JP6485363B2 - Transparent resin laminate and front plate - Google Patents

Description

  The present invention provides a transparent resin laminate having a high light transmittance in a wide wavelength range such that the total light transmittance is 80% or more, the light transmittance at 550 nm is 80% or more, and the light transmittance at 400 nm is 60% or more. About.

  BACKGROUND ART Transparent resin films or sheets represented by polymethyl methacrylate (PMMA), polycarbonate (PC), and polyethylene terephthalate (PET) are widely used as optical materials for electrical and electronic devices such as liquid crystal displays and mobile phones. In recent years, the front panel (front plate) of portable display devices such as mobile phone terminals, portable electronic play equipment, and personal digital assistants (PDAs) has transparency and visibility, weather resistance that can be used outdoors, and finger There are demands for characteristics such as scratch resistance for preventing damage when contacting and carrying, and impact resistance and rigidity for preventing damage due to impact and load.

  Due to these problems, there are many cases where chemically tempered glass is used for the front plate of liquid crystal displays, etc., but instead of glass due to problems such as workability, difficulty of handling, cost, high specific gravity, and easy cracking. There is a strong demand for resin films or sheets having characteristics such as high rigidity and dimensional stability.

  Candidates for front plate materials for display devices include films and sheets composed of polymethyl methacrylate (PMMA) and polycarbonate (PC), and polyester films in which fine particles as fillers are uniformly dispersed in polyester (Patent Document 1). ), A laminate (Patent Document 2) in which an acrylic resin layer (PMMA layer) is provided on at least one surface of a polycarbonate resin layer (PC layer), and a silicone resin molded article obtained by radical copolymerization of a silicone resin composition ( Patent Document 3), a laminate (Patent Document 4) in which a biaxially stretched PET film is bonded to a PC have been proposed.

JP 2003-26826 A Japanese Patent Laid-Open No. 11-58627 JP 2006-89685 A JP 2012-183822 A

  However, with the materials described above, it has been difficult to achieve both transparency and rigidity required for the front plate material of the display device. In particular, as a portable display device is increased in size, a resin member having higher rigidity is required as a resin member that can be used for a front plate.

  For example, polymethyl methacrylate (PMMA) has a low glass transition temperature and is prone to cracking, so that it is inferior in workability. Polycarbonate (PC) has a glass transition temperature as good as about 145 ° C., but its surface hardness and rigidity are inferior, making it difficult to employ as a front panel for a display or the like. As for polyethylene terephthalate (PET), the biaxially stretched one has a softening temperature of 200 ° C. or higher and a good surface hardness, but it is difficult to increase the plate thickness, and it is difficult to cope with thick film applications (Patent Document 1). ). Research on a laminate having a PMMA layer and a PC layer has also been made (Patent Document 2), and some of them have been used, but have problems such as workability problems due to warpage during heat treatment and lack of rigidity. Yes.

  Moreover, although high rigidity is aimed at by the silicone resin molded object as a glass substitute use in patent document 3, and the laminated body of PC and a biaxially-stretched polyethylene terephthalate (PET) film in patent document 4, it can be said that it is still enough. Absent.

  An object of this invention is to provide the transparent resin laminated body which solved the said subject.

  As a result of intensive research, the inventors have obtained transparency by providing a transparent layer (B) containing a glass fiber cloth and a resin composition containing a sulfur compound on both sides of the transparent resin layer (A). The inventors have found that a transparent resin laminate excellent in rigidity can be obtained, and have reached the present invention. That is, one form of the present invention provides the following transparent resin laminate and display front plate.

(1) A transparent resin laminate in which a transparent layer (B) containing a glass fiber cloth and a resin composition containing a sulfur compound is disposed on both sides of the transparent resin layer (A).
(2) Transparent layer (B) formed of a resin composition containing glass fiber cloth, compound (a) having a thiol group and compound (b) having an alkenyl group on both surfaces of the transparent resin layer (A) The transparent resin laminate according to (1), wherein
(3) A transparent layer obtained by impregnating a glass fiber cloth with a resin composition containing a curable resin having a tensile modulus of elasticity of 10 MPa or more when cured at a thickness of 1 mm on both surfaces of the transparent resin layer (A) (B ) Is disposed, the transparent resin laminate according to (1) or (2).
(4) The transparent resin laminate according to any one of (1) to (3), which has an adhesive layer containing a transparent adhesive between the transparent resin layer (A) and the transparent layer (B). body.
(5) The transparent resin laminate according to (4), wherein the adhesive layer has a thickness of 1 μm to 100 μm.
(6) The transparent resin laminate according to (4) or (5), wherein a tensile elastic modulus at the time of curing at a thickness of 1 mm of the transparent adhesive is 1 MPa or more.
(7) A transparent layer (B) having a tensile elastic modulus of 10 GPa or more by impregnating and curing a glass fiber cloth with a resin composition containing a curable resin on both surfaces of the transparent resin layer (A) at a thickness of 1 mm The transparent resin laminate according to any one of (1) to (6), which is bonded with a transparent adhesive having a tensile elastic modulus at curing of 1 MPa or more.
(8) The transparent adhesive is at least one selected from the group consisting of an acrylic adhesive, an epoxy adhesive, and a urethane adhesive, and is described in any one of (4) to (7). Transparent resin laminate.
(9) The transparent resin laminate according to any one of (1) to (8), wherein the flexural modulus of the transparent resin laminate is 5 GPa or more.
(10) The transparent resin according to any one of (1) to (9), wherein the transparent resin layer (A) has a thickness of 100 μm to 2000 μm, and the transparent layer (B) has a thickness of 20 μm to 300 μm. Resin laminate.
(11) The transparent resin laminate according to any one of (1) to (10), wherein the total light transmittance is 80% or more.
(12) The difference between the Abbe number when the resin composition in the transparent layer (B) is cured and the Abbe number of the glass fiber cloth is 15 or less, according to any one of (1) to (11). Transparent resin laminate.
(13) The difference between the refractive index of the resin composition in the transparent layer (B) and the refractive index of the glass fiber cloth is 0.01 or less, according to any one of (1) to (12). Transparent resin laminate.
(14) The transparent resin laminate according to any one of (1) to (13), wherein the resin composition in the transparent layer (B) contains a polymer of a thiol compound and an epoxy resin.
(15) The transparent resin laminate according to any one of (1) to (14), wherein the refractive index of the glass fiber cloth in the transparent layer (B) is greater than 1.55.
(16) The transparent resin laminate according to any one of (1) to (15), wherein the glass fiber cloth of the transparent layer (B) is an E glass cloth.
(17) Any one of (1) to (16), wherein the resin component in the transparent resin layer (A) includes at least one selected from the group consisting of polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polymethyl methacrylate. The transparent resin laminate described in 1.
(18) The transparent resin laminate according to (17), wherein the resin component in the transparent resin layer (A) contains polycarbonate.
(19) The transparent resin laminate according to any one of (1) to (18), wherein a polyethylene terephthalate film layer is disposed on at least one outer side of the transparent layer (B).
(20) The transparent resin laminate according to (19), wherein a hard coat layer is further disposed on at least one outer side of the polyethylene terephthalate film layer.
(21) The transparent resin laminate according to (19) or (20), wherein a transparent conductive film layer is disposed on at least one outer side of the polyethylene terephthalate film layer.
(22) A display front plate using the transparent resin laminate according to any one of (1) to (21).

According to another embodiment of the present invention, the following display front plate is provided.
(1) For display, comprising a transparent resin laminate (C) in which a transparent layer (B) formed of a resin composition containing a glass fiber cloth and a sulfur compound is disposed on both sides of the transparent resin layer (A). Front plate.
(2) The display front plate according to (1), wherein the transparent resin layer (A) has a thickness of 100 μm to 2000 μm, and the transparent layer (B) has a thickness of 20 μm to 300 μm.
(3) The display front plate according to (1) or (2), wherein the flexural modulus of the transparent resin laminate (C) is 5 GPa or more.
(4) The display front plate according to any one of (1) to (3), wherein the total light transmittance is 80% or more.
(5) Any of (1) to (4), wherein the difference between the Abbe number at the time of curing of the resin composition containing a sulfur compound and the Abbe number of the glass fiber cloth in the transparent layer (B) is 15 or less. The display front plate according to claim 1.
(6) The difference of the refractive index at the time of hardening of the resin composition containing a sulfur compound in the transparent layer (B) and the refractive index of the glass fiber cloth is 0.01 or less, (1) to (5) The display front plate according to any one of the above.
(7) The resin composition containing a sulfur compound in the transparent layer (B) contains a polymer of a thiol compound and an epoxy resin, as described in any one of (1) to (6). Front plate for display.
(8) The display front plate according to any one of (1) to (7), wherein the refractive index of the glass fiber cloth in the transparent layer (B) is greater than 1.55.
(9) Any of (1) to (8), wherein the resin component in the transparent resin layer (A) is at least one selected from the group consisting of polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polymethyl methacrylate. The display front plate according to claim 1.
(10) The display front plate according to any one of (1) to (9), wherein a polyethylene terephthalate film layer is disposed on at least one outer side of the transparent resin laminate (C).
(11) The display front plate according to (10), wherein a hard coat layer is disposed on at least one outer side of the polyethylene terephthalate film layer.
(12) The display front plate according to (10), wherein a transparent conductive film layer is disposed on at least one outer side of the polyethylene terephthalate film layer.

According to still another embodiment of the present invention, the following display front plate is provided.
(1) A transparent layer formed of a photocurable resin composition containing a glass fiber cloth and a compound (a) having a thiol group and a compound (b) having an alkenyl group on both surfaces of the transparent resin layer (A) ( A display front plate comprising a transparent resin laminate (C) in which B) is disposed.
(2) The display front plate according to (1), wherein the transparent resin layer (A) has a thickness of 100 μm to 2000 μm, and the transparent layer (B) has a thickness of 20 μm to 300 μm.
(3) The display front plate according to (1) or (2), wherein the flexural modulus of the transparent resin laminate (C) is 5 GPa or more.
(4) The display front plate according to any one of (1) to (3), wherein the total light transmittance is 80% or more.
(5) Any one of (1) to (4), wherein the difference between the Abbe number at the time of curing the photocurable resin composition and the Abbe number of the glass fiber cloth in the transparent layer (B) is 15 or less. The display front plate according to Item.
(6) Any of (1) to (5), wherein the difference between the refractive index when the photocurable resin composition is cured and the refractive index of the glass fiber cloth in the transparent layer (B) is 0.01 or less. The display front plate according to claim 1.
(7) The display front plate according to any one of (1) to (6), wherein the refractive index of the glass fiber cloth in the transparent layer (B) is greater than 1.55.
(8) Any of (1) to (7), wherein the resin component in the transparent resin layer (A) is one or more selected from the group selected from polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polymethyl methacrylate. The display front plate according to claim 1.
(9) The display front plate according to any one of (1) to (8), wherein a polyethylene terephthalate film layer is disposed on at least one outer side of the transparent resin laminate (C).
(10) The display front plate according to (9), wherein a hard coat layer is disposed on at least one outer side of the polyethylene terephthalate film layer.
(11) The front plate for display according to (10), wherein a transparent conductive film layer is further arranged on at least one outer side of the polyethylene terephthalate film layer.

Moreover, according to another one form of this invention, the following transparent laminated bodies are provided.
(1) A transparent layer (B) in which a glass fiber cloth is impregnated with a curable resin having a tensile modulus of elasticity of 10 MPa or more when cured at a thickness of 1 mm is disposed on both surfaces of the polycarbonate resin layer (A). A transparent laminate having a flexural modulus of 5 GPa or more as a whole. (2) The transparent laminate according to (1), wherein the polycarbonate resin layer (A) has a thickness of 100 μm to 2000 μm, and the transparent layer (B) has a thickness of 20 μm to 300 μm.
(3) The transparent laminate according to (1) or (2), wherein the curable resin of the transparent layer (B) contains an epoxy resin.
(4) The transparent laminated body as described in any one of (1)-(3) whose glass fiber cloth of the said transparent layer (B) is E glass cloth.
(5) The transparent laminated body as described in any one of (1)-(4) whose total light transmittance of the said transparent layer (B) is 80% or more.
(6) A transparent laminate in which a polyethylene terephthalate film layer is further arranged on at least one outer side of the transparent laminate according to any one of (1) to (5).
(7) The transparent laminate according to (6), wherein a hard coat layer is further disposed on at least one outer side of the polyethylene terephthalate film layer.
(8) The transparent laminate according to (6), wherein a transparent conductive film layer is further arranged on at least one outer side of the polyethylene terephthalate film layer.
(9) A display front plate using the transparent laminate according to any one of (1) to (8).
It is.

Moreover, according to another one form of this invention, the following transparent laminated bodies are provided.
(1) On both surfaces of the polycarbonate resin layer (A), a transparent layer (B) having a tensile elastic modulus of 10 GPa or more by impregnating and curing a glass fiber cloth with a curable resin is tensile elastic at the time of curing at a thickness of 1 mm. A transparent laminate having a bending elastic modulus of 5 GPa or more as a whole, which is a transparent laminate bonded with a transparent adhesive having a rate of 1 MPa or more.
(2) The transparent laminate according to (1), wherein the total light transmittance is 80% or more.
(3) The transparent laminate according to (1) or (2), wherein the polycarbonate resin layer (A) has a thickness of 100 μm to 2000 μm, and the transparent layer (B) has a thickness of 20 μm to 300 μm.
(4) A transparent laminate in which a polyethylene terephthalate film layer is disposed on at least one outer side of the transparent laminate according to any one of (1) to (3).
(5) The transparent laminate according to (4), wherein a hard coat layer is disposed on at least one outer side of the polyethylene terephthalate film layer.
(6) The transparent laminate according to (4), wherein a transparent conductive film layer is further arranged on at least one outer side of the polyethylene terephthalate film layer.
(7) A display front plate using the transparent laminate according to any one of (1) to (6).

  Since the transparent resin laminate of the present invention is excellent in transparency and rigidity and excellent in workability, it is suitable as a substitute for glass.

