WO2014192941A1 - Hard substrate laminate and hard substrate laminate manufacturing method - Google Patents

Abstract

Provided is a hard substrate laminate useful for manufacturing sheet glass products with high production efficiency and low cost. A hard substrate laminate in which at least two hard substrates have been bonded to each other with an adhesive, the hard substrate laminate being intended for cutting of said laminate in the thickness direction to obtain a desired number of divided hard substrate laminates. Between the respective hard substrates, the adhesive is continuously present straddling all of the lines to be processed during cutting and between the respective hard substrates, there is a gap, in which there is no adhesive, in at least one of the areas surrounded by the processing lines.

Description

Rigid substrate laminate and method for producing rigid substrate laminate

The present invention relates to a method for manufacturing a hard substrate laminate.

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

Such a flat glass product is obtained by processing a flat glass into a size and shape suitable for each display device, but it needs to be manufactured with good production efficiency in order to meet the price level required in the market. .

Therefore, Patent Document 1 discloses a glass laminate in which a plurality of plate glasses having substantially the same shape and size in plan view are sequentially laminated in producing a chamfered plate glass product. And manufacturing the sheet glass product characterized by chamfering the individual sheet glass constituting the glass laminate by etching the glass laminate. In paragraphs 0029 and 0030 of Patent Document 1, it is also described that it is preferable to form an adhesive material layer on the entire bonding surface (main surface) of the plate glasses to be bonded to each other.

On the other hand, Patent Document 2 stacks a large number of material sheet glasses (1) and integrates each material sheet glass (1) with a peelable fixing material (2) interposed between each material sheet glass (1). A material glass block (A) formed by adhering is formed, the material glass block (A) is divided in a plane direction to form a small-area divided glass block (B), and at least the divided glass block (B) A product glass block (C) having a product shape in plan view is formed by processing the outer periphery, and the product glass block (C) is individually separated after the end face processing of the product glass block (C). The processing method of the plate glass to perform is described. In paragraph 0009 of Patent Document 2, it is described that the material plate glasses are stacked while interposing a liquid sticking agent, and by pressing them in the thickness direction, the sticking agent is spread between the material plate glasses in a film shape. Yes.

JP 2000-169166 A JP 2009-256125 A

In the above prior art documents, it is recommended or presupposed that the entire main surface of each glass constituting the plate glass laminate is covered with an adhesive, and there is no idea that the adhesive is patterned and applied. Therefore, in the above-mentioned prior art documents, it is still improved in terms of shortening the time when separating the plate glass laminate into individual plate glasses, cleaning the residual adhesive after separation into individual plate glasses, and optimizing the amount of adhesive used. There is room for it. In particular, the larger the area of the main surface of the flat glass product, the more the amount of adhesive used and the peeling time are expected to increase, and further technical improvements are required to produce a flat glass product with high production efficiency at low cost. is there.

This invention is made | formed in view of the said situation, and makes it a subject to provide a hard substrate laminated body useful when manufacturing a plate glass product with high production efficiency and low cost. Moreover, this invention makes it another subject to provide the manufacturing method of such a hard board | substrate laminated body. Moreover, this invention makes it another subject to provide the manufacturing method of the plate-shaped product using the hard board | substrate laminated body which concerns on this invention.

The present inventors have intensively studied in order to solve the above-mentioned problems. As a result, an adhesive is applied to the main surface of the hard substrate in a predetermined pattern, and the hard substrates are bonded to each other. It has been found that the production efficiency of the plate-like product can be significantly increased without sacrificing the processing dimensional accuracy by making the laminate positively provided with voids.

The present invention completed on the basis of the above knowledge is a hard substrate laminate in which two or more hard substrates are bonded together with an adhesive in the first aspect, and the laminate is cut in the thickness direction. It is planned to obtain a desired number of divided hard substrate laminates, and an adhesive is continuously present between the hard substrates across all the processing lines at the time of cutting, and each hard substrate Between the layers, there is a laminate in which a void without an adhesive exists in at least one of the regions surrounded by the processing line.

In one embodiment of the hard substrate laminate according to the first aspect of the present invention, no adhesive is present in a region of 40% or more of the regions surrounded by the processing lines between the hard substrates. There are voids.

In one embodiment of the hard substrate laminate according to the first aspect of the present invention, no adhesive is present in 92% or more of the regions surrounded by the processing lines between the hard substrates. There are voids.

In the second aspect, the present invention is at least one hard substrate laminate that is divided after the laminate according to the invention is cut in the thickness direction along a processing line.

In one embodiment of the hard substrate laminate according to the second aspect of the present invention, the porosity is 5 to 99.5%.

In one embodiment of the hard substrate laminate according to the second aspect of the present invention, the porosity is 40 to 95%.

In one embodiment of the hard substrate laminate according to the second aspect of the present invention, the divided hard substrate laminate is scheduled to be further processed in shape, and the hard substrate in a portion to be removed by the shape processing There are no voids between them.

In one embodiment of the hard substrate laminate according to the first aspect of the present invention, the width dimension of the adhesive straddling the processing line from the processing line is 0.1 mm or more.

In one embodiment of the hard substrate laminate according to the first or second aspect of the present invention, the adhesive is curable.

In one embodiment of the hard substrate laminate according to the first or second aspect of the present invention, the adhesive comprises (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C ) Contains a polymerization initiator.

In one embodiment of the hard substrate laminate according to the first or second aspect of the present invention, (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, (C-1) photopolymerization Contains an initiator.

In one embodiment of the hard substrate laminate according to the first or second aspect of the present invention, the adhesive comprises (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, (C— 2) Contains a thermal polymerization initiator.

In one embodiment of the hard substrate laminate according to the first or second aspect of the present invention, the adhesive comprises (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, (C— 1) contains a photopolymerization initiator, and (C-2) a thermal polymerization initiator.

In one embodiment of the hard substrate laminate according to the first or second aspect of the present invention, the adhesive further contains (F) a decomposition accelerator.

The present invention, in the third aspect, is a method for producing a hard substrate laminate according to the first aspect of the present invention,
Step 1 of preparing a first hard substrate;
Step 2 for preparing a second hard substrate;
Step 3 of applying an adhesive to the bonding surface of the first hard substrate and / or the second hard substrate;
After contacting the first hard substrate and the second hard substrate at the respective one side edges, the step 4 of sequentially bonding the two hard substrates toward the side edges facing the one side edges;
Including
In step 3, the amount of adhesive applied is such that a gap is generated between the hard substrates after step 4, and the adhesive is a first parallel to the bonding direction along the processing line at the time of cutting. Forming a second application line perpendicular to the laminating direction with the application line, the first application line is continuous or discontinuous, and the second application line is discontinuous;
It is a manufacturing method.

In one embodiment of the manufacturing method according to the third aspect of the present invention, the first coating line is continuous.

In one embodiment of the manufacturing method according to the third aspect of the present invention, the second coating line and the first coating line are formed so as not to intersect.

In an embodiment of the manufacturing method according to the third aspect of the present invention, the hard substrate laminate is regarded as a first hard substrate, and Steps 1 to 4 are repeated at least once to obtain at least three hard substrates. A step of forming the bonded hard substrate laminate is performed.

In one embodiment of the manufacturing method according to the third aspect of the present invention, the adhesive is curable.

In one embodiment of the production method according to the third aspect of the present invention, the adhesive comprises (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C) a polymerization initiator. contains.

In one embodiment of the production method according to the third aspect of the present invention, the adhesive comprises (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, and (C-1) photopolymerization initiation. Step 4 includes irradiating light for curing the adhesive between the bonded hard substrates.

In one embodiment of the production method according to the third aspect of the present invention, the adhesive comprises (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, and (C-2) thermal polymerization initiation. Contains agents.

In one embodiment of the production method according to the third aspect of the present invention, the adhesive comprises (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, and (C-1) photopolymerization initiation. Step 4 includes irradiating light for curing the adhesive between the two hard substrates bonded together, and (C-2) a thermal polymerization initiator.

