TW201538328A - Transparent resin laminate and front surface plate - Google Patents

Abstract

Provided is a transparent resin laminate having excellent transparency and rigidity. The transparent resin laminate has transparent layers (B) including a glass fiber cloth and a resin composition containing a sulfur compound, arranged on both surfaces of a transparent resin layer (A).

Description

Transparent resin laminate and front panel

The present invention relates to a transparent resin laminate having a high light transmittance in a wide wavelength range such as a total light transmittance of 80% or more, a light transmittance of 550 nm of 80% or more, and a light transmittance of 400 nm of 60% or more.

A transparent resin film or sheet represented by polymethyl methacrylate (PMMA), polycarbonate (PC), or polyethylene terephthalate (PET), widely used as an electric and electronic device such as a liquid crystal display or a mobile phone. Optical materials such as equipment. In recent years, the front panel (front panel) of a portable display device such as a mobile phone terminal, a portable electronic game machine, and a portable information terminal (PDA) requires not only transparency and visibility, but also It has weather resistance that can be used in the field, scratch resistance due to finger contact, carrying and handling, and impact resistance and rigidity to prevent damage due to impact and weight.

Because of these problems, chemically strengthened glass is often used for front panels such as liquid crystal displays. However, considering the problems of processability, difficulty in operation, cost, large size, and easy breakage, there is a strong demand for resins that have high rigidity and dimensional stability in place of glass. Film or sheet.

A candidate for the material of the front panel of the display device has been proposed: a film and a sheet composed of polymethyl methacrylate (PMMA) and polycarbonate (PC), which are uniformly dispersed as a filler in the polyester. A polyester film (Patent Document 1), a laminated plate in which an acrylic resin layer (PMMA layer) is provided on at least one surface of a polycarbonate resin layer (PC layer) (Patent Document 2), and an oxime resin composition is used. A fluorene ketone resin molded article obtained by radical polymerization (Patent Document 3), a laminate in which a biaxially stretched PET film is attached to a PC (Patent Document 4), and the like. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin

[The subject to be solved by the invention]

However, the materials described above are difficult to achieve both transparency and rigidity required for the panel material of the display device. In particular, with the increase in the size of the portable display device, it is required to make the resin member for the front panel more rigid.

For example: polymethyl methacrylate (PMMA), glass has a low transfer temperature and is easily broken, so the processability is inferior. Polycarbonate (PC) has a glass transition temperature of about 145 ° C, but its surface hardness and rigidity are not good, and it is difficult to use it as a front panel such as a display. Regarding polyethylene terephthalate (PET), the softening temperature of the biaxially stretched one is higher than 200 ° C, and the surface hardness is also good, but the thickness of the sheet is difficult to be thickened, and it is difficult to cope with thick film use (Patent Document 1) ). A laminate having a PMMA layer and a PC layer has been examined (Patent Document 2), and some of them have been used, but there are problems in that the warpage of the heat treatment in the processing step causes problems in workability and insufficient rigidity.

Further, Patent Document 3 discusses an oxime resin molded article which is used as a glass substitute, and Patent Document 4 discloses a laminate using PC and a biaxially stretched polyethylene terephthalate (PET) film to achieve high rigidity. But not satisfactory.

An object of the present invention is to provide a transparent resin laminate which solves the above problems. [How to solve the problem]

The inventors of the present invention have made an effort to obtain a transparent resin layer excellent in transparency and rigidity by providing a transparent layer (B) comprising a glass fiber cloth and a resin composition containing a sulfur compound on both surfaces of the transparent resin layer (A). The layer body is the completion of the present invention. That is, one aspect of the present invention provides the following transparent resin laminate and front panel for display.

(1) A transparent resin laminate having a transparent layer (B) disposed on both surfaces of a transparent resin layer (A), the transparent layer (B) comprising a glass fiber cloth and a resin composition containing a sulfur compound. (2) The transparent resin laminate according to (1), wherein a transparent layer (B) is disposed on both surfaces of the transparent resin layer (A), the transparent layer (B) being composed of a glass fiber cloth and containing a mercaptan The base compound (a) is formed with a resin composition of the alkenyl group-containing compound (b). (3) The transparent resin laminate according to (1) or (2), wherein a transparent layer (B) is disposed on both surfaces of the transparent resin layer (A), and the transparent layer (B) is made to have a thickness of 1 mm. In the case where the resin composition of the curable resin having a tensile modulus of 10 MPa or more is impregnated into the glass fiber cloth. (4) The transparent resin laminate according to any one of (1) to (3), wherein an adhesive layer containing a transparent adhesive is provided between the transparent resin layer (A) and the transparent layer (B). . (5) The transparent resin laminate according to (4), wherein the thickness of the adhesive layer is from 1 μm to 100 μm. (6) The transparent resin laminate according to (4) or (5), wherein the transparent adhesive is cured to a thickness of 1 mm and has a tensile modulus of elasticity of 1 MPa or more. (7) The transparent resin laminate according to any one of (1) to (6), which is a transparent adhesive having a tensile modulus of elasticity of 1 MPa or more when the thickness of the transparent resin layer (A) is 1 mm. The transparent layer (B) is obtained by laminating the transparent layer (B), and the resin composition containing the curable resin is impregnated into the glass fiber cloth and cured to have a tensile modulus of elasticity of 10 GPa or more. The transparent resin laminate according to any one of (4), wherein the transparent adhesive is selected from the group consisting of an acrylic adhesive, an epoxy adhesive, and an amine ester. At least one of the group consisting of adhesives. (9) The transparent resin laminate according to any one of (1) to (8), wherein the transparent resin laminate has a bending elastic modulus of 5 GPa or more. (10) The transparent resin laminate according to any one of (1) to (9), wherein the transparent resin layer (A) has a thickness of from 100 μm to 2000 μm, and the transparent layer (B) has a thickness of 20 μm. 300 μm. (11) The transparent resin laminate according to any one of (1) to (10), which has a total light transmittance of 80% or more. The transparent resin laminate according to any one of (1) to (11), wherein the Abbe number of the resin composition of the transparent layer (B) is hardened and the Abbe number of the glass fiber cloth The gap is below 15. The transparent resin laminate according to any one of (1) to (12), wherein a difference between a refractive index of the resin composition of the transparent layer (B) and a refractive index of the glass fiber cloth is 0.01 or less . The transparent resin laminate according to any one of (1) to (13), wherein the resin composition of the transparent layer (B) contains a polymer of a thiol compound and an epoxy resin. The transparent resin laminate according to any one of (1) to (14) wherein the glass fiber cloth of the transparent layer (B) has a refractive index greater than 1.55. 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. The transparent resin laminate according to any one of (1) to (16), wherein the resin component of the transparent resin layer (A) is selected from the group consisting of polycarbonate and polyethylene terephthalate. At least one of the group consisting of an alcohol ester, polybutylene terephthalate, and polymethyl methacrylate. (18) The transparent resin laminate according to (17), wherein the resin component of the transparent resin layer (A) contains polycarbonate. The transparent resin laminate according to any one of (1) to (18), wherein a polyethylene terephthalate film layer is disposed on at least one side of the transparent layer (B). (20) The transparent resin laminate according to (19), wherein a hard coat layer is disposed at least on one of the outer sides 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 of the outer sides of the polyethylene terephthalate film layer. (22) A front panel for a display, which is a transparent resin laminate according to any one of (1) to (21).

Moreover, according to another aspect of the present invention, the following front panel for a display is provided. (1) A front panel for a display comprising a transparent resin laminate (C) having a transparent layer (B) disposed on both surfaces of a transparent resin layer (A), the transparent layer (B) It is formed of a glass fiber cloth and a resin composition containing a sulfur compound. (2) The front panel for a display 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 front panel for a display according to (1) or (2), wherein the transparent resin laminate (C) has a bending elastic modulus of 5 GPa or more. (4) The front panel for a display according to any one of (1) to (3), which has a total light transmittance of 80% or more. (5) The front panel for a display according to any one of (1) to (4), wherein the resin composition containing the sulfur compound in the transparent layer (B) is cured with an Abbe number and a glass fiber cloth. The difference between the number of shells is 15 or less. (6) The front panel for a display according to any one of (1) to (5), wherein the refractive index of the resin composition containing the sulfur compound of the transparent layer (B) is hardened and the refractive index of the glass fiber cloth The difference is 0.01 or less. (7) The front panel for a display according to any one of (1) to (6), wherein the resin composition containing a sulfur compound in the transparent layer (B) contains a polymer of a thiol compound and an epoxy resin. (8) The front panel for a display according to any one of (1) to (7) wherein the refractive index of the glass fiber cloth in the transparent layer (B) is larger than 1.55. (9) The front panel for a display according to any one of (1) to (8) wherein the resin component in the transparent resin layer (A) is selected from the group consisting of polycarbonate and polyethylene terephthalate. Any one or more of the group consisting of an alcohol ester, polybutylene terephthalate, and polymethyl methacrylate. (10) The front panel for a display according to any one of (1) to (9), wherein at least one of the outer sides of the transparent resin laminate (C) is provided with polyethylene terephthalate. Film layer. (11) The front panel for a display according to (10), wherein a hard coat layer is disposed on at least one of the outer sides of the polyethylene terephthalate film layer. (12) The front panel for a display according to (10), wherein a transparent conductive film layer is disposed on at least one of the outer sides of the polyethylene terephthalate film layer.

Moreover, according to still another aspect of the present invention, the following front panel for a display is provided. (1) A front panel for a display comprising a transparent resin laminate (C) having a transparent layer (B) disposed on both surfaces of a transparent resin layer (A), the transparent layer (B) It is formed of a glass fiber cloth and a photocurable resin composition containing a compound (b) having a thiol group-containing compound (a) and an alkenyl group. (2) The front panel for a display 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 front panel for a display according to (1) or (2), wherein the transparent resin laminate (C) has a bending elastic modulus of 5 GPa or more. (4) The front panel for a display according to any one of (1) to (3), which has a total light transmittance of 80% or more. (5) The front panel for a display according to any one of (1) to (4), wherein the Abbe number after hardening of the photocurable resin composition in the transparent layer (B) and the Abe of the glass fiber cloth The difference between the numbers is 15 or less. (6) The front panel for a display according to any one of (1) to (5), wherein the refractive index of the photocurable resin composition in the transparent layer (B) is hardened and the refractive index of the glass fiber cloth The difference is 0.01 or less. (7) The front panel for a display according to any one of (1) to (6) wherein the glass fiber cloth of the transparent layer (B) has a refractive index greater than 1.55. The front panel for a display according to any one of (1) to (7) wherein the resin component in the transparent resin layer (A) is selected from the group consisting of polycarbonate and polyethylene terephthalate. Any one or more of the group consisting of an alcohol ester, polybutylene terephthalate, and polymethyl methacrylate. The front panel for a display according to any one of (1) to (8), wherein at least one of the outer sides of the transparent resin laminate (C) is provided with a polyethylene terephthalate film. Floor. (10) The front panel for a display according to (9), wherein a hard coat layer is disposed on at least one side of the polyethylene terephthalate film layer. (11) The front panel for a display according to (10), wherein a transparent conductive film layer is disposed on at least one side of the polyethylene terephthalate film layer.