1 is a schematic cross-sectional view showing a display front plate according to an embodiment of the present invention. 1 is a schematic cross-sectional view showing a display front plate according to an embodiment of the present invention. It is a cross-sectional photograph of the transparent resin laminated body which concerns on one Embodiment of this invention, Comprising: It is a cross-sectional photograph of the transparent resin laminated body manufactured in Example A-2.

  Hereinafter, the present invention will be described with reference to the accompanying drawings. The following are examples for explaining the present invention, and the present invention is not limited only to the embodiment. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

  One embodiment of the present invention is a transparent resin laminate in which a transparent layer (B) containing a glass fiber cloth and a resin composition containing a sulfur compound is disposed on both sides of the transparent resin layer (A).

  The transparent resin laminate of the present invention is transparent and excellent in rigidity, and excellent in workability and impact resistance. Therefore, the transparent resin laminate is used as a transparent substrate material, a transparent protective material, and the like, and particularly preferably used as a substitute for glass for various glazing materials, substrate materials, and front plate materials such as a display front plate. In the present specification, the “transparent resin laminate” is also simply referred to as “transparent laminate” or “laminate”.

  The term “transparent” in the present invention means that the total light transmittance is 80% or more. Further, in the present invention, the light transmittance at 550 nm, which is a general wavelength in the visible light region, is preferably 80% or more, and the light transmittance at 400 nm is preferably 60% or more. In particular, the light transmittance at 400 nm is important from the viewpoint of image contrast and color reproducibility, and it is preferable to increase the light transmittance in the wavelength region. The total light transmittance and the light transmittances of 400 nm and 550 nm can be measured by the methods described in Examples described later.

  One embodiment of the present invention is a display front plate using a transparent resin laminate. FIG. 1 is a schematic cross-sectional view illustrating a display front plate according to an embodiment of the present invention. The display front plate 10 shown in FIG. 1 has an adhesive layer 3 on both surfaces of a transparent resin layer (A) 1 and a transparent layer (B) 2 containing a glass fiber cloth and a resin composition containing a sulfur compound. It consists of the transparent resin laminated body (C) laminated | stacked in order. That is, the front plate 10 of this embodiment has an adhesive layer 3 including a transparent adhesive between the transparent resin layer (A) 1 and the transparent layer (B) 2. However, the front plate 10 may not have the adhesive layer 3.

  FIG. 2 is a schematic cross-sectional view illustrating a display front plate according to another embodiment of the present invention. The display front plate 10 shown in FIG. 2 is a transparent resin laminate in which a transparent layer (B) 2 containing a glass fiber cloth and a resin composition containing a sulfur compound is disposed on both sides of the transparent resin layer (A) 1. (C). In this embodiment, the transparent layer (B) 2 is directly disposed on the transparent resin layer (A). The transparent resin layer (A) and the transparent layer (B) may not be bonded, but more preferably, the transparent resin layer (A) and the transparent layer (B) are bonded from a highly rigid surface. Yes. That is, in one embodiment of the present invention, the transparent resin layer (A) and the transparent layer (B) are directly bonded or bonded via the adhesive layer 3.

  FIG. 3 is a cross-sectional photograph of the transparent resin laminate according to one embodiment of the present invention, and corresponds to a cross-sectional photograph of the transparent resin laminate produced in Example A-2 below. The transparent resin laminate shown in FIG. 3 is formed by sequentially laminating a GC reinforced film as a transparent layer (B) 2 and a polyethylene terephthalate film layer 4 as a resin layer on both sides of a PC plate as a transparent resin layer (A) 1. It has become. In addition, the layer 5 in FIG. 3 is a sheet | seat used in order to fix a transparent resin laminated body at the time of a cutting | disconnection. In FIG. 3, the transparent layer (B) is composed of a GC reinforced film formed from a glass fiber cloth 21, a resin composition 22 comprising a compound having a thiol group and a compound having an epoxy group. In the present embodiment, the glass fiber cloth 21 is an E glass cloth, and is formed by knitting warp yarns and weft yarns (glass yarns) (white portion in the figure). The transparent layer (B) 2 is formed by impregnating and curing the resin composition in the glass cloth.

  Generally, the transparent layer (B) containing a glass fiber cloth and a resin composition containing a sulfur compound has higher rigidity (such as tensile elastic modulus) than the transparent resin layer (A). Thus, the rigidity of the layer containing the glass fiber cloth is reflected by arranging the high rigidity layer (B) containing the glass fiber cloth on both surfaces of the relatively low rigidity layer (A). The rigidity of can be increased. For example, when a polycarbonate resin is used as the transparent resin layer, the rigidity (bending elastic modulus) is 2.6 GPa, but the rigidity can be improved by arranging the layers containing glass fiber cloth on both sides.

  The transparent resin laminate (C) includes a transparent resin layer (A), a transparent layer (B), and an adhesive layer, a resin layer (smoothing layer), a hard coat layer, and a transparent conductive film layer that are arranged as necessary. Have Hereinafter, each component of the transparent resin laminate of the present invention will be described.

  The transparent resin layer (A) is a transparent layer (film / sheet) mainly composed of a resin. Although the thickness of a transparent resin layer (A) is not specifically limited, 100 micrometers-2000 micrometers are preferable, and it is more preferable that they are 200 micrometers-1000 micrometers. If the thickness of the transparent resin layer (A) is within this range, the rigidity becomes high, and an increase in the mass of the entire transparent resin laminate (C) can be suppressed.

  The resin (resin component) used in the transparent resin layer (A) is not particularly limited, but polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, cyclic cycloolefin resin, norbornene resin, acrylic resin, polystyrene, polyethersal Examples include phon, polyarylate, polyester resin, polyacetal resin, polyvinyl butyral, polyvinyl alcohol, and urethane resin. Among them, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polymethyl methacrylate are selected from the viewpoint of transparency and rigidity. At least one kind is preferable, and polycarbonate resin is particularly preferable from the viewpoint of transparency and punchability. These resins may be used alone or in combination.

  The transparent resin layer (A) is processed into a layer mainly by molding. The molding method is not particularly limited, and for example, a general extrusion method such as a thermoplastic resin film forming method, a melt casting method, a calendering method, or the like can be used.

  In a preferred embodiment, the transparent resin layer (A) is composed of a layered polycarbonate resin. By using a layered polycarbonate resin, a laminate having excellent transparency, rigidity, impact resistance, flexibility, and punchability can be obtained. As such a layered polycarbonate resin, for example, Iupilon NF-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd. can be preferably used.

  Moreover, it is preferable that the total light transmittance of the transparent resin layer (A) molded to a thickness used when forming the transparent resin laminate is 80% or more. If it is 80% or more, the transmittance | permeability of the laminated body (front plate for a display) obtained can suppress a fall.

  The transparent resin layer (A) can contain various additives in addition to the resin without departing from the spirit of the present invention. Additives include heat stabilizers, antioxidants, flame retardants, flame retardant aids, UV absorbers, mold release agents, colorants, antistatic agents, fluorescent whitening agents, antifogging agents, fluidity improvers, Examples include plasticizers, dispersants, and antibacterial agents. These may be used singly or in combination of two or more.

  Examples of the heat stabilizer include phenol-based, phosphorus-based, and sulfur-based heat stabilizers. Specifically, phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, acidic calcium pyrophosphate; potassium phosphate , Sodium phosphate, cesium phosphate, zinc phosphate, etc., Group 1 or Group 10 metal phosphates; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like. Alternatively, a phosphite compound (a), phosphorous acid (b), and at least one ester in the molecule esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms Mention may be made of at least one selected from the group of tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite (c). These may be used alone or in combination of two or more.

  When blended, the addition ratio of the heat stabilizer is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, with respect to 100 parts by mass of the resin component. Moreover, it is 1 mass part or less, Preferably it is 0.7 mass part or less, More preferably, it is 0.5 mass part or less. If the amount of the heat stabilizer is too small, the heat stabilizing effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.

  Examples of the antioxidant include phenolic antioxidants, hindered phenolic antioxidants, bisphenolic antioxidants, polyphenolic antioxidants, and the like.

  When added, the addition ratio of the antioxidant is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, and 1 part by mass or less, preferably 0 with respect to 100 parts by mass of the resin component. .5 parts by mass or less. If the addition ratio of the antioxidant is below the lower limit, the effect as an antioxidant may be insufficient, and if the addition ratio of the antioxidant exceeds the upper limit, the effect reaches a peak and is economical. There is a possibility of disappearing.

  Examples of the flame retardant include organic sulfonic acid metal salts. Examples of the organic sulfonic acid metal salts include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts. These may be used alone or in combination of two or more. Moreover, as a metal salt, an alkali metal salt and an alkaline-earth metal salt are preferable. Moreover, you may mix | blend flame retardants other than organic sulfonic acid metal salt.

  The added mass of the flame retardant with respect to 100 parts by mass of the resin component is, for example, 0.005 parts by mass to 0.1 parts by mass, preferably 0.01 parts by mass to 0.1 parts by mass, and more preferably 0.03 parts by mass. Parts by mass to 0.09 parts by mass.

  For example, a silicone compound can be added as a flame retardant aid. As a silicone compound, what has a phenyl group in a molecule | numerator is preferable. By having a phenyl group, the dispersibility of the silicone compound in a resin component (particularly polycarbonate) is improved, and the transparency and flame retardancy are excellent.

  When blended, the addition ratio of the flame retardant aid is, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more, and 7.5 parts by mass or less, relative to 100 parts by mass of the resin component Preferably it is 5 mass parts or less. If the addition rate of flame retardant aid is below the lower limit, flame retardancy may be insufficient, and if the addition rate of flame retardant aid exceeds the upper limit, appearance defects such as delamination will occur and transparency , The flame retardancy reaches its peak, and it may not be economical.

  In addition to inorganic UV absorbers such as cerium oxide and zinc oxide, UV absorbers include benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds, phenyl salicylates Examples thereof include organic ultraviolet absorbers such as compounds. Of these, benzotriazole-based and benzophenone-based organic ultraviolet absorbers are preferred.

  When added, the addition ratio of the ultraviolet absorber is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and 3 parts by mass or less, preferably 1 with respect to 100 parts by mass of the resin component. It is below mass parts. If the addition ratio of the UV absorber is below the lower limit, the effect of improving the weather resistance may be insufficient, and if the addition ratio of the UV absorber exceeds the upper limit, mold deposits, etc. will occur and mold contamination (Cooling roll contamination) may occur.

  Examples of the release agent include carboxylic acid esters, polysiloxane compounds, and paraffin wax (polyolefin type). Two or more of these may be used in combination.

  When added, the addition ratio of the release agent is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and 2 parts by mass or less, based on 100 parts by mass of the resin component. Preferably it is 1 mass part or less. If the addition ratio of the release agent is below the lower limit value, the effect of the release property may not be sufficient, and if the addition ratio of the release agent exceeds the upper limit value, hydrolysis resistance decreases, gold during injection molding Mold contamination may occur.

  Examples of the dye / pigment as a colorant include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include, for example, sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, and zinc-iron. Oxide pigments such as chrome brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black, copper-iron black; chromic pigments such as yellow lead and molybdate orange; ferrocyans such as bitumen And pigments. Examples of organic pigments and organic dyes as colorants include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, and quinacridone And condensed polycyclic dyes such as dioxazine, isoindolinone, and quinophthalone; quinoline, anthraquinone, heterocyclic, and methyl dyes. Of these, titanium oxide, carbon black, cyanine, quinoline, anthraquinone, phthalocyanine dyes and the like are preferable from the viewpoint of thermal stability. In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio. In addition, dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.

  When added, the proportion of the colorant added is, for example, 1 part by mass or less, preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less with respect to 100 parts by mass of the resin component. If the addition ratio of the colorant is too large, the impact resistance may not be sufficient.

  The transparent layer (B) includes a glass fiber cloth and a resin composition containing a sulfur compound. The transparent layer (B) is made transparent by adjusting so that the Abbe number of the resin composition containing the sulfur compound and the glass fiber cloth matches the refractive index of 589 nm.

  The thickness of the transparent layer (B) is preferably 20 μm to 300 μm, and more preferably 50 μm to 200 μm. When the thickness of the transparent layer (B) is within this range, rigidity and transparency tend to be improved.

  The sulfur compound is not particularly limited as long as the transparency and rigidity of the transparent layer (B) can be secured. Examples of the sulfur compound include a sulfur atom-containing resin selected from the group consisting of a thermoplastic resin containing a sulfur atom, a thermosetting resin containing a sulfur atom, and a photocurable resin containing a sulfur atom. . Among these, a thermosetting resin or a photocurable resin containing a sulfur atom is preferable from the viewpoint of optical characteristics (transparency).

  The thermoplastic resin containing a sulfur atom is not particularly limited, and examples thereof include thermoplastic resins such as polythiocarbonate resin, polythioester resin, polyoxothioester resin, polythioether resin, and sulfur-containing cyclic polyolefin resin.

  Although the thermosetting resin containing a sulfur atom is not particularly limited, a thermosetting resin formed by subjecting a composition containing an epoxy resin and a polyfunctional thiol compound to a thermosetting reaction may be mentioned.

  The photocurable resin containing a sulfur atom is not particularly limited, but light formed by photocuring a photocurable resin composition containing a compound having a carbon-carbon double bond and a (polyfunctional) thiol compound. Photocurable resin formed by carrying out photocuring reaction of the photocurable resin composition containing curable resin, an epoxy resin, and a polyfunctional thiol compound is mentioned.

  The actinic ray used for curing the photocurable resin composition of the transparent layer (B) is not limited as long as it is used for curing the photocurable resin composition. Ultraviolet light, visible light, near infrared light, or the like can be used. From the viewpoint that side reactions hardly occur, it is preferable to use ultraviolet rays. Examples of the light source for irradiating the ultraviolet light include a metal halide type and a high-pressure mercury lamp lamp.