In one embodiment of the manufacturing method according to the third aspect of the present invention, the adhesive further contains (F) a decomposition accelerator.

In one embodiment of the manufacturing method according to the third aspect of the present invention, the bonding in step 4 is performed by a roll press.

In the fourth aspect of the present invention,
Cutting the hard substrate laminate according to the first aspect of the present invention in the thickness direction to obtain a desired number of divided hard substrate laminates; and
Step 6 of processing the divided hard substrate laminate to obtain a product-shaped hard substrate laminate,
Step 7 of peeling the product-shaped hard substrate laminate to obtain a plurality of plate products,
Is a method of manufacturing a plate-like product.

In one embodiment of the manufacturing method according to the fourth aspect of the present invention, the step 6 of obtaining the product-shaped hard substrate laminate by processing the divided hard substrate laminate includes shape processing.

According to the present invention, production efficiency can be increased without sacrificing processing dimensional accuracy in the production of glass substrates and the like. That is, in the present invention, the adhesive for bonding the hard substrates to each other exists only on a part of the main surface, so that the operation of separating the individual hard substrates from the laminate becomes easy, and the separation operation can be performed in a short time. On the other hand, since the adhesive is arranged in an appropriate pattern, the processing dimensional accuracy is not impaired. Furthermore, since the amount of the adhesive, which is a consumable agent, can be reduced, the processing cost can be reduced, and the time for cleaning the adhesive adhered to the surface of the hard substrate after the separation operation can be shortened. Thus, the present invention is extremely useful in industrially producing a large number of plate products.

It is a schematic diagram which shows an example of the large-sized hard board | substrate laminated body before a division | segmentation. It is a schematic diagram which shows an example of the cutting process line of a hard board | substrate laminated body. It is a schematic diagram which shows the mode of the spreading | diffusion of the adhesive agent after bonding large format hard board | substrates. It is a schematic diagram which shows an example of the application pattern of the adhesive agent which concerns on this invention. It is a schematic diagram which shows an example of the application pattern of the adhesive agent which concerns on a comparative example. It is a figure showing the planar view shape of the divided hard substrate laminated body after an external shape process.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Hereinafter, unless otherwise specified, the present invention will describe a case where a photocurable adhesive containing a (C-1) photopolymerization initiator is used.

<1. Rigid substrate laminate>
The hard substrate that can be used in the present invention is not particularly limited, but it needs to be translucent when a photocurable adhesive is used as an adhesive or for the purpose of protecting a display element. For example, plate glass (material plate glass, tempered plate glass, glass substrate with a transparent conductive film, glass substrate with electrodes and circuits formed thereon), sapphire substrate, quartz substrate, plastic substrate, magnesium fluoride substrate, etc. can be suitably used. is there. Moreover, even if it is a hard board | substrate which has translucency, the adhesive agent etc. whose main hardening forms are a thermosetting type and a moisture hardening type can be used. Examples of the thermosetting type include a two-component mixed type and a one-component type. In the present invention, the thermosetting adhesive includes those that cure at room temperature. A hard substrate that does not have translucency can also be used as the hard substrate. In this case, an adhesive whose main curing form is a thermosetting type or a moisture curing type can be used.

Not particularly limited to the size of the hard substrate before cutting large-sized, but typically have a ² degree of area 10000 ~ 250000mm, having a thickness of about 0.1 ~ 2 mm. Each hard substrate is generally the same size. Although not limited, the surface of each hard substrate can be provided with a predetermined printing pattern or plating pattern for performing one of the functions of the plate-like product. An example of the print pattern is a design of a display screen of a mobile phone, and an example of the plating pattern is a rotary encoder provided with a chrome plating pattern. Further, the substrate surface may be provided with one or more selected from the group consisting of a metal layer, a resin layer, a silica layer, an organosilicate layer, and a transparent electrode layer.

FIG. 1 shows a schematic diagram of an example of a large-sized hard substrate laminate before division. In the hard substrate laminate 10, two or more hard substrates 11 are bonded together with an adhesive. The laminate 10 is scheduled to be cut in the thickness direction along the dotted line 13 (cutting line) shown in FIG. 2 to obtain a desired number of divided hard substrate laminates 14. The “cutting line” as used in the present invention is a virtual line for convenience to indicate the location of the hard substrate laminate to be cut, and whether or not a line is actually drawn on the surface of the hard substrate laminate. Absent. Accordingly, it is possible to provide a “line” or “mark” for specifying a cutting position at the time of cutting, or not to provide it.

If the overall thickness of the large-sized hard substrate laminate 10 is too thin, the mechanical strength becomes weak, and it becomes easy to break when peeling the hard substrate laminate 10 fixed to the cradle with an adhesive for processing. Although it depends on the material of the hard substrate 11, preferably 5 or more (the total thickness of the substrate 11 is 0.52 mm or more), more preferably about 10 to 30 (the total thickness of the substrate 11 is 1.5). (About 66 mm) is laminated with an adhesive.

Referring to FIG. 3, the spread state of the adhesive 12 after the large-sized hard substrates 11 are bonded to each other is schematically shown here. The adhesive 12 is continuously present between the hard substrates 11 across all the processing lines 13 at the time of cutting, and the hard substrates 11 are bonded to at least one of the regions surrounded by the processing lines 13. There are voids 16 where no agent is present. Each area surrounded by cutting lines 13 on the four sides is an area that is processed into a plate-like product after division, and is provided with a print pattern 15.

Since the adhesive 12 exists continuously (or integrally) across all the processing lines 13 at the time of cutting, it becomes possible to prevent the hard substrate constituting the laminate from being separated at the time of cutting processing. Accuracy is improved. In addition, it prevents the processing liquid used for cutting and the etching liquid used for end face processing from entering the voids and causing the harmful effect that the main surface or part of the film formed on the main surface is corroded. Also plays a role. On the other hand, the presence of voids without adhesive reduces the peeling time, improves the work efficiency when separating each hard substrate from the laminate, reduces the amount of adhesive used, and further the separation operation There is an advantage that it contributes to shortening of the time for cleaning the adhesive adhered to the surface of the hard substrate later.

From the viewpoint of peelability, production efficiency and cost reduction, a larger number of voids is preferable. Specifically, it is preferable that voids without an adhesive exist in a region of 40% or more of the regions surrounded by the processing lines 13 between the hard substrates, and a number of 50% or more. More preferably, there are voids without adhesive in the region, more preferably voids without adhesive in the region of 80% or more, and presence of adhesive in the region of 92% or more. It is more preferable that voids that do not exist are present, and it is even more preferable that voids that do not have an adhesive exist in 100% of the number of regions. Taking FIG. 3 as an example, there are twelve regions surrounded by the cutting line 13, and if there are gaps in six or more of them, the condition of 50% or more is satisfied.

The degree of voids can also be evaluated using the void ratio defined by the following equation as an index. When the adhesive mass in the divided laminate after cutting is W _1, and the adhesive mass when assuming that the porosity of the divided laminate is 0% is W ₀ , the porosity (%) = It is represented by (1−W ₁ / W ₀ ) × 100. W ₁ can be calculated by subtracting the mass of the hard substrate from the mass of the laminate. W ₀ can be calculated from the thickness of each adhesive layer, the area of the hard substrate, and the specific gravity of the adhesive.

Since the porosity is preferably higher for the reasons described above, the porosity should be more than 0%, preferably 5% or more, more preferably 10% or more, and 40% or more. Is most preferred. However, if the porosity is too high, it is necessary to use a positively-controllable positive displacement application device when applying the adhesive, and in addition, it is necessary to use a member with a small nozzle diameter, and the adhesive itself In addition to increasing the cost of the apparatus, such as the need for temperature control equipment for strictly controlling the viscosity (and instability), tact is reduced. Therefore, it should be less than 100%, preferably 99.5% or less, more preferably 95% or less, still more preferably 90% or less, and 85% or less. Most preferred.