Moreover, according to another aspect of the present invention, the following transparent laminate is provided. (1) A transparent laminate obtained by disposing a transparent layer (B) on both surfaces of a transparent resin layer (A), and has a bending elastic modulus of 5 GPa or more as a whole, and the transparent layer (B) is a glass. The fiber cloth is obtained by impregnating a hardening resin having a tensile modulus of 10 MPa or more when the fiber cloth is impregnated to a thickness of 1 mm. (2) The transparent laminate according to (1), wherein the polycarbonate resin layer (A) has a thickness of from 100 μm to 2000 μm, and the transparent layer (B) has a thickness of from 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 laminate according to any one of (1) to (3) wherein the glass fiber cloth of the transparent layer (B) is an E glass cloth. (5) The transparent laminate according to any one of (1) to (4) wherein the transparent layer (B) has a total light transmittance of 80% or more. (6) A transparent laminate in which a polyethylene terephthalate film layer is disposed at least one 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 disposed on at least one side of the polyethylene terephthalate film layer. (8) The transparent laminate according to (6), wherein a transparent conductive film layer is disposed on at least one side of the polyethylene terephthalate film layer. (9) A front panel for a display, which is a transparent laminate according to any one of (1) to (8). Moreover, according to another aspect of the present invention, the following transparent laminate is provided. (1) A transparent laminate obtained by laminating a transparent layer (B) with a transparent adhesive having a tensile modulus of 1 MPa or more when the both sides of the transparent resin layer (A) are cured to a thickness of 1 mm. The flexural modulus of elasticity is 5 GPa or more. The transparent layer (B) is obtained by impregnating a glass fiber cloth with a curable resin and hardening the tensile modulus of elasticity to 10 GPa 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 from 100 μm to 2000 μm, and the transparent layer (B) has a thickness of from 20 μm to 300 μm. (4) A transparent laminate in which a polyethylene terephthalate film layer is disposed at least one side of the transparent laminate according to any one of (1) to (3). (5) The transparent laminate according to (4), wherein at least one of the outer sides of the polyethylene terephthalate film layer is provided with a hard coat layer. (6) The transparent laminate according to (4), wherein a transparent conductive film layer is disposed at least on one side of the polyethylene terephthalate film layer. (7) A front panel for a display, which is a transparent laminate according to any one of (1) to (6). [Effects of the Invention]

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

The invention will be described below with reference to the accompanying drawings. Further, the following is intended to illustrate the invention, and the invention is not limited to the embodiment. In the description of the drawings, the same components are designated by the same reference numerals, and the repeated description is omitted. Moreover, the schema size ratio is for convenience of explanation and is exaggerated, and sometimes it is different from the actual ratio.

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

The transparent resin laminate of the present invention is transparent and excellent in rigidity, and is excellent in workability and impact resistance. Therefore, the transparent resin laminate is suitably used as a transparent substrate material, a transparent protective material, and the like, and is used as a glass substitute, and is used as a front panel material such as various glazing materials, substrate materials, and front panels for displays. Further, in the present specification, the "transparent resin laminate" may be simply referred to as "transparent laminate" or "laminate".

In the present invention, transparent means that the total light transmittance is 80% or more. Further, in the present invention, the light transmittance at a general wavelength of 550 nm in the visible light region is 80% or more, and the light transmittance at 400 nm is preferably 60% or more. In particular, the light transmittance of 400 nm is important in view of the contrast and color reproducibility of an image, and the light transmittance in the wavelength region is preferably high. The total light transmittance and the light transmittance at 400 nm and 550 nm can be measured by the method described in the examples below.

One embodiment of the present invention is a front panel for a display using a transparent resin laminate. Fig. 1 is a schematic cross-sectional view showing a front panel for a display according to an embodiment of the present invention. The front panel 10 for a display shown in FIG. 1 includes a transparent resin laminate (C) in which an adhesive layer 3 is laminated in order on both surfaces of a transparent resin layer (A) 1 and The transparent layer (B) 2 comprising a glass fiber cloth and a resin composition containing a sulfur compound is used. That is, the panel 10 of the present embodiment has an adhesive layer 3 containing a transparent adhesive between the transparent resin layer (A) 1 and the transparent layer (B) 2. However, the front panel 10 may also have no adhesive layer 3.

Fig. 2 is a schematic cross-sectional view showing a front panel for a display according to another embodiment of the present invention. The front panel 10 for a display shown in FIG. 2 includes a transparent resin laminate (C) which is provided on both surfaces of the transparent resin layer (A) 1 and contains a glass fiber cloth and a sulfur compound. The transparent layer (B) 2 of the resin composition is formed. In the present 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 adhered, and from the viewpoint of high rigidity, the transparent resin layer (A) and the transparent layer (B) are preferably adhered. That is, in one embodiment of the present invention, the transparent resin layer (A) and the transparent layer (B) are directly adhered or adhered to each other via the adhesive layer 3.

Fig. 3 is a cross-sectional photograph of a transparent resin laminate according to an embodiment of the present invention, and corresponds to a cross-sectional photograph of the transparent resin laminate produced in the following Example A-2. In the transparent resin laminate shown in Fig. 3, a GC-reinforced film as a transparent layer (B) 2 and a polyparaphenylene resin as a resin layer are laminated in this order on both sides of a PC plate as the transparent resin layer (A) 1. The ethylene glycol formate film layer 4 is integrated. Further, the layer 5 in Fig. 3 is a sheet for fixing when the transparent resin laminate is cut. In Fig. 3, the transparent layer (B) is composed of a GC-reinforced film composed of a glass fiber cloth 21 and a resin composition 22 including a compound having a thiol group and a compound having an epoxy group. In the present embodiment, the glass cloth 21 is an E glass cloth which is formed by knitting a longitudinal yarn and a cross yarn (glass yarn) (white portion in the drawing). The transparent layer (B) 2 can be formed by impregnating the glass composition with the resin composition and hardening.

In general, the transparent layer (B) containing a glass fiber cloth and a resin composition containing a sulfur compound has higher rigidity (tensile elastic modulus, etc.) than the transparent resin layer (A). As described above, by arranging the layer (B) having a high rigidity including the glass fiber cloth on both sides of the layer (A) having low rigidity, the rigidity of the layer containing the glass fiber cloth is reflected, and the rigidity of the entire layer can be made high. . For example, when a polycarbonate resin is used as the transparent resin layer, the rigidity (bending elastic modulus) itself is 2.6 GPa, but the rigidity can be improved by arranging the layer containing the glass fiber cloth on both surfaces.

The transparent resin laminate (C) has 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 which are optionally disposed. Hereinafter, each constituent element 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. The thickness of the transparent resin layer (A) is not particularly limited, and is preferably 100 μm to 2000 μm, more preferably 200 μm to 1000 μm. When the thickness of the transparent resin layer (A) is within this range, the rigidity is improved, and the increase in mass of the entire transparent resin laminate (C) can be suppressed.

The resin (resin component) used for the transparent resin layer (A) is not particularly limited, and examples thereof include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polymethyl methacrylate. Cyclic cycloolefin resin, norbornene resin, acrylic resin, polystyrene, polyether oxime, polyarylate, polyester resin, polyacetal resin, polyvinyl butyral, polyvinyl alcohol, uric acid An ester resin or the like, wherein, in view of transparency and rigidity, it is preferably selected from the group consisting of polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polymethyl methacrylate. At least one of the groups is preferable, and polycarbonate resin is particularly preferable in terms of transparency and press formability. These resins may be used alone or in combination of two or more.

The transparent resin layer (A) is mainly processed into a layer shape by molding. The molding method is not particularly limited, and for example, a film forming method of a general thermoplastic resin, that is, a melt extrusion molding 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, it is possible to obtain a laminate excellent in transparency, rigidity, impact resistance, flexibility, and press formability. As such a layered polycarbonate resin, for example, Iupilon NF-2000 of Mitsubishi Gas Chemical Co., Ltd., or the like can be preferably used.

The total light transmittance of the transparent resin layer (A) formed to form the transparent resin laminate is preferably 80% or more. When it is 80% or more, the transmittance of the obtained laminate (front panel for display) can be suppressed from decreasing.

The transparent resin layer (A) may contain various additives in addition to the resin, without departing from the scope of the invention. The additives may be listed as heat stabilizers, antioxidants, flame retardants, flame retardant auxiliaries, ultraviolet absorbers, release agents, colorants, antistatic agents, fluorescent whitening agents, antifogging agents, fluidity improvers, plastics Chemical agents, dispersing agents, and antibacterial agents. These may be used alone or in combination of two or more.

Examples of the thermal stabilizer include a phenol-based, phosphorus-based, and sulfur-based thermal stabilizer. Specific examples thereof include phosphorus oxyacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acid pyrophosphate metal salts such as acid sodium pyrophosphate, acid potassium pyrophosphate, and acid calcium pyrophosphate; a phosphate of a Group 1 or Group 10 metal such as potassium phosphate, sodium phosphate, strontium phosphate or zinc phosphate; an organic phosphate compound, an organic phosphite compound, an organic phosphonite compound or the like. Or a phosphite compound (a) or a phosphorous acid (b) obtained by esterifying at least one ester of a molecule selected from a phenol and/or a phenol having at least one alkyl group having 1 to 25 carbon atoms. And at least one of the group of bismuth (2,4-di-t-butylphenyl)-4,4'-biphenylene-diphosphinate (c). These may be used alone or in combination of two or more.

The amount of the heat stabilizer to be added is, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and further preferably 1 part by mass or less, based on 100 parts by mass of the resin component. It is preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less. If there are too few heat stabilizers, the heat stability effect may be insufficient. If there are too many heat stabilizers, the effect will not be better and may not be economical.

Examples of the antioxidant include a phenol-based antioxidant, a hindered phenol-based antioxidant, a bisphenol-based antioxidant, and a polyphenol-based antioxidant.