  In one Embodiment of this invention, the resin composition of a transparent layer (B) contains curable resin. When a curable resin is included, it is preferable in terms of refractive index adjustment and processability. More preferably, the resin composition of the transparent layer (B) includes a curable resin having a tensile elastic modulus at the time of curing at a thickness of 1 mm of 10 MPa or more. That is, the transparent resin laminate of one embodiment of the present invention is made of a resin composition containing a curable resin having a tensile elastic modulus of 10 MPa or more when cured at a thickness of 1 mm on both surfaces of the transparent resin layer (A). A transparent layer (B) formed by impregnating a fiber cloth is provided. In a particularly preferred embodiment, the transparent resin layer (A) is a polycarbonate resin layer because it is excellent in transparency, rigidity, impact resistance, flexibility, and punchability. In the present specification, the “tensile modulus at curing” means the tensile modulus of the resin after thermosetting or photocuring.

  In particular, the present inventors made the curable resin used for the layer (B) having high rigidity transparent and have a tensile elastic modulus of 10 MPa or more when cured at a thickness of 1 mm, so that the layer as a whole becomes rigid. It was found that an excellent laminate (preferably having a flexural modulus of 5 GPa or more) was obtained, and a laminate suitable for a display front (protection) plate was obtained. If it is less than 10 MPa, the flexural modulus as a whole transparent laminate may rather be lower than the flexural modulus (2.6 GPa) of the polycarbonate resin layer (A). The tensile elastic modulus at the time of curing of the curable resin used for the transparent layer (B) is more preferably 70 MPa or more, further preferably 100 MPa or more, and particularly preferably 500 MPa or more.

  Moreover, since the crack etc. which generate | occur | produce when a load is added to a material will become a problem if the tensile elasticity modulus of curable resin is too high, it is preferable that the tensile elasticity modulus at the time of hardening of curable resin is 5 GPa or less. As the curable resin having such characteristics, for example, an epoxy resin, an acrylic resin, a polyimide resin, a benzoxazine resin, an oxetane resin, or the like can be used.

  From the viewpoint of transparency, the resin composition preferably contains a polymer of a thiol compound and an epoxy resin, and particularly preferably the resin composition contains a polymer obtained by thermosetting reaction of the thiol compound and the epoxy resin.

  In one embodiment of the present invention, the transparent layer (B) is obtained by impregnating and curing a glass fiber cloth with a resin composition containing a curable resin, and when the transparent layer (B) is cured (after curing). Has a tensile modulus of 10 GPa or more.

  Examples of a method for obtaining a transparent layer (B) having a tensile modulus of elasticity of 10 GPa or more include a method using a specific curable resin. The curable resin having such characteristics is not particularly limited, and an epoxy resin, an acrylic resin, a polyimide resin, a benzoxazine resin, an oxetane resin, or the like can be used, but depending on the type of the curable resin used, it is transparent. The tensile modulus of the layer (B) may be less than 10 GPa, and it is not preferable to use such a curable resin.

  By sticking such a transparent layer (B) on both sides of the transparent resin layer (A) with the transparent adhesive, a transparent laminate having a transparent flexural modulus of 5 GPa or more as a whole and excellent in rigidity is obtained. be able to. This transparent laminate can be suitably used as a display front plate from the viewpoint of transparency and rigidity. In a particularly preferred embodiment, the transparent resin layer (A) is a polycarbonate resin layer because it is excellent in transparency, rigidity, impact resistance, flexibility, and punchability.

  The total light transmittance of the transparent layer (B) is preferably 80% or more, and more preferably 85% or more. If the total light transmittance of a transparent layer (B) is this range, the transparency of the whole transparent resin laminated body can be made favorable, and it is preferable as a front plate for a display.

  In order to obtain high transparency, the Abbe number difference between the Abbe number of the resin composition constituting the transparent layer (B) and the glass fiber cloth is preferably 15 or less, and more preferably 10 or less. The lower limit of the Abbe number difference is not particularly limited, and is preferably as small as possible from the viewpoint of obtaining high transparency, and is most preferably 0. In addition, the Abbe number of a resin composition means the Abbe number after hardening, when a resin composition contains curable resin. When the Abbe number difference is 15 or less, the obtained transparent layer (B) has a high light transmittance at a short wavelength near 400 nm, which is preferable as a display front plate. The Abbe number is an index of the wavelength dependence of the refractive index of visible light. Generally, glass has a value larger than that of resin, and it is more difficult to match the larger the refractive index. By using a resin composition containing a sulfur compound, the Abbe number of the resin approaches the Abbe number of the glass fiber cloth, the light transmittance in a wide wavelength region is improved, and high transparency is obtained.

  Further, the refractive index difference of the resin composition constituting the transparent layer (B) and the refractive index of the glass fiber cloth is preferably 0.01 or less, more preferably 0.005 or less in order to obtain high transparency. . Specifically, the refractive index difference of the D line (589 nm) between the resin composition and the glass fiber cloth is preferably 0.01 or less, and more preferably 0.005 or less. . The lower limit of the refractive index difference of the D line (589 nm) is not particularly limited, and is preferably as small as possible from the viewpoint of obtaining high transparency, and is most preferably 0. In addition, the refractive index of a resin composition means the refractive index after hardening, when a resin composition contains curable resin so that it may mention later. When the difference in refractive index is 0.01 or less, the transmittance of the obtained transparent layer (B) becomes high, which is preferable as a display front plate. When the transparent layer (B) is obtained by setting the difference in refractive index between the glass fiber cloth and the D line to 0.01 or less, a resin having a difference in refractive index between the glass fiber cloth and the D line of 0.01 or less is used alone. It may be used, or a resin having a higher refractive index of the D line and a lower resin than the glass fiber cloth may be used in combination.

  In applications where transparency is important, not only the refractive index of D-line but also the total light transmittance of the transparent layer (B) is 80% or more, which is a general wavelength in the visible light region of 550 nm. It is preferable that the light transmittance at 70 is 70% or more.

In order to set the Abbe number difference between the resin composition containing the sulfur compound constituting the transparent layer (B) and the glass fiber cloth to 15 or less and the refractive index difference to 0.01 or less, (1) A method of selecting a resin containing a sulfur atom matching the Abbe number and refractive index,
(2) By combining a resin having a higher refractive index than the glass fiber cloth and a resin having a lower refractive index than the glass fiber cloth, the Abbe number and the refractive index of the resin composition containing the sulfur compound are matched with those of the glass fiber cloth. A method or the like can be adopted. In order to obtain high transparency, it is preferable to precisely match the refractive index of the resin composition and the glass fiber cloth. Therefore, in the method (1), a plurality of reactive monomers (curable resins) and a curing agent are used. The method or the method (2) is preferred. In the present specification, “matching the refractive index” means that the refractive index difference is 0.01 or less, preferably 0.005 or less. Further, that the Abbe numbers coincide with each other means that the Abbe number difference is 15 or less, preferably 10 or less.

Method (1)
When the refractive index of the resin containing sulfur atoms and the refractive index of the glass fiber cloth match, the resin containing sulfur atoms can be used as it is. For example, the refractive index can be configured to match that of the glass fiber by adjusting the types and amounts of monomers and curing agents that constitute the copolymer resin and the curable resin. Examples of such a resin include at least one sulfur atom-containing resin selected from a thermoplastic resin containing a sulfur atom, a thermosetting resin containing a sulfur atom, and a photocurable resin containing a sulfur atom. Is mentioned. In this case, only one type of resin containing sulfur atoms may be used, or two or more types may be used in combination. By mixing a plurality of sulfur atom-containing resins (monomers) having different refractive indexes, the resin composition and the refractive index of the glass fiber cloth can be precisely matched, and high transparency can be achieved.

  As the resin containing sulfur atoms matching the Abbe number and refractive index of the glass fiber cloth selected in the above (1), for example, the glass type of the glass fiber cloth is E glass (Abbe number 58, refractive index 1.56). ), A thermoplastic copolymer resin such as a copolymer of polythioester and polyester, a thermosetting resin such as an episulfide resin, and the like. Similarly, when the glass type is S glass or T glass (Abbe number 68, refractive index 1.53), a thermoplastic copolymer resin such as a copolymer of polythioester and polyester or an episulfide resin is used. A thermosetting resin etc. are mentioned. In the case of the copolymer, the refractive index and the Abbe number depend on the ratio of the sulfur compound (sulfur atom-containing compound) to be copolymerized and the compound not containing sulfur, and the smaller the sulfur compound, the lower the refractive index. The amount used depends on the glass type. Further, the refractive index and Abbe number of the episulfide resin vary depending on the sulfur content in the episulfide resin, and the smaller the sulfur content, the lower the refractive index. When an S glass or T glass is used, an episulfide resin having a sulfur content corresponding to that is used.

  Further, as the sulfur atom-containing resin having the same Abbe number and refractive index as those of the glass fiber cloth of (1), the curability formed by a curing reaction between a reactive monomer of a curable resin and a curing agent containing a sulfur atom. Resin (thermosetting resin or photocurable resin) can also be used. For example, a method of adjusting by combining a curing agent containing a sulfur atom having a refractive index higher than that of glass fiber cloth and a reactive monomer (resin monomer containing no sulfur atom) of a resin having a refractive index lower than that of glass fiber cloth is preferable. . More specifically, as the sulfur atom-containing curable resin, a thermosetting resin or a photocurable resin composed of an epoxy resin as a reactive monomer and a curing agent containing a sulfur compound, an alkenyl group as a reactive monomer. And a photo-curable resin comprising a compound having a sulfur and a curing agent containing a sulfur compound. As these production methods, a sulfur atom-containing curing agent having a refractive index higher than that of the glass fiber cloth and a reactive monomer of a curable resin having a low refractive index are mixed one by one or two or more, respectively. Or the method of hardening with active energy, such as light, is mentioned. For example, a method of curing a resin (for example, an epoxy resin) having a refractive index lower than that of the glass fiber cloth using a sulfur atom-containing compound (for example, a polyfunctional thiol compound) having a higher refractive index than that of the glass fiber cloth as a curing agent may be mentioned. . A curable resin composed of an epoxy resin and a sulfur atom-containing curing agent is preferable from the viewpoint of transparency.

  As said sulfur atom containing hardening | curing agent, the polyfunctional thiol type compound whose refractive index is higher than glass fiber cloth is mentioned, for example. The polyfunctional thiol compound having a higher refractive index than that of the glass fiber cloth is not particularly limited, but 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol 2,2′-oxybis (1-mercaptoethane), 2,2′-thiobis (1-mercaptoethane), 1,4-dimercaptobutane-2,3-diol, ethylene glycol bis (1-mercaptoethane) , Ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptopropionate), ethylene glycol bis (3-mercaptobutanoate), butanediol bis ( 2-mercaptoacetate), butanediol bis (3-mer Ptopropionate), butanediol bis (2-mercaptopropionate), butanediol bis (3-mercaptobutanate), pentaerythritol, triazine trithiol, glycerol tris (2-mercaptoacetate), glycerol tris ( 3-mercaptopropionate), glycerol tris (2-mercaptopropionate), glycerol tris (3-mercaptobutanate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate) (PETP), pentaerythritol tetrakis (2-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutanate), trimethylolpropane tris (2- Lucaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), trimethylolpropane tris (3-mercaptobutanate), trimethylolethane tris (2- Mercaptoacetate), trimethylolethanetris (3-mercaptopropionate), trimethylolethanetris (2-mercaptopropionate), trimethylolethanetris (3-mercaptobutanoate), 4-mercaptomethyl-1,8 -Dimercapto-3,6-dithiaoctane (GST), bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundecane, 2,5-bis (mercaptomethyl) -1,4-dithiane, Tris-[(3-Me And lucaptopropionyloxy) -ethyl] -isocyanurate (TEMPIC), dipentaerythritol hexakis (3-mercaptopropionate), and the like. These may be used alone or in combination of two or more. Among these, pentaerythritol tetrakis (3-mercaptopropionate) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane are preferable from the viewpoint of adjusting the refractive index.

  In addition to the polyfunctional thiol compound, a cyclic carboxylic acid anhydride having a refractive index lower than that of the glass fiber cloth can be used as a curing agent for the epoxy resin. Such cyclic carboxylic acid anhydrides are not particularly limited, but for example, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, nadic anhydride, glutaric anhydride, tetrahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, dodecenyl succinic anhydride, dichlorosuccinic anhydride, benzophenone tetracarboxylic anhydride and chlorendic anhydride Thing etc. are mentioned. These may be used alone or in combination of two or more. Among these, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride are preferable from the viewpoint of transparency, and hexahydrophthalic anhydride is more preferable from the viewpoint of transparency. Hydrophthalic anhydride, methylhexahydrophthalic anhydride.

  Examples of the epoxy resin having a refractive index lower than that of the glass fiber cloth combined with the curing agent containing a sulfur atom include an epoxy resin containing no aromatic ring. Such an epoxy resin is not particularly limited, but hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, triazine skeleton-containing epoxy resin, linear aliphatic epoxy resin, cyclohexane oxide skeleton-containing epoxy resin, cyclohexane Examples include polyether skeleton-containing epoxy resins, glycidylamine-type epoxy resins, dicyclopentadiene skeleton-containing epoxy resins, and the like. These may be used alone or in combination of two or more.

  The combination of the polyfunctional thiol compound having a higher refractive index than that of the glass fiber cloth and the epoxy resin not containing an aromatic ring having a lower refractive index is not particularly limited. However, since the glass fiber cloth has a higher Abbe number than a general resin having a close refractive index, the difference between the Abbe number and a resin containing an aromatic ring or a resin having a large amount of carbonyl bonds tends to increase. Therefore, a combination of a thiol compound such as pentaerythritol tetrakis (3-mercaptopropionate) and / or 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and a cyclohexane oxide skeleton-containing epoxy resin is used. preferable.