Refer to FIG. 3 again. Assuming that the width dimension of the adhesive straddling the processing line from the processing line is d, the larger d is, the higher the adhesive strength is, so that the dimensional accuracy at the time of cutting processing is improved, and the processing liquid and etching liquid Since the penetration preventing effect is also enhanced, d is preferably 0.1 mm or more, and more preferably 0.3 mm or more. The upper limit of d is not particularly limited as long as the porosity satisfies the above-described range.

<2. Manufacturing method of hard substrate laminate>
In one embodiment of the method for producing a hard substrate laminate according to the present invention,
Step 1 of preparing a first hard substrate;
Step 2 for preparing a second hard substrate;
Step 3 of applying an adhesive to the bonding surface of the first hard substrate and / or the second hard substrate;
After contacting the first hard substrate and the second hard substrate at the respective one side edges, the step 4 of sequentially bonding the two hard substrates toward the side edges facing the one side edges;
including.

By considering the hard substrate laminate as a first hard substrate and repeating steps 1 to 4 at least once, it is possible to form a hard substrate laminate in which at least three hard substrates are bonded together. . Any number of hard substrates can be stacked depending on the number of repetitions.

In manufacturing the hard substrate laminate according to the present invention, it is important to apply the adhesive in an appropriate pattern in Step 3. In step 3, the amount of adhesive applied is such that a gap is generated between the hard substrates after step 4, and the adhesive is a first parallel to the bonding direction along the processing line at the time of cutting. A second coating line orthogonal to the coating line and the bonding direction is formed.

The first coating line may be formed either continuously or discontinuously, but it is preferable that the first application line is continuous because the adhesive is easily continuous along the cutting line after bonding. In the case of a discontinuous application line, conditions occur in the application interval and amount, and if the conditions are not met, voids are generated on the processing line, whereas in the case of a continuous application line, discontinuity occurs when pasting. This means that it is not necessary to fill in a large part, that is, it can be continuous without depending on the interval or the amount. In addition, since the second coating line is discontinuous, there is an aspect in which both the first coating line and the second coating line become complicated if both are discontinuous.

As described above, the second coating line is formed discontinuously. This is to create a passage for air. If you only want to create an air escape path, it is possible to make the first application line discontinuous and make the second application line continuous, but force is applied in the direction of bonding, and air easily moves in the same direction. Therefore, by creating a laminar flow state as much as possible, the coating shape is easily stabilized, so that the second coating line is made discontinuous. In addition, it is preferable to prevent the second coating line from intersecting the first coating line because voids are less likely to occur on the cutting line. If a gap is generated on the cutting line, the dimensional accuracy at the time of the cutting process is adversely affected, such as the ingress of liquid used in the subsequent process and the positional shift due to the small adhesion area.

Note that the coating line may be formed on either the first hard substrate or the second hard substrate, or may be formed on both. The above-described coating line may be formed by partially coating each substrate. In short, it is only necessary that the adhesive spreads between the hard substrates so that a gap is generated at an appropriate position after bonding, and the above-mentioned coating pattern is an example and is not limited thereto.

FIG. 4 shows an example of a suitable application pattern of the adhesive. The vertical linear application line 17 is continuously formed on the cutting line 13, while the horizontal linear application line 18 is applied discontinuously so as not to intersect with the vertical application line 17. . The vertical linear coating line 17 is parallel to the bonding direction, and the horizontal linear coating line 18 is perpendicular to the bonding direction.

The thickness of the coating line is preferably 6.0 × 10 ⁻⁵ cm ² or more in terms of a cross-sectional area from the viewpoint of effectively preventing the generation of voids on the cut processing line, and 1.91 × 10 ^−3. More preferably, it is cm ² or more. The thickness of the coating line is preferably 11.9 × 10 ⁻³ cm ² or less in terms of cross-sectional area and 7.54 × 10 ⁻³ cm ² or less from the viewpoint of securing a sufficient gap. It is more preferable.

In step 4, the first hard substrate and the second hard substrate are brought into contact with each other at one end edge, and then both the hard substrates are sequentially bonded to the side edge facing the one side edge. For example, in FIG. 4, the first hard substrate and the second hard substrate are sequentially bonded together from the bottom to the top along the vertical coating line. Thereby, it is possible to provide a gap at an intended place and to prevent a gap from being generated at an unintended place. In addition, the adhesive spreads between the hard substrates by pressing at the time of bonding, the discontinuous second application line is connected to the first application line, and the entire adhesive as shown in FIG. 3 is connected. A continuous (or integrated) coating pattern is obtained. The bonding is preferably carried out by a roll press capable of extruding excess air existing between the layers of the hard substrate without depending on the size of the hard substrate.

In Step 4, when the vertical and horizontal application lines are crossed as shown in FIG. 5, it is easy to entrain air at the time of bonding, and voids are likely to be generated on the cutting line.

Examples of the adhesive include, but are not limited to, a moisture curable adhesive, a thermosetting adhesive, a photocurable adhesive, or a combination thereof. From the viewpoint of productivity and workability, a photo-curing adhesive is preferable. On the other hand, from the viewpoint of making the curing property of the interlayer adhesive between hard substrates as uniform as possible, the main reaction form is thermosetting adhesion. The use of an agent is preferred. Examples of the thermosetting adhesive include a two-component mixed adhesive and a one-component adhesive. When using a photocurable adhesive, it can be laminated by irradiating light for curing the adhesive spread between both substrates after the light-transmitting hard substrates are bonded together. . In order to suppress the movement of the adhesive sandwiched between the substrates, it is desirable to perform the light irradiation every time one transparent hard substrate is laminated.

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

The translucent hard substrate 11 is laminated, for example, by bonding the translucent hard substrates 11 each having a photocurable adhesive applied to one or both bonded surfaces in a predetermined pattern, and then transmitting both translucent substrates. It can be carried out by irradiating light for curing the adhesive spread between the conductive hard substrates 11. By repeating this a desired number of times, the light transmissive hard substrate laminate 10 in which the desired number of light transmissive hard substrates 11 are laminated can be produced. The light irradiation may be performed every time one light-transmitting hard substrate 11 is stacked, or may be performed collectively after stacking a plurality of sheets as long as light reaches the adhesive. At this time, if the light irradiation amount is too strong, the peelability and appearance of the translucent hard substrate laminate are likely to deteriorate over time, while if the light irradiation amount is too weak, the adhesive is not sufficiently cured. Furthermore, if the amount of light irradiation is too large, the cured adhesive layer may not be uniform and unevenness may occur. Due to such unevenness, the cutting fluid, abrasive slurry, and etchant used during cutting, cutting, grinding, and polishing enter between the substrates, causing the substrate to peel off or corrode the metal pattern or printing paint formed on the substrate. May occur. From these viewpoints, it is preferable that the amount of light irradiated for curing the adhesive every time the light-transmitting hard substrate is bonded is 10 to 10000 mJ / cm ^2, and 1000 to 6000 mJ / cm ^2. Is more preferably 10 to 3000 mJ / cm ² . The irradiation time is preferably 1 to 200 seconds, and more preferably 1 to 100 seconds.

Any known adhesive can be used as the curable adhesive, and is not particularly limited. For example, (A) a polyfunctional (meth) acrylate as described in WO2008 / 018252, WO2012 / 0667205, WO2013 / 039226, (B Adhesive compositions containing monofunctional (meth) acrylates and (C) polymerization initiators are preferred.