The amount of the antioxidant added is, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and further preferably 1 part by mass or less, preferably 0.5 parts by mass or less, based on 100 parts by mass of the resin component. When the ratio of addition of the antioxidant is less than or equal to the lower limit, the effect as an antioxidant may be insufficient, and when the ratio of the addition of the antioxidant exceeds the upper limit, the effect may not be better and may be uneconomical.

The flame retardant may, for example, be an organic sulfonic acid metal salt or the like. The organic sulfonic acid metal salt may be an aliphatic sulfonic acid metal salt or an aromatic sulfonic acid metal salt. These may be used alone or in combination of two or more. Further, the metal salt is preferably an alkali metal salt or an alkaline earth metal salt. Further, a flame retardant other than the organic sulfonic acid metal salt may be blended.

The addition amount of the flame retardant 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, more preferably 0.03 parts by mass to 0.09 parts by mass.

For example, an anthrone compound can be added as a flame retardant aid. The anthrone compound is preferably one having a phenyl group in the molecule. By having a phenyl group, the oxime compound has improved dispersibility in a resin component (especially polycarbonate), and is excellent in transparency and flame retardancy.

The blending ratio of the flame retardant auxiliary agent is, for example, 0.1 part by mass or more, preferably 0.2 part by mass or more, and further 7.5 parts by mass or less, preferably 5 parts by mass or less, based on 100 parts by mass of the resin component. . When the ratio of addition of the flame retardant auxiliary agent is less than or equal to the lower limit 値, the flame retardancy may be insufficient, and when the addition ratio of the flame retardant auxiliary agent exceeds the upper limit 値, appearance defects such as delamination may occur, transparency may be lowered, and flame retardancy may be obtained. It won't be better, it may not be economical.

Examples of the ultraviolet absorber include an inorganic ultraviolet absorber such as cerium oxide or zinc oxide, and a benzotriazole compound, a diphenyl ketone compound, a salicylate compound, a cyanoacrylate compound, and the like. An organic ultraviolet absorber such as a compound, a grassy anilide compound, a malonic ester compound, a hindered amine compound, or a phenyl salicylate compound. Among these, a benzotriazole-based or diphenylketone-based organic ultraviolet absorber is preferred.

The blending ratio of the ultraviolet absorber is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and further preferably 3 parts by mass or less, preferably 1 part by mass or less, based on 100 parts by mass of the resin component. When the addition ratio of the ultraviolet absorber is less than or equal to the lower limit ,, the improvement effect of the weather resistance may be insufficient, and when the addition ratio of the ultraviolet absorber exceeds the upper limit 模具, mold fouling may occur, and mold contamination (cooling roller contamination) may occur. Sex.

Examples of the release agent include a carboxylic acid ester, a polyoxyalkylene compound, and a paraffin (polyolefin). Two or more of these may be used in combination.

The amount of the release agent to be added is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and further preferably 2 parts by mass or less, more preferably 1 part by mass or less based on 100 parts by mass of the resin component. . When the addition ratio of the release agent is less than or equal to the lower limit 値, the effect of the release property may be insufficient. When the addition ratio of the release agent exceeds the upper limit 値, the hydrolysis resistance may be lowered, and mold contamination may occur during injection molding.

As the dye of the colorant, for example, an inorganic pigment, an organic pigment, an organic dye, or the like. Inorganic pigments such as: carbon black, cadmium red, cadmium yellow and other sulfide pigments; cinnamate pigments such as ultramarine; titanium oxide, zinc oxide, red dan, chromium oxide, iron black, titanium yellow, zinc-iron brown, Titanium-cobalt-based green, cobalt green, cobalt blue, copper-chromium black, copper-iron black oxide-based pigments; yellow lead, molybdate orange and other chromanic pigments; indigo and other iron (II) cyanide pigments Wait. Further, as the organic pigment and the organic dye of the coloring agent, for example, phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine; azo dyes such as nickel azo yellow; thioindigo and fluorenone ( Perinone), lanthanide, quinophthalone, two A condensed polycyclic dye such as an isoindolinone or a quinophthalone system; a quinoline, an anthraquinone, a heterocyclic, or a methyl dye. Among these, thermal stability is considered, and it is preferably a titanium oxide, a carbon black, a cyanine, a quinoline, an anthraquinone, or a phthalocyanine dye. Further, the dye may be contained in one type or in combination of two or more kinds in any combination and in any ratio. In addition, the dyeing pigment can be used as a masterbatch after being prepared as a masterbatch with a polystyrene resin, a polycarbonate resin, or an acrylic resin in order to improve the workability during extrusion and improve the dispersibility in the resin composition.

In the case of the blending, the amount of the coloring agent is, for example, 1 part by mass or less, preferably 0.5 part by mass or less, more preferably 0.1 part by mass or less based on 100 parts by mass of the resin component. If the addition ratio of the colorant is too large, the impact resistance may become insufficient.

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

The thickness of the transparent layer (B) is preferably 20 μm to 300 μm, 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 it can ensure transparency and rigidity of the transparent layer (B). The sulfur compound is, for example, a resin containing a sulfur atom 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 them, in view of optical properties (transparency), a thermosetting resin or a photocurable resin containing a sulfur atom is preferred.

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

The thermosetting resin containing a sulfur atom is not particularly limited, and examples thereof include a thermosetting resin formed by thermally curing a composition containing an epoxy resin and a polyfunctional thiol compound.

The photocurable resin containing a sulfur atom is not particularly limited, and examples thereof include photocuring properties obtained by photocuring a photocurable resin composition containing a compound having a carbon-carbon double bond and a (polyfunctional) thiol compound. A resin, a photocurable resin formed by photocuring a photocurable resin composition containing an epoxy resin and a polyfunctional thiol compound.

The active light to be used for curing the photocurable resin composition of the transparent layer (B) is not limited as long as it can cure the photocurable resin composition, for example, ultraviolet rays, near ultraviolet rays, visible rays, and near infrared rays. Considering the point that it is not easy to cause side reactions, ultraviolet light is preferred. A light source for illuminating the ultraviolet light, for example, a metal halide type and a high pressure mercury bulb.

In one embodiment of the present invention, the resin composition of the transparent layer (B) contains a curable resin. When a curable resin is contained, it is preferable in terms of refractive index adjustment and workability. More preferably, the resin composition of the transparent layer (B) contains a curable resin having a tensile modulus of elasticity of 10 MPa or more when the thickness is 1 mm. In the transparent resin layered body of the embodiment of the present invention, a resin containing a curable resin having a tensile modulus of 10 MPa or more at a thickness of 1 mm is disposed on both surfaces of the transparent resin layer (A). The composition was impregnated with a transparent layer (B) of glass fiber cloth. In particular, in view of transparency, rigidity, impact resistance, flexibility, and press workability, the transparent resin layer (A) is a polycarbonate resin layer. Moreover, in this specification, "the tensile modulus of elasticity at the time of hardening" means the tensile-elastic coefficient of the resin after thermo-hardening or light-hardening.

In particular, the inventors of the present invention found that when the curable resin used for the layer (B) having high rigidity is transparent and cured to a thickness of 1 mm, the tensile modulus is 10 MPa or more, and the layer is excellent in rigidity as a whole. The laminate (preferably having a flexural modulus of elasticity of 5 GPa or more) can be obtained as a laminate for a front (protective) sheet for a display. If it is less than 10 MPa, the flexural modulus of elasticity of the entire transparent laminate may be lower than the flexural modulus of elasticity (2.6 GPa) possessed by the polycarbonate resin layer (A). When the curable resin used for the transparent layer (B) is cured, the tensile modulus of elasticity is preferably 70 MPa or more, more preferably 100 MPa or more, and particularly preferably 500 MPa or more.

When the tensile modulus of the curable resin is too high, cracks or the like which occur when a load is applied to the material may cause a problem. Therefore, the tensile modulus of elasticity at the time of curing the curable resin is preferably 5 GPa or less. A curable resin having such characteristics, for example, an epoxy resin, an acrylic resin, a polyimide resin, a benzoic acid Resin, oxetane resin, and the like.

In view of transparency, it is more preferable that the resin composition contains a polymer of a thiol compound and an epoxy resin, and particularly preferably a resin composition containing a polymer obtained by a thermosetting reaction between a thiol compound and an epoxy resin.

Moreover, in one embodiment of the present invention, the transparent layer (B) is obtained by impregnating and curing a resin composition containing a curable resin, and the transparent layer (B) is cured (after hardening) The tensile modulus of elasticity is 10 GPa or more.

A method of obtaining a transparent layer (B) having a tensile modulus of elasticity of 10 GPa or more includes a method of 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, or a benzo can be used. Resin, oxetane resin, etc., depending on the type of curable resin to be used, the tensile modulus of the transparent layer (B) may be less than 10 GPa, and such a curable resin is not suitable.

By laminating such a transparent layer (B) on both surfaces of the transparent resin layer (A), a transparent laminate having a bending elastic modulus of 5 GPa or more and transparency and excellent rigidity can be obtained. . From the standpoint of transparency and rigidity, this transparent laminate is ideally used as a front panel for displays. In particular, in view of transparency, rigidity, impact resistance, flexibility, and press workability, the transparent resin layer (A) is a polycarbonate resin layer.

The total light transmittance of the transparent layer (B) is preferably 80% or more, and more preferably 85% or more. When the total light transmittance of the transparent layer (B) is in this range, the transparency of the entire transparent resin laminate is good, and it can be suitably used as a front panel for a display.

In order to obtain high transparency, the difference between the Abbe number of the resin composition constituting the transparent layer (B) and the Abbe number of the glass fiber cloth is preferably 15 or less, more preferably 10 or less. The lower limit of the Abbe number difference is not particularly limited, and the viewpoint of obtaining high transparency is considered to be as small as possible, and the optimum is 0. Further, the Abbe number of the resin composition refers to the Abbe number after curing when the resin composition contains a curable resin. When the Abbe number difference is 15 or less, the transmittance of the transparent layer (B) obtained at a short wavelength of around 400 nm is increased, and it is suitable as a front panel for a display. The Abbe number is an index of the wavelength dependence of the refractive index of the visible light. Generally, the glass is larger than the resin, and the larger the refractive index, the more difficult it is to make it uniform. By using a resin composition containing a sulfur compound, the Abbe number of the resin is close to the Abbe number of the glass fiber cloth, and the light transmittance in the wide wavelength region is improved, and high transparency can be obtained.