  When a polyfunctional thiol compound is used alone as a curing agent for a curable resin, the total content of thiol functional groups contained in the polyfunctional thiol compound is preferably 1 equivalent to the epoxy group of an epoxy resin that is a cured plastic resin. 0.5 to 1.0 equivalent, more preferably 0.7 to 1.0 equivalent. If the content is within this range, curability does not decrease, and odor due to residual thiol functional groups can be suppressed. When the polyfunctional thiol compound and the cyclic carboxylic acid anhydride are used in combination as the curing agent, the thiol functional group contained in the polyfunctional thiol compound and the carboxylic acid anhydride functional group contained in the cyclic carboxylic acid anhydride The total content is preferably 0.5 to 1.0 equivalent, more preferably 0.7 to 1.0 equivalent, with respect to 1 equivalent of the epoxy group of the epoxy resin which is a cured plastic resin. If the content is within this range, curability does not decrease, and odor due to residual thiol functional groups can be suppressed.

  When a polyfunctional thiol compound having a high refractive index and a cyclic carboxylic acid anhydride having a low refractive index as a curing agent for a curable resin are used in combination, the polyfunctional thiol compound and the cyclic carboxylic acid anhydride as a curing agent, and The compounding ratio of the epoxy resin is adjusted depending on the glass fiber cloth used. When an E glass fiber cloth having a high refractive index is used as the glass fiber cloth, the compounding ratio of the polyfunctional thiol compound having a high refractive index is increased to match the refractive index with the glass fiber cloth. Moreover, when using T glass fiber cloth with low refractive index, S glass fiber cloth, NE glass fiber cloth, etc. as said glass fiber cloth, the compounding ratio of resin containing a high refractive index sulfur compound is decreased, and glass fiber is used. Match the refractive index with the cloth.

  Further, as a sulfur atom-containing resin having a refractive index identical to that of the glass fiber cloth of (1), a composition containing a compound having a carbon-carbon double bond and a (polyfunctional) thiol compound is subjected to a photocuring reaction. A photocurable resin may be used. Among these, preferably, a photocurable resin (hereinafter referred to as “thiol-ene photocurable resin”) formed from a photocurable resin composition containing a compound (a) having a thiol group and a compound (b) having an alkenyl group. Also referred to). Such a thiol-ene photocurable resin has a thiol group and an alkenyl group in the same molecule. That is, in one embodiment of the present invention, on both surfaces of the transparent resin layer (A), a glass fiber cloth and a resin composition containing a compound (a) having a thiol group and a compound (b) having an alkenyl group. It is a transparent resin laminate (C) in which the formed transparent layer (B) is arranged.

  The transparent layer (B) according to one embodiment of the present embodiment is obtained by impregnating a glass fiber cloth with a photocurable resin composition containing a compound (a) having a thiol group and a compound (b) having an alkenyl group. , Processed into layers.

  The photocurable resin composition as described above reacts with a thiol group and an alkenyl group by an actinic ray (thiol-ene reaction) by a thiol group of the compound having a thiol group and an alkenyl group of the compound having an alkenyl group. Can be used. The advantages of the photocurable resin produced by the thiol-ene reaction are that the reaction proceeds easily with active light regardless of the presence or absence of a polymerization initiator, the reaction is not inhibited by oxygen, and the curing shrinkage is small. The point that the resin after hardening has a high weather resistance is mentioned, and the hardened | cured material suitable for the front board of this invention can be obtained.

  Furthermore, the photo-curable resin composition that generates a thiol-alkenyl reaction has a ratio of reactive functional groups in the molecule, that is, compared to a thiol-epoxy reaction that can produce a curable resin using a similar photo-curing reaction, that is, It is not necessary to adjust the ratio of the thiol group and the epoxy group, and it is easy to adjust the refractive index of the resin.

  The compound having a thiol group is not particularly limited as long as it is a compound having a thiol group, but as mentioned above, a polyfunctional thiol having a higher refractive index than the glass fiber cloth used as a sulfur atom-containing curing agent. System compounds can be used. These may be used individually by 1 type and may use 2 or more types together. Among them, the thiol compound in the thiol-alkenyl reaction is preferably pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane from the viewpoint of refractive index adjustment. is there.

  The compound having an alkenyl group is not particularly limited as long as it is a compound having an alkenyl group. For example, 2-methacryloyloxyethylphthalic acid, methoxypolyethylene glycol methacrylate, 1,9-nonanediol dimethacrylate, neopentyl glycol diester. Methacrylate, ethoxylated polypropylene glycol dimethacrylate, glycerin dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ethoxylated o-phenylphenol acrylate, methoxy polyethylene glycol acrylate, phenoxy polyethylene glycol acrylate, 2-acryloyloxyethyl succinate, Isostearyl acrylate, 2-hydroxy-3-acryloiro Xoxypropyl methacrylate, polyethylene glycol diacrylate, propoxylated ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, propoxylated bisphenol A diacrylate , Tricyclodecane dimethanol diacrylate, 1,10-decanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol Diacrylate, polytetramethylene glycol diacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone modification Tris- (2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, dipentaerythritol Hexaacrylate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, 1,3-diallyl-5-methoxycarbonyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3-diallyl-5- (cyclohexen-4-yl) methoxycarbonyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trio And triallyl isocyanurate. These may be used individually by 1 type and may use 2 or more types together. Among these, tricyclodecane dimethanol diacrylate is preferable from the viewpoint of refractive index adjustment.

  According to the glass fiber cloth used, the compound (a) having a thiol group and the compound (b) having an alkenyl group described above are combined, and the Abbe number and refractive index of the cured photocurable resin are the Abbe of the glass fiber cloth. The number and refractive index should be matched.

  Specifically, a compound having a higher refractive index than that of the glass fiber cloth and a compound having a lower refractive index are mixed to be transparent. At that time, in order to obtain high transparency, it is preferable to precisely match the refractive index of the resin and the glass fiber cloth. Therefore, the compound (a) having a thiol group having a refractive index higher than that of the glass fiber cloth and the glass fiber cloth. The method of mixing and adjusting the photocurable resin containing the compound (b) having an alkenyl group having a lower refractive index than that is preferable. In addition, when mixing a photocurable resin containing a compound (a) having a thiol group having a higher refractive index than the glass fiber cloth and a compound (b) having an alkenyl group having a lower refractive index than the glass fiber cloth, One type may be mixed, or two or more types may be used.

  For example, when E glass cloth is used as the glass fiber cloth, the E glass fiber cloth has a higher Abbe number than a general resin having a refractive index close to that of a resin containing an aromatic ring or a resin having a large amount of carbonyl bonds. The numbers do not match. Therefore, pentaerythritol tetrakisthioglycolate and / or 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol is used as a compound having a thiol group, and tricyclodecane dimethanol is used as a compound having an alkenyl group. It is preferable to combine using diacrylate.

Method (2)
If the refractive index of the resin containing the sulfur compound and the glass fiber cloth do not match, adjust by mixing a resin with a higher refractive index than the glass fiber cloth and another resin with a lower refractive index than the glass fiber cloth. be able to. Specific examples of the resin composition constituting the transparent layer (B) include, for example, a thermoplastic resin containing a sulfur atom, a thermosetting resin containing a sulfur atom, and a light containing a sulfur atom. The structure containing at least 1 sort (s) of sulfur atom containing resin selected from curable resin and other resin (sulfur atom non-containing resin) from which a refractive index differs from the said sulfur atom containing resin is mentioned. For example, the refractive index of the resin composition of the transparent layer (B) is a resin containing a sulfur atom having a refractive index higher than that of the glass fiber cloth and another resin having a refractive index lower than that of the glass fiber cloth (a sulfur atom-free resin). And a method of adjusting by mixing. When mixing resin containing sulfur atoms with higher refractive index than glass fiber cloth (sulfur atom-containing resin) and resin with lower refractive index (other resins), sulfur atom-containing resin and other resins (not containing sulfur atoms) One type of resin may be mixed, or two or more types may be used.

  Optimally appropriate by adjusting the refractive index of the entire resin according to the glass type of the glass fiber cloth to be used, the amount of the resin having a higher refractive index than the glass fiber cloth and the amount of the resin having a lower refractive index than the glass fiber cloth. A difference in refractive index and an Abbe number difference can be obtained.

  When the resin containing a sulfur atom is a thermoplastic resin, the resin containing a sulfur atom (sulfur atom-containing resin) has a higher refractive index than a glass fiber cloth, such as a polythiocarbonate resin, a polythioester resin, or a polyoxo. Examples include thioester resins, polythioether resins, sulfur-containing cyclic polyolefin resins, and the like. In addition, resins having a refractive index lower than that of glass fiber cloth (other resins; sulfur atom-free resins) combined with the sulfur atom-containing resin include cyclic cycloolefin resins, polymethyl methacrylate resins, acrylic resins, polyacetals. Examples thereof include resins.

  As a combination of a sulfur atom-containing resin having a higher refractive index than the glass fiber cloth and another resin having a lower refractive index, as long as the refractive index difference between the glass fiber cloth and the resin composition can be adjusted to a desired range, It is not limited. However, since the glass fiber cloth generally has a higher Abbe number than a general resin having a similar refractive index, the difference between the Abbe number and a resin containing an aromatic ring or a resin having a large amount of carbonyl bonds increases. A combination of cyclic cycloolefin resins is preferred.

  When the resin containing a sulfur atom is a curable resin, the resin containing a sulfur atom is a thermosetting resin or a photocurable resin comprising an epoxy resin and a curing agent containing a sulfur compound, a compound having an alkenyl group And a curing agent containing a sulfur compound, more preferably a thermosetting resin or a photocurable resin consisting of an epoxy resin and a curing agent containing a sulfur compound. From the viewpoint of Examples of the curing agent containing a sulfur atom include a polyfunctional thiol compound having a refractive index higher than that of the glass fiber cloth, and the polyfunctional thiol compound as the sulfur atom-containing curing agent in the method (1) is used in the same manner. be able to. Also in this embodiment, in addition to the polyfunctional thiol compound as a curing agent, a cyclic carboxylic acid anhydride having a refractive index lower than that of the glass fiber cloth as mentioned in the method (1) is used. Can do.

  The amount of the resin with respect to the transparent layer (B) is appropriately selected according to the purpose of use, but is usually 10 to 80% by mass, preferably 20 with respect to the total mass (100% by mass) of the transparent layer (B). It is the range of -70 mass%. If the amount of the resin is too small, the resin may be insufficient and the transparency may decrease. Conversely, if the amount of the resin is too large, the rigidity may be insufficient.

  In any of the methods (1) and (2), a resin mixing method when two or more kinds of resins are used will be described below. In the case of using a thermoplastic resin, there is a method in which the resin to be used is heated and mixed using a kneading apparatus such as a lab plast mill, a twin screw extruder, a Banbury mixer, and a vessel. In the case of using a thermosetting resin, the resin composition can be adjusted according to a conventional method. If the resin composition containing the resin to be used and other optional components can be obtained uniformly, the adjustment can be made. The method is not particularly limited. For example, a resin composition can be easily adjusted by blending a polyfunctional thiol compound and an epoxy resin that does not contain an aromatic ring and stirring sufficiently.

  Moreover, at the time of preparing the resin composition of the transparent layer (B), a known process (such as stirring, mixing, kneading process) for uniformly dissolving or dispersing each component can be performed. The above stirring, mixing, and kneading treatment can be appropriately performed using, for example, a known device such as a ball mill, a bead mill or the like for mixing, or a revolution / spinning type mixing device.

  The resin composition constituting the transparent layer (B) may further contain an inorganic filler as long as the desired properties are not impaired as required. Examples of inorganic fillers include silica-based inorganic fillers such as quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine powder amorphous silica, alumina, zircon, zinc oxide, and oxidation. Titanium, silicon nitride, boron nitride, aluminum nitride, glass fiber, glass flake, alumina fiber, mica, ferrite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, titanium It is preferably at least one selected from the group consisting of potassium acid, calcium silicate, inorganic balloon, silver powder and the like. The said inorganic filler can be used individually by 1 type or in combination of 2 or more types as appropriate.

  When the resin composition of the transparent layer (B) contains a thermosetting resin, it may contain a curing accelerator for adjusting the curing rate as needed when adjusting the resin composition. Examples of such compounds include organic peroxides exemplified by imidazole compounds, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate, and the like. Azobisnitrile azo compound, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N -Tertiary amines such as methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine, phenols such as phenol, xylenol, cresol, resorcin, catechol, lead naphthenate, lead stearate Zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, acetylacetone iron and other organic metal salts, dissolved in hydroxyl group-containing compounds such as phenol and bisphenol Inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride, dioctyl tin oxide, other organic tin compounds such as alkyl tin and alkyl tin oxide, quaternary ammonium salts, tetrabutylphosphonium O, O-diethylphospho Examples include quaternary phosphonium salts such as rosiothioate, phosphorus compounds, urea compounds, and the like. These curing accelerators can be used alone or in combination of two or more.

  The resin composition containing the sulfur compound that forms the transparent layer (B) may contain an organic solvent, if necessary. That is, the transparent layer (B) can be used as an embodiment (varnish) in which at least a part or all of the above-described resin is dissolved or compatible with an organic solvent. Any known organic solvent can be used as long as it can dissolve or be compatible with at least a part, preferably all of the resin monomer, and the kind thereof is not particularly limited. Specific examples thereof include, for example, benzene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone (2-butanone), acetone, methanol, ethanol, isopropyl alcohol, 2-butanol, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, propylene Glycol monomethyl ether acetate, diacetone alcohol, N, N′-dimethylformamide, N, N′-dimethylacetamide, acetonitrile and the like are exemplified, but not limited thereto. An organic solvent can be used individually by 1 type or in combination of 2 or more types as appropriate.

  When the resin composition containing the sulfur compound forming the transparent layer (B) contains an organic solvent, the solid content concentration of the solution is usually preferably 10 to 99% by mass, and preferably 20 to 90% by mass. Is more preferable. If the solution concentration is too low, the impregnation resin may be insufficient and the transparency may be lowered. Conversely, if the solution concentration is high, the solution viscosity may be increased, resulting in poor impregnation.