(A) As a polyfunctional (meth) acrylate, two or more (meth) acryloylated polyfunctional (meth) acrylate oligomer / polymer or two or more (meth) acryloyl groups at the oligomer / polymer terminal or side chain Polyfunctional (meth) acrylate monomers having can be used. For example, as the polyfunctional (meth) acrylate oligomer / polymer, 1,2-polybutadiene-terminated urethane (meth) acrylate (for example, “TE-2000”, “TEA-1000” manufactured by Nippon Soda Co., Ltd.), hydrogenated product thereof ( For example, “TEAI-1000” manufactured by Nippon Soda Co., Ltd.), 1,4-polybutadiene terminated urethane (meth) acrylate (eg “BAC-45” manufactured by Osaka Organic Chemical Co., Ltd.), polyisoprene terminated (meth) acrylate, polyester urethane (Meth) acrylate (for example, “UV-2000B”, “UV-3000B”, “UV-7000B” manufactured by Nippon Synthetic Chemical Co., Ltd. “KHP-11”, “KHP-17” manufactured by Negami Kogyo Co., Ltd.), polyether type Urethane (meth) acrylate (for example, “UV-3700B”, “UV- 6100B "), or bisphenol A type epoxy (meth) acrylate. Among these, polyester urethane (meth) acrylate is 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) (for example, , Urethane (meth) acrylate obtained by polyaddition reaction).

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 a polyhydric alcohol such as trimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polytetramethylene glycol, or a block or random copolymer of polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide Polyether polyol having one type of structure, a polycondensate of the polyhydric alcohol or polyether polyol and a polybasic acid such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, and isophthalic acid Polyester polyols, caprolactone-modified polyols such as caprolactone-modified polytetramethylene 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 diiso Polyisocyanates such as anate (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. Of these, hydrogenated xylylene diisocyanate (H-XDI) and / or isophorone diisocyanate (IPDI) are preferred.

Examples of the hydroxy (meth) acrylate (Z) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, 4-butylhydroxy (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, Caprolactone-modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate Over doors and the like. Among these, one or more members selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate are preferable.

The weight average molecular weight of the polyfunctional (meth) acrylate oligomer / polymer is preferably 7000 to 60000, more preferably 8000 to 40000, and most preferably 8500 to 30000. In the examples, the weight average molecular weight is determined by preparing a calibration curve with commercially available standard polystyrene using GPC system (SC-8010 manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent under the following conditions. It was.
Flow rate: 1.0 ml / min
Setting temperature: 40 ° C. Column configuration: “TSK guardcolumn MP (× L)” manufactured by Tosoh Corporation, 6.0 mm ID × 4.0 cm 1 and “TSK-GELMULTIPREHXL-M” manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm (theoretical plate number) 16,000 stages) 2 in total, 3 total (32,000 theoretical stages 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 tripropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol diester. (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) Acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxy Fe Le) 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 tetrafunctional or higher functional (meth) acrylate monomers include dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipenta Examples include erythritol hexa (meth) acrylate.

Among the polyfunctional (meth) acrylates, it is preferable to contain a polyfunctional (meth) acrylate oligomer / polymer and / or a bifunctional (meth) acrylate monomer in terms of high effect. It is more preferable to use a polymer and a bifunctional (meth) acrylate monomer in combination. When the polyfunctional (meth) acrylate oligomer / polymer and the bifunctional (meth) acrylate monomer are used in combination, the content ratio is 100 parts by mass in total of the polyfunctional (meth) acrylate oligomer / polymer and the bifunctional (meth) acrylate monomer. Multifunctional (meth) acrylate oligomer / polymer: bifunctional (meth) acrylate monomer = 10 to 90:90 to 10, preferably 25 to 75:75 to 25, more preferably 40 to 65:60 to 35 Is most preferred.

(A) The polyfunctional (meth) acrylate is preferably hydrophobic. Hydrophobic polyfunctional (meth) acrylate refers to (meth) acrylate having no hydroxyl group. In the case of water-solubility, the cured product of the composition swells at the time of cutting, so that the position shift occurs and the processing accuracy may be inferior. Even if it is hydrophilic, it may be used as long as the cured product of the composition is not greatly swollen or partially dissolved by water.

(B) Monofunctional (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate , Isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo Pentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydro Cypropyl (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) (meta Acrylate, phenol (ethylene oxide 4 mol modified) (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol (ethylene oxide 4 mol modified) (meth) acrylate, nonylphenol ( Ethylene oxide 8 mol modified) (meth) acrylate, nonylphenol (propylene oxide 2.5 mol modified) (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid ( (Meth) acrylate, trifluoroethyl (meth) acrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid, ω-carbo Si-polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, (meth) acrylic acid dimer, β- (meth) acryloyloxyethyl hydrogen succinate, n- (meth) acryloyloxyalkylhexa Examples include hydrophthalimide, 2- (1,2-cyclohexadicarboximido) ethyl (meth) acrylate, ethoxyethylene glycol di (meth) acrylate, and benzyl (meth) acrylate.

Among the monofunctional (meth) acrylates, one or more of the group consisting of the phenol alkylene oxide modified (meth) acrylate of the formula (1) and the imide (meth) acrylate of the formula (2) are effective. preferable. In formula (1), R ¹ is preferably hydrogen. R ² is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms.
The hydrogen of the alkylene group may be substituted with a hydroxyl group. m is preferably 1 to 3. In the formula (1), one or more members selected from the group consisting of 2-hydroxy-3-phenoxypropyl (meth) acrylate and phenol ethylene oxide 2 molar modified (meth) acrylate are preferable. In formula (2), R ⁴ is preferably hydrogen. R ⁵ is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms. n is preferably 1 to 3. Among the formulas (2), 2- (1,2-cyclohexadicarboximido) ethyl (meth) acrylate is preferable.

(R ¹ is hydrogen or an alkyl group. R ² is an alkylene group, and hydrogen in the alkylene group may be substituted with a hydroxyl group. R ³ is hydrogen or a methyl group. M is 1-6.)

(R ⁴ is hydrogen or an alkyl group. R ⁵ is an alkylene group, and hydrogen in the alkylene group may be substituted with a hydroxyl group. R ⁶ is hydrogen or a methyl group. N is 1 to 6.)

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

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

(B) Monofunctional (meth) acrylate is more preferably hydrophobic as in (A). Hydrophobic polyfunctional (meth) acrylate refers to (meth) acrylate having no hydroxyl group. In the case of water-solubility, the cured product of the composition swells at the time of cutting, so that the position shift occurs and the processing accuracy may be inferior. Even if it is hydrophilic, it may be used as long as the cured product of the composition is not swollen or partially dissolved by water.

The amount of (A) polyfunctional (meth) acrylate used is preferably 15 to 95 parts by mass, and preferably 20 to 50 parts by mass, out of 100 parts by mass of the total amount of (A) and (B). If it is 15 parts by mass or more, the property that the cured product is peeled off from the adherend when the cured product of the composition is immersed in warm water (hereinafter simply referred to as “peelability”) is sufficiently promoted. The cured product can be peeled into a film. If it is 95 mass parts or less, there is no possibility that initial adhesiveness will fall.

(C) The polymerization initiator is blended to accelerate the curing of the resin composition, and various known polymerization initiators can be used. Examples of the polymerization initiator include (C-1) photoradical polymerization initiator (hereinafter also referred to as photopolymerization initiator), (C-2) thermal radical polymerization initiator (hereinafter also referred to as thermal polymerization initiator), and the like. Is mentioned.