Further, in order to obtain high transparency, the difference between the refractive index 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. Specifically, the difference in refractive index between the resin composition and the D-line (589 nm) of the glass cloth is preferably 0.01 or less, 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 the viewpoint of obtaining high transparency is preferably as small as possible, and most preferably 0. In addition, when the resin composition contains a curable resin as described later, the refractive index of the resin composition means the refractive index after curing. When the refractive index difference is 0.01 or less, the transmittance of the obtained transparent layer (B) is increased, and it is suitable for the front panel for a display. When the difference in refractive index of the D line between the glass fiber cloth and the glass fiber cloth is 0.01 or less to obtain the transparent layer (B), the resin having a refractive index difference of 0.01 or less with the D line between the glass fiber cloths may be used alone or in combination. A resin having a higher refractive index than the D line of the glass cloth and a resin having a lower resin are mixed.

Further, in the use of transparency, it is preferable that the refractive index of the D line is not only the total light transmittance of the transparent layer (B) but also 80% or more of the light transmittance of the general wavelength of 550 nm in the visible light region. Preferably.

In order to make the Abbe number difference between the resin composition containing the sulfur compound constituting the transparent layer (B) and the glass fiber cloth 15 or less and the refractive index difference 0.01 or less, the following method can be employed: (1) Selecting a matching glass fiber cloth a method of using a sulfur atom-containing resin having an Abbe number and a refractive index, and (2) a sulfur-containing compound by combining a resin having a refractive index higher than that of the glass fiber cloth and a resin having a refractive index lower than that of the glass fiber cloth The method of the Abbe number of the resin composition, the refractive index, and the glass fiber cloth are the same. In order to obtain high transparency, it is preferred to closely match the refractive index of the resin composition and the glass fiber cloth, and it is preferred to use a method of using a plurality of reactive monomers (curable resin) and a hardener in the method of (1) or The method of (2) is preferred. Further, in the present specification, the refractive index is uniform, and the refractive index difference is 0.01 or less, preferably 0.005 or less. Further, the Abbe number is the same, which means that the Abbe number difference is 15 or less, preferably 10 or less.

Method (1) When the refractive index of the sulfur atom-containing resin is the same as the refractive index of the glass fiber cloth, a resin containing a sulfur atom can be used as it is. For example, the refractive index and the glass fiber can be made uniform by adjusting the type and amount of the monomer constituting the copolymer resin, the curable resin, and the curing agent. Such a resin is, for example, a resin selected from a sulfur atom-containing thermoplastic resin, a sulfur atom-containing thermosetting resin, and a sulfur atom-containing photocurable resin. In this case, only one type of resin containing a sulfur atom 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 indices, the refractive index of the resin composition and the glass fiber cloth can be precisely matched, and high transparency can be achieved.

In the above-mentioned (1), the resin having a sulfur atom in the Abbe number and the refractive index of the selected glass fiber cloth, for example, the glass type of the glass fiber cloth is E glass (Abe number 58 and refractive index 1.56), and polysulfuric acid is exemplified. A thermoplastic copolymer resin such as a copolymer of an ester and a polyester, a thermosetting resin such as a cyclic thioether resin, or the like. Further, when the glass type is S glass or T glass (Abbe number 68 and refractive index 1.53), a thermoplastic copolymer resin such as a copolymer of a polythioester and a polyester, or a cyclic thioether resin may be mentioned. Thermosetting resin, etc. In the case of the copolymer, the refractive index and the Abbe number differ depending on the ratio of the sulfur compound (sulfur atom-containing compound) to the sulfur-free compound, and the lower the sulfur compound, the lower the refractive index, so that it is appropriate The amount of use is determined depending on the type of glass used. Further, the refractive index and Abbe number of the episulfide resin vary depending on the sulfur content in the episulfide resin, and the lower the sulfur content, the lower the refractive index. Therefore, for example, when the E glass type is used, the sum is used. When a sulphur-containing cyclic thioether resin is used, when S glass or T glass is used, a sulfur-containing cyclic thioether resin commensurate with it is used.

Further, in the case of the sulfur atom-containing resin having the same Abbe number and refractive index as the glass fiber cloth, the reactive monomer of the curable resin and the hardening agent containing the sulfur atom may be used. A curable resin (thermosetting resin or photocurable resin) formed by the reaction. For example, it is preferable to combine a hardener containing a sulfur atom having a refractive index higher than a refractive index of the glass fiber cloth with a reactive monomer (a resin monomer containing no sulfur atom) having a refractive index lower than that of the glass fiber cloth. The method of adjustment is preferred. More specifically, the curable resin containing a sulfur atom may be a thermosetting resin or a photocurable resin composed of an epoxy resin as a reactive monomer and a curing agent containing a sulfur compound, and may be used as a reactive single. A photocurable resin composed of a compound having an alkenyl group and a curing agent containing a sulfur compound. Examples of the method for producing the resin include a curing agent containing a sulfur atom having a refractive index higher than a refractive index of the glass fiber cloth, and a reactive monomer having a refractive index lower than a refractive index of the glass fiber cloth. A method in which one type or two or more types are mixed and then hardened by active energy such as heat or light. For example, a compound containing a sulfur atom (for example, a polyfunctional thiol compound) having a refractive index higher than that of a glass fiber cloth as a hardener and a resin having a lower refractive index than a glass fiber cloth (for example, an epoxy resin) The method of hardening. From the viewpoint of transparency, a curable resin composed of an epoxy resin and a hardener containing a sulfur atom is preferred.

The sulfur atom-containing hardener is, for example, a polyfunctional thiol compound having a higher refractive index than glass fiber cloth. The polyfunctional thiol compound having a refractive index higher than that of the glass fiber cloth is not particularly limited, and examples thereof include 1,2-ethanedithiol, 1,3-propanedithiol, and 1,4-butanedithiol. 6-hexanedithiol, 2,2'-hydroxybis(1-decylethane), 2,2'-thiobis(1-decylethane), 1,4-didecylbutane-2,3- Glycol, ethylene glycol bis(1-decylethane), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptopropane) Acid ester), ethylene glycol bis(3-mercaptobutyrate), butanediol bis(2-mercaptoacetate), butanediol bis(3-mercaptopropionate), butanediol double (2- Mercaptopropionate, butanediol bis(3-mercaptobutyrate), neopentyltetrathiol, three Trithiol, glyceryl ginseng (2-mercaptoacetate), glyceryl ginseng (3-mercaptopropionate), glycerol ginseng (2-mercaptopropionate), glycerol ginseng (3-mercaptobutyrate), neopentyl Tetrapropanol (2-mercaptoacetate), neopentyl sterol (3-mercaptopropionate) (PETP), neopentyl sterol (2-mercaptopropionate), neopentyl sterol (3) - mercaptobutyrate), trimethylolpropane ginseng (2-mercaptoacetate), trimethylolpropane ginseng (3-mercaptopropionate), trimethylolpropane ginseng (2-mercaptopropionate) ), trimethylolpropane ginseng (3-mercaptobutyrate), trimethylolethane ginseng (2-mercaptoacetate), trimethylolethane ginseng (3-mercaptopropionate), three Hydroxymethylethane ginseng (2-mercaptopropionate), trimethylolethane ginseng (3-mercaptobutyrate), 4-mercaptomethyl-1,8-dimercapto-3,6-disulfide Heterooctane (GST), bis(indolylmethyl)-1,11-dimercapto-3,6,9-trithiaundecane, 2,5-bis(decylmethyl)-1,4-di Thio , ginseng-[(3-mercaptopropoxy)-ethyl]-isocyanurate (TEMPIC), dipentaerythritol tert-(3-mercaptopropionate), and the like. These may be used alone or in combination of two or more. Among them, from the viewpoint of adjusting the refractive index, pentaerythritol strontium (3-mercaptopropionate) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane are preferable.

As the epoxy resin curing agent, a polyvalent thiol compound can be used, and a cyclic carboxylic anhydride having a lower refractive index than glass fiber cloth can also be used. Such a cyclic carboxylic acid anhydride is not particularly limited, and examples thereof include maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, nepiconic anhydride, glutaric anhydride, tetrahydrophthalic anhydride, and methyltetramine. Hydrogen phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnaic acid anhydride, dodecenyl succinic anhydride, dichlorosuccinic anhydride, diphenyl ketone tetracarboxylate Anhydride, chloredic acid anhydride, and the like. These may be used alone or in combination of two or more. Among them, considering transparency, it is preferably tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and transparency is considered. Preferably, it is hexahydrophthalic anhydride or methylhexahydrophthalic anhydride.

An epoxy resin having a lower refractive index than a glass fiber cloth in combination with a hardener containing a sulfur atom may, for example, be an epoxy resin containing no aromatic ring. Such an epoxy resin is not particularly limited, and examples thereof include a hydrogenated bisphenol A type epoxy resin, a hydrogenated bisphenol F type epoxy resin, and three Skeleton epoxy resin, linear aliphatic epoxy resin, epoxy resin containing epoxy hexane skeleton, epoxy resin containing cyclohexane polyether skeleton, epoxy propylamine epoxy resin, containing dicyclopentane Epoxy resin of the olefin skeleton and the like. These may be used alone or in combination of two or more.

The combination of the polyfunctional thiol compound having a refractive index higher than the refractive index of the glass fiber cloth and the epoxy resin having no refractive index lower than that of the glass fiber cloth is not particularly limited. However, the glass fiber cloth has a higher Abbe number than the general resin having a refractive index close to each other, so the difference in the Abbe number between the resin containing the aromatic ring and the resin containing a large amount of carbonyl bond tends to increase. Therefore, it is preferably a thiol compound such as neopentyl alcohol (3-mercaptopropionate) and/or 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and a ring-containing compound. The combination of epoxy resins of oxyhexane backbone is preferred.

When the polyfunctional thiol compound is used alone as a curing resin hardener, the total content of the thiol functional group contained in the polyfunctional thiol compound is preferably 1 equivalent to the epoxy group of the epoxy resin of the hardened plastic resin. It is 0.5 to 1.0 equivalent, more preferably 0.7 to 1.0 equivalent. If the content is within this range, the hardenability does not decrease, and the odor caused by the residual thiol functional group can be suppressed. Further, when a polyfunctional thiol compound and a cyclic carboxylic anhydride are used together as the curing agent, the total content of the thiol functional group contained in the polyfunctional thiol compound and the carboxylic anhydride functional group contained in the cyclic carboxylic anhydride is relative to The epoxy group of the hardened plastic resin has an epoxy group of 1 equivalent, preferably 0.5 to 1.0 equivalent, more preferably 0.7 to 1.0 equivalent. When the content is within this range, the hardenability does not decrease, and the odor caused by the residual thiol functional group can be suppressed.

