the direction axis of the laminate, at least a part of the recess. A laminate having the following distance.

[32]
The laminate according to [31], wherein the fixing layer in the concave portion is cured, and the fixing layer in the flat portion is not cured.

[33]
The laminate according to [31] or [32], wherein an area of one or both of the outermost surfaces of the light-transmitting hard substrate is larger than that of the light-transmitting hard substrate other than one or both of the outermost surfaces. .

  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 a method of mass-producing a glass laminate using, for example, a thin glass having a thickness of 0.2 mm or less.

It is a perspective view for demonstrating the local pressurization process (6) which concerns on embodiment of this invention. It is a perspective view which shows the outline | summary of the pressurization for providing the recessed part which concerns on embodiment of this invention. It is a perspective view for showing a mode that a crevice concerning an embodiment of the present invention was provided. It is a schematic diagram which shows the example in which the laminated body of a translucent hard board | substrate becomes an inappropriate state in the case where it differs from embodiment of this invention. It is a schematic diagram which shows the principle of a roll press. It is a perspective view which shows the one aspect | mode at the time of performing the roll press which concerns on embodiment of this invention. It is a schematic diagram which shows the example of a combination of the recessed part (locking part) which concerns on embodiment of this invention, and the direction (starting point) of a roll press. It is a schematic diagram which shows the example of the translucent hard board | substrate bonding apparatus which concerns on embodiment of this invention. It is a schematic diagram which shows the example of the lower surface of an upper stage according to embodiment of this invention. It is a figure which shows the state which mounted the 1st board | substrate on the lower stage according to embodiment of this invention. It is a figure which shows the state which conveyed the 1st board | substrate mounted in the lower stage according to embodiment of this invention directly under the upper stage. It is a figure which shows the state which descends the upper stage and vacuum-sucks the 1st board | substrate according to embodiment of this invention. It is a figure which shows the state which raised the upper stage, hold | maintaining the adsorbed 1st board | substrate according to embodiment of this invention. It is a figure which shows the state which mounted the 2nd board | substrate on the lower stage according to embodiment of this invention. It is a figure which shows the state which has apply | coated the adhesive on the upper surface of the 2nd board | substrate according to embodiment of this invention. It is a figure which shows the state which has apply | coated the adhesive on the lower surface of the 1st board | substrate currently hold | maintained at the upper stage according to embodiment of this invention. It is a figure which shows the state which raised the upper stage after light irradiation according to embodiment of this invention. It is a figure which shows the state which the board | substrate bonded together according to embodiment of this invention was conveyed by the lower stage, and returned to the original position. In a comparative example, it is a figure which shows the unpreferable example which a laminated body will collapse by the load (pressurization) by 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 adhesive to the first surface of the first translucent hard substrate and / or the first surface of the second translucent hard substrate;
4) a step of causing the first surface of the first translucent hard substrate and the first surface of the second translucent hard substrate to face each other;
5) bonding the first surface of the first translucent hard substrate and the first surface of the second translucent hard substrate to produce a laminate;
6) By applying pressure to one or both of the outermost surfaces of the laminated body bonded together, the laminated body is provided with a pressurized concave portion and a non-pressurized flat portion, The area projected on the surface perpendicular to the direction axis of the laminate of the laminate is smaller than the area projected on the surface of the flat portion perpendicular to the direction axis of the laminate, and the recess The shortest distance from the end face parallel to the stacking direction axis of the laminate is the length of the entire circumference of the contour projected onto the plane perpendicular to the stacking direction axis of the stack. A step of 5% or less;
7) At least a part of the pressed recess is subjected to light irradiation treatment, and the first light-transmitting hard substrate and the second light-transmitting hard substrate are locally locked by the cured recess. A step of producing a temporary translucent hard substrate laminate,
8) Apply pressure from the end to the other end using the roll press so that the end on the side where the temporarily fixed translucent hard substrate laminate is locked is the starting side of the roll press. By performing, the said flat part can be pressurized and the process of forming the laminated body by which the translucent hard board | substrate was bonded together can be performed.

In step (1) and step (2), a light-transmitting hard substrate (hereinafter also referred to as “substrate” for simplicity) to be processed is prepared. The light-transmitting hard substrate is not particularly limited, but plate glass (tempered plate glass, material plate glass, especially cover glass on which no electrode or circuit is formed; and sensor glass, particularly glass substrate with transparent conductive film, electrode or circuit Formed glass substrate, etc.), sapphire substrate, quartz substrate, plastic substrate, magnesium fluoride substrate and the like. 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, Typically, it has an area of about 10,000-250,000 mm < ² >, and thickness of about 0.02 mm (20 micrometers)-2 mm, Preferably it is 0.02-0. It has a thickness of about 2 mm. A typical translucent hard substrate may be a rectangle having a side length of about 100 to 1000 mm × 100 to 1000 mm, preferably a side length of about 450 to 600 mm × 350 to 550 mm. The shape of the translucent hard substrate is not particularly limited, but a polygon is preferable. The shape included in the polygon is, for example, generally a shape such as a quadrangle (for example, a square, a rectangle, a trapezoid, or a rhombus) or a substantially quadrangle (for example, a shape along the screen of a tablet or smartphone), or any one of them. There may be notches or protrusions on the sides. Although it is common that each translucent hard board | substrate is the same size, it is not limited to it. The length of the entire circumference of the outline of the translucent hard substrate is not particularly limited, but may be, for example, about 400 to 4000 mm, preferably about 1600 to 2300 mm in view of the place where the work is performed and the size of the machine. For example, the length of the entire circumference of the outline of the translucent hard substrate means the total of the four sides when the translucent hard substrate is square. It should be noted that the present invention preferably also includes an embodiment using translucent hard substrates (for example, protective translucent hard substrates) having different sizes as described later.

  In the step (3), a fixing agent is applied to the first surface of the first translucent hard substrate and / or the first surface of the second translucent hard substrate. This fixing agent can have photocurability, and is cured by irradiating light such as visible light or ultraviolet light. The fixing agent may be applied to the bonding surface of either one of the translucent hard substrates, but from the viewpoint of improving the adhesion (adhesiveness), it should be applied to the bonding surfaces of both the translucent hard substrates. Is preferred. Note that this application need not be performed on the entire surface of the translucent hard substrate. For example, the adhesive may be applied linearly with an appropriate interval. That is, this stage is a pretreatment for temporary fixing, and it is not necessary that the adhesive spreads uniformly between the two light-transmitting hard substrates when bonded in the subsequent step (5). There may be a gap between the two translucent hard substrates in which no sticking agent is contained. The fact that such simple bonding is possible contributes to the effect of the present invention, which is a reduction in manufacturing cost.

  As a preferable mode, the fixing agent is a two-component composition containing an organic peroxide and a decomposition accelerator for the organic peroxide, and the first agent component or the second agent component of the two-agent composition. It is characterized by containing a photopolymerization initiator in at least one of the above, and is a fixing agent that cures when the two components are mixed and softens when heated to a high temperature after curing. Such a preferred fixing agent is also called a redox adhesive, and can be cured by light or by standing, so that, for example, a printed pattern that does not transmit light to a translucent hard substrate has a good design. Even if it has been applied, there is an effect that the curability is surely obtained. An adhesive can be used as a sticking agent.

  Examples of the fixing agent suitably used in the present invention include a composition containing (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C) a photopolymerization initiator.

  (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” manufactured by Nippon Synthetic Chemical Industry, Negami “UN-6202” “UN-6301”) manufactured by the company, or bisphenol A type epoxy (meth) acrylate. 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, polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block or random copolymerization Condensation of a polyether polyol having one structure, the polyhydric alcohol or polyether polyol with a polybasic acid such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid Polyester polyol, caprolactone-modified polytetramethylene polyol, and other caprolactone-modified polyols, polyolefin-based polyols, polycarbonate-based polyols Ol, 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 5000 to 60000, more preferably 8000 to 30000. 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 MULTIPIOREHXL-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, tripropylene glycol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, 2,2-bis (4- (meth) acrylic Roxydiethoxy Eniru) propane, 2,2-bis (4- (meth) acryloxy 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. Among these, one or more members selected from the group consisting of dimethylol-tricyclodecane di (meth) acrylate and tripropylene glycol di (meth) acrylate are preferable.