(C-1) The photopolymerization initiator is used for a photocurable adhesive, and is blended to accelerate photocuring of the resin composition by sensitizing with actinic light of visible light or ultraviolet light. Yes, various known photopolymerization initiators can be used. Specifically, benzophenone or a derivative thereof; benzyl or a derivative thereof; anthraquinone or a derivative thereof; benzoin; a benzoin derivative such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, or benzyl dimethyl ketal; diethoxyacetophenone, 4 Acetophenone derivatives such as t-butyltrichloroacetophenone; 2-dimethylaminoethyl benzoate; p-dimethylaminoethyl benzoate; diphenyl disulfide; thioxanthone or derivatives thereof; camphorquinone; 7,7-dimethyl-2,3-dioxobicyclo [ 2.2.1] Heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2 Bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2 2.1] Camphorquinone derivatives such as heptane-1-carboxylic acid chloride; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Α-aminoalkylphenone derivatives such as amino-1- (4-morpholinophenyl) -butanone-1; benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, 2, 4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2 Acylphosphine oxide derivatives such as 1,4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and / or oxy-phenyl -Acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester and the like. 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-1) The content of the photopolymerization initiator is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 25 parts by mass with respect to 100 parts by mass in total of (A) and (B). Most preferred is 1 to 20 parts by mass. 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 in 20 mass parts or less. The addition of 1 part by mass or more of component (C-1) makes it possible to cure without depending on the amount of light irradiation, further increases the degree of crosslinking of the cured product of the composition, and does not cause misalignment during cutting, It is further preferable in terms of improving peelability.

(C-2) The thermal polymerization initiator is used for a thermosetting adhesive, and is blended in order to promote thermal curing of the resin composition by heat. Various known thermal polymerization initiators are used. It can be used. When the (C-2) thermal polymerization initiator is used, curability can be reliably obtained when it is used for laminating the hard substrate 11 having no translucency.

(C-2) Among the thermal polymerization initiators, organic peroxides are preferable. (C-2) Organic peroxides include diacyl peroxides such as lauroyl peroxide and benzoyl peroxide, t-butylperoxy-3,5,5-trimethylhexanoate, cumylperoxyneodecanoate Hexyl peroxybivalate, t-butyl peroxyisobutyrate, t-butyl peroxybivalate, t-butyl peroxyacetate, t-butyl peroxybenzoate, tertiary butyl peroxy-2-ethylhexanate, etc. Alkyl peroxyesters, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, dinormalpropyl peroxydicarbonate, bis (4-tertiarybutylcyclohexyl) peroxydicarbonate, di-2- Peroxydicarbonates such as toxiethylperoxydicarbonate, dimethoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate and diallylperoxydicarbonate, t-butylperoxyisopropylcarbonate Peroxycarbonates such as di-t-butylperoxycyclohexane and di- (t-butylperoxy) butane, dicumyl peroxide, t-butylcumyl peroxide, di-t Dialkyl peroxides such as butyl peroxide, hydroperoxides such as cumene hydroperoxide and tetramethylbutyl hydroperoxide, and ketone peroxides such as cyclohexanone peroxide And the like. Among these, alkyl peroxyesters and / or hydroperoxides are preferable, hydroperoxides are more preferable, and cumene hydroperoxide is most preferable.

(C-2) The amount of the thermal polymerization initiator used is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of (A) and (B). Preferably, 1 to 3 parts by mass is most preferable. If it is 0.01 mass part or more, sclerosis | hardenability will be obtained reliably, and if it is 10 mass parts or less, sufficient storage stability will be obtained and skin irritation will become low.

The curable adhesive preferably contains a particulate substance (D) that does not dissolve in the components (A), (B), and (C) of the adhesive. Thereby, since the composition after hardening can hold | maintain fixed thickness, a process precision improves as mentioned later.

As the material of the particulate material (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. Inorganic particles include ceramic particles such as glass, silica, alumina, and titanium. Among these, organic particles are preferable, and crosslinked polystyrene particles are more preferable.

The granular material is preferably spherical from the viewpoint of improving processing accuracy, that is, controlling the thickness of the adhesive layer 12. The average particle diameter of the granular material by the laser method is preferably in the range of 50 to 200 μm. If the average particle size of the granular material is less than 50 μm, the cutting tool tip having poor strength is used in the cutting tool, so that the life of the cutting tool is reduced, and further, the cutting efficiency may be reduced. If it exceeds 1, the amount of adhesive used will increase and the cost will be high, which may result in poor productivity. A more preferable average particle diameter (D50) is 70 to 150 μm, and further preferably 80 to 120 μm. The particle size distribution is measured by a laser diffraction type particle size distribution measuring device.

The amount of the granular material (D) used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B), from the viewpoint of adhesiveness, processing accuracy, and peelability. 2 to 10 parts by mass is more preferable, and 0.2 to 6 parts by mass is most preferable.

A polymerization inhibitor (E) can be added to the curable adhesive to improve storage stability. Polymerization inhibitors include methyl hydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol), catechol, hydroquinone monomethyl ether, monotertiary butyl hydroquinone, 2,5-ditertiary butyl hydroquinone. P-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butylcatechol, 2-butyl-4-hydroxyanisole and 2 , 6-ditertiary butyl-p-cresol and the like.

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

(C-2) When a thermal polymerization initiator is used, (F) a decomposition accelerator may be contained. Thereby, sclerosis | hardenability is reliably acquired also at normal temperature.
(F) The decomposition accelerator is preferably a decomposition accelerator that accelerates the decomposition of the organic peroxide. (F) The following is mentioned as a decomposition accelerator which accelerates | stimulates decomposition | disassembly of an organic peroxide.

When using organic peroxides such as hydroperoxides and ketone peroxides, examples of the decomposition accelerator include organic acid metal salts and organic metal chelates. Examples of organic acid metal salts and organic metal chelates include cobalt naphthenate, copper naphthenate, manganese naphthenate, cobalt octenoate, copper octenoate, manganese octenoate, cobalt octylate, copper acetylacetonate, and titanium acetylacetonate. Manganese acetylacetonate, chromium acetylacetonate, iron acetylacetonate, vanadyl acetylacetonate, cobalt acetylacetonate and the like. Among these, cobalt octylate and / or vanadyl acetylacetonate are preferable, and cobalt octylate is most preferable. Other decomposition accelerators include thiourea derivatives, mercaptobenzimidazoles, amines and the like. These (F) decomposition accelerators can use 1 type (s) or 2 or more types.

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

(C-2) A curable adhesive containing a thermal polymerization initiator and (F) a decomposition accelerator is typically provided as a two-component composition. For the two-component type, it is preferable that all the essential components of the curable adhesive are not mixed during storage, and the curable adhesive is stored separately in the first agent and the second agent. In this case, it can be used as a two-part curable adhesive by applying both agents simultaneously or separately to a member and contacting and curing. When used as a two-component curable adhesive, it is preferable that the first agent contains at least (C-2) a thermal polymerization initiator and the second agent contains at least (F) a decomposition accelerator. In the present invention, the composition can be cured only by mixing two components without heating.

In the present invention, (C-1) a photopolymerization initiator, (C-2) a thermal polymerization initiator, and (F) a decomposition accelerator may be used in combination. Thereby, even if the printing pattern which does not permeate | transmit light is given to the translucent hard board | substrate from the point of the designability, sclerosis | hardenability is obtained reliably. When (C-1) a photopolymerization initiator, (C-2) a thermal polymerization initiator, and (F) a decomposition accelerator are used in combination, (C-1) the photopolymerization initiator includes the first agent and the second agent. It may be contained in either one or both.

<3. Manufacturing method of plate products>
A plate-like product can be produced from the hard substrate laminate according to the present invention. In one embodiment of the plate-shaped product manufacturing method according to the present invention, the hard substrate laminate is cut in the thickness direction to obtain a desired number of divided hard substrate laminates, and the divided hard substrates. The process 6 includes a step 6 of obtaining a product-shaped hard substrate laminate by processing the laminate, and a step 7 of peeling the product-shaped hard substrate laminate to obtain a plurality of plate-like products.

First, in step 5, the hard substrate laminate is divided in the thickness direction to form a desired number of divided hard substrate laminates. The dividing method is not particularly limited, but a disk cutter (diamond disc, cemented carbide disc), fixed abrasive type or loose abrasive type wire saw, laser beam, etching (eg, chemical etching using hydrofluoric acid, sulfuric acid, etc.) And electrolytic etching), water jet, and electrotrophic (nichrome wire) may be used alone or in combination to divide 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 6, desired shape processing is performed on each of the divided hard substrate laminates. This process has an advantage that the production rate of the plate-like product can be significantly increased because the processing can be performed integrally with the shape of the target plate-like product for each of the divided hard substrate laminates. 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 Water jets can also be used. The processing methods can be used alone or in combination. Etching can also be used for surface treatment after shape processing.