When a polyfunctional thiol compound having a high refractive index and a cyclic carboxylic anhydride having a low refractive index are used as a curing resin curing agent, a polyfunctional thiol compound as a curing agent, a cyclic carboxylic acid anhydrous agent, and an epoxy resin are blended. The ratio can be adjusted according to the fiberglass cloth used. When the glass fiber cloth is made of an E glass fiber cloth or the like having a high refractive index, the blending ratio of the polyfunctional thiol compound having a high polyrefractive index can be matched to the refractive index of the glass fiber cloth. Further, when the glass fiber cloth is made of T glass fiber cloth, S glass fiber cloth, NE glass fiber cloth or the like having a low refractive index, the blending ratio of the resin containing a sulfur compound having a high refractive index and the glass fiber cloth can be reduced. Index matching.

Further, as the sulfur atom-containing resin having the same refractive index as that of the glass fiber cloth, it is also possible to photoharden a composition containing a compound having a carbon-carbon double bond and a (polyfunctional) thiol compound. A photocurable resin formed by the reaction. Among them, a photocurable resin formed of a photocurable resin composition containing a compound having a thiol group (a) and a compound (b) having an alkenyl group (hereinafter also referred to as "thiol-ene photohardening" is preferable. Resin"). The thiol-ene photocurable resin has a thiol group and an alkenyl group in the same molecule. That is, one embodiment of the present invention is a transparent resin laminate (C) having a transparent layer (B) disposed on both surfaces of the transparent resin layer (A), the transparent layer (B) being composed of a glass fiber cloth, and A resin composition containing a compound having a thiol group (a) and a compound (b) having an alkenyl group is formed.

The transparent layer (B) according to the embodiment of the present invention 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. It is made in layers.

The photocurable resin composition can be reacted with a thiol group and an alkenyl group which is generated by a thiol group of a compound having a thiol group and an alkenyl group having an alkenyl group (thiol-ene reaction) . The advantage of the photocurable resin produced by the reaction of the thiol-ene reaction is that the reaction can be easily carried out by using active light rays with or without a polymerization initiator, the reaction is not inhibited by oxygen, the hardening shrinkage is small, and the resin after hardening is used. With high weather resistance and the like, a cured product suitable for the front panel of the present invention can be obtained.

Further, when the photocurable resin composition which generates a thiol-alkenyl reaction is compared with a thiol-epoxy reaction which can produce a curable resin by the same photohardening reaction, it is not necessary to adjust the reactive functional group in the molecule. The ratio, that is, the ratio of the thiol group to the epoxy group is not adjusted, and the refractive index of the resin is easily adjusted.

The thiol group-containing compound is not particularly limited as long as it has a thiol group-containing compound, and the refractive index used as the sulfur atom-containing hardener as described above can be used to be higher than the refractive index of the glass fiber cloth. A polyfunctional thiol compound. These may be used alone or in combination of two or more. Among them, the thiol compound in the thiol-alkenyl reaction, from the viewpoint of adjusting the refractive index, is preferably neopentyl quinone (3-mercaptopropionate) or 4-mercaptomethyl-1,8-didecyl. -3,6-dithiaoctane.

The above-mentioned alkenyl group-containing compound is not particularly limited as long as it is an alkenyl group-containing compound, and is, for example, 2-methylpropenyloxyethylphthalic acid, methoxypolyethylene glycol methacrylate, 1,9 -decanediol dimethacrylate, neopentyl glycol dimethacrylate, ethoxylated polypropylene glycol dimethacrylate, glycerol dimethacrylate, polypropylene glycol dimethacrylate, trishydroxyl Propane trimethacrylate, ethoxylated o-phenylphenol acrylate, methoxy polyethylene glycol acrylate, phenoxy polyethylene glycol acrylate, 2-propenyl oxyethyl succinate, acrylic acid Isostearyl ester, 2-hydroxy-3-propenyl propyl methacrylate, polyethylene glycol diacrylate, propoxylated ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A Diacrylate, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene, propoxylated bisphenol A diacrylate, tricyclodecane dimethanol diacrylate, 1, 10-decanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol Acrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified ginseng-(2-propene oxiranyl) Isocyanurate, neopentyl alcohol triacrylate, trimethylolpropane triacrylate, bis(trimethylolpropane) tetraacrylate, ethoxylated pentaerythritol tetraacrylate, neopenta tetra Alcohol tetraacrylate, dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, monoallyl epoxypropyl isocyanurate, diallyl monoepoxypropyl isocyanurate Acid ester, 1,3-diallyl-5-methoxycarbonyl-1,3,5-three -2,4,6(1H,3H,5H)-trione, 1,3-diallyl-5-(cyclohexen-4-yl)methoxycarbonyl-1,3,5-three -2,4,6(1H,3H,5H)-trione, triallyl isocyanurate, and the like. These may be used alone or in combination of two or more. Among them, from the viewpoint of adjusting the refractive index, tricyclodecane dimethanol diacrylate is preferred.

The thiol group-containing compound (a) and the alkenyl group-containing compound (b) are combined with the glass fiber cloth to be used, and the Abbe number and refractive index of the photocurable resin after hardening and the glass fiber cloth are combined. The Abbe number and the refractive index are the same.

Specifically, a compound having a refractive index higher than that of the glass fiber cloth and a compound having a refractive index lower than that of the glass fiber cloth are mixed and transparent. In this case, in order to obtain high transparency, it is preferable to precisely match the refractive index of the resin and the glass fiber cloth, and it is preferable to use a compound having a thiol group having a refractive index higher than that of the glass fiber cloth (a). A method of mixing and adjusting a photocurable resin having an alkenyl group-containing compound (b) having a lower refractive index than the glass fiber cloth is preferred. Further, when a compound having a thiol group having a refractive index higher than that of a glass fiber cloth (a) and a photocurable resin having an alkenyl group (b) having a lower refractive index than the glass fiber cloth are mixed, One type may be used, 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 the general resin having a refractive index close to the same, and the Abbe number of the resin containing the aromatic ring and the resin having a large amount of carbonyl bond is inconsistent. . Therefore, it is preferred to use a neopentyl thioglycolate and/or 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol as a compound having a thiol group. Tricyclodecane dimethanol diacrylate is preferred, and such combinations are preferred.

Method (2) When the refractive index of the resin containing a sulfur compound is not the same as the refractive index of the glass fiber cloth, the resin having a refractive index higher than that of the glass fiber cloth can be mixed and adjusted with another resin having a lower refractive index than the glass fiber cloth. The resin composition of the transparent layer (B) configured as described above specifically includes, for example, 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. A resin containing a sulfur atom and a resin having a refractive index different from that of the sulfur atom-containing resin (a resin containing no sulfur atom). For example, it is preferable to use a resin composition having a transparent layer (B) having a refractive index higher than a refractive index of a glass fiber cloth and a resin having a sulfur atom and a resin having a refractive index lower than that of the glass fiber cloth (excluding A method of mixing and adjusting a resin of a sulfur atom is preferred. A resin containing a sulfur atom (a resin containing a sulfur atom) having a refractive index higher than that of a glass fiber cloth, and a resin containing a sulfur atom and other resins (containing no sulfur atom) when mixed with a resin (other resin) having a lower refractive index. The resin may be used in combination of one type or two or more types.

According to the glass type of the glass fiber cloth to be used, the refractive index of the glass fiber cloth, and the resin having a lower refractive index than the glass fiber cloth, the refractive index of the entire resin can be adjusted. Appropriate optimum refractive index difference, Abbe number difference.

When the sulfur atom-containing resin is a thermoplastic resin, the sulfur atom-containing resin (sulfur atom-containing resin) may be a polythiocarbonate resin, a polythioester resin, or a polycondensation having a refractive index higher than that of the glass fiber cloth. A pendant oxy thioester resin, a polythioether resin, a sulfur-containing cyclic polyolefin resin, or the like. Further, a resin having a lower refractive index than a glass fiber cloth (other resin; a resin containing no sulfur atom) in combination with the sulfur atom-containing resin may, for example, be a cyclic cycloolefin resin or a polymethyl methacrylate resin. , acrylic resin, polyacetal resin, and the like.

The combination of the sulfur atom-containing resin having a refractive index higher than the refractive index of the glass fiber cloth and the other resin having a lower refractive index can be adjusted to a desired range as long as the refractive index difference between the glass fiber cloth and the resin composition is adjusted. Special restrictions. However, in general, a glass fiber cloth has a higher Abbe number than a general resin having a refractive index close to each other, so the difference in Abbe number between a resin containing an aromatic ring and a resin having a large amount of a carbonyl bond is increased, preferably The combination of the sulfur-containing cyclic polyolefin and the cyclic cycloolefin resin is preferred.

When the resin containing a sulfur atom is a curable resin, the resin containing a sulfur atom may be a thermosetting resin or a photocurable resin composed of an epoxy resin and a curing agent containing a sulfur compound, or a compound having an alkenyl group. When the photocurable resin composed of a curing agent containing a sulfur compound is a thermosetting resin or a photocurable resin composed of an epoxy resin and a curing agent containing a sulfur compound, it is more preferable from the viewpoint of transparency. The hardener containing a sulfur atom may be a polyfunctional thiol compound having a refractive index higher than that of the glass fiber cloth, and the polyfunctional thiol compound as a hardener containing a sulfur atom in the above method (1) may be similarly use. Further, in the present embodiment, a polyfunctional thiol compound can be used as the curing agent, and a cyclic carboxylic anhydride having a refractive index lower than that of the glass fiber cloth as described for the curing agent in the above method (1) can be used.

The amount of the resin relative to the transparent layer (B) can be appropriately selected depending on the purpose of use, and is usually 10 to 80% by mass, preferably 20 to 70% by mass based on the total mass (100% by mass) of the transparent layer (B). . If the amount of the resin is too small, the resin is insufficient, and the transparency is lowered. On the other hand, if the amount of the resin is too large, the rigidity may be insufficient.

In the methods (1) and (2), the method of mixing the resins when two or more kinds of resins are used is described below. When a thermoplastic resin is used, a method of heating and mixing the resin to be used using a laminating apparatus such as a Laboplastomill, a biaxial extruder, a Banbury mixer, and a VESSEL can be mentioned. Moreover, when a thermosetting resin is used, a resin composition can be prepared by a usual method, and a method of preparing a resin composition which uniformly contains a resin to be used and other optional components can be obtained, and the preparation method is not particularly limited. For example, the resin composition can be easily prepared by blending a polyfunctional thiol compound, an aromatic ring-free epoxy resin, and sufficiently stirring.