  When an epoxy resin is used as the curable resin in the resin composition of the transparent layer (B), a diluent such as a monoepoxy compound is added so as not to impair the reaction in order to improve workability and workability after curing the epoxy resin. It is preferable to add. When such a diluent is added, workability and processability are improved by lowering the monomer viscosity, and flexibility can be imparted to the cured epoxy resin, and the flexibility of the transparent layer (B) , Impact resistance, toughness and the like can be improved. Diluents include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, cresyl glycidyl ether, sec-butylphenyl glycidyl ether, cardanol glycidyl ether, Glycidyl methacrylate, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide, dodecene oxide, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin Triglycidyl ether, trimethylolpropane triglycid Ether and the like, it may be used in combination of two or more of these.

  As a quantity of a diluent, less than 100 mass parts is preferable with respect to 100 mass parts of epoxy resins, and 15 mass parts or less are still more preferable. If the amount of the diluent is within this range, the tensile elastic modulus of the transparent layer (B) is 15 GPa or more, and the bending elastic modulus of the transparent resin laminate as a whole can be 5 GPa or more.

  When using a thiol-ene photocurable resin in the resin composition of the transparent layer (B), a resin composition containing the compound (a) having a thiol group and the compound (b) having an alkenyl group is used as an ultraviolet ray or the like. In order to crosslink and cure with actinic rays, a photopolymerization initiator that generates radicals may be added to the resin composition. Examples of the photopolymerization initiator include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, and benzoin methyl. Ether, benzoin propyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4 -Morph Phosphorin-4-yl-phenyl) -butan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, t-butylanthraquinone, 1-chloroanthraquinone, 2,3 -Dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenyl Anthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 4- (p-methoxyphenyl) -2,6-di- (trichloro Methyl) -s-triazi Or the like. The said photoinitiator can be used individually by 1 type or in combination of 2 or more types as appropriate. Examples of commercially available photopolymerization initiators include Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907, and Lucilin TPO (all trade names manufactured by BASF).

  The content in the resin composition in the case of using the photopolymerization initiator may be an amount that can be appropriately cured, and is, for example, 0.8% relative to a total of 100 parts by mass of compounds having two or more alkenyl groups. 01-2 mass parts is preferable, More preferably, it is 0.02-1 mass part, Most preferably, it is 0.1-0.5 mass part. When the amount of the photopolymerization initiator added is too large, the polymerization proceeds rapidly, and problems such as increased birefringence, coloring, and cracks during curing occur. On the other hand, if the amount is too small, the composition cannot be sufficiently cured, and there is a possibility that problems such as adhesion to other substrates after crosslinking and removal cannot occur.

  Moreover, when using thiol-ene photocurable resin in the resin composition of a transparent layer (B), in order to improve the storage stability before hardening, the storage stabilizer which suppresses thiol-ene reaction can be mix | blended. In particular, when the photopolymerization initiator mentioned above is used, since the storage stability of the resin composition tends to be lowered, it is preferable to use such a storage stabilizer in combination. Examples of such storage stabilizers include phosphorus compounds such as triphenylphosphine and triphenyl phosphite; p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t -Butylphenol), N-nitrosophenylhydroxylamine aluminum salt, diphenylnitrosamine and other radical polymerization inhibitors; benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, Tertiary amines such as diazabicycloundecene; 2-methylimidazole, 2-ethyl-4-methyli Examples include imidazoles such as midazole, 2-ethylhexylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-methylimidazole. The said storage stabilizer can be used individually by 1 type or in combination of 2 or more types as appropriate.

  Although the kind of glass fiber cloth used for the transparent layer (B) is not particularly limited, for example, from among publicly known ones used for various transparent fiber reinforced resins, appropriately selected and used depending on the intended use and performance Can do. For example, glass fiber cloths, such as E glass, S glass, T glass, NE glass, L glass, D glass, Q glass, UN glass, are mentioned. Among them, the refractive index of the glass fiber cloth is preferably larger than 1.55, and E glass fiber cloth (preferably E glass cloth) is more preferable from the viewpoints of transparency, rigidity, workability and cost.

  When a glass cloth is used as the glass fiber cloth, a plain weave, a nanako weave, a satin weave, a twill weave, etc. can be applied as the weave, and a plain weave is preferred because of excellent dimensional stability and tensile resistance in the planar direction. The thickness of the glass fiber cloth (fibrous filler) is usually preferably 10 μm to 200 μm, and more preferably 40 μm to 150 μm. Moreover, only one sheet of these glass fiber cloths may be used, and a plurality of sheets may be used in a stacked manner. Moreover, the thing surface-treated with the silane coupling agent etc., and the thing which performed the fiber opening process physically in the woven fabric (cloth) can be used suitably from the surface of moisture absorption heat resistance.

  The method for producing the transparent layer (B) used in the display front plate of the present embodiment may be a method of processing the resin composition used for the transparent layer (B) and a glass fiber cloth together to form a layer. If it does not specifically limit. When the resin containing the sulfur atom is a thermoplastic resin, the glass fiber cloth is immersed in a solution in which the resin containing the sulfur compound is dissolved and impregnated with the resin containing the sulfur compound, and then heated with a dryer or the like. Thus, the solvent can be volatilized and removed. Thereafter, the resin may be heated to a temperature equal to or higher than the softening temperature of the resin containing the sulfur compound, and may be compression molded, or may be rolled using a metal roll. Moreover, after putting a glass fiber cloth in a cell and inject | pouring the resin composition containing the sulfur compound before superposition | polymerization into this cell, it may heat and superpose | polymerize.

  When the resin containing a sulfur atom is a curable resin, after impregnating the glass fiber cloth with the curable resin-soluble composition, the glass fiber cloth is dried as necessary, and pressed or laminated with another base material to increase the thickness. It is prepared by a method of adjusting, crosslinking and curing the curable resin composition by at least one of heating and irradiation with actinic rays. The curable resin composition here refers to a mixed liquid of a curable resin monomer and a curing accelerator.

  More specifically, when the resin containing sulfur atoms is a thermosetting resin, the glass fiber cloth may be immersed in a resin composition containing a sulfur compound having fluidity at room temperature or under heating. Alternatively, the glass fiber cloth may be immersed in a solution in which a resin containing sulfur atoms is dissolved to impregnate the resin containing sulfur atoms. After impregnating the resin composition containing the sulfur compound, it is dried if necessary, pressed or laminated with another substrate, the thickness is adjusted, and the resin composition containing the sulfur compound is crosslinked by heating, A curing method is possible. Here, the resin composition containing a sulfur compound represents a composition containing a resin monomer before curing.

  When the resin containing sulfur atoms is a photocurable resin, for example, a glass fiber cloth is immersed in a photocurable resin composition containing a compound (a) having a thiol group and a compound (b) having an alkenyl group. By pressing or laminating with a base material such as SUS plate, glass plate, polyethylene terephthalate, etc., which has been dried and subjected to a release treatment as necessary, the thickness is adjusted, and actinic rays such as ultraviolet light are irradiated. Add a compound (a) having a thiol group after immersing the glass fiber cloth in a solution in which the resin composition containing the compound (b) having an alkenyl group or a method of curing the curable resin composition is dissolved, The glass fiber cloth was impregnated by irradiating with actinic rays such as ultraviolet light by adjusting the thickness by pressing or laminating with the same base material as described above, which was dried as necessary and subjected to release treatment. Method of curing the curable resin composition can be used. Further, the reaction often proceeds further by heating after light irradiation, and heat treatment after light irradiation may be performed.

  The method for producing the transparent resin laminate (C) of the present embodiment is not particularly limited. For example, as shown in FIG. 1, the transparent layer (B) is formed on the transparent resin layer (A) via an adhesive layer. ) And adhering the transparent resin layer (A) and the transparent layer (B), the transparent resin layer (A) and the transparent layer (B) are prepared using a transparent adhesive as a method for producing the transparent resin laminate. If it sticks together, it will not be specifically limited. For example, after applying an appropriate transparent adhesive made of a photocurable resin, a thermosetting resin, a hot melt resin, etc. on both sides or one side of the transparent resin layer (A), the transparent layer (B) is laminated and transparently bonded. The method of hardening an agent is mentioned.

  The type and method of the transparent adhesive for laminating the transparent resin layer (A) and the transparent layer (B) are not particularly limited, but various types such as a photocurable adhesive, a thermosetting adhesive, and a room temperature curable adhesive. An adhesive can be used. In addition, if an adhesive containing a solvent is used, bubbles may be generated at the time of curing, and the transparency of the entire transparent laminate may be lowered. Use a solventless adhesive that does not contain a solvent. It is preferable. The adhesive may be a one-component type or a two-component type.

  Specific examples of the transparent adhesive that bonds the transparent resin layer (A) and the transparent layer (B) include, for example, an epoxy adhesive, an acrylic adhesive, and a urethane adhesive. A transparent adhesive may be used individually by 1 type, or multiple may be mixed and used for it. For example, Daikin Industries, Ltd.'s optodyne series acrylic UV adhesives (for example, optodyne UV-2000, optodyne UV-3000, etc.), Henkel's Loctite series acrylic UV adhesives (eg, Loctite 3193HS), Kyoritsu Chemical Sangyo Co., Ltd. World Lock series modified acrylate UV adhesive (for example, World Lock XVL-90, World Lock 8807, World Lock HRJ-21, etc.), Acrylic UV adhesive from Glu Lab, Ltd. (for example, GLX 18-73N, etc.) Acrylic adhesives such as DIC; Urethane adhesives such as DIC's Unidic V-9500 series urethane UV adhesives (eg, Unidic V-9520, Unidic V-9540, etc.); Optodyne series epoxy UV adhesives (for example, Optodyne UV-1000, Optodyne UV-4000, etc.), EA series epoxy thermosetting adhesives, Sanyu Rec Co., Ltd. (EA-409, EA-415, etc.) And epoxy adhesives such as ADEKA OPTOMER KR series epoxy photo-curing adhesives (such as KR-401) manufactured by ADEKA Corporation.

  In one embodiment of the present invention, the adhesive for laminating the transparent resin layer (A) and the transparent layer (B) has a tensile elastic modulus of 1 MPa or more at the time of curing (after curing) at a thickness of 1 mm and at the time of curing. Use something that is transparent. The reason is as follows. In order to demonstrate the properties generally required of adhesives that make it difficult to peel off the object to be bonded even when bending or bending force is applied, tensile elasticity at the time of curing of the adhesive is high. It is better to have a low rate, but if the tensile modulus at the time of curing of the adhesive is low, the adhesive layer will be deformed when bending or bending force is applied, and the hardness of the transparent layer (B) will be in the entire transparent laminate. It is presumed not to be reflected. Therefore, in this embodiment, a certain degree of tensile elastic modulus is ensured in the adhesive layer, and the transparent resin layer (B) is bonded to both sides of the transparent resin layer (A), whereby the transparent resin layer ( A) Higher rigidity can be exhibited compared to the single case. The tensile elastic modulus at the time of curing (after curing) at a thickness of 1 mm of the adhesive is preferably 10 MPa or more, more preferably 20 MPa or more. On the other hand, if the tensile modulus of the adhesive is too high, the occurrence of cracks in processing may become a problem. From this viewpoint, the tensile elastic modulus at the time of curing (after curing) at a thickness of 1 mm of the adhesive is preferably 4 GPa or less, more preferably 2 GPa or less.

  Examples of transparent adhesive application methods include dip coating, spray coating, spinner coating, bead coating, wire bar coating, blade coating, roller coating, curtain coating, slit die coater, and gravure. Examples include a coater method, a slit reverse coater method, a micro gravure method, and a comma coater method. There is a method in which a transparent adhesive is applied by applying a photocurable adhesive with a transparent resin layer, covering the transparent layer (B), and applying light. Since warping may occur when bonding one surface at a time, it is preferable to bond both surfaces of the transparent resin layer (A) simultaneously. When the transparent resin layer (A), the transparent layer (B), and the adhesive are transparent, the transparent layer (B) is laminated on both sides of the transparent resin layer (A), and light is emitted from one side. By irradiating, light reaches the other surface and both surfaces can be cured simultaneously.

  The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm. If the adhesive layer is too thick, the rigidity of the entire transparent laminate is lowered, and if it is too thin, the adhesiveness is lowered. When the thickness is in the above range, the rigidity and adhesiveness of the entire transparent resin laminate are improved.

  The viscosity at 23 ° C. before curing of the adhesive is preferably 10000 mPa · s or less, more preferably 5000 mPa · s or less. When it is in the above range, the coating film of the adhesive layer does not become too thick and is controlled to a desired thickness, so that a decrease in rigidity of the transparent resin laminate can be suppressed. Further, the lower limit of the viscosity is not particularly limited as long as a good coating film is formed, but is preferably 1 mPa · s or more in terms of workability at the time of application. The viscosity of the adhesive before curing can be measured according to JIS7117-1: 1999 using a rotary B-type viscometer.

  Moreover, since transparency of the whole transparent resin laminated body will fall when transparency of an adhesive agent is low, it is preferable to use an adhesive agent also with high transparency. For example, the total light transmittance of the adhesive layer is preferably 80% or more, and more preferably 85% or more. If it is 80% or more, the transparency is high and it is suitable as a display front plate.

If the shrinkage rate (curing shrinkage rate) associated with the curing of the adhesive is large, it causes a decrease in adhesion and warpage. Therefore, the curing shrinkage rate of the adhesive is preferably small. For example, the cure shrinkage is preferably 10% or less, and more preferably 8% or less.
(Method of measuring cure shrinkage)
The liquid specific gravity of the adhesive is obtained from 3.1 (1) of JIS K 7232: 1986, the specific gravity of the cured product of the adhesive is obtained from 3.2 (1) of JIS K 7232, and the cure shrinkage ratio is calculated from the following formula. taking measurement.
(Curing shrinkage) = (cured body specific gravity−liquid specific gravity) / (cured body specific gravity) × 100 (%)

The adhesive is preferably fast-curing from the viewpoint of productivity. For example, when a photo-curing adhesive is used, an adhesive that cures with an integrated light quantity of 5000 mJ / cm ² or less is preferable.