If there is a gap that does not have an adhesive between the hard substrates in the area to be removed by the shape processing, it means fouling damage due to the intrusion of the processing liquid, or chipping and cracking due to changes in the stress applied to the hard substrate laminate during processing. Bad effects occur. Therefore, it is preferable that no gap exists between the hard substrates in the region to be removed by the shape processing.

Furthermore, in step 7, the hard substrates laminated after the shape processing are heated to separate the hard substrates that have been bonded together to form a plurality of plate-like products. Although there is no restriction | limiting in particular as a heating method, Since the fixing agent softens to film shape and isolate | separates into each plate-shaped product well, the method of immersing the translucent hard board | substrate laminated body after shape processing in water is preferable. The suitable water temperature varies depending on the adhesive employed, but is preferably 40 ° C. or higher, more preferably 60 to 95 ° C., and most preferably 80 to 90 ° C.

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

In order to better understand the present invention and its advantages, the following experimental examples are provided.

(Experimental example 1)
1. Preparation of photocurable adhesive 1 Photocurable adhesive 1 was prepared by mixing the following components (A) to (E).
(A) As a polyfunctional (meth) acrylate, “UV-3000B” (urethane acrylate, weight average molecular weight 18000, manufactured by Nihon Gosei Co., Ltd., polyol compound is polyester polyol, organic polyisocyanate compound is isophorone diisocyanate, hydroxy (meth) acrylate is 2 -Hydroxyethyl acrylate) 15 parts by mass, dicyclopentanyl diacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd.), 15 parts by mass,
(B) As monofunctional (meth) acrylate, 45 parts by mass of 2- (1,2-cyclohexadicarboximido) ethyl acrylate (“Aronix M-140” manufactured by Toa Gosei Co., Ltd.), phenol ethylene oxide 2 mol modified acrylate (Toa 25 parts by mass of “Aronix M-101A” manufactured by Gosei Co., Ltd.
(C-1) 10 parts by mass of benzyldimethyl ketal (“IRGACURE651” manufactured by BASF) as a photopolymerization initiator,
(D) 1 part by weight of spherical crosslinked polystyrene particles having an average particle diameter (D50) of 100 μm (“GS-100S” manufactured by Ganz Kasei Co., Ltd.)
(E) 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S” manufactured by Sumitomo Chemical Co., Ltd.) as a polymerization inhibitor

2. Production of Plate Glass Laminate Twelve plate glasses (horizontal 530 mm × vertical 420 mm × thickness 0.7 mm) were prepared as translucent hard substrates. Metal wiring, ITO film, organic resin film, and organosilicate film are formed on the surface of each plate glass. On the 1st sheet glass, the said photocurable adhesive agent was apply | coated predetermined weight in the horizontal direction and the vertical direction along the cutting process line. Here, the mark which shows a cutting location was provided in the margin part of plate glass, and the cutting process line was specified based on this.
The application pattern was the pattern shown in FIG. 4 or 5 depending on the test number. In FIG. 4, the vertical linear application lines are continuously formed on the cutting line, while the horizontal linear application lines are applied discontinuously so as not to intersect the vertical application lines. In FIG. 5, both the vertical and horizontal application lines were continuously formed on the cutting line. As a result, intersections occurred in the vertical and horizontal coating lines. Moreover, the porosity between plate glass was changed by changing the thickness (cross-sectional area) of an application line for every test piece. For the cross-sectional area of the coating line, an average value was calculated from the coating amount and line length of the adhesive.

Next, after overlapping one side edge of the long side of the second sheet glass on one side edge of the long side of the first sheet glass, the second sheet glass is used as the first sheet glass with this as an axis. While tilting down, they were bonded together in the roll press format toward the opposite side edges so as to push out excess air. Then, UV irradiation was carried out from the surface side of the 2nd sheet glass, and the said photocurable adhesive agent was hardened. The light irradiation amount was 500 mJ / cm ² (measured by an integrating illuminometer with a 365 nm light receiver), and the UV irradiation time was 10 seconds. After each bonding step, the ratio of the number of regions with voids was visually confirmed with respect to the total number of regions surrounded by the cutting line, and the average ratio of the entire laminate was calculated.
By repeating this procedure, plate glass laminates having various void ratios of 12 mm and having a thickness of 8 mm (this thickness is a thickness of a laminate obtained by adding 12 plate glasses) were produced.

3. Next, after fixing the plate glass laminated body to the cradle, it cut | disconnected in the thickness direction along the predetermined cutting process line with the disc cutter, and produced the laminated body of the plate glass divided | segmented. At this time, each plate glass is divided into 24 plate glass laminates each having a size of 100 mm in length, 50 mm in width, and 0.7 mm in thickness (this thickness is the thickness of one sheet glass), except for the edge material at the periphery. It was.

4). Next, the outer shape is processed into a shape as shown in FIG. 6 in a plan view by a method of grinding the end face by applying a rotating grindstone so as to face the cut end faces of each of the divided laminates. Was given.

5. End face processing of sheet glass laminated body Next, the sheet glass laminated body after the outer shape processing was immersed in an etching tank for etching. The etching solution in the etching tank was hydrofluoric acid having a concentration of 15% by mass, and etching was performed for 10 minutes while controlling the solution temperature at 25 ° C.

6). Evaluation of Plate Glass Laminate The following evaluation was performed on the plate glass laminate.
(1) Porosity: In the hard substrate laminate prepared so as to generate a void by controlling the coating amount, the adhesive mass of the divided laminate after cutting is set to W ₁ , and the divided laminate When the mass of the adhesive when the porosity is assumed to be 0% is W ₀ , the porosity (%) = (1−W ₁ / W ₀ ) × 100. W ₁ can be calculated by subtracting the mass of the plate glass from the mass of the laminate. W ₀ can be calculated from the thickness of each adhesive layer, the area of the plate glass, and the specific gravity of the adhesive.
(2) Peeling time: The laminate after cutting was immersed in warm water heated to 90 ° C., and the average time until each of the 12 laminated glass plates was separated into individual glass sheets was observed. .
(3) Gap shape: whether or not a gap is formed inside the cutting line in the large-sized state where an adhesive is applied and bonded, and whether or not this gap part exists on the cutting line. evaluated. Moreover, the range of the width dimension from the cutting process line of the adhesive after hardening existing between plate glasses was measured.
(4) Process dimensional accuracy: In the cutting process, whether or not the adhesive strength of the bonded adhesive could be maintained was evaluated by whether or not the adhesive layer and the substrate interface were peeled from the laminate during the process. Whether or not it was peeled off was judged by visual observation based on whether or not the working fluid entered the interface. ○ If the machining fluid did not enter at all during cutting, ○, although there is some liquid ingress during cutting, the degree of penetration is very slight, and it is configured on the board so that it does not cause functional problems in appearance. In the case where no abnormalities such as defects were observed in the film to be obtained, Δ, and invasion was observed, the film was damaged, and in the case where defects in appearance and functions were observed, it was marked as x.
(5) Intrusion of machining fluid: Is the cutting fluid used during cutting and outline machining invaded into the gap inside the machining line, or whether the machining liquid has penetrated from the gap on the machining line toward the main surface of the hard substrate? The presence or absence of contamination of the substrate surface caused by intrusion was visually evaluated.
(6) Etching solution intrusion: After end face processing, the etching solution enters the gap inside the cutting line from the interface between the adhesive and the hard substrate, or the etching solution penetrates from the gap on the processing line toward the main surface of the hard substrate It was visually evaluated whether or not. The case where the etchant did not enter was ○, and there was a part of the solution, but the etchant was infiltrated very little, and there were no defects such as defects in the film formed on the substrate. The case was Δ, and the case where penetration was observed and the film was lost was marked as x. In addition, it is visually evaluated whether a part or all of the main surface of the substrate is etched with the gap on the processing line as a base point, ○ if there is no liquid ingress, and x if it is etched by liquid ingress. .
The evaluation results are shown in Table 1.