  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 50 to 80:50 to 20 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-cyclohexanedicarboximido) ethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate and the like. Maleic acid and fumaric acid can also be used.

  Among (B), phenol (ethylene oxide 2 mol modified) (meth) acrylate, 2- (1,2-cyclohexanedicarboximido) ethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate One or more members of the group consisting of 2- (1,2-cyclohexanedicarboximido) ethyl (meth) acrylate and phenol (ethylene oxide 2 mol modified) (meth) acrylate may be used in combination.

  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, 30-90 mass parts is preferable in the total amount of 100 mass parts of (A) and (B), and 40-80 mass parts is more preferable.

  (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 benzyldimethyl 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, oxy-phenyl-acetic And 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) Content of a photoinitiator can be made into the range of 0.1-25 mass parts with respect to a total of 100 mass parts of (A) and (B), for example, and 0.1-20 Mass parts are preferred, 0.5 to 15 parts by mass are more preferred, and 1 to 8 parts by mass are even more preferred. 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. Adding 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 cross-linking of the cured product of the composition, and securely secures a bundle of translucent hard substrates ( It is further preferable in that it can be locked) and the peelability is improved.

  The fixing agent preferably contains a particulate substance (D) that does not dissolve in the components (A), (B) and (C) of the fixing agent. Thereby, since the composition after hardening can hold | maintain fixed thickness, a processing precision improves. Furthermore, since the linear expansion coefficient is different between the cured product of the sticking agent (components (A), (B) and (C)) and the granular material (D), the light-transmitting hard substrate is bonded using the sticking agent. In addition, the effect of improving the releasability at the time of peeling is also obtained.

  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 poly (meth) acrylate methyl particles, and crosslinked polystyrene particles. Examples of the inorganic particles include ceramic particles such as glass, silica, alumina, and titanium. Among these, organic particles are preferable, and one or more members in the group consisting of crosslinked poly (meth) acrylate particles and crosslinked polystyrene particles are more preferable.

  Preferably, the particulate material (D) may be an inorganic or organic filler (filler). When an appropriate amount of filler is contained in the fixing agent, an appropriate repulsive force is generated with respect to the pressure. Therefore, the thickness of the substrate laminate can be preferably controlled when a roll press is applied in step (8) described later.

The granular material (D) is preferably spherical from the viewpoint of improving processing accuracy, that is, controlling the film thickness of the fixing agent. The average particle diameter of the granular material (D) by the laser method is preferably in the range of 10 to 150 μm. When the average particle size of the granular material is 20 μm or more, the peelability is excellent, and when it is 150 μm or less, the temporarily fixed member is less likely to be displaced during processing, and the dimensional accuracy is excellent. The average particle diameter (D ₅₀ ) is more preferably 15 to 80 μm, and further preferably 20 to ₅₀ μm, from the viewpoints 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 in total of (A) and (B), from the viewpoints of adhesiveness, processing accuracy, and peelability. 05-10 mass parts is more preferable, and 0.1-6 mass parts is the most preferable.

  (E) Organic peroxides include diacyl peroxides such as lauroyl peroxide and benzoyl peroxide, t-butylperoxy-3,5,5-trimethylhexanoate, cumylperoxyneodecanoate, 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 -Keto such as dialkyl peroxides such as butyl peroxide, hydroperoxides such as cumene hydroperoxide, tetramethylbutyl hydroperoxide, ketone peroxide, cyclohexanone peroxide Peroxides and the like.

  (E) As for the usage-amount of an organic peroxide, 0.05-10 mass parts is preferable with respect to a total of 100 mass parts of (A) and (B). More preferably, 1-8 mass parts is preferable. If it is 0.5 mass part or more, sclerosis | hardenability will be acquired reliably. If it is 10 mass parts or less, since sufficient storage stability is obtained and skin irritation becomes low, it is preferable.

  (F) The decomposition accelerator is a decomposition accelerator for the above organic peroxide. For example, when a hydroperoxide or a ketone peroxide is used as the organic peroxide, an organic acid metal salt, Organometallic chelates can be used. Examples of organic acid metal salts and organic metal chelates include cobalt naphthenate, copper naphthenate, manganese naphthenate, cobalt octenoate, cobalt octylate, copper octenoate, manganese octenoate, copper acetylacetonate, titanium acetylacetonate. Manganese acetylacetonate, chromium acetylacetonate, iron acetylacetonate, vanadinyl acetylacetonate, cobalt acetylacetonate, and the like can be used. Of these, cobalt octylate is preferred.

  As other organic peroxide decomposition accelerators, thiourea derivatives and amines can be used.

  These (F) organic peroxide decomposition accelerators may be used alone or in combination of two or more.

  As for the usage-amount of the decomposition accelerator of (F) organic peroxide of a sticking agent, 0.05-20 mass parts is preferable with respect to a total of 100 mass parts of (A) and (B). More preferably, 0.3-8 mass parts is preferable. If it is 0.05 mass part or more, sclerosis | hardenability will be acquired reliably. Moreover, if it is 20 mass parts or less, since sufficient storage stability is obtained, it is preferable.

  It is preferable that the fixing agent further contains (G) 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, 2 to 250 times, and peelability is expressed. Thereby, peeling of the substrates fixed by the fixing agent after curing can be promoted.

  (G) The use amount of the thermally expandable microcapsule is 0 with respect to 100 parts by mass of the total amount of (A) and (B) from the viewpoint of the balance between the above-described peeling promotion effect and sufficient adhesiveness. 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass.

  (G) 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 property of the composition before peeling may be reduced. It is possible to balance adhesiveness.

  The thermal expansion start temperature is 70 to 130 ° C, preferably 75 to 100 ° C. If the thermal expansion 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 thermal expansion start temperature within this range, the balance between dimensional accuracy and peelability is excellent.

  Further, in the fixing agent suitably used in the present invention, a small amount of a polymerization inhibitor can be used for improving 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 and more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass in total of (A) and (B). When the amount used is within this range, storage stability is ensured, and there is no uncured and good adhesiveness can be obtained.

  In an embodiment of the present invention, for example, use of a two-part adhesive as a fixing agent can be mentioned. Regarding the two-component type, it is preferable that all the essential components of the fixing agent (composition) according to the present invention are not mixed during storage, and the composition of the fixing agent is stored separately for the first agent and the second agent. In this case, both agents can be applied to the member simultaneously or separately, and then contacted and cured to be used as a two-component type temporary fixing fixing agent. When used as a two-component type fixing agent, it is preferable that the first agent contains at least (E) an organic peroxide and the second agent contains at least (F) a decomposition accelerator for the organic peroxide. . (C) The photopolymerization initiator, (D) particulate material, and (G) the thermally expandable microcapsule may be contained in one or both of the first agent and the second agent. In the embodiment of the present invention, the fixing agent can be cured only by mixing two components.

  As a method of using the fixing agent of the present invention, a method of applying an appropriate amount of the fixing agent to the adhesive surface of one member to be fixed or temporarily fixed, and then superimposing the other member, or a member to be fixed or temporarily fixed in advance For example, a method of applying a fixing agent by a method of laminating a large number of particles and applying the fixing agent by infiltrating the fixing agent into the gap may be used.

  The sticking agent of the present invention does not require accurate metering of the two agents, and cures at room temperature even with incomplete metering or mixing, and sometimes only contact of the two agents. For this reason, the fixing agent of the present invention is excellent in workability.

  When both agents are applied to the member simultaneously or separately to contact and cure, and the members are fixed (temporarily fixed), after mixing the two agents and applying to the member, for example, it is allowed to stand at room temperature for 1 to 500 hours By doing so, the members can be bonded to each other. If it is 1 hour or more, the composition is cured and sufficient adhesive strength is obtained, and if it is 500 hours or less, sufficient adhesiveness is obtained. The stationary time for fixing or temporarily fixing the members is more preferably 4 to 300 hours, further preferably 12 to 200 hours, and most preferably 24 to 100 hours. Room temperature refers to 10 to 40 ° C., for example. As described above, in another embodiment, the fixing agent can be cured by irradiating with light instead of standing still.