Further, in the preparation of the resin composition of the transparent layer (B), a known treatment (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component can be carried out. The agitation, mixing, and kneading treatment can be suitably carried out, for example, by a known device such as a ball mill or a bead mill for mixing, or a known device such as a revolving/introducing mixing device.

The resin composition constituting the transparent layer (B) may further contain an inorganic filler in a range that does not impair the desired properties. The inorganic filler is selected from the group consisting of quartz, smoked cerium oxide, precipitated cerium oxide, anhydrous ceric acid, molten cerium oxide, crystalline cerium oxide, ultrafine powder, amorphous cerium oxide, and the like. Inorganic filler, alumina, zircon, zinc oxide, titanium oxide, tantalum nitride, boron nitride, aluminum nitride, glass fiber, glass flakes, alumina fiber, mica, ferrite At least one of the group consisting of diatomaceous earth, clay, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium citrate, inorganic balloons, silver powder, and the like is preferred. The inorganic filler may be used singly or in combination of two or more kinds as appropriate.

When the resin composition of the transparent layer (B) contains a thermosetting resin, the resin composition may optionally contain a hardening accelerator for appropriately adjusting the curing rate. Such compounds, for example, imidazole compounds, benzammonium peroxide, lauric acid peroxide, ethidium peroxide, p-chlorobenzothymidine, di-tert-butyl diperoxyphthalate, etc. An azo compound such as an oxide or azobisnitrile, N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol , tri-n-butylamine, pyridine, quinoline, N-methyl Tertiary amines such as porphyrin, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; Lead metal naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetyl ketone, etc., organic The metal salt is dissolved in a hydroxyl group-containing compound such as phenol or bisphenol, an inorganic metal salt such as tin chloride, zinc chloride or aluminum chloride, dioctyltin oxide, other alkyl tin, alkyl tin oxide, etc. An organotin compound, a quaternary ammonium salt, a quaternary phosphonium salt such as O, O-diethylphosphonium tetrabutyl sulfonate, a phosphorus compound, a urea compound, and the like. These hardening accelerators may be used alone or in combination of two or more.

The resin composition containing a sulfur compound which forms the transparent layer (B) may contain an organic solvent as needed. That is, the transparent layer (B) may be used in the form of at least a part or all of the above resin dissolved in an organic solvent or a mutually soluble state (varnish). The organic solvent may be at least a part, preferably all, of the resin monomer, and may be appropriately dissolved or miscible, and may be appropriately used, and the type is not particularly limited. Specific examples are, for example, benzene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone (2-butanone), acetone, methanol, ethanol, isopropanol, 2-butanol, ethyl acetate, butyl acetate, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diacetone alcohol, N, N'-dimethylformamide, N, N'-dimethylacetamide, acetonitrile, etc., but not particularly limited thereto . The organic solvent may be used singly or in combination of two or more kinds 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 10 to 99% by mass, preferably 20 to 90% by mass. If the concentration of the solution is too low, the impregnation of the resin is insufficient, and the transparency is lowered. On the other hand, if the concentration of the solution is too high, the viscosity of the solution is increased, and there is a case where the impregnation is poor.

When an epoxy resin is used as the curable resin in the resin composition of the transparent layer (B), it is preferable to add a diluent such as a monoepoxy compound to the extent that the reaction is not impaired in order to improve workability and processability after curing of the epoxy resin. Preferably. When such a diluent is added, workability and workability can be improved by lowering the viscosity of the monomer, and flexibility can be imparted to the epoxy resin after curing, and flexibility and impact resistance of the transparent layer (B) can be obtained. Increased temperament. Examples of the diluent include styrene oxide, epoxycyclohexane, propylene oxide, methyl glycidyl ether, ethyl epoxidized propyl ether, n-butyl epoxidized propyl ether, and 2-ethylhexyl epoxidized ether. Cresol epoxidized propylene ether, second butyl phenyl epoxidized ether, cardanol epoxidized propyl ether, glycidyl methacrylate, phenyl epoxidized propyl ether, allyl epoxide Ether, epoxy octane, epoxy dodecane, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol bicyclo Ethyl propyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, or the like may be used in combination of two or more kinds.

The amount of the diluent is preferably less than 100 parts by mass based on 100 parts by mass of the epoxy resin, and more preferably 15 parts by mass or less. When 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 flexural modulus of elasticity of the entire transparent resin laminate can be 5 GPa or more.

When a thiol-ene photocurable resin is used as the resin composition of the transparent layer (B), the resin composition containing the thiol group-containing compound (a) and the alkenyl group-containing compound (b) is activated by ultraviolet rays or the like. The light is crosslinked and hardened, and a photopolymerization initiator which generates a radical can be added to the resin composition. The photopolymerization initiator, for example: diphenyl ketone, N, N'-tetraki-4,4'-diaminodiphenyl ketone, 4-methoxy-4'-dimethylaminodiphenyl Ketone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyl Butyl benzophenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl benzophenone, 2-methyl-1-[4-(methylthio)phenyl]-2- Olinone propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Oleinophenyl)-butanone-1,2-dimethylamino-2-(4-methyl-benzyl)-1-(4- -Phenyl-4-yl-phenyl)-butan-1-one, 2,6-dimethylbenzimidyldiphenylphosphine oxide, 2,4,6-trimethylbenzhydryldiphenyl oxide Phosphine, tert-butyl hydrazine, 1-chloroindole, 2,3-dichloropurine, 3-chloro-2-methylindole, 2-ethylhydrazine, 1,4-naphthoquinone, 9 , 10-phenanthrene, 1,2-benzopyrene, 1,4-dimethylhydrazine, 2-phenylindole, 2-(o-chlorophenyl)-4,5-diphenylimidazolium Polymer, 2-mercaptobenzothiazole, 2-mercaptobenzoene Azole, and 4-(p-methoxyphenyl)-2,6-di-(trichloromethyl)-s-three Wait. The photopolymerization initiator may be used singly or in combination of two or more kinds as appropriate. Commercial products of the photopolymerization initiators include Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907, and Lucirin TPO (both manufactured by BASF Corporation).

When the photopolymerization initiator is used, the content in the resin composition may be an amount which can be moderately cured. For example, the total amount of the compound of two or more alkenyl groups is 0.01 to 2 parts by mass. The mass fraction is preferably 0.02 to 1 part by mass, preferably 0.1 to 0.5 part by mass. If the amount of the photopolymerization initiator added is too large, the polymerization proceeds violently, and problems such as an increase in birefringence, coloring, and cracking during hardening occur. Moreover, if it is too small, the composition cannot be sufficiently hardened, and there is a fear that adhesion to another substrate or the like may occur after crosslinking, and the problem may not be removed.

Moreover, when a thiol-ene photocurable resin is used for the resin composition of the transparent layer (B), in order to improve the storage stability before hardening, a storage stabilizer which suppresses a thiol-ene reaction can be blended. In particular, when the photopolymerization initiators listed above are used, the storage stability of the resin composition tends to decrease, and it is preferred to use such a storage stabilizer in combination. Examples of such a storage stabilizer include phosphorus compounds such as triphenylphosphine and triphenyl phosphite; p-methoxyphenol, hydroquinone, gallic phenol, naphthylamine, t-butylcatechol, and chlorination. Copper (I), 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylene Radical polymerization inhibitors such as bis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine aluminum salt, diphenylnitrosamine, etc.; benzyldimethylamine, 2-( 3-aminoamines such as dimethylaminomethyl)phenol, 2,4,6-glucos(diaminomethyl)phenol, diazabicycloundecene, etc.; 2-methylimidazole, 2-ethyl-4 - Imidazoles such as methylimidazole, 2-ethylhexyl imidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole. These storage stabilizers may be used alone or in combination of two or more.

The type of the glass fiber cloth to be used for the transparent layer (B) is not particularly limited. For example, it can be appropriately selected from various known products used for various transparent fiber reinforced resins depending on the intended use and performance. For example, glass cloth such as E glass, S glass, T glass, NE glass, L glass, D glass, Q glass, UN glass, or the like. Among them, the refractive index of the glass fiber cloth is preferably greater than 1.55, and the E glass fiber cloth (preferably E glass cloth) is more desirable from the viewpoints of transparency, rigidity, workability, and cost.

When the glass cloth is used for the glass fiber cloth, the weaving method may be flat weave, twill weave, satin weave, weave, or the like, and the flatness is excellent in terms of dimensional stability and tensile resistance in the planar direction. The thickness of the glass fiber cloth (fibrous filler) is usually preferably from 10 μm to 200 μm, more preferably from 40 μm to 150 μm. Further, these glass fiber cloths may be used alone or in multiple pieces. Further, those who have been subjected to surface treatment with a decane coupling agent or the like, or those who perform physical fiber opening treatment on a woven fabric (cloth) can be preferably used in consideration of moisture absorption and heat resistance.

The method for producing the transparent layer (B) used in the front panel for a display of the present embodiment is not particularly limited as long as it is processed into a layered shape by using the resin composition used for the transparent layer (B) in combination with the glass fiber cloth. When the resin containing a sulfur atom is a thermoplastic resin, the glass fiber cloth may be impregnated with a resin containing a sulfur compound to impregnate the resin containing the sulfur compound, and then heated by a dryer or the like to volatilize and remove the solvent. To make. Thereafter, it may be heated to a temperature higher than the softening temperature of the resin containing the sulfur compound and compression-molded, or may be calendered using a metal roll. Further, a glass fiber cloth may be placed in a chamber, and a resin composition containing a sulfur compound before polymerization may be injected into the chamber to be heated and polymerized.

In the case where the resin containing a sulfur atom is a curable resin, it is produced by impregnating a curable resin composition with a glass fiber cloth, and drying it as needed, and pressing or layer-bonding with another substrate to adjust the thickness, and heating And a method of crosslinking and hardening the curable resin composition by at least one of active light irradiation. The curable resin composition referred to herein means a mixed liquid of a curable resin monomer and a curing accelerator.

More specifically, when the resin containing a sulfur atom is a thermosetting resin, the glass fiber cloth may be immersed in a fluid composition containing a sulfur compound at normal temperature or under heating, or the glass fiber cloth may be impregnated. A resin containing a sulfur atom is impregnated in a solution in which a resin containing a sulfur atom is dissolved. The resin composition containing a sulfur compound may be dried, and dried or laminated by another substrate to adjust the thickness, and the resin composition containing the sulfur compound may be crosslinked and hardened by heating. Here, the resin composition containing a sulfur compound means a composition containing a resin monomer before curing.