  Moreover, as shown in FIG. 2, when the transparent layer (B) is laminated directly on the transparent resin layer (A) and the transparent resin layer (A) and the transparent layer (B) are bonded, for example, transparent When the resin composition forming the layer (B) contains a curable resin, the resin composition before curing of the transparent layer (B) was applied to both sides of the transparent resin layer (A) to form a coating film. Thereafter, the coating film is cured by active energy such as heat or light, and thereby the transparent resin layer (A) and the transparent layer (B) are bonded.

  More specifically, when the resin composition forming the transparent layer (B) contains a thermosetting resin such as an epoxy resin, the transparent layer (B) before curing is superimposed on both sides of the transparent resin layer (A). The layers may be laminated while being cured by heating to the required temperature while pressing with a hot platen. Moreover, when the resin composition which forms a transparent layer (B) contains a thermoplastic resin, after heating a transparent layer (B) in advance to the temperature which the said thermoplastic resin softens, the softened transparent layer (B) There is a method in which the transparent resin layer (A) and the transparent layer (B) are adhered by solidifying by cooling to a temperature below the softening point while applying pressure on both sides of the transparent resin layer (A). When the resin composition forming the transparent layer (B) contains a photocurable resin, a glass fiber is used as the photocurable resin composition containing the compound (a) having a thiol group and the compound (b) having an alkenyl group. A method of photocuring a photocurable resin composition after laminating a coating film (transparent layer (B)) immersed in a cloth onto the transparent resin layer (A), a compound (a) having a thiol group and alkenyl A method of photocuring a coating film (transparent layer (B)) obtained by immersing a photocurable resin composition containing a group-containing compound (b) in a glass fiber cloth while adhering to the transparent resin layer (A). Is mentioned.

The physical properties of typical adhesives that can be used in the present invention are shown below. In the table, the value expressed as (actual measurement) is a physical property value measured by the measurement method used in the following examples.

  The transparent resin laminate (C) used in the display front plate of the present embodiment is transparent as a laminate because the transparent resin layer (A) and the transparent layer (B) are transparent. Moreover, also when laminating | stacking using a transparent adhesive agent, since a transparent resin layer (A), a transparent layer (B), and a transparent adhesive agent are transparent, it becomes transparent as a laminated body.

  The flexural modulus of the transparent resin laminate (C) used in the display front plate of the present embodiment is preferably 5 GPa or more, more preferably 7 GPa or more, and more preferably 8 GPa or more. If the flexural modulus of the transparent resin laminate is 5 GPa or more, the rigidity is improved and it is suitably used as a display front plate. For example, a transparent resin laminate having a bending elastic modulus of 5 GPa or more can be obtained by arranging a transparent layer (B) having a tensile elastic modulus of 10 GPa or more on both surfaces of a polycarbonate resin layer (A) having a bending elastic modulus of 2.6 GPa. And you can use it. Further, for example, a transparent layer (B) containing a curable resin having a tensile elastic modulus of 10 MPa or more at a thickness of 1 mm is disposed on both surfaces of a polycarbonate resin layer (A) having a flexural modulus of 2.6 GPa. A transparent resin laminate having an elastic modulus of 5 GPa or more is obtained and can be used. When the flexural modulus of the transparent resin laminate is 5 GPa or more, the rigidity is improved and it is suitably used as a display front plate.

  The transparent resin laminate according to an embodiment of the present invention is a transparent resin layer (A) having a tensile elastic modulus of 10 GPa or more by impregnating and curing a glass fiber cloth with a resin composition containing a curable resin on both sides of the transparent resin layer (A). It is a transparent laminated body which bonded together the layer (B) with the transparent adhesive whose tensile elasticity modulus after hardening in thickness 1mm is 1 Mpa or more.

  A transparent layer (B) of a transparent layer (B) having a tensile elastic modulus of 10 GPa or more is bonded to both surfaces of the polycarbonate resin layer (A) with the transparent adhesive, so that it is transparent and excellent in rigidity as a whole. The body can be obtained. This transparent laminate can be suitably used as a display front plate from the viewpoint of transparency and rigidity. When the tensile elastic modulus of the transparent layer (B) is smaller than 10 GPa, even if it is bonded to both surfaces of the polycarbonate resin layer (A) with a transparent adhesive having a tensile elastic modulus of 1 MPa or more when cured at a thickness of 1 mm, As a result, a transparent laminate having a bending elastic modulus of 5 GPa or more may not be obtained.

  The total light transmittance of the transparent resin laminate (C) used in the display front plate of the present embodiment is 80% or more, preferably 85% or more. When it is 80% or more, the transparency is high and it is suitably used as a display front plate. Further, from the viewpoint of image contrast and color reproducibility, the light transmittance at 400 nm of the transparent resin laminate (C) is preferably 60% or more, more preferably 70% or more, and particularly preferably 75%. That's it.

  In order to impart functionality such as scratch resistance to the transparent resin laminate (C) used in the display front plate of the present embodiment, a resin layer (smoothing layer) is provided on at least one surface of the transparent layer (B). ), And the resin layer is more preferably a polyethylene terephthalate film layer. The resin layer improves the surface smoothness and makes it easy to provide functionality. That is, in the transparent resin laminate of one embodiment of the present invention, a polyethylene terephthalate film layer is disposed on at least one outer side of the transparent layer (B).

  About the said polyethylene terephthalate film, when a surface hardness is required, it is preferable to perform a hard-coat process etc. By performing the hard coat treatment, the scratch resistance is improved, and it is suitably used as a front plate for a display.

  When performing a hard coat treatment on the polyethylene terephthalate film, a polyethylene terephthalate film as a hard coat layer that has been subjected to a hard coat treatment may be bonded together, or after a polyethylene terephthalate film is bonded, a hard coat treatment may be performed. A hard coat layer may be formed. That is, in the transparent resin laminate of one embodiment of the present invention, a hard coat layer is disposed on at least one outer side of the resin layer (for example, a polyethylene terephthalate film layer).

  When used as a display front plate, the polyethylene terephthalate film is preferably subjected to a transparent conductive film to form an electrode layer integrated material. By using an electrode layer-integrated material, an electrode layer becomes unnecessary, and material costs and process costs can be suppressed. That is, in the transparent resin laminate of one embodiment of the present invention, a transparent conductive film layer is disposed on at least one outer side of a resin layer (for example, a polyethylene terephthalate film layer).

  When a transparent electrode film is applied to the above polyethylene terephthalate film, a polyethylene terephthalate film that has been subjected to a transparent electrode film in advance may be bonded, or a transparent electrode film may be applied after the polyethylene terephthalate film has been bonded. When patterning the film, it may be performed after the polyethylene terephthalate film is bonded, or may be performed after the polyethylene terephthalate film is bonded.

  The method for attaching the polyethylene terephthalate film (layer) to the transparent layer (B) is not particularly limited. For example, a photocurable resin is formed on both sides of the transparent layer (B) constituting the transparent resin laminate (C), An example is a method in which a suitable transparent adhesive made of a thermosetting resin, a hot melt resin, or the like is applied, and then a polyethylene terephthalate film is laminated to cure the transparent adhesive. Moreover, when the resin composition which forms a transparent layer (B) contains a thermosetting resin, the transparent layer (B) before hardening is laminated | stacked on both surfaces of a transparent resin layer (A), and also as a resin layer on the outer side When the sulfur atom-containing resin forming the transparent layer (B) is a thermoplastic resin, the polyethylene terephthalate film may be laminated while being cured by heating to a required temperature while pressing with a heating plate. After the transparent layer (B) is preheated to a temperature at which it softens, it is stacked on both sides of the transparent resin layer (A), and a polyethylene terephthalate film as a resin layer is further stacked on the outside of the transparent layer (B). You may laminate | stack, solidifying by cooling.

  Although it does not specifically limit as a transparent adhesive which bonds a polyethylene terephthalate film and a transparent layer (B), An epoxy adhesive, an acrylic adhesive, and a urethane type adhesive can be used.

  The transparent resin laminate (C) of this embodiment is formed into the shape of a display front plate by punching the transparent resin laminate (C) as necessary as a display front plate, and is used as a liquid crystal display device, organic electro -It is attached to the surface mainly for the purpose of protecting a display device of a flat display device such as a luminescence (organic EL) device.

  An example of a method for setting the weave angle of the glass fiber cloth of the display front plate of the present embodiment to have an inclination of 1 ° or more with respect to the pixel portion row of the display element in order to prevent moire.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. In addition, about the produced transparent resin laminated body, the light transmittance, the Abbe number, and the elasticity modulus were measured by the method shown below.

(1) Total light transmittance and light transmittance of each wavelength (transparency)
The total light transmittance is measured using a haze meter NDH-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the light transmittance at each wavelength is measured using a spectrophotometer MULTISPEC-1500 (manufactured by Shimadzu Corporation). It was measured.

(2) Refractive index / Abbe number (Transparent layer (B))
Using a multi-wavelength Abbe refractometer DR-M4 (manufactured by Atago Co., Ltd.), the refractive index and the Abbe number were measured.

(Glass fiber cloth)
The Abbe number of E glass fiber cloth was measured by the following method. Using contact liquids (manufactured by Shimadzu Device Manufacturing Co., Ltd.) having different refractive indexes, a liquid having a refractive index of 589 nm and a refractive index of 1.535 to 1.570 is adjusted in steps of a refractive index difference of 0.001 to obtain an E glass fiber cloth (3313 53 S101S (manufactured by Nitto Boseki Co., Ltd.) and sandwiched in a slide glass with a 100 μm slit to produce a 100 μm-thick contact liquid-impregnated E glass fiber cloth, and a spectrum measurement is performed using a spectrophotometer It was.

  Measure the refractive index of D-line (589 nm), F-line (486 nm), and C-line (656 nm) of various adjusted contact liquids, and plot the horizontal axis as the refractive index of the contact liquid and the vertical axis as the light transmittance for each wavelength. Then, the refractive index with the highest light transmittance was taken as the refractive index of the E glass fiber cloth having that wavelength.

  The Abbe number was derived from the refractive indexes of the D line (589 nm), F line (486 nm), and C line (656 nm) of the E glass fiber cloth.

(3) Flexural modulus Measured by a three-point bending test using a precision universal testing machine AG-5000B (manufactured by Shimadzu Corporation). The distance between fulcrums was 20 mm, and the stroke speed was 1 mm / min. A 1 kN load cell was used.

(4) Tensile modulus (transparent layer (B) and resin)
The tensile elastic modulus was measured using a dynamic viscoelasticity measuring device DMS6100 (manufactured by SII Nano Technology Co., Ltd.). The test length was 20 mm and the frequency was 1 Hz. The tensile elastic modulus in the present invention means a storage elastic modulus at 20 ° C.

<Preparation of transparent resin laminate>
[Example A-1]
54 parts by mass of a cyclohexane oxide skeleton-containing epoxy resin (Celoxide 2021P, manufactured by Daicel Corp., refractive index 1.51), which is a resin having a lower refractive index than E glass fiber cloth, and sulfur having a higher refractive index than E glass fiber cloth Pentaerythritol tetrakisthiopropionate (hereinafter referred to as PETP, manufactured by Sakai Chemical Co., Ltd., refractive index 1.60) 43 parts by mass, 4-mercaptomethyl-3,6-dithia-1 which is a resin containing a compound , 8-octanedithiol (hereinafter referred to as GST, synthesized in accordance with Japanese Patent No. 3048929, refractive index 1.70) was mixed with 3 parts by mass and stirred for 5 minutes with a magnetic stirrer. Further, 1 part by mass of Tetrabutylphosphonium O, O-Diethyl Phosphorodithioate (Wako Pure Chemical Industries, Ltd.) was added as a curing accelerator, and the mixture was stirred with a magnetic stirrer for 5 minutes to obtain a monomer mixture.

  The monomer mixed solution is put into a vat, and an E glass fiber cloth (3313 53 S101S, manufactured by Nitto Boseki Co., Ltd., refractive index 1.56) is immersed in the monomer mixed solution, and the mold release treatment is completed. Of polyethylene terephthalate film. This was placed in a blown oven and held at 40 ° C. for 5 hours, then heated to 120 ° C. at 0.5 ° C./min, and cured by holding at 120 ° C. for 5 hours to obtain a transparent layer 1.

A transparent epoxy adhesive KR-401 (manufactured by ADEKA Co., Ltd.) is applied to a polycarbonate resin plate (Iupilon NF-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 700 μm) with a bar coater to a thickness of about 30 μm, and air bubbles The transparent layer 1 was stacked so as not to enter. Similarly, the other surface was coated with an adhesive, and the transparent layer 1 was layered thereon, irradiated with UV at 1000 mJ / cm ² using a UV irradiation device, and turned over to be irradiated with 1000 mJ / cm ² and cured. Thereby, a three-layer transparent resin laminate of transparent layer / transparent resin layer (PC) / transparent layer was formed to produce a display front plate. The thickness of the display front plate was 913 μm. In addition, light also reached the other transparent layer 1 by irradiation from one side, and both adhesive surfaces of the transparent resin layer (PC) were cured simultaneously, but light was also irradiated from the other side just in case.

[Example A-2]
The monomer mixed solution prepared in Example A-1 was put in a vat, and E glass fiber cloth (3313 53 S101S, manufactured by Nitto Boseki Co., Ltd.) was immersed therein to allow the monomer mixed solution to be immersed thereinto. It was sandwiched between a plate (thickness 700 μm) and a 50 μm stretched polyethylene terephthalate film. This was placed in a blown oven and held at 40 ° C. for 5 hours, then heated to 120 ° C. at 0.5 ° C./min, cured by holding at 120 ° C. for 5 hours, and stretched polyethylene terephthalate film / transparent layer / A five-layer transparent resin laminate of transparent resin layer (PC) / transparent layer / stretched polyethylene terephthalate film was formed to produce a display front plate. The thickness of the display front plate was 990 μm.