  In the step (4), the first surface of the first translucent hard substrate and the first surface of the second translucent hard substrate are opposed to each other. The first surface of the first translucent hard substrate and the first surface of the second translucent hard substrate may or may not be parallel.

  In step (5), the first surface of the first light-transmitting hard substrate and the first surface of the second light-transmitting hard substrate that are opposed to each other in step (4) are bonded to form a laminate. To do. This bonding does not necessarily require pressurization. For example, the two light-transmitting hard substrates may be simply laminated (or placed). In another embodiment, it is also possible to use means such as a roll press for bonding. Since the fixing agent is cured by mixing the two components (standing) or irradiating with light, the two substrates are not immediately bonded at this stage.

  It should also be noted that the bonding in step (5) does not necessarily require a high degree of positional accuracy. Due to the effect brought about by local pressurization in step (6) to be described later, even a laminated body bonded with low positional accuracy can be suitably used in the embodiment of the present invention. There is no limitation on the allowable positional deviation between the translucent hard substrates, but from the viewpoint of workability or the yield of the final product, for example, the allowable positional deviation is within 15 mm, preferably within 10 mm. Can do.

  In the step (5 '), the steps (2) to (5) are repeated at least once, assuming that the translucent hard substrate laminate obtained in the step (5) is a 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 plate-like products, manufacture a translucent hard substrate laminate in which three or more translucent hard substrates, more typically 20 to 300 translucent hard substrates, are laminated. It is preferable to do. In the embodiment of the present invention, for example, a very thin light-transmitting hard substrate of 0.2 mm or less can be used, so that even if a large number of layers are stacked, the total thickness does not become too large and can be processed at once. it can. The thickness (total thickness) of the laminate is not particularly limited, but may be, for example, in the range of 10 to 25 mm, preferably in the range of 10 to 15 mm. For reference, when the thickness of the laminated body is 25 mm, it can be considered that it corresponds to one using 180 light-transmitting hard substrates having a thickness of 0.1 mm.

  The translucent hard substrate laminate obtained by carrying out the steps (6), (7), and (8) described below for the translucent hard substrate laminate that has undergone the step (5 ′) is used as the first translucent substrate. The light-transmitting hard substrate laminate can also be produced by repeating the steps (1) to (8) in the manner of a flexible hard substrate. Thereby, the productivity of the translucent hard substrate laminate is significantly improved.

  In the step (6), by pressing the one or both of the outermost surfaces of the laminate obtained in the step (5), the depressed portion and the pressurized portion are pressed on the laminate. Provide no flat part. Here, the area projected onto the plane perpendicular to the directional axis of the laminated body of the concave portion is smaller than the area projected onto the plane perpendicular to the directional axis of the laminated body of the flat portion. If the area projected onto the surface perpendicular to the stacking direction axis of the laminate of recesses is too large, excessive stress may be applied to the translucent hard substrate, which may cause damage and take time and labor. Cost issues will also arise.

  In addition, the shortest distance from the end surface parallel to the directional axis of the laminated body of the pressurizing portion for providing the concave portion in the step (6) is projected onto a plane perpendicular to the directional axis of the laminated body. It is 5% or less of the total perimeter of the contour, preferably 0% or more and 5% or less, more preferably 0.1% or more and 4% or less. If the pressurization location is too far from the end surface parallel to the stacking direction axis of the laminate (for example, exceeding 5% of the entire circumference of the contour), the substrate may be displaced during pressing in the step (8) described later. . Note that the length of the entire circumference of the contour does not directly affect the effect of the embodiment of the present invention, and can be appropriately selected according to the place where the work is performed and the size of the machine. As an example, the length of the entire circumference of the outline of the substrate can be 400 mm or more, 800 mm or more, 1600 mm or more, but is not limited thereto. As an example, when the translucent hard substrate is a quadrangle having a size of about 350 to 550 mm × 450 to 600 mm, the pressurization location is a distance of about 10 to 100 mm from the side of the quadrangle, preferably about 10 to 10 mm. The distance can be 75 mm, more preferably about 10-50 mm.

  FIG. 1 is a perspective view for explaining this step (6). FIG. 1 illustrates a laminated body 100 being manufactured as an example. The laminated body 100 in the middle of manufacture has a laminated transparent substrate 110 and a protective layer placed under the laminated transparent substrate 110 (hereinafter also referred to as “substrate bundle 110” for simplicity). And a translucent hard substrate 112 for use. In addition, the number of the translucent hard board | substrate shown by FIG. 1 is an illustration to the last. The function of the protective translucent hard substrate 112 will be described later. In another embodiment, the laminated body 100 during manufacture may not include the protective translucent hard substrate 112.

  The substrate bundle 110 in FIG. 1 is provided with a pressurized recess 120. The portion other than the concave portion 120 corresponds to a “flat portion that is not pressurized”. In the recess 120, the uncured fixing agent sandwiched between the light-transmitting hard substrates is pressed and the thickness is reduced. That is, in the substrate bundle 110, the thickness in the recess 120 is smaller than the thickness in the flat portion.

  In FIG. 1, the concave portion is illustrated as having only one location, but this is an example, and a plurality of concave portions may be provided. For example, it is possible to provide a plurality of recesses so as to sandwich the starting side so that the substrate does not rotate in response to a force from the starting side of the roll press in the step (8) described later.

  Further, in FIG. 1, the concave portion is drawn as a dot (black circle), but this is only a schematic shape, and the concave portion can take any shape, for example, a point shape, a substantially circular shape, It can be a rod or the like. The position of the recess 120 shown in FIG. 1 is also an example, and the recess 120 can be provided at an arbitrary position as long as the effect of the embodiment of the present invention is exhibited.

In creating the recess 120, pressurization can be performed by any method. In one embodiment, for example, a depression 120 having a desired shape is created by pressing a pressing means having a dot shape, a rod shape, a circular shape, a spherical shape, or the like from the upper surface or the lower surface of the substrate bundle 110 or both. Is possible. The pressurizing means may be a machine such as a press device, or may be manually (manually) pressurized. As such a press apparatus, for example, a known apparatus such as a vacuum press or a pressure press can be used. The force applied to the pressurization for creating the recess 120 can be, for example, about 0.5 to ²⁰ kg / cm ² . The method of applying this force can be preferably along a direction parallel to the thickness direction of the substrates (direction perpendicular to the outermost surface of the substrate bundle). In other embodiments, this force may be applied with respect to the thickness direction of the substrate. Preferably, the magnitude of the force is such that the substrate is not damaged.

The area to be pressed to create the recess 120 is not limited because it depends on the size of the translucent hard substrate. As an example, when the light-transmitting hard substrate is a rectangle having a length of 450~600mm × 350~550mm about sides, the area pressurized, for example, 1 mm ² or more 50,000 mm ² or less, more typically 5mm is ² or 30,000 mm ² or less, even more typically it may be 5 mm ² or more 5000 mm ² or less. Moreover, it is preferable that the area to be pressed exists in a margin area (a margin area that is discarded in the course of producing the final product and discarded) that does not form a part of the final product. The area to be pressurized may be one place or a plurality of areas. The area to be pressed is less than 50% of the surface area of the light-transmitting hard substrate, but may be, for example, an area of 0.1% to 40%, 0.2% to 30%. Moreover, the hardening rate of the recessed part 120 can be 50% or less, for example. The margin area can be, for example, about 15 to 20 mm from the outer end of the stacked body (end surface parallel to the thickness direction of the substrate bundle) from the viewpoint of achieving both yield and workability.

  FIG. 1 also shows an arrow 130 indicating an example of a direction in which a roll press is applied in a later process. Although details will be described later with reference to FIG. 6, it is preferable that the direction in which the roll press is applied is started from the end on the side where the recess 120 is located (that is, the side on which the substrate bundle 110 is locked). The arrow 130 may point in the same direction as the arrow 604 in FIG. 6, but may point in another direction.