(Experimental example 2)
1. Preparation of Photocurable Adhesive 2 Photocurable adhesive 2 was prepared by mixing the following components (A) to (E).
(A) As a polyfunctional (meth) acrylate, “UV-3000B” (urethane acrylate, weight average molecular weight 18000, manufactured by Nihon Gosei Co., Ltd., polyol compound is polyester polyol, organic polyisocyanate compound is isophorone diisocyanate, hydroxy (meth) acrylate is 2 -Hydroxyethyl acrylate) 20 parts by mass, dicyclopentanyl diacrylate (Nippon Kayaku Co., Ltd. "KAYARAD R-684") 25 parts by mass,
(B) As monofunctional (meth) acrylate, 35 parts by mass of 2-hydroxy-3-phenoxypropyl acrylate (“Aronix M-5700” manufactured by Toa Gosei Co., Ltd.), 2 mol modified phenol ethylene oxide (“Aronix” manufactured by Toa Gosei Co., Ltd.) M-101A ") 20 parts by mass,
(C-1) 10 parts by mass of benzyldimethyl ketal (“IRGACURE651” manufactured by BASF) as a photopolymerization initiator,
(D) 1 part by weight of spherical crosslinked polystyrene particles having an average particle size of 100 μm (“GS-100S” manufactured by Ganz Kasei Co., Ltd.)
(E) 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S” manufactured by Sumitomo Chemical Co., Ltd.) as a polymerization inhibitor

Using the curable adhesive 2, production of a plate glass laminate, cutting processing of the plate glass laminate, outer shape processing and end face processing were performed in the same manner as in Experimental Example 1. In addition, the same evaluation as in Experimental Example 1 was performed. The evaluation results are shown in Table 2.

(Experimental example 3)
1. Preparation of Photocurable Adhesive 3 The following components (A) to (F) were mixed to prepare a photocurable adhesive 3.
<First Agent> (A) As a polyfunctional (meth) acrylate, “UV-3000B” manufactured by Nippon Gosei Co., Ltd. (urethane acrylate, weight average molecular weight 18000, polyol compound is polyester polyol, organic polyisocyanate compound is isophorone diisocyanate, hydroxy ( (Meth) acrylate is 2-hydroxyethyl acrylate) 15 parts by mass, dicyclopentanyl diacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd., hereinafter abbreviated as “R-684”),
(B) As monofunctional (meth) acrylate, 45 parts by mass of 2- (1,2-cyclohexadicarboximido) ethyl acrylate (“Aronix M-140” manufactured by Toa Gosei Co., Ltd.), phenol ethylene oxide 2 mol modified acrylate (Toa 25 parts by mass of “Aronix M-101A” manufactured by Gosei Co., Ltd.
(C-1) 25 parts by mass of benzyldimethyl ketal (“IRGACURE651” manufactured by BASF) as a photopolymerization initiator,
(D) 1 part by weight of spherical crosslinked polystyrene particles having an average particle size of 100 μm (“GS-100S” manufactured by Ganz Kasei Co., Ltd.)
(E) 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S” manufactured by Sumitomo Chemical Co., Ltd.) as a polymerization inhibitor;
(C-2) 2 parts by weight of cumene hydroperoxide (Nippon Yushi Co., Ltd. “Park Mill H”) as an organic peroxide <Second Agent> (A) As a polyfunctional (meth) acrylate, “UV- 3000B "(urethane acrylate, weight average molecular weight 18000, polyol compound is polyester polyol, organic polyisocyanate compound is isophorone diisocyanate, hydroxy (meth) acrylate is 2-hydroxyethyl acrylate), 15 parts by mass, dicyclopentanyl diacrylate (Nipponization) 15 parts by mass of “KAYARAD R-684” manufactured by Yakuhin Co., Ltd.
(B) As monofunctional (meth) acrylate, 45 parts by mass of 2- (1,2-cyclohexacarboximide) ethyl acrylate (“Aronix M-140” manufactured by Toa Gosei Co., Ltd.), 2 mol of phenol ethylene oxide modified acrylate (Toa 25 parts by mass of “Aronix M-101A” manufactured by Gosei Co., Ltd.
(C-1) 25 parts by mass of benzyldimethyl ketal (“IRGACURE651” manufactured by BASF) as a photopolymerization initiator,
(D) 1 part by weight of spherical crosslinked polystyrene particles having an average particle size of 100 μm (“GS-100S” manufactured by Ganz Kasei Co., Ltd.)
(E) 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S” manufactured by Sumitomo Chemical Co., Ltd.) as a polymerization inhibitor;
(F) 2 parts by mass of cobalt octylate (“Cobalt octylate” manufactured by Shinto Paint Co., Ltd.) as a decomposition accelerator

2. Production of plate glass laminate A plate glass laminate was produced in the same manner as in Experimental Example 1 using the photocurable adhesive 3. As the photocurable adhesive 3, an equal amount of the first agent and the second agent were weighed and mixed.

The cutting processing of the plate glass laminate, the outer shape processing and the end face processing of the plate glass laminate were performed in the same manner as in Experimental Example 1. In addition, the same evaluation as in Experimental Example 1 was performed. The evaluation results are shown in Table 3.

(Experimental example 4)
1. Preparation of thermosetting adhesive 4 The following components (A) to (F) were mixed to prepare a thermosetting adhesive 4.
<First Agent> (A) As a polyfunctional (meth) acrylate, “UV-3000B” manufactured by Nippon Gosei Co., Ltd. (urethane acrylate, weight average molecular weight 18000, polyol compound is polyester polyol, organic polyisocyanate compound is isophorone diisocyanate, hydroxy ( (Meth) acrylate is 20 parts by mass of 2-hydroxyethyl acrylate), 30 parts by mass of tripropylene glycol diacrylate (NK ester APG-200, hereinafter referred to as “APG-200” manufactured by Shin-Nakamura Chemical Co., Ltd.),
(B) As monofunctional (meth) acrylate, 2- (1,2-cyclohexadicarboximide) ethyl acrylate (“Aronix M-140” manufactured by Toa Gosei Co., Ltd.), 40 parts by mass, phenol ethylene oxide 2 mol modified acrylate (Toa 10 parts by mass of “Aronix M-101A” manufactured by Gosei Co., Ltd.
(C-2) 3 parts by weight of cumene hydroperoxide (Nippon Yushi Co., Ltd. “Park Mill H”) as an organic peroxide,
(D) Cross-linked polymethyl methacrylate particles having an average particle size of 35 μm (Negami Kogyo Art Pearl GR-200, spherical, hereinafter abbreviated as “GR-200”) 0.6 parts by mass;
<Second Agent> (A) As a polyfunctional (meth) acrylate, “UV-3000B” manufactured by Nippon Gosei Co., Ltd. (urethane acrylate, weight average molecular weight 18000, polyol compound is polyester polyol, organic polyisocyanate compound is isophorone diisocyanate, hydroxy ( (Meth) acrylate is 20 parts by mass of 2-hydroxyethyl acrylate), 30 parts by mass of tripropylene glycol diacrylate (NK ester APG-200, hereinafter referred to as “APG-200” manufactured by Shin-Nakamura Chemical Co., Ltd.),
(B) As monofunctional (meth) acrylate, 2- (1,2-cyclohexacarboximide) ethyl acrylate (“Aronix M-140” manufactured by Toa Gosei Co., Ltd.), 40 parts by mass of phenol ethylene oxide 2 mol modified acrylate (Toa 10 parts by mass of “Aronix M-101A” manufactured by Gosei Co., Ltd.
(D) Cross-linked polymethyl methacrylate particles having an average particle size of 35 μm (Negami Kogyo Art Pearl GR-200, spherical, hereinafter abbreviated as “GR-200”) 0.6 parts by mass;
(E) 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S” manufactured by Sumitomo Chemical Co., Ltd.) as a polymerization inhibitor;
(F) 3 parts by mass of cobalt octylate (“Cobalt octylate” manufactured by Shinto Paint Co., Ltd.) as a decomposition accelerator

2. Production of Plate Glass Laminate A plate glass laminate was produced in the same manner as in Experimental Example 1 using the thermosetting adhesive 4. The thermosetting adhesive 4 was prepared by weighing and mixing the first agent and the second agent in equal amounts.