[Comparative Example A-1]
47 parts by mass of a triazine skeleton-containing epoxy resin (TEPIC-S (Nissan Chemical Industry Co., Ltd., refractive index 1.54)), which is a resin having a lower refractive index than E glass fiber cloth, and a refractive index than E glass fiber cloth 21 parts by mass of an epoxy resin (Techmore VG3101, manufactured by Printec Co., Ltd., refractive index 1.61) and a curing agent (Ricacid MH700 (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride) Acid = 70/30) (manufactured by Shin Nippon Rika Co., Ltd., refractive index 1.49)) 32 parts by mass were mixed, diluted with 2-butanone to 50 wt%, and then stirred with a magnetic stirrer for 10 minutes. Further, as a curing accelerator, Tetrabutylphosphonium O, O-Diethyl Phosphodithioate ( By Wako Pure Chemical Pure Chemical Industries Co., Ltd.) 0.8 parts by mass was added and stirred for 5 minutes with a magnetic stirrer, was a monomer mixture solution.

  The above monomer mixture solution is immersed in E glass fiber cloth (3313 53 S101S, Nittobo Co., Ltd., refractive index 1.56) and heated at 130 ° C. for 4 minutes to remove the solvent and resin. Semi-cured to prepare a prepreg. Then, this single prepreg is sandwiched between surface-treated SUS plates, set in a hot and cold press VH2-1630 (manufactured by Kitagawa Seiki Co., Ltd.), heated to 200 ° C. at 3 ° C./min, and at 200 ° C. for 1 hour. Holding and hardening, the transparent layer 2 was obtained.

Apply a transparent epoxy adhesive KR-401 (manufactured by ADEKA Co., Ltd.) to a polycarbonate resin plate (Mitsubishi Gas Chemical Co., Ltd., thickness 700 μm) with a bar coater to a thickness of about 30 μm to prevent bubbles from entering. The transparent layer 2 was overlaid on the surface. Similarly, the other surface was coated with an adhesive, and the transparent layer 2 was layered thereon. Using a UV irradiation device, UV was irradiated at 1000 mJ / cm ² , and then turned over and irradiated at 1000 mJ / cm ² to be cured. Thereby, a three-layer transparent resin laminate of transparent layer / transparent resin layer (PC) / transparent layer was formed to produce a display front plate. The thickness of the display front plate was 951 μm.

<Evaluation>
For the transparent resin laminate produced as described above, the refractive index, total light transmittance, and Abbe number of the transparent layer or glass fiber cloth; and the total light transmittance of the transparent resin laminate, 400 nm, according to the evaluation method described above. Alternatively, the light transmittance at 550 nm and the flexural modulus were measured.

<Preparation of transparent resin laminate>
[Example B-1]
Tricyclodecane dimethanol diacrylate of an alicyclic resin having an alkenyl group, which is a resin having a lower refractive index than the E glass fiber cloth used (hereinafter referred to as A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.53) 83 parts by mass and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol (hereinafter referred to as GST) which is a resin having a thiol group having a refractive index higher than that of the E glass fiber cloth used. (Mitsui Chemicals Co., Ltd., 1.70) 17 parts by mass were mixed and stirred with a magnetic stirrer for 5 minutes. Further, 0.5 part by mass of Irgacure 184 as a photopolymerization initiator was added to the resin part by mass, and the mixture was stirred with a magnetic stirrer for 5 minutes to obtain a monomer mixture.

  The monomer mixed solution is put into a pad, and an E glass fiber cloth (3313 53 S101S, manufactured by Nitto Boseki Co., Ltd., refractive index 1.56) is immersed therein to allow the monomer mixed solution to be immersed therein. Of polyethylene terephthalate film. Using an ultraviolet light irradiation device (eye ultraviolet curing device, manufactured by Eye Graphics Co., Ltd.), ultraviolet light is 1000 mJ / cm. ²Irradiate and turn over again 1000 mJ / cm²Irradiated and cured to obtain a transparent fiber reinforced resin 1.

A transparent epoxy adhesive KR-401 (manufactured by ADEKA Co., Ltd.) was applied to a polycarbonate resin plate (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 800 μm) with a bar coater at a thickness of about 30 μm. The transparent fiber reinforced resin 1 is layered so that bubbles do not enter, and ultraviolet light is irradiated at 1000 mJ / cm ² using an ultraviolet light irradiation device (eye ultraviolet curing device, manufactured by Eye Graphics Co., Ltd.). / Cm ² irradiation and curing. Thus, a three-layer transparent resin laminate of transparent fiber reinforced resin layer (transparent layer) / transparent resin layer (polycarbonate) / transparent fiber reinforced resin layer (transparent layer) was obtained. The thickness of this transparent resin laminate was 1080 μm. In addition, although light also reached the other transparent layer by irradiation from one side and both adhesive surfaces of the transparent resin layer (PC) were cured simultaneously, light was also irradiated from the other side just in case.

[Comparative Example B-1]
70 parts by mass of A-DCP (made by Shin-Nakamura Chemical Co., Ltd., refractive index 1.53) of an alicyclic resin having an alkenyl group, which is a resin having a refractive index lower than that of the used E glass fiber cloth, was used. Shin-Nakamura Chemical, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (hereinafter referred to as A-BPEF), which is an aromatic resin having an alkenyl group having a higher refractive index than E glass fiber cloth Industrial Co., Ltd. product, refractive index 1.62) 30 mass parts was mixed, and it stirred with a magnetic stirrer at 50 degreeC for 30 minutes. Furthermore, 0.5 part by mass of Irgacure 184 as a photopolymerization initiator was added to the resin part by mass, and the mixture was stirred with a magnetic stirrer at 50 ° C. for 5 minutes to obtain a monomer mixture.

  The monomer mixed solution is put into a pad, and an E glass fiber cloth (3313 53 S101S, manufactured by Nitto Boseki Co., Ltd., refractive index 1.56) is immersed therein to allow the monomer mixed solution to be immersed therein. Of polyethylene terephthalate film. Using an ultraviolet light irradiation device (eye ultraviolet curing device, manufactured by Eye Graphics Co., Ltd.), ultraviolet light is 1000 mJ / cm. ²Irradiate and turn over again 1000 mJ / cm²Irradiated and cured to obtain transparent fiber reinforced resin 2.

Apply a transparent epoxy adhesive KR-401 (manufactured by ADEKA Corporation) with a thickness of about 30 μm to a polycarbonate resin plate (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 800 μm) with a bar coater, The transparent fiber reinforced resin 2 is layered so that bubbles do not enter, and ultraviolet light is irradiated at 1000 mJ / cm ² using an ultraviolet light irradiation device (eye ultraviolet curing device, manufactured by Eye Graphics Co., Ltd.). / Cm ² irradiation and curing. Thus, a three-layer transparent resin laminate of transparent fiber reinforced resin layer (transparent layer) / transparent resin layer (polycarbonate) / transparent fiber reinforced resin (transparent layer) was obtained. The thickness of this transparent resin laminate was 1060 μm.

<Evaluation>
For the transparent resin laminate produced as described above, the refractive index, total light transmittance and Abbe number of the transparent layer (transparent fiber reinforced resin layer) or glass fiber cloth; The total light transmittance, the light transmittance at 400 nm or 550 nm, and the flexural modulus were measured.

<Preparation of transparent resin laminate>
[Example C-1]
51 parts by mass of a cyclohexane oxide skeleton-containing epoxy resin (Celoxide 2021P, manufactured by Daicel Corporation, refractive index 1.51), which is a resin having a lower refractive index than E glass cloth, and a cyclohexane oxide skeleton-containing epoxy resin (Celoxide 2000Z, ( Co., Ltd., manufactured by Daicel Corporation, refractive index 1.50) 3 parts by mass, pentaerythritol tetrakisthiopropionate (hereinafter referred to as PETP, manufactured by Sakai Chemical Co., Ltd.), which is a resin having a higher refractive index than the E glass cloth used. (Refractive index 1.60) 43 parts by mass, 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol (hereinafter referred to as GST, synthesized in accordance with Japanese Patent No. 3048929, refractive index 1.70) 3 parts by mass The parts were mixed and stirred with a magnetic stirrer for 5 minutes. Further, 1 part by mass of Tetrabutylphosphonium O, O-Diethyl Phosphorodithioate (Wako Pure Chemical Industries, Ltd.) was added as a curing accelerator, and the mixture was stirred with a magnetic stirrer for 5 minutes to obtain a monomer mixture.

  The monomer mixed solution is put into a vat, and E glass cloth (3313 53 S101S, manufactured by Nitto Boseki Co., Ltd., refractive index 1.56) is immersed in the monomer mixed solution so that the release treatment is completed. It was sandwiched between polyethylene terephthalate films. This was placed in a blown oven and held at 40 ° C. for 5 hours, then heated to 120 ° C. at 0.5 ° C./min and cured by holding at 120 ° C. for 5 hours to obtain a transparent layer. The total thickness of the transparent layer was 186 μm (single side: 93 μm).

A transparent epoxy adhesive KR-401 (manufactured by ADEKA Co., Ltd.) is applied to a polycarbonate resin plate (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 800 μm) with a thickness of about 20 μm using a bar coater. The transparent layer was layered so that no bubbles could enter. Similarly, the other surface was coated with an adhesive, and a transparent layer was laminated thereon. Using a UV irradiation device, UV was irradiated at 1000 mJ / cm ² , and turned over to be irradiated at 1000 mJ / cm ² to be cured. Thereby, a three-layer transparent laminate of transparent layer / polycarbonate resin layer / transparent layer was obtained. The thickness of this transparent laminate was 1020 μm. In addition, light also reached the other transparent layer 1 by irradiation from one side, and both adhesive surfaces of the transparent resin layer (PC) were cured simultaneously, but light was also irradiated from the other side just in case.

[Example C-2]
Transparent layer / polycarbonate resin layer / transparent in the same manner as in Example 1 except that 48 parts by mass of Celoxide 2021P, 6 parts by mass of Celoxide 2000Z, 43 parts by mass of PETP, and 3 parts by mass of GST were mixed to obtain a monomer mixture. A three-layer transparent laminate of layers was obtained. The total thickness of this transparent layer was 178 μm (one side: 89 μm), and the thickness of the transparent laminate was 1028 μm.

[Example C-3]
Transparent layer / polycarbonate resin layer in the same manner as in Example C-1, except that 42 parts by mass of Celoxide 2021P, 12 parts by mass of Celoxide 2000Z, 41 parts by mass of PETP, and 5 parts by mass of GST were mixed to obtain a monomer mixture. / A three-layer transparent laminate of transparent layers was obtained. The total thickness of this transparent layer was 182 μm (single side: 91 μm), and the thickness of the transparent laminate was 1037 μm.

[Example C-4]
A transparent layer / polycarbonate resin layer in the same manner as in Example C-1, except that 36 parts by mass of Celoxide 2021P, 18 parts by mass of Celoxide 2000Z, 42 parts by mass of PETP, and 4 parts by mass of GST were mixed to obtain a monomer mixture. / A three-layer transparent laminate of transparent layers was obtained. The total thickness of the transparent layer was 172 μm (one side: 86 μm), and the thickness of the transparent laminate was 1045 μm.

[Example C-5]
Transparent layer / polycarbonate resin layer in the same manner as in Example C-1, except that 27 parts by mass of Celoxide 2021P, 27 parts by mass of Celoxide 2000Z, 40 parts by mass of PETP, and 6 parts by mass of GST were mixed to obtain a monomer mixture. / A three-layer transparent laminate of transparent layers was obtained. The total thickness of the transparent layer was 210 μm (single side: 105 μm), and the thickness of the transparent laminate was 1016 μm.

<Evaluation>
With respect to the transparent laminate produced as described above, the total light transmittance and tensile elastic modulus of the transparent layer; the tensile elastic modulus of the curable resin used for the transparent layer (B) and the transparent resin by the evaluation method described above The flexural modulus of the laminate was measured.

The tensile modulus of the curable resin for the transparent layer was measured by the following method. A SUS frame (thickness 1 mm) with a hole of 2 cm × 4 cm is placed on a release-treated glass plate, filled with each monomer mixture into the hole, covered with the release-treated glass plate, and UV irradiation device The sample was irradiated with UV at 1000 mJ / cm ² , further turned over, and cured by irradiation at 1000 mJ / cm ² to obtain a curable resin test piece. About the obtained curable resin test piece, the tensile elasticity modulus was measured by said method.

  As shown in Table C1 below, the total light transmittance of the transparent layer was 80% or more in all Examples.

  The flexural modulus of the polycarbonate resin layer (thickness 800 μm) as the transparent resin layer (A layer) was 2.6 GPa. As shown in Table C2, in Examples C-1 to C-4, the flexural modulus of the transparent laminate was all 5 GPa or more. From this, it is confirmed that the rigidity (bending elastic modulus) of the laminate can be further improved by including a curable resin having a tensile elastic modulus of 10 MPa or more in the transparent layer.

<Preparation of transparent resin laminate>
[Example D-1]
(Preparation of transparent layer (B-1))
E glass fiber cloth (3313 53 S101S, manufactured by Nitto Boseki Co., Ltd.) was used as the glass fiber cloth. 54 parts by mass of a cyclohexane oxide skeleton-containing epoxy resin (Celoxide 2021P, manufactured by Daicel Corporation, refractive index 1.51), which is a resin having a lower refractive index than the used E glass fiber cloth, is refracted more than the used E glass cloth. 43 parts by mass of pentaerythritol tetrakisthiopropionate (manufactured by Sakai Chemical Industry Co., Ltd., refractive index 1.60), which is a resin containing a sulfur compound having a high rate, and 4-mercaptomethyl-3,6-dithia-1, 3 parts by mass of 8-octanedithiol (hereinafter referred to as GST, synthesized in accordance with Japanese Patent No. 3048929, refractive index 1.70) was mixed and stirred for 5 minutes with a magnetic stirrer. Furthermore, 1 part by mass of Tetrabutylphosphonium O, O-Diethyl Phosphorodithioate (Wako Pure Chemical Industries, Ltd.) was added as a curing accelerator, and stirred for 5 minutes with a magnetic stirrer to obtain a curable resin composition.