  FIG. 2 is a perspective view showing an outline of pressurization for providing the recess 120. FIG. 2 is a perspective view of FIG. 1 viewed from a direction perpendicular to the thickness direction of the laminated body. Note that FIG. 2 is drawn with exaggerated thickness for ease of understanding. The protective translucent hard substrate 112 is laid on the lower surface of the substrate bundle 110 as in FIG. The substrate bundle 110 includes a plurality of substrates 111. There is an uncured adhesive layer 114 between the substrates 111, but the adhesive does not need to be applied to the entire surface of the substrate as described above for step (3). There is also a void 116 without a gap. In FIG. 2, the recess 120 is still to be provided, and a portion 122 where the recess 120 is to be provided is shown.

  FIG. 3 is a perspective view for showing a state in which the substrate bundle 110 shown in FIG. It can be seen that the substrate 111 on the uppermost surface of the substrate bundle 110 and the underlying substrate are recessed, and the uncured adhesive agent layer 114 is squeezed to form a recess 120 with a small thickness. It should be noted that the thickness is exaggerated for simplicity in FIG. In FIG. 3, the lower substrate is drawn so as to be bent, but this is an example, and only a part of the substrate may be bent. Although FIG. 3 exaggerates the thickness, the substrate 111 is drawn so as to be extremely bent with respect to the thickness direction. However, the substrate 111 is actually not damaged (the width of the substrate 111). It is preferable that the bending be modest (compared to the size of the direction).

  Although the depth of the recess 120 (that is, the depth from the outermost surface of the substrate bundle 110) is arbitrary, the translucent hard substrate is hard. Because it should hardly change, you will naturally be restricted. In an embodiment, for example, the depth of the recess 120 can be in the range of 0.5 to 50 mm. Since the uncured fixing agent in the recess 120 is cured in the step (7) described later, the depth at this time is fixed by the curing of the fixing agent. Moreover, the position of the location where the depth from the outermost surface of a board | substrate bundle is the largest among recessed parts can be stored in the area | region of 0-50 mm from the end surface parallel to the axis | shaft of the lamination direction of a laminated body, for example. In other words, the recess may be not only a uniform mortar shape but also a wedge-like shape (a shape in which the wall of the recess is not closed) entering an end face parallel to the thickness direction of the substrate bundle. Preferably, the location where the pressure is applied and the location where the depth of the concave portion is maximized can be substantially matched. In another embodiment, for example, the portion where the pressure is applied may be shifted from the portion where the depth of the concave portion is maximized by inclining the pressurizing direction with respect to the outermost surface of the substrate bundle.

  In the step (7), at least a part of the pressed recesses is subjected to light irradiation treatment, and the bundle of translucent hard substrates is locally locked by the cured recesses to temporarily fix the translucent hard substrate stack. Create a body. By performing locking in this way, it is possible to suppress a problem that the translucent hard substrate is displaced by a roll press in step (8) described later.

In the step (7), the light energy required for light irradiation is locally applied to a part or all of the depressed recess 120 using a black light, an LED, or a spot irradiator, thereby locally applying the fixing agent. Harden. In this light irradiation treatment, it is preferable to use a UV irradiator such as a spot irradiator that can easily control the irradiation area. Further, by controlling the irradiation area, it is possible to perform the light irradiation process 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 area to be irradiated should be an area with a certain area. When it becomes larger, not only is it difficult to make the thickness of the substrate uniform in the pressurizing step (8) described later, but the irradiation time becomes longer, so the production efficiency is lowered. Typically, the area to perform the light irradiation treatment is 1 mm ² or more 50,000 mm ² or less, more typically 5 mm ² or more 30,000 mm ² or less, even more typically at 5 mm ² or more 5000 mm ² or less. Moreover, it is preferable that the area to be irradiated with light (the portion where the concave portion is provided) exists in a margin region where a part of the final product is not formed.

  The wavelength of the light irradiated in the light irradiation treatment may be appropriately changed according to the characteristics of the fixing agent 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 the light irradiation treatment may be an irradiation amount necessary to temporarily fix the light-transmitting hard substrate, and is generally 1 to 500 mJ / cm as measured by an integrating illuminometer using a 365 nm light receiver. ² , 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 addition, this irradiation amount has pointed out the irradiation amount per location, when performing a light irradiation process to multiple locations.

  When the light irradiation treatment is performed outside the area pressurized in the step (7), the area where the thickness of the fixing agent other than the recess is not controlled is also cured, and the area is not compressed and cured. Then, when pressurizing with a roll press in the step (8) described later, the substrate bundle has a so-called “women” as shown in FIG. For this reason, it is preferable to perform a light irradiation process only on part or all of the pressurized area. By this light irradiation treatment step, the pressure treatment can be performed without displacement in the pressure treatment step in the step (8). The thickness of the concave portion after the fixing agent is cured is considered to be substantially equal to the case where the depth when pressed in the step (6) is subtracted from the thickness of the original substrate bundle. Taking into account the amount of shrinkage, for example, it can be in the range of 0.5 to 50 mm. Note that the relationship where the values are “substantially equal” refers to a relationship in which the difference between the values is ± 10% or less, preferably ± 5% or less.

  In step (8), the end on the side where the temporarily fastened translucent hard substrate laminate is locked is on the starting side of the roll press, and the other end to the other end using the roll press. By applying pressure, the flat portion is pressurized, and a laminated body in which the light-transmitting hard substrate is bonded is formed. In this pressure treatment step, a substrate having a uniform thickness can be obtained by bonding the substrates together. By applying pressure with a roll press, the thickness accuracy after the roll press is improved. When the thickness accuracy is improved, troubles during shape processing are reduced. When only the roll press is performed without the pressure treatment in the step (6), the thickness of the fixing agent is likely to be uneven.

  If the step (7) is not performed, the substrate may be greatly displaced during the roll press, or the fixing agent may not spread over the entire surface of the substrate depending on the application pattern of the fixing agent. Then, not only the substrates are in 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, cracking, etc. 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. Even if the fixing agent over the entire surface of the substrate is suddenly photocured without temporarily fixing (locking) in the step (7), the laminate is actually thick and the light is not transmitted uniformly. Inadequate curing of the sticking agent causes problems such as the laminate being warped.

  From the viewpoint of stacking accuracy, it is preferable that the sticking agent that has undergone the step (8) spreads on the bonding surface to a whole 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. Moreover, since the leaking adhesive can be collected on the outermost surface by enlarging one or both of the outermost surfaces of the translucent hard substrate laminate, the trouble of wiping can be saved. , Productivity is greatly improved.

  In the step (7 '), the steps (2) to (7) are repeated at least once, assuming that the translucent hard substrate laminate obtained in the step (7) is a first translucent hard substrate. Thereby, the temporarily fixed 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 temporary fixing light-transmitting rigid body in which 5 or more temporarily fixed light-transmitting hard substrate laminates, typically 5 to 300 light-transmitting hard substrates are stacked. It is preferable to manufacture a substrate laminate. The number of the temporarily fixed translucent hard substrate laminate is typically 3 to 300, although it depends on the thickness of the translucent hard substrate, and is more typically 20 from the viewpoint of productivity and workability. ~ 300, and still more typically 50-150. If the thickness of the translucent hard substrate laminate is increased, the processability in the step (11) and the step (12) described later decreases, and the yield decreases. Assume the translucent hard substrate laminate obtained by carrying out the step (8) for the temporarily fixed translucent hard substrate laminate subjected to the step (7 ′) as the first translucent hard substrate, Steps (1) to (8) can be repeated to produce a translucent hard substrate laminate. Thereby, the productivity of the translucent hard substrate laminate is significantly improved.

  In the step (8), as described above, it is preferable to roll-press the translucent hard substrate subjected to pressure treatment. The principle of the roll press is shown in FIG. The roll press has at least a pair of rolls 502 installed in the vertical direction, and the substrate 504 sandwiched between the rolls 502 is fed forward by the rotation of the rolls. During this time, the substrate 504 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 further, the temporary fastening in the step (7) may occur during the roll press. On the other hand, the area where the fixing agent is not irradiated with light is not cured, so that the fluidity is maintained. In addition, the first pressurizing area in the roll press includes the area where the light irradiation is performed in step (7) and temporarily fixed, so that the positional deviation does not occur at the time of the roll press even more reliably.