In the case where the sulfur atom-containing resin is a photocurable resin, a method in which, for example, a glass fiber cloth is immersed in a photocurable resin containing a compound having a thiol group (a) and a compound having an alkenyl group (b) The composition is dried as needed, and is pressed or laminated with a substrate such as a SUS plate, a glass plate, or a polyethylene terephthalate which has been subjected to release treatment to adjust the thickness, and irradiated with active light such as ultraviolet light to make The method of hardening the photocurable resin composition, or immersing the glass fiber cloth in a solution in which the resin composition containing the alkenyl group-containing compound (b) is dissolved, and then adding the compound (a) having a thiol group, if necessary, drying Further, a method of pressing or laminating the same substrate as that of the above-mentioned release treatment to adjust the thickness, and irradiating the active light such as ultraviolet light to harden the photocurable resin composition impregnated with the glass fiber cloth is used. Further, the reaction is often further progressed by heating after the light is applied, and the heat treatment after the irradiation may be applied.

The method for producing the transparent resin laminate (C) of the present embodiment is not particularly limited. For example, the transparent layer (B) is interposed between the transparent resin layer (A) and the adhesive layer as shown in FIG. When the transparent resin layer (A) is adhered to the transparent layer (B), the transparent resin layer (A) and the transparent layer (B) are used as long as the transparent resin layer is formed by using a transparent adhesive. The method of fitting can be carried out without particular limitation. For example, a suitable transparent adhesive composed of a photocurable resin, a thermosetting resin, a hot melt resin, or the like is applied to both surfaces or one surface of the transparent resin layer (A), and then the transparent layer (B) is laminated to be transparently adhered. The method of hardening the agent.

The type and method of the transparent adhesive to which the transparent resin layer (A) and the transparent layer (B) are bonded are not particularly limited, and various adhesives such as a photocurable adhesive, a thermosetting adhesive, and a room temperature curable adhesive can be used. . Further, when a solvent-containing adhesive is used, bubbles may occur during curing, and the transparency of the entire transparent laminate may be lowered. Therefore, it is preferred to use a solvent-free solvent-free adhesive. The adhesive may be one liquid type or two liquid type.

Specific examples of the transparent adhesive to which the transparent resin layer (A) and the transparent layer (B) are bonded are, for example, an epoxy-based adhesive, an acrylic adhesive, or an urethane-based adhesive. The transparent adhesive may be used singly or in combination. For example: Daikin Industries Co., Ltd.'s OPTODYNE series of acrylic UV adhesives (eg OPTODYNE UV-2000, OPTODYNE UV-3000, etc.), Henkel Loctite series of acrylic UV adhesives (such as Loctite 3193HS), Lithium Chemicals Co., Ltd.'s World Rock series of modified acrylate UV adhesives (eg World Rock XVL-90, World Rock 8807, World Rock HRJ-21, etc.), Gluelabo Co., Ltd. Acrylic UV adhesives Acrylic adhesives such as GLX18-73N, etc.; urethane adhesives such as DIC's Unidic V-9500 series of urethane-based UV adhesives (eg Unidic V-9520, Unidic V-9540, etc.) Otto-based UV adhesives of OPTODYNE series (such as OPTODYNE UV-1000, OPTODYNE UV-4000, etc.) and epoxy thermosetting of EA series of Sanyu-rec Co., Ltd. An epoxy-based adhesive such as an adhesive (EA-409, EA-415, etc.) or an Adekaoptomer KR series epoxy-based photocurable adhesive (KR-401, etc.) from ADEKA Co., Ltd.

In one embodiment of the present invention, the adhesive which bonds the transparent resin layer (A) and the transparent layer (B) is cured to a thickness of 1 mm (after curing) and has a tensile modulus of elasticity of 1 MPa or more and hardens. It becomes transparent. The reasons are as follows. In order to make the adhesiveness high, even if bending and flexing force are applied, the bonding object is not easily peeled off. The properties generally required for the adhesive are fully exerted, and the tensile elastic modulus at the time of curing of the adhesive is preferably low, but if it is adhered When the agent is hardened, the tensile modulus is low. When bending and flexing force are applied, it is presumed that the adhesive layer is deformed, and the hardness of the transparent layer (B) cannot be reflected to the entire transparent laminate. Therefore, in the present embodiment, by ensuring that the adhesive layer has a certain degree of tensile modulus and bonding the transparent layer (B) having high rigidity to both surfaces of the transparent resin layer (A), the transparent resin layer can be used alone. A), play a higher rigidity. When the adhesive is hardened to a thickness of 1 mm (after hardening), the tensile modulus of elasticity is preferably 10 MPa or more, more preferably 20 MPa or more. If the tensile modulus of the adhesive is too high, there is a problem that cracking or the like occurs in the processing. From this point of view, when the adhesive is hardened to a thickness of 1 mm (after hardening), the tensile modulus of elasticity is preferably 4 GPa or less, more preferably 2 GPa or less.

A method for coating a transparent adhesive, for example, a dip coating method, a spray coating method, a spin coating method, a bead coating method, a wire bar coating method, a knife coating method, a roll coating method, a curtain coating method, and a slit die coating method A gravure coater method, a reverse slit coating method, a micro gravure printing method, a comma coater method, or the like. The method of adhering the transparent adhesive has the following method: applying a photocurable adhesive to the transparent resin layer to cover the transparent layer (B), and then adhering to the light to adhere. If the one side is adhered one by one, warping sometimes occurs, so it is preferable to adhere to both sides of the transparent resin layer (A) at the same time. Further, when the transparent resin layer (A), the transparent layer (B), and the adhesive are transparent, since the transparent layer (B) is laminated on both sides of the transparent resin layer (A) and light is irradiated from one side, the light also reaches the other On one side, both sides can be hardened at the same time.

Further, the thickness of the adhesive layer is preferably from 1 μm to 100 μm, more preferably from 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 within the above range, the rigidity and adhesion of the entire transparent resin laminate are good.

The viscosity at 23 ° C before the curing of the adhesive is preferably 10,000 mPa·s or less, more preferably 5,000 mPa·s or less. In the above range, the coating film of the adhesive layer does not become too thick, can be controlled to a desired thickness, and the rigidity of the transparent resin laminate can be suppressed from being lowered. In addition, the lower limit of the viscosity is not particularly limited as long as it can form a good coating film, and it is preferably 1 mPa·s or more in terms of workability at the time of coating. The viscosity of the adhesive before hardening can be measured using a rotary B-type viscometer according to JIS7117-1:1999.

Further, if the transparency of the adhesive is low, the transparency of the entire transparent resin laminate is lowered. Therefore, it is preferred that the adhesive be used 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, it has high transparency and is suitable as a front panel for displays.

If the shrinkage ratio (hardening shrinkage ratio) of the curing of the adhesive is large, the adhesion is lowered and the warpage is caused. Therefore, the curing shrinkage ratio of the adhesive is preferably small. As an example, the hardening shrinkage ratio is preferably 10% or less, more preferably 8% or less. (Measurement method of hardening shrinkage ratio) The specific gravity of the adhesive is determined from 3.1 (1) of JIS K 7232:1986. The specific gravity of the cured body of the adhesive is determined from 3.2 (1) of JIS K 7232, and is determined by the following formula. Hardening shrinkage rate. (hardening shrinkage ratio) = (hardened specific gravity - liquid specific gravity) / (hardened specific gravity) × 100 (%)

From the viewpoint of productivity, the adhesive is preferably a rapid hardening property. For example, when a photocurable adhesive is used, the cumulative light amount hardening at 5000 mJ/cm ² or less is preferred.

Further, in the form shown in Fig. 2, when the transparent layer (B) is laminated on the transparent resin layer (A) and the transparent resin layer (A) is adhered to the transparent layer (B), for example, a transparent layer is formed. When the resin composition of (B) contains a curable resin, the resin composition before the transparent layer (B) is applied to both surfaces of the transparent lipid layer (A) may be used, and after the coating film is formed, the coating film may be made to be heated or A method in which the active energy is hardened by light, whereby the transparent resin layer (A) and the transparent layer (B) are adhered.

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 superposed on both surfaces of the transparent resin layer (A), and hot plate is added thereto. The press edge is heated until the required temperature, and it is laminated while hardening. Further, when the resin composition forming the transparent layer (B) contains a thermoplastic resin, a method in which the transparent layer (B) is heated in advance until the temperature at which the thermoplastic resin is softened is superposed, and the softened transparent layer (B) is superposed. The transparent resin layer (A) is adhered to both surfaces of the transparent resin layer (A) while being pressed to a temperature lower than the softening point to be cured, and the transparent resin layer (A) and the transparent layer (B) are adhered. When the resin composition forming the transparent layer (B) contains a photocurable resin, a method of immersing the photocurable resin composition containing the thiol group-containing compound (a) and the alkenyl group-containing compound (b) a method in which a coating film (transparent layer (B)) obtained by using a glass fiber cloth is bonded to the transparent resin layer (A), photocuring the photocurable resin composition, or containing a compound having a thiol group ( a) a coating film (transparent layer (B)) obtained by immersing the photocurable resin composition of the compound having an alkenyl group (b) in a glass fiber cloth, and bonding the light to the transparent resin layer (A) The method of hardening.

The physical properties of the adhesive represented by the present invention are shown below. In the table, the oxime described as (measured) is a physical property measured by the measurement method used in the following examples. 【Table 1】 Elastic coefficient (measured): tensile modulus of elasticity at a thickness of 1 mm

In the transparent resin laminate (C) used for the front panel for a display of the present embodiment, since the transparent resin layer (A) and the transparent layer (B) are transparent, the laminate is transparent. Further, when laminating with a transparent adhesive, since the transparent resin layer (A), the transparent layer (B), and the transparent adhesive are transparent, the laminate is transparent.

The transparent resin laminate (C) used for the front panel for a display of the present embodiment has a bending elastic modulus of 5 GPa or more, more preferably 7 GPa or more, and more preferably 8 GPa or more. When the flexural modulus of the transparent resin laminate is 5 GPa or more, the rigidity is improved, and it is suitable as a front panel for a display. For example, by disposing a transparent layer (B) having a tensile modulus of 10 GPa or more on both surfaces of a polycarbonate resin layer (A) having a flexural modulus of elasticity of 2.6 GPa, a transparent resin laminate having a flexural modulus of 5 GPa or more can be obtained. This laminate can be used. Further, for example, by providing a transparent layer (B) containing a curable resin having a tensile modulus of 10 mm or more and a thickness of 1 mm on both surfaces of the polycarbonate resin layer (A) having a bending elastic modulus of 2.6 GPa, bending flexibility can be obtained. A laminate of a transparent resin having a coefficient of 5 GPa or more can be used. When the flexural modulus of the transparent resin laminate is 5 GPa or more, the rigidity is improved, and it is suitable as a front panel for a display.