  The curable resin composition was placed in a vat, and an E glass fiber cloth was immersed therein to infiltrate the curable resin composition, and was sandwiched between release-treated PET films. This was placed in a blown oven and held at 40 ° C. for 5 hours, then heated to 120 ° C. at 0.5 ° C./min, cured by holding at 120 ° C. for 5 hours, and a transparent layer (B -1) was obtained. The tensile elastic modulus of the transparent layer (B-1) was 19 GPa.

(Adhesion of polycarbonate resin layer (A) and transparent layer (B-1))
Transparent epoxy adhesive KR-401 (manufactured by ADEKA Co., Ltd.) with a bar coater on a polycarbonate resin plate (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Inc., thickness 700 μm, flexural modulus 2.6 GPa) The tensile elastic modulus at 1 mm was 1593 MPa) was applied in a thickness of 30 μm, and the transparent layer (B-1) was layered so as not to contain bubbles. Similarly, the other surface was coated with an adhesive, and the transparent layer (B-1) was layered thereon. Using a UV irradiation device, UV was irradiated at 1000 mJ / cm ² , and the film was turned over and irradiated at 1000 mJ / cm ² to be cured. This obtained the three-layer transparent laminated body of transparent layer (B-1) / polycarbonate resin layer (A) / transparent layer (B-1). The thickness of this transparent laminate was 1013 μm. In addition, light also reaches the other transparent layer (B-1) by irradiation from one side, and both adhesive surfaces of the polycarbonate resin layer (A) are cured at the same time, but light is also irradiated from the other side just in case. did.

[Example D-2]
(Preparation of transparent layer (B-2))
E glass fiber cloth (3313 53 S101S, Nittobo Co., Ltd.) was used as the glass fiber cloth in the same manner as in Example 1. 83 parts by mass of tricyclodecane dimethanol diacrylate (made by Shin-Nakamura Chemical Co., Ltd., refractive index 1.53) of an alicyclic acrylate resin which is a resin having a lower refractive index than the E glass fiber cloth used 17 parts by mass of GST, which is a resin having a higher refractive index than the conventional E glass fiber cloth, was mixed and stirred for 5 minutes with a magnetic stirrer. Further, 0.5 part by mass of Irgacure 184 was added as a photopolymerization initiator, and the mixture was stirred with a magnetic stirrer for 5 minutes to obtain a curable resin composition. The curable resin composition was placed in a pad, and an E glass fiber cloth was immersed therein to infiltrate the curable resin composition, and was sandwiched between the release-treated PET films. This was irradiated with 1000 mJ / cm ^{2 of} UV using a UV irradiation apparatus, turned over and further irradiated with 1000 mJ / cm ² and cured to obtain a transparent layer (B-2) having a thickness of 119 μm. The tensile elastic modulus of the transparent layer (B-2) was 18 GPa.

(Adhesion of polycarbonate resin layer (A) and transparent layer (B-2))
Except that the transparent layer (B-1) was changed to (B-2), it was adhered in the same manner as in Example 1 to obtain a transparent laminate having a thickness of 1021 μm.

[Example D-3]
A transparent layer (B-1) / polycarbonate resin layer (as in Example D-1) except that GLX18-73N (manufactured by Guru Lab, tensile elastic modulus at a thickness of 1 mm is 26 MPa) was used as an adhesive. A three-layer transparent laminate of A) / transparent layer (B-1) was obtained. The thickness of this transparent laminate was 1058 μm.

[Example D-4]
A transparent layer (B) was prepared in the same manner as in Example D-1, except that Worldlock HRJ-21 (manufactured by Kyoritsu Chemical Industry Co., Ltd., tensile elastic modulus at a thickness of 1 mm was 0.32 MPa) was used as an adhesive. -1) A three-layer transparent laminate of polycarbonate resin layer (A) / transparent layer (B-1) was obtained. The thickness of this transparent laminate was 1061 μm.

[Comparative Example D-1]
A transparent epoxy adhesive KR-401 is applied to a polycarbonate resin plate (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness 700 μm) with a bar coater at a thickness of about 30 μm, and polyethylene is prevented from entering bubbles. A terephthalate (PET) resin film (thickness: 100 μm) was stacked. Similarly, the other surface was coated with an adhesive, overlapped with a PET resin film, irradiated with UV at 1000 mJ / cm ² using a UV irradiation device, and further turned over and irradiated with 1000 mJ / cm ² to be cured. Thus, a three-layer transparent laminate of PET resin film / polycarbonate resin layer / PET resin film was obtained. The thickness of this transparent laminate was 1014 μm.

  About the sample produced as described above, the total light transmittance and bending elastic modulus of the transparent resin laminate; the tensile elastic modulus of the adhesive; and the tensile elastic modulus of the transparent layer (B) were evaluated by the evaluation methods described above. . The tensile modulus of the adhesive was measured by the following method.

(Measurement of tensile modulus of adhesive)
Place a SUS frame (thickness 1 mm) with a 2 cm x 4 cm hole on a glass plate that has been subjected to a release treatment, fill each hole with an adhesive, cover the glass plate that has been subjected to a release treatment, and then apply a UV irradiation device. The sample was irradiated with UV at 1000 mJ / cm ² , further turned over and irradiated with 1000 mJ / cm ² to be cured. This was used as a sample for elastic modulus measurement, and the tensile elastic modulus was measured with a viscoelasticity measuring device DMS6100 in the same manner as the measurement method for tensile elastic modulus described above.

  As shown in Table D1, the total light transmittance of the transparent layer was 80% or more in all Examples. Further, as shown in Table D1, in Examples D-1 to D-3, the transparent laminate has a flexural modulus of 5 GPa or more, and is used as a substitute for glass for various glazing materials, substrate materials, front plate materials such as display front plates. Therefore, a preferable rigidity can be obtained. From this, the rigidity (bending elastic modulus) of the laminate can be further improved by using an adhesive having a tensile elastic modulus of the transparent layer (B) of 10 GPa or more and an elastic modulus of 1 MPa or more. It is confirmed. In Comparative Example D-1 using a film having a tensile modulus of 10 GPa or less for the transparent layer (B), an adhesive having a modulus of elasticity of 1 MPa or less was used, but the flexural modulus of the transparent laminate was 5 GPa or less. It was.

1 Transparent resin layer (A)
2 Transparent layer (B)
3 Adhesive Layer 4 Polyethylene Terephthalate Film Layer 5 Sheet 10 Display Front Plate 21 Glass Fiber Cloth 22 Resin Composition

Claims (24)

A transparent resin laminate in which a transparent layer (B) including a glass fiber cloth and a resin composition containing a sulfur atom-containing resin is disposed on both sides of the transparent resin layer (A) ,
The sulfur atom-containing resin is at least one selected from the group consisting of a thermoplastic resin containing a sulfur atom, a thermosetting resin containing a sulfur atom, and a photocurable resin containing a sulfur atom,
The thermoplastic resin containing sulfur atoms is selected from polythiocarbonate resins, polythioester resins, polyoxothioester resins, polythioether resins, and sulfur-containing cyclic polyolefin resins,
The thermosetting resin containing a sulfur atom is selected from an episulfide resin and a thermosetting resin composed of a polyfunctional thiol compound and an epoxy resin,
The photocurable resin containing a sulfur atom is selected from a photocurable resin composed of a polyfunctional thiol compound and an epoxy resin, and a photocurable resin composed of a polyfunctional thiol compound and a compound having an alkenyl group. To be
Transparent resin laminate. And the Abbe number at the time of curing of the resin composition in the transparent layer (B), the difference between the Abbe number of the glass fiber cloth Ri der 15 or less,
And the refractive index of the resin composition in the transparent layer (B), the difference between the refractive index of the glass fiber cloth is 0.01 or less, the transparent resin laminate according to claim 1.   On both surfaces of the transparent resin layer (A), a transparent layer (B) comprising a glass fiber cloth impregnated with a resin composition containing a curable resin having a tensile modulus of elasticity of 10 MPa or more at a thickness of 1 mm is disposed. The transparent resin laminate according to claim 1 or 2. It has an adhesive layer containing a transparent adhesive between the transparent resin layer (A) and the transparent layer (B), or the transparent resin layer (A) and the transparent layer (B) are directly bonded. and it has a transparent resin laminate according to any one of claims 1 to 3.   The transparent resin laminate according to claim 4, wherein the adhesive layer has a thickness of 1 μm to 100 μm.   The transparent resin layered product according to claim 4 or 5 whose tensile elastic modulus at the time of hardening in thickness 1mm of said transparent adhesive is 1 Mpa or more.   A transparent layer (B) having a tensile elastic modulus of 10 GPa or more by impregnating and curing a glass fiber cloth with a resin composition containing a curable resin on both sides of the transparent resin layer (A) is cured at a thickness of 1 mm. The transparent resin laminated body as described in any one of Claims 1-6 bonded together with the transparent adhesive whose tensile elasticity modulus is 1 Mpa or more.   The transparent resin laminate according to any one of claims 4 to 7, wherein the transparent adhesive is at least one selected from the group consisting of an acrylic adhesive, an epoxy adhesive, and a urethane adhesive. .   The transparent resin laminate according to any one of claims 1 to 8, wherein the flexural modulus of the transparent resin laminate is 5 GPa or more.   The transparent resin layered product according to any one of claims 1 to 9, wherein the transparent resin layer (A) has a thickness of 100 µm to 2000 µm, and the transparent layer (B) has a thickness of 20 µm to 300 µm.   The transparent resin laminated body as described in any one of Claims 1-10 whose total light transmittance is 80% or more.   The polyfunctional thiol compound includes 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 2,2′-oxybis (1-mercaptoethane), 2,2′-thiobis (1-mercaptoethane), 1,4-dimercaptobutane-2,3-diol, ethylene glycol bis (1-mercaptoethane), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptopropionate), ethylene glycol bis (3-mercaptobutanoate), butanediol bis (2-mercaptoacetate), butanediol bis (3-mercaptopro Pionate), butanediol bis (2-mer) Ptopropionate), butanediol bis (3-mercaptobutanoate), pentaerythritol, triazine trithiol, glycerol tris (2-mercaptoacetate), glycerol tris (3-mercaptopropionate), glycerol tris (2 -Mercaptopropionate), glycerol tris (3-mercaptobutanate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate) , Pentaerythritol tetrakis (3-mercaptobutanate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-merca) Topropionate), trimethylolpropane tris (2-mercaptopropionate), trimethylolpropane tris (3-mercaptobutanate), trimethylolethanetris (2-mercaptoacetate), trimethylolethanetris (3-mercaptopropionate) ), Trimethylolethane tris (2-mercaptopropionate), trimethylolethane tris (3-mercaptobutanate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, bis (mercaptomethyl)- 1,11-dimercapto-3,6,9-trithiaundecane, 2,5-bis (mercaptomethyl) -1,4-dithiane, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, and Dipentae The transparent resin laminate according to any one of claims 1 to 11, which is at least one selected from the group consisting of lithitol hexakis (3-mercaptopropionate).   The compound having an alkenyl group is 2-methacryloyloxyethyl phthalic acid, methoxypolyethylene glycol methacrylate, 1,9-nonanediol dimethacrylate, neopentyl glycol dimethacrylate, ethoxylated polypropylene glycol dimethacrylate, glycerin dimethacrylate, polypropylene glycol Dimethacrylate, trimethylolpropane trimethacrylate, ethoxylated o-phenylphenol acrylate, methoxypolyethylene glycol acrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, isostearyl acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate , Polyethylene glycol diacrylate, Lopoxylated ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, propoxylated bisphenol A diacrylate, tricyclodecane dimethanol diacrylate, 1,10-decanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate , Ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, pentaerythritol Tall triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl Isocyanurate, 1,3-diallyl-5-methoxycarbonyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3-diallyl-5- (cyclohexene-4- At least one selected from (lyl) methoxycarbonyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, and triallyl isocyanurate That, the transparent resin laminate according to any one of claims 1 to 12. The transparent resin laminate according to any one of claims 1 to 13, wherein the sulfur atom-containing resin is a photocurable resin comprising the polyfunctional thiol compound and a compound having an alkenyl group. It said sulfur atom-containing resin, the polyfunctional thiol compound and a thermosetting resin or a photocurable resin comprising a epoxy resin, a transparent resin laminate according to any one of claims 1 to 1 3. Refractive index of the glass fiber cloth in the transparent layer (B) is 1.55 greater than the transparent resin laminate according to any one of claims 1 to 1 5. The transparent resin laminate according to any one of claims 1 to 16 , wherein the glass fiber cloth of the transparent layer (B) is an E glass cloth. The resin component in the transparent resin layer (A) is polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, cyclic cycloolefin resin, norbornene resin, acrylic resin, polystyrene, polyethersulfone, polyarylate, polyester resin, The transparent resin laminated body as described in any one of Claims 1-17 containing at least 1 type selected from the group which consists of a polyacetal resin, polyvinyl butyral, polyvinyl alcohol, and a urethane resin . Wherein the resin component in the transparent resin layer (A), polycarbonate, polyethylene terephthalate, polybutylene terephthalate, containing at least one selected from the group consisting of polymethyl methacrylate, of any one of claims 1 to 1 8 Transparent resin laminate. The transparent resin laminated body of Claim 19 in which the resin component in the said transparent resin layer (A) contains a polycarbonate. The transparent resin laminate according to any one of claims 1 to 20 , wherein a polyethylene terephthalate film layer is disposed on at least one outer side of the transparent layer (B). The transparent resin laminate according to claim 21 , wherein a hard coat layer is further disposed on at least one outer side of the polyethylene terephthalate film layer. Further the transparent conductive film layer on at least one outer was arranged, the transparent resin laminate according to claim 21 or 2 of said polyethylene terephthalate film layer. Using the transparent resin laminate according to any one of claims 1-2 3, a display front plate.