  The apparatus for roll pressing is known per se and is considered not to require detailed explanation. In the present invention, however, it is preferable to determine the operating conditions in consideration of the following points. First, the roll is preferably 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 is difficult to press uniformly over 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 air bubbles can be removed. Can not. It is preferable to appropriately adjust the roll pressure so as to remove bubbles and obtain a desired thickness. For example, the roll press machine can be operated so that the linear pressure of the roll is 0.1 to 10 kN / m, typically 0.2 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 fast, bubbles cannot be removed and the desired thickness cannot be obtained. On the other hand, if it is too slow, the productivity is inferior. 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.

  In addition, it is preferable that the roll press is performed starting from the end on the side where the temporarily fixed light-transmitting hard substrate laminate is locked, in view of suppressing substrate displacement and extending the fixing agent uniformly. FIG. 6 is a perspective view showing one mode when performing roll press. FIG. 6 shows a state in which roll pressing as shown in FIG. 5 is applied to the substrate bundle 110 as shown in FIG. is there. Here, the position 610 where the recess is provided is set as the starting point of the roll press, but the starting point may be a different position as long as the effect of the present invention is exhibited. (The position 610 may be the same position as the concave portion 120 of FIG. 1 described above, or may be a different position.) The uncured fixing agent 602 in the substrate bundle 110 is centered on the starting point by roll pressing. Will spread. For this reason, it is possible to control the direction in which the uncured adhesive is spread. Further, since the starting point of the roll press is on the side where the concave portion (not shown in FIG. 6) is present, the effect that the laminate can be obtained with a uniform thickness is also achieved. If the starting point of the roll press is on the opposite side of the recess, the force is applied in the direction that the substrate is turned up, as if it was lifted by applying a force from the opposite side of the side where the paper booklet bundled up in a cantilevered manner. Therefore, there is a disadvantage that the laminate cannot be obtained with good quality.

  FIG. 7 schematically shows some suitable combinations of the recesses (locking portions) and the roll press direction (starting point). Here, for simplicity, the substrate is shown as a rectangle, the locking portion is indicated by a black dot, and the direction of the roll press is indicated by an arrow. By combining in this way, even if a roll press is used, a force is applied in the direction in which the substrates rotate, and the substrates are not displaced, and the adhesive between the substrates can be easily spread. As can be seen from these examples, there may be a plurality of locking portions, and it is also possible to hang the roll press from the apex rather than from the side. Moreover, what was shown in FIG. 7 is an illustration to the last, and there may be other combinations of the locking portion and the roll press direction.

  In the step (9), the light-transmitting hard substrate laminate produced in the step (8) is regarded as a first light-transmitting hard substrate, and the steps (2) to (8) are repeated at least once, and at least 3 sheets The translucent hard board | substrate laminated body by which this translucent hard board | substrate was bonded together can be formed. The number of laminated layers in the step (9) is typically 3 to 300 sheets depending on the thickness of the translucent hard substrate, more typically 20 to 300 sheets from the viewpoint of productivity and workability, and much more. More typically, it can be 50 to 100 sheets. If the thickness of the translucent hard substrate laminate is increased, the processability in the step (11) and the step (12) described later decreases, and the yield decreases.

  In the step (10), after the last pressurizing step of the step (8), the obtained translucent hard substrate laminate can be allowed to stand for 1 hour or longer to cure the fixing agent. By standing, the (E) organic peroxide in the fixing agent reacts with the (F) decomposition accelerator of the organic peroxide, and the fixing agent is gradually cured. Since the fixing agent is gradually cured, the distortion generated during the curing is alleviated simultaneously with the curing, so that the distortion of the fixing agent is suppressed. As a result, distortion of the substrate in the portion can be suppressed. The standing time may be about 1 hour, but in order to complete the curing, 4 hours or more is recommended, and typically 12 hours or more is recommended.

  In order for the translucent hard substrate laminate to increase the number of sheets that can be laminated and improve the productivity while maintaining the workability in the step (11) and step (12) to be described later, the thinner the translucent hard substrate is. Preferably, it is 0.2 mm or less. If it is a light-transmitting hard substrate having a thickness of 0.2 mm, the number of laminated layers of the final laminate capable of maintaining workability is about 100, and if it is a light-transmitting hard substrate having a thickness of 0.1 mm, the workability The number of laminated layers of the final laminated body that can maintain the thickness is about 200, and it is still more preferable that the thickness is 0.1 mm or less. In the case of a light-transmitting hard substrate having a thickness of 0.05 mm, the final laminated body capable of maintaining workability is about 300, and it is even more preferable if the thickness is 0.05 mm or less. The thickness should just be 0.005 mm or more.

  In a preferred embodiment, a protective translucent hard substrate having a so-called dummy function can be used as the lowermost surface, the uppermost surface, or both (outermost surface) of the laminate. This dummy corresponds to the protective translucent hard substrate 112 in FIGS. The area of the protective translucent hard substrate is preferably larger than that of the other translucent hard substrates in the substrate bundle. More preferably, the dimension of the side of the protective translucent hard substrate that is not the starting point side of the roll press (the side where no concave portion is provided) is larger than that of the other translucent hard substrates. For example, in one embodiment, when the translucent hard substrate is a quadrangle, the length of the side on which the concave portion is not provided is longer than that of the other translucent hard substrate in the protective translucent hard substrate. The size can be increased by about 20 to 100 mm, preferably about 30 to 40 mm. By enlarging the dummy in this way, even if the uncured adhesive spread by the roll press in the step (8) protrudes from between the substrates and spills out, it falls on the dummy, so it is very easy to clean the workbench. A remarkable effect is achieved. In addition, the dummy also has a role of protecting the substrate laminate, and has an effect that it is less likely to be damaged even when the substrate laminate is stacked. The thickness of the dummy can be the same as that of the other light-transmitting hard substrate. Alternatively, the dummy thickness can be made thicker than the above, for example, about 0.5 to 0.7 mm. Note that although this is referred to as a dummy for simplicity, it is also possible to make this protective translucent hard substrate part of the final product.

  By manufacturing the light-transmitting hard substrate laminate through the steps as described above, extremely efficient production becomes possible. In the prior art, every time one piece of glass is bonded, the fixing agent needs to be cured in a large area. Therefore, there is a problem that the working time (tact time) becomes long particularly in a laminate having a large number of contained substrates. . On the other hand, in the embodiment of the present invention, as described above, two or more than two substrates can be processed together, and therefore, the working efficiency is extremely high. As an example, when a laminate is obtained using 60 substrates, if the method according to the embodiment of the present invention is used, the work time in the method according to the prior art is approximately one-fourth the time. It is also possible to complete the work.

<Manufacture of plate products>
A plate-like product can be produced (for example, as a final product) from the translucent hard substrate laminate obtained by the method for producing a translucent hard substrate laminate.

  First, in the step (11), 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 (12), 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 (13), the translucent hard substrates bonded together by heating the translucent hard substrate laminate after the shape processing are peeled 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 99 ° C, preferably 80 to 98 ° C.

Furthermore, in the step (13), 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, whereby 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 (11) and the step (13). . 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 manufacturing method>
A specific manufacturing method is illustrated based on the example of a translucent hard board | substrate bonding apparatus. The example of the translucent hard board | substrate bonding apparatus which can be used when producing a translucent hard board | substrate is demonstrated. For simplicity, only two transparent translucent substrates are shown and described here, but this is only an example. It should be noted that in the preferred embodiment, a larger number of translucent rigid substrates can be used together.

  FIG. 8 is a schematic view showing an example of a translucent hard substrate laminating apparatus that can be suitably used in an embodiment of the present invention. The translucent hard substrate laminating apparatus 10 has 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 an embodiment, the LED unit 16 can be used to perform temporary fastening (locking) in the step (6). In another embodiment, the temporary fastening (locking) of the step (6) may be performed by other means (for example, an independent light irradiating instrument (not shown) or standing still).