However, after overlapping one side edge of the long side of the second sheet glass on one side edge of the long side of the first sheet glass, the second sheet glass is used as the first sheet glass with this as an axis. While tilting down, they were bonded together in the roll press format toward the opposite side edges so as to push out excess air. By repeating this procedure, plate glass laminates having various porosity ratios of 12 mm and a thickness of 8 mm (this thickness is a thickness of a laminate obtained by adding 12 plate glasses) were produced. After laminating 12 sheets, the plate glass laminate was produced by allowing it to stand at room temperature for 30 minutes to ensure the curing of the adhesive and to fix it to the cradle.

The cutting processing of the plate glass laminate, the outer shape processing and the end face processing of the plate glass laminate were performed in the same manner as in Experimental Example 1. In addition, the same evaluation as in Experimental Example 1 was performed. The evaluation results are shown in Table 4.

(Discussion)
About the plate glass laminated body which concerns on an Example, the vertical application line was formed linearly and continuously at the time of adhesive agent application | coating, and it was not made to cross | intersect with the horizontal application line. Even at the time of bonding, the sheets were bonded from one side edge of the plate glass toward the opposite side edge along the continuous coating line direction so as to push out excess air. For this reason, there is a void that does not form an adhesive layer, and the adhesive layer is formed so as to surround the void. The machining dimensional accuracy was good, and there was no penetration of machining liquid or etching liquid. The stripping time was shortened as the porosity increased. The porosity is preferably 5% or more, and more preferably 10% or more. The porosity is preferably 99.5% or less, more preferably 95% or less, and most preferably 85% or less.
On the other hand, since the hard substrate laminate according to the comparative example was a continuous application line (that is, a lattice shape) in which the adhesive application pattern was orthogonal, it was involved at the time of bonding regardless of the application amount or the adhesive type. The air filled in the cut surface and the like was pushed out by the air, and voids were generated on the cut line. In addition, when the coating amount is small and the porosity is high, it is not possible to obtain a sufficient area to cover the cutting line with the adhesive. Almost the entire surface of the laminate was covered with the adhesive.

DESCRIPTION OF SYMBOLS 10 Hard board | substrate laminated body 11 before a division | segmentation Hard board | substrate 12 Adhesive 13 Dividing process line 14 Divided hard board | substrate laminated body 15 Print pattern 16 Space | gap 17 Vertical coating line 18 Horizontal coating line 20 Hard substrate laminate d Width dimension from cutting line of adhesive

Claims (27)

1. It is a hard substrate laminate in which two or more hard substrates are bonded together with an adhesive, and the laminate is scheduled to be cut in the thickness direction to obtain a desired number of divided hard substrate laminates. The adhesive is continuously present between the hard substrates across all the processing lines at the time of cutting, and the hard substrates are bonded to at least one of the regions surrounded by the processing lines. A laminate in which there are voids where no agent is present.
2. 2. The laminate according to claim 1, wherein voids in which no adhesive is present exist in a region of 40% or more of the regions surrounded by the processing lines between the hard substrates.
3. 2. The laminate according to claim 1, wherein voids in which no adhesive is present exist in 92% or more of the regions surrounded by the processing lines between the hard substrates.
4. 4. At least one hard substrate laminate that is divided after the laminate according to any one of claims 1 to 3 is cut in a thickness direction along a processing line.
5. The laminate according to claim 4, wherein the porosity is 5 to 99.5%.
6. The laminate according to claim 4, wherein the porosity is 40 to 95%.
7. The divided hard substrate laminate is scheduled to be further processed in shape, and no gap exists between the hard substrates in a portion to be removed by the shape processing. Laminated body.
8. The laminate according to any one of claims 1 to 3, wherein a width dimension of the adhesive straddling the processing line from the processing line is 0.1 mm or more.
9. The laminate according to any one of claims 1 to 8, wherein the adhesive is curable.
10. The laminate according to claim 9, wherein the adhesive contains (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, and (C) a polymerization initiator.
11. The laminate according to claim 9, wherein the adhesive contains (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C-1) a photopolymerization initiator.
12. The laminate according to claim 9, wherein the adhesive contains (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C-2) a thermal polymerization initiator.
13. The adhesive contains (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, (C-1) photopolymerization initiator, and (C-2) thermal polymerization initiator. The laminated body as described in.
14. The laminate according to claim 12 or 13, wherein the adhesive further contains (F) a decomposition accelerator.
15. A method for producing a laminate according to any one of claims 1 to 3 and 8 to 14,
    Step 1 of preparing a first hard substrate;
    Step 2 for preparing a second hard substrate;
    Step 3 of applying an adhesive to the bonding surface of the first hard substrate and / or the second hard substrate;
    After contacting the first hard substrate and the second hard substrate at the respective one side edges, the step 4 of sequentially bonding the two hard substrates toward the side edges facing the one side edges;
    Including
    In step 3, the amount of adhesive applied is such that a gap is generated between the hard substrates after step 4, and the adhesive is a first parallel to the bonding direction along the processing line at the time of cutting. Forming a second application line perpendicular to the laminating direction with the application line, the first application line is continuous or discontinuous, and the second application line is discontinuous;
    Production method.
16. The manufacturing method according to claim 15, wherein the first coating line is continuous.
17. The manufacturing method according to claim 15 or 16, wherein the second coating line and the first coating line are formed so as not to intersect.
18. The steps 1 to 4 are repeated at least once while the hard substrate laminate is regarded as a first hard substrate, and a step of forming a hard substrate laminate in which at least three hard substrates are bonded is performed. The manufacturing method according to any one of 17.
19. The production method according to any one of claims 15 to 18, wherein the adhesive is curable.
20. The production method according to claim 19, wherein the adhesive contains (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C) a polymerization initiator.
21. The adhesive contains (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C-1) a photopolymerization initiator, and step 4 is an adhesion between the two hard substrates bonded together. The manufacturing method of Claim 19 including irradiating the light for hardening an agent.
22. The production method according to claim 19, wherein the adhesive contains (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C-2) a thermal polymerization initiator.
23. The adhesive contains (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, (C-1) photopolymerization initiator, and (C-2) thermal polymerization initiator, and Step 4 21. The manufacturing method according to claim 19, comprising irradiating light for curing the adhesive between the two hard substrates bonded together.
24. The manufacturing method according to claim 22 or 23, wherein the adhesive further contains (F) a decomposition accelerator.
25. The manufacturing method according to any one of claims 15 to 24, wherein the bonding in the step 4 is performed by a roll press.
26. Cutting the hard substrate laminate according to any one of claims 1 to 3 and 8 to 14 in a thickness direction to obtain a desired number of divided hard substrate laminates;
    Step 6 of processing the divided hard substrate laminate to obtain a product-shaped hard substrate laminate,
    Step 7 of peeling the product-shaped hard substrate laminate to obtain a plurality of plate products,
    A method for producing a plate-like product including
27. 27. The manufacturing method according to claim 26, wherein the step 6 of obtaining the product-shaped hard substrate laminate by processing the divided hard substrate laminate includes shape processing.

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