  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 a 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. 9 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. As the suction unit 14, a vacuum pump, a vacuum ejector, or the like can be used.

  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. 9 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 (X-axis) direction, the Y-axis (Y-axis) direction, and the θ-axis (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. In another embodiment, instead of the side clamp 19, a positioning contact jig 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 manually in the direction indicated by the arrow, and placed at a position fixed by the contact jig. Further, in order to prevent the position of the translucent hard substrate from being displaced, the lower translucent hard substrate 24 can also be held by vacuum suction in the same manner as the upper stage 12.

  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 applies the fixing agent 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. 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 sticking agent is applied from the tip of the rotary 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.

  Moreover, when forming a laminated body using sensor glass as a translucent hard board | substrate, you may perform the advanced positioning requested | required for lamination | stacking of sensor glass by using the imaging unit 22. FIG. In this embodiment, the imaging unit 22 uses alignment marks provided on the respective surfaces of the upper light-transmitting hard substrate 25 and the lower light-transmitting hard substrate 24 at the tip of the arm. Images are taken with the digital cameras 22a attached to the upper and lower portions. The electrical unit 23 detects a relative positional shift state between the upper translucent hard substrate 25 and the lower translucent hard substrate 24 based on the captured image information. Based on the detection result, the position of the lower stage 17 is finely adjusted by the lower stage moving means 18 in the X-axis direction, the Y-axis direction, and the θ-axis direction, and an operation for correcting the positional deviation is executed. After correcting the positional deviation, the two light-transmitting hard substrates are bonded together. As a camera, an analog camera can be used in addition to a digital camera using a CCD or CMOS as an image sensor, but a digital camera is preferable from the viewpoint of high resolution. In this embodiment, the imaging device images the respective bonding surfaces of the upper translucent hard substrate and the lower translucent hard substrate, but the imaging device may be changed to other arrangements.

  The imaging unit 22 includes moving means 22b driven by motors in the X-axis and Y-axis directions, and the digital camera 22a moves to a predetermined position where the alignment mark enters the field of view during imaging. When the imaging is completed, the digital camera 22a moves so as not to obstruct the pasting of the translucent hard substrates.

  A procedure for laminating a translucent hard substrate using the translucent hard substrate laminating apparatus 10 according to an example of stacking cover glasses will be described with reference to FIGS.

  First, the first translucent hard substrate 26 is placed on the first lower stage 17 and fixed to a predetermined position by a side clamp 19 (not shown) (FIG. 10). 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. 11). 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. 12). The adsorbed translucent hard substrate 26 rises with the upper stage 12 while being held, and waits for the second substrate (FIG. 13).

  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. 14). 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. 15). 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. 16). In the embodiment shown in FIG. 16, the adhesive (28, 29) is applied to the upper and lower light-transmitting hard substrates (26, 27), but this is merely an example. In another embodiment, the process can be suitably performed by applying a fixing agent only to one light-transmitting hard substrate.

  In FIG. 17, after applying the fixing agent (28, 29) to the upper and lower light-transmitting hard substrates (26, 27), the upper stage 12 is lowered by the press unit 13 to provide two light-transmitting hard substrates. After pasting (26, 27), the suction to the upper substrate 26 is released, and only the upper stage 12 is lifted. Thereafter, the bonded light-transmitting hard substrate is conveyed by the lower stage 17 and returned to the original position (FIG. 18). The laminated body thus obtained (laminated body in which the upper and lower light-transmitting hard substrates (26, 27) are bonded) is pressed by a pressing means (not shown) as described above. The concave portion can be provided at a desired position. Thereafter, the concave portion can be cured by, for example, ultraviolet irradiation from the LED unit 16 or other means. The temporary fixing (locking) of the translucent hard substrate is completed by the above steps.

  In a preferred embodiment, the state shown in FIGS. 10 to 18 is further repeated after the state of FIG. 18 to obtain a laminate in which a desired number of translucent hard substrates are laminated. Thereafter, the laminated body can be pressurized in the same manner, provided with a concave portion and cured, and the laminated body can be temporarily fixed (locked).

  Then, the laminated body in which the translucent hard board | substrate of several sheets was bonded together can be obtained by pressing the translucent hard board | substrate laminated body temporarily fixed (locked) through a roll press machine. In a certain embodiment, you may laminate | stack a translucent hard board | substrate again with respect to the said laminated body after this. For example, the next translucent hard substrate 26 is placed using the second lower stage 17 by the method shown in FIGS. 10 to 13 and finally held on the upper stage 12 side. Then, as shown in FIGS. 14 to 18, the substrate 26 held on the upper stage 12 is placed on the surface of the upper substrate 26 of the laminated body obtained by bonding the substrates 26 and 27 previously produced. Bonding can be performed in a state in which a fixing agent is applied to the surface of each substrate. The above operation can be repeated for the number of substrates to be stacked.

  Next, the entire sticking agent is cured (for example, by standing for a predetermined time or by additional light irradiation), whereby a translucent hard substrate laminate can be formed in a lump. In a preferred embodiment, the entire fixing agent can be cured by standing. In another embodiment, the obtained 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.

  In another embodiment, when the sensor glass is laminated, the second translucent hard substrate 27 placed on the first lower stage 17 after the application in FIG. After moving right below, the alignment mark is imaged with a camera attached to the arm tip of the imaging unit 22, the position of the first lower stage 17 is finely adjusted according to the imaging result, and both translucent rigid substrates The position adjustment of (26, 27) may be performed.

  Although the embodiments of the present invention have been described above, 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 (G) were mixed to prepare a two-agent type fixing agent. Two types of fixing agents were prepared. Unless otherwise specified, the fixing agent used was a mixture of the first agent and the second agent.
(Fixing agent 1)
"First Agent"
(A) As a polyfunctional (meth) acrylate, “urethane acrylate 1” (urethane acrylate. Details are as follows. Polyester urethane acrylate having a weight average molecular weight of 15000. The polyol compound is a condensate of ethylene glycol and adipic acid. It has both a certain polyester polyol, 1,4-butanediol, and a polyester polyol that is a condensate of adipic acid, an organic polyisocyanate compound is isophorone diisocyanate, and hydroxy (meth) acrylate is 2-hydroxyethyl acrylate. Parts, dimethylol-tricyclodecane diacrylate (“Kyoeisha Chemical Co., Ltd.“ Light acrylate DCP-A ”, hereinafter abbreviated as“ DCP-A ”) 15 parts by mass,
(B) As a monofunctional (meth) acrylate, 40 parts by mass of 2- (1,2-cyclohexanedicarboximide) ethyl acrylate (“Aronix M-140” manufactured by Toa Gosei 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, 20 parts by mass of BDK: benzyldimethyl ketal (“IRGACURE651” manufactured by BASF),
(D) 0.2 parts by mass of monodispersed spherical cross-linked polystyrene particles (“GS-220” manufactured by Sekisui Chemical Co., Ltd.) having an average particle size (D50) of 30 μm as a particulate material not dissolved in (A) to (C);
(E) As an organic peroxide, 3 parts by mass of cumene hydroperoxide (Nippon Yushi Co., Ltd. “Park Mill H”),
(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.) 0.2 parts by mass “ Second agent "
(A) As a polyfunctional (meth) acrylate, 20 parts by mass of “urethane acrylate 1”, dimethylol-tricyclodecane diacrylate (“light acrylate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd., hereinafter abbreviated as “DCP-A”) 15 Parts by mass,
(B) As a monofunctional (meth) acrylate, 40 parts by mass of 2- (1,2-cyclohexanedicarboximide) ethyl acrylate (“Aronix M-140” manufactured by Toa Gosei 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.)
(D) 0.2 parts by mass of monodispersed spherical cross-linked polystyrene particles (“GS-220” manufactured by Sekisui Chemical Co., Ltd.) having an average particle size (D50) of 30 μm as a particulate material not dissolved in (A) to (C);
(F) As an organic peroxide decomposition accelerator, 0.7 part by mass of cobalt octylate (“Oct-Co” manufactured by Shinto Paint Co., Ltd.)
(Other) 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol) (“Sumilyzer MDP-S (In-D)” manufactured by Sumitomo Chemical Co., Ltd.) 0.2 parts by mass as a polymerization inhibitor

(Fixing agent 2)
"First Agent"
(A) As a polyfunctional (meth) acrylate, "urethane acrylate 2" (urethane acrylate. Details are as follows. Polyether urethane acrylate having a weight average molecular weight of 13000. Polyol compound is polypropylene glycol. Organic polyisocyanate compound is isophorone. Diisocyanate.hydroxy (meth) acrylate is 2-hydroxyethyl acrylate) 35 parts by mass, tripropylene glycol diacrylate (“APG-200” manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter abbreviated as “APG-200”), 10 parts by mass,
(B) As a monofunctional (meth) acrylate, 55 parts by mass of 2- (1,2-cyclohexanedicarboximide) ethyl acrylate (“Aronix M-140” manufactured by Toagosei Co., Ltd., hereinafter abbreviated as “M-140”),
(C) 5 parts by mass of BDK: benzyldimethyl ketal (“IRGACURE651” manufactured by BASF) as a photopolymerization initiator,
(D) Monodisperse spherical cross-linked polymethyl methacrylate particles having an average particle diameter (D50) of 27 μm (“SSX-127” manufactured by Sekisui Plastics Co., Ltd.) as a granular material not dissolved in (A) to (C) 0.2 mass Part,
(E) As an organic peroxide, 3 parts by mass of cumene hydroperoxide (Nippon Yushi Co., Ltd. “Park Mill H”),
(G) Thermally expandable microcapsules encapsulating isobutane and encapsulating with a thermoplastic resin comprising a copolymer of methyl acrylate, methyl methacrylate and acrylonitrile (“F-” manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) 36D ") 10 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.) 0.2 parts by mass “ Second agent "
(A) As a polyfunctional (meth) acrylate, 35 parts by mass of “urethane acrylate 2”, 10 parts by mass of tripropylene glycol diacrylate (“APG-200” manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter abbreviated as “APG-200”) ,
(B) As a monofunctional (meth) acrylate, 55 parts by mass of 2- (1,2-cyclohexanedicarboximide) ethyl acrylate (“Aronix M-140” manufactured by Toagosei Co., Ltd., hereinafter abbreviated as “M-140”),
(C) 5 parts by mass of BDK: benzyldimethyl ketal (“IRGACURE651” manufactured by BASF) as a photopolymerization initiator,
(D) Monodisperse spherical cross-linked polymethyl methacrylate particles having an average particle diameter (D50) of 27 μm (“SSX-127” manufactured by Sekisui Plastics Co., Ltd.) as a granular material not dissolved in (A) to (C) 0.2 mass Part,
(F) As an organic peroxide decomposition accelerator, 1 part by mass of cobalt octylate (“Oct-Co” manufactured by Shinto Paint Co., Ltd.)
(G) Thermally expandable microcapsules encapsulating isobutane and encapsulating with a thermoplastic resin comprising a copolymer of methyl acrylate, methyl methacrylate and acrylonitrile (“F-” manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) 36D ") 10 parts by mass,
(Other) 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol) (“Sumilyzer MDP-S (In-D)” manufactured by Sumitomo Chemical Co., Ltd.) 0.2 parts by mass as a polymerization inhibitor

2. Bonding of light-transmitting hard substrate A plate glass (plate glass of width 470 mm × length 370 mm × thickness 0.1 mm) is used as a light-transmitting hard substrate, and 100 plate glasses are bonded together with an adhesive, and the adhesive is in an uncured state. A laminate was created. The operating conditions of the device are as follows. The amount of the sticking agent applied to the glass at one time was 18 g.
<Operation conditions for bonding equipment>
Pressurization location (recessed portion): location where the shortest distance from the end surface parallel to the stacking direction axis of the laminate is 30 mm (length of the entire circumference of the contour projected on the plane perpendicular to the stacking direction axis of the laminate) 1.8% of the height) is installed at one location.
・ Pressure area (recess) area: 10 mm ²
・ Temporary fastening UV irradiation amount: 10 mJ / cm ² (measured by an integrating illuminometer with a 365 nm light receiver)
・ Pressure location (recess) depth: 1mm from the outermost surface
・ Pressure location (recess) shape: substantially circular ・ Pressure location (recess) thickness obtained by pressurization: 1 mm
-Area of light irradiation area: 10 mm ²
-Method of performing light irradiation: Spot irradiator-UV light source: LED light-Pressure applied to create a recess: 1 kg / cm ²
-Thickness of the pressed part (concave part) after the fixing agent is cured: 1 mm
-Temporary UV irradiation time: 3 seconds

3. Roll press The produced plate glass was roll-pressed. The operating conditions of the roll press are as follows.
<Roll press operating conditions>
Pressurization was performed from the end to the other end using a roll press so that the end on the side where the temporarily fixed translucent hard substrate laminate was locked was the starting point side of the roll press.
-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: Urethane

4). Curing of Fixing Agent The laminate of sheet glass after roll pressing was allowed to stand at 23 ° C. for 12 hours.

5. Presence / absence of deviation After standing, the maximum value of the amount of lateral deviation between the plate glasses was measured. The results are shown in Table 1. A comparative example 1 was prepared without the pressing step.

6). Physical properties Physical properties of each fixing agent were measured according to the following. The results are shown in Table 1.
<Viscosity of the fixing agent (viscosity)>
The viscosity of each fixing agent was measured using a B-type viscometer at a temperature of 25 ° C. The results are shown in Table 1.

<Tensile shear adhesive strength (adhesive 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 speed of 10 mm / min under 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. After fixing the equal amount of the first agent and the second agent using a belt conveyor type metal halide lamp, irradiating light from the upper surface under the condition of an integrated light amount of 2000 mJ / cm ² at a wavelength of 365 nm, Furthermore, light was irradiated from the lower surface under the condition of an integrated light quantity of 2000 mJ / cm ² with a wavelength of 365 nm from the lower surface, and a cured body having a thickness of 5 mm was produced. The produced cured body was cut into a cylindrical shape having a diameter of 30 mm with a cutter to obtain a cured body for Shore D hardness measurement. The value of the obtained cured product was measured by ASTM D-2240 using a D-type Shore hardness meter.

<Peel test>
A peel test of each fixing agent was performed according to the following. The results are shown in Table 1.

<Adhesive 1-2>
After sticking 80 mm square blue plates using the adhesives 1 and 2 and curing at 23 ° C. for 24 hours, using a UV irradiator, an integrated light quantity of 2000 mJ / cm ² (365 nm illuminance: 160 mW / It was cured under the conditions of cm ² , “ECS-401GX (UV curing device equipped with a metal halide lamp)” manufactured by Eye Graphics Co., Ltd., and a test piece for a peel test was produced. The produced test piece was measured for time (minutes) until it was immersed in 90 ° C. warm water and peeled off.

  From the above results, it was confirmed that in any of the examples, there was no lateral deviation with any of the fixing agents, and a laminate could be suitably produced. On the other hand, in Comparative Example 1 in which the pressurizing step was omitted, the plate glass inside the laminated body slipped out due to the load applied by the roll press, and the lamination could not be performed (the situation is shown in FIG. 19).

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 Rotary nozzle 21b Robot 22 Imaging unit 22a Digital camera 22b Moving means 23 Electrical unit 24 Lower substrate (also referred to as lower translucent hard substrate)
25 Upper substrate (sometimes referred to as upper translucent hard substrate)
26 Translucent hard substrate (sometimes referred to as substrate)
27 Translucent hard substrate (sometimes referred to as substrate)
28 Adhesive 29 Adhesive 100 Laminate 110 (during manufacture) Translucent hard substrate laminate (sometimes referred to as substrate bundle)
111 Substrate 112 Protective translucent hard substrate 114 Layer of uncured fixing agent 116 Void 120 Recess 122 Recessed portion 130 A portion 130 showing an example of a direction to apply a roll press 502 Roll 504 Substrate 602 Uncured Adhesive 604 Arrow 610 indicating direction of roll press

Claims (33)

1) preparing a first translucent hard substrate;
2) preparing a second translucent hard substrate;
3) A step of applying a photocurable adhesive to the first surface of the first translucent hard substrate and / or the first surface of the second translucent hard substrate;
4) a step of causing the first surface of the first translucent hard substrate and the first surface of the second translucent hard substrate to face each other;
5) bonding the first surface of the first translucent hard substrate and the first surface of the second translucent hard substrate to produce a laminate;
6) By applying pressure to one or both of the outermost surfaces of the laminated body bonded together, the laminated body is provided with a pressurized concave portion and a non-pressurized flat portion, The area projected on the surface perpendicular to the direction axis of the laminate of the laminate is smaller than the area projected on the surface of the flat portion perpendicular to the direction axis of the laminate, and the recess The shortest distance from the end face parallel to the stacking direction axis of the laminate is the length of the entire circumference of the contour projected onto the plane perpendicular to the stacking direction axis of the stack. A step of 5% or less;
7) At least a part of the pressed recess is subjected to light irradiation treatment, and the first light-transmitting hard substrate and the second light-transmitting hard substrate are locally locked by the cured recess. A step of producing a temporary translucent hard substrate laminate,
8) Apply pressure from the end to the other end using the roll press so that the end on the side where the temporarily fixed translucent hard substrate laminate is locked is the starting side of the roll press. And a step of pressurizing the flat portion to form a laminate on which the translucent hard substrate is bonded, and a method for manufacturing the translucent hard substrate laminate. 5 ′) Considering the laminate produced in step (5) as the first light-transmitting hard substrate, steps (2) to (5) are repeated at least once, and at least three light-transmitting hard substrates are attached. The manufacturing method of the translucent hard board | substrate laminated body of Claim 1 including the process of forming the match | combined laminated body. 7 ′) Steps (2) to (7) are repeated at least once, assuming that the temporarily fixed light-transmitting hard substrate laminate produced in step (7) is the first light-transmitting hard substrate, and at least three sheets The manufacturing method of the translucent hard board | substrate laminated body of Claim 1 or 2 including the process of forming the laminated body on which the translucent hard board | substrate was bonded together.   The translucency as described in any one of Claims 1-3 whose depth from the said outermost surface in the pressurization location of the said recessed part pressurized by process (6) is the range of 0.5-50 mm. Manufacturing method of hard substrate laminate.   The manufacturing method of the translucent hard board | substrate laminated body as described in any one of Claims 1-4 which forms a some recessed part by repeating a process (6) in multiple times. The method for producing a translucent hard substrate laminate according to any one of claims 1 to 5, wherein an area of the concave portion to be pressed in the step (6) is 1 mm ² or more.   Of the recesses obtained by pressurization in step (6), the portion where the depth from the outermost surface is the maximum is a distance of 0 to 50 mm from the end surface parallel to the axis in the stacking direction of the laminate. The manufacturing method of the translucent hard board | substrate laminated body as described in any one of Claims 1-6 which fits in an area | region.   The translucent hard substrate laminate according to any one of claims 1 to 7, wherein a shape of the concave portion obtained by pressurization in the step (6) is a dot shape, a substantially circular shape, or a rod shape. Production method.   The translucency as described in any one of Claims 1-8 whose thickness of the said recessed part obtained by pressing by a process (6) is substantially equal to the thickness of the laminated body obtained by a process (8). Manufacturing method of hard substrate laminate.   The manufacturing method of the translucent hard board | substrate laminated body as described in any one of Claims 1-9 whose thickness of the said recessed part obtained by pressurizing by a process (6) is the range of 0.5-50 mm. . Method for producing a translucent rigid substrate laminate according to any one of claims 1 to 10 area in the area where the light irradiation is 1 mm ² or more in the step (7).   The method for producing a translucent hard substrate laminate according to any one of claims 1 to 11, wherein the method of performing light irradiation in the step (7) is light irradiation by a spot irradiator. 9) Considering the temporarily fixed light-transmitting hard substrate laminate produced in step (8) as the first light-transmitting hard substrate, steps (2) to (8) are repeated at least once, and at least three transparent The manufacturing method of the translucent hard board | substrate laminated body as described in any one of Claims 1-12 including the process of forming the translucent hard board | substrate laminated body by which the optical hard board | substrate was bonded together.   The method for producing a translucent hard substrate laminate according to any one of claims 1 to 13, wherein the number of laminated translucent hard substrate laminates is in the range of 20 to 300.   The manufacturing method of the translucent hard board | substrate laminated body as described in any one of Claims 1-14 with which a translucent hard board | substrate has a polygonal shape. 10) After forming a translucent hard board | substrate laminated body by a process (8) or / and a process (9), it further includes the process of standing still at normal temperature for 1 hour or more and hardening a fixing agent. The manufacturing method of the translucent hard board | substrate laminated body as described in any one.   The area of the translucent hard board | substrate of one or both of the outermost surfaces of a translucent hard board | substrate laminated body is larger than translucent hard boards other than the translucent hard board | substrate of one or both outermost surfaces. The manufacturing method of the translucent hard board | substrate laminated body as described in any one of these. The amount of light irradiation in the step (7) is in the range of 5 to 5000 mJ / cm ² as measured with an integrating illuminometer using a 365 nm light receiver. Manufacturing method of optical hard board | substrate laminated body.   The method for producing a light-transmitting hard substrate laminate according to any one of claims 1 to 18, wherein the light-transmitting hard substrate is a plate glass having a thickness of 0.2 mm or less. 11) The translucent hard substrate laminate obtained by using the method for producing a translucent hard substrate laminate according to any one of claims 1 to 19 is divided in a thickness direction, and a desired number of divisions are made. Forming a light-transmitting hard substrate laminate,
12) A step of performing a desired shape processing on each of the divided light-transmitting hard substrate laminates;
13) 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-like products;
A method for producing a plate-like product including   21. The method for producing a plate-like product according to claim 20, wherein the step (13) includes immersing the translucent hard substrate laminate after shape processing in warm water and softening the fixing agent in a film form.   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 1-19. In producing the light-transmitting hard substrate laminate according to claim 22, 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 Agent.   The photocurable fixing agent according to claim 23, further comprising (D) a particulate material in addition to (A) to (C).   The photocurable fixing agent according to claim 24, wherein the particulate material (D) is a filler.   Furthermore, (E) The photocurable sticking agent as described in any one of Claims 23-25 containing an organic peroxide.   The photocurable fixing agent according to claim 26, further comprising (F) a decomposition accelerator for the organic peroxide.   Furthermore, (G) The photocurable sticking agent as described in any one of Claims 23-27 containing a thermally expansible microcapsule.   The light according to any one of claims 23 to 28, wherein the content of (B) monofunctional (meth) acrylate is 30 to 90 parts by mass in 100 parts by mass of the total amount of (A) and (B). Curable sticker.   (C) Content of a photoinitiator is 0.1-25 mass parts with respect to 100 mass parts of total amounts of (A) and (B), It is any one of Claims 23-29 Photo-curing adhesive. A laminate of translucent hard substrates,
A plurality of laminated transparent substrates,
Including a fixing layer made of a fixing agent disposed between the translucent hard substrates,
The laminate has a concave portion and a flat portion,
The recess is for locking a plurality of the translucent hard substrates,
The thickness of the concave portion along the stacking direction of the stacked body is smaller than the thickness of the flat portion along the stacking direction of the stacked body,
The area projected on the surface perpendicular to the direction axis of the laminate of the laminate of the concave portion is smaller than the area projected on the surface of the flat portion perpendicular to the direction axis of the laminate.
5% of the total perimeter of the contour projected on a plane perpendicular to the direction axis of the laminate as viewed from the end surface parallel to the direction axis of the laminate, at least a part of the recess. A laminate having the following distance.   32. The laminate according to claim 31, wherein the fixing layer in the concave portion is cured, and the fixing layer in the flat portion is not cured.   33. The laminate according to claim 31 or 32, wherein an area of one or both of the outermost light-transmitting hard substrates is larger than the light-transmitting hard substrate other than one or both of the outermost light-transmitting hard substrates.