The transparent resin laminate according to the embodiment of the present invention is a transparent adhesive layer (B) which is cured by a transparent adhesive having a tensile modulus of 1 MPa or more when the thickness of the transparent resin layer (A) is 1 mm. In the transparent layer (B), the resin composition containing the curable resin is impregnated into the glass fiber cloth and cured to have a tensile modulus of elasticity of 10 GPa or more.

The transparent layer (B) having a tensile modulus of 10 GPa or more is bonded to both surfaces of the polycarbonate resin layer (A) by the above-mentioned transparent adhesive, and a transparent laminate which is transparent and excellent in rigidity as a whole can be obtained. The transparent laminate is suitable as a front panel for display from the viewpoint of transparency and rigidity. The transparent layer (B) has a tensile elastic modulus of less than 10 GPa, and is bonded to a transparent adhesive having a tensile modulus of 1 MPa or more when the both sides of the polycarbonate resin layer (A) are cured to a thickness of 1 mm. At the same time, a transparent laminate having a bending elastic modulus of 5 GPa or more was not obtained as a whole.

The transparent resin laminate (C) used for the front panel for a display of the present embodiment has a total light transmittance of 80% or more and 85% or more. When it is 80% or more, transparency is high and it is suitable as a front panel for displays. Further, from the viewpoint of image contrast and color reproducibility, the light transmittance of 400 nm of the transparent resin laminate (C) is preferably 60% or more, more preferably 70% or more, and still more preferably 75% or more.

In order to impart scratch resistance and the like to the transparent resin laminate (C) used for the front panel for a display of the present embodiment, it is preferred to form a resin layer (smoothing layer) on at least one surface of the transparent layer (B). The layer is preferably a polyethylene terephthalate film layer. The use of a resin layer can improve surface smoothness and easily impart functionality. In the transparent resin laminate according to the embodiment of the present invention, a polyethylene terephthalate film layer is disposed on at least one of the outer sides of the transparent layer (B).

In the case of the above polyethylene terephthalate film, it is preferable to carry out a hard coat treatment or the like in the case where the surface hardness is required. By performing hard coating treatment, the scratch resistance is improved, and it is suitable as a front panel for a display.

When the above-mentioned polyethylene terephthalate film is subjected to a hard coat treatment, a polyethylene terephthalate film as a hard coat layer which has been subjected to a hard coat treatment in advance may be bonded, and it may also be a pair of polyethylene terephthalate. The ethylene phthalate film is bonded and then subjected to a hard coating treatment to form a hard coat layer. In the transparent resin laminate according to the embodiment of the present invention, at least one of the resin layers (for example, a polyethylene terephthalate film layer) is provided with a hard coat layer.

When it is used as a front panel for a display, it is preferable that the polyethylene terephthalate film is a material which is an electrode layer-integrated material by applying a transparent conductive film. By forming the electrode layer integrated material, the electrode layer can be omitted, and the material cost and the processing cost can be reduced. In the transparent resin laminate according to the embodiment of the present invention, at least one of the resin layers (for example, a polyethylene terephthalate film layer) is provided with a transparent conductive film layer.

When the transparent electrode film is applied to the above polyethylene terephthalate film, the polyethylene terephthalate film to which the transparent electrode film has been applied in advance may be attached, or the polyethylene terephthalate may be attached thereto. The transparent electrode film is applied after the diol ester film, and when the transparent electrode film is patterned, it may be carried out after bonding the polyethylene terephthalate film.

The method of bonding the polyethylene terephthalate film (layer) to the transparent layer (B) is not particularly limited, and for example, coating on both sides of the transparent layer (B) constituting the transparent resin laminate (C) A method of laminating a polyethylene terephthalate film and curing the transparent adhesive by a suitable transparent adhesive comprising a photocurable resin, a thermosetting resin, a hot melt resin or the like. Further, when the resin composition forming the transparent layer (B) contains a thermosetting resin, the transparent layer (B) before the curing is superposed on both surfaces of the transparent resin layer (A), and the resin layer is superposed on the outer side thereof. After the polyethylene terephthalate film is heated to a desired temperature by a hot plate, it is laminated while being hardened, and the sulfur atom-containing resin forming the transparent layer (B) is a thermoplastic resin. In the case where the transparent layer (B) is heated to a temperature at which the resin is softened, it is superposed on both sides of the transparent resin layer (A), and the polyethylene terephthalate film as a resin layer is superposed on the outer side thereof. The mixture is cooled to a temperature lower than the softening point by pressurization, and may be laminated while being cured.

The transparent adhesive to which the polyethylene terephthalate film and the transparent layer (B) are bonded is not particularly limited, and an epoxy-based adhesive, an acrylic adhesive, or an urethane-based adhesive can be used.

The transparent resin laminate (C) of the present embodiment is formed into a front panel for a display by press working of the transparent resin laminate (C), and is attached to the surface of the front panel for display, and is mainly used for the surface. A display device for protecting a flat panel display device such as a liquid crystal display device or an organic electroluminescence (organic EL) device.

The woven hole angle of the glass fiber cloth of the front panel for a display of the present embodiment is a method of preventing the interference fringe from being inclined by one degree or more with respect to the pixel portion of the display element. [Examples]

The invention will be more specifically described below by way of examples, but the invention is not limited thereto. Further, with respect to the obtained transparent resin laminate, the light transmittance, the Abbe number, and the elastic modulus were measured by the following methods.

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

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

(Glass fiber cloth) The Abbe number of the E glass fiber cloth was measured by the following method. A liquid having a refractive index of 535 nm and a refractive index of 1.535 to 1.570 was prepared by using a contact liquid having a different refractive index (manufactured by Shimadzu Corporation) at a refractive index difference of 0.001, and impregnated with an E glass cloth (3313 53 S101S, Nitto) A glass slide having a slit of 100 μm was sandwiched between the spinning fabrics to prepare a contact liquid impregnated with E glass cloth having a thickness of 100 μm, and spectrophotometry was carried out using a spectrophotometer.

The refractive indices of the D line (589 nm), the F line (486 nm), and the C line (656 nm) of the various contact liquids prepared were measured, and the refractive index of the contact liquid was plotted as the horizontal axis and the light transmittance was plotted as the vertical axis by wavelength. The refractive index having the highest light transmittance is taken as the refractive index of the E glass fiber cloth at this wavelength.

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

(3) Bending elastic modulus The measurement was carried out by a three-point bending test using a precision universal testing machine AG-5000B (manufactured by Shimadzu Corporation). The distance between the fulcrums is 20 mm and the stroke speed is 1 mm/min. The load weight is 1kN.

(4) Tensile modulus (transparent layer (B) and resin) The tensile modulus of elasticity was measured using a dynamic viscoelasticity measuring apparatus DMS6100 (manufactured by SII Nanotechnology Co., Ltd.). Set the test length to 20mm and the frequency to 1Hz. The tensile modulus of elasticity of the present invention refers to the storage modulus at 20 °C.

<Preparation of Transparent Resin Laminate> [Example A-1] A resin having a lower refractive index than glass fiber cloth, that is, an epoxy resin having an epoxy group skeleton (Celloxide 2021 PDaicel, refractive index 1.51) 54 parts by mass of a resin containing a sulfur compound having a refractive index higher than that of a glass fiber cloth, that is, neopentyl thiopropionate (hereinafter referred to as PETP, manufactured by Seiko Chemical Co., Ltd., refractive index: 1.60) 43 parts by mass of 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol (hereinafter referred to as GST, synthesized according to Japanese Patent No. 3048929, refractive index of 1.70) was mixed in an amount of 3 parts by mass. Stir for 5 minutes using a magnetic stirrer. Further, 1 part by mass of Tetrabutylphosphonium O (O-Diethyl Phosphorodithioate) (Wako Pure Chemical Industries, Ltd.) as a hardening accelerator was added and stirred with a magnetic stirrer. A monomer mixture was prepared for 5 minutes.

The monomer mixture liquid was placed in a tank, and an E glass fiber cloth (3313 53 S101S, manufactured by Nippon Seiko Co., Ltd., refractive index: 1.56) was immersed therein, and the above monomer mixture liquid was immersed to undergo a release treatment. Cleaved on ethylene glycol film. This was placed in a blower oven, and after holding at 40 ° C for 5 hours, the temperature was raised to 120 ° C at 0.5 ° C / min, and the temperature was kept at 120 ° C for 5 hours and hardened to obtain a transparent layer 1.

A transparent epoxy adhesive KR-401 (made by ADEKA Co., Ltd.) was applied to a polycarbonate resin plate (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness: 700 μm) to a thickness of about 30 μm. The transparent layer 1 is overlapped in a bubble-free manner. On the other surface, the adhesive was applied in the same manner, and the transparent layer 1 was placed thereon, and UV of 1000 mJ/cm ² was irradiated with a UV irradiation device, and then irradiated with a surface of 1000 mJ/cm ² to be hardened. Thereby, a three-layer transparent resin laminate of a transparent layer/transparent resin layer (PC)/transparent layer was formed, and a front panel for a display was produced. The front panel of this display has a thickness of 913 μm. Further, when the light is irradiated from one side, the light also reaches the transparent layer 1 on the other side, and the two adhesive faces of the transparent resin layer (PC) are simultaneously hardened, but for the sake of safety, the other side is illuminated.

[Example A-2] The monomer mixture liquid prepared in Example A-1 was placed in a tank, and E glass fiber cloth (3313 53 S101S, manufactured by Nitto Spin Co., Ltd.) was immersed therein to prepare the above monomer mixture. It was immersed and sandwiched with a polycarbonate resin plate (thickness: 700 μm) and a 50 μm extended polyethylene terephthalate film. It was placed in a forced air oven, and after being kept at 40 ° C for 5 hours, it was heated to 120 ° C at 0.5 ° C / min, and kept at 120 ° C for 5 hours to be hardened to form an extended polyethylene terephthalate film / transparent. A five-layer transparent resin laminate of a layer/transparent resin layer (PC)/transparent layer/extending polyethylene terephthalate film to form a front panel for display. The front panel of this display has a thickness of 990 μm.

[Comparative Example A-1] A resin having a lower E refractive index than a glass fiber cloth, that is, three Epoxy resin of the skeleton (TEPIC-S (manufactured by Nissan Chemical Industry Co., Ltd., refractive index 1.54) 47 parts by mass, E-resin is a resin containing no sulfur, which is higher than the refractive index of glass fiber cloth (Techmore) VG3101, Printec (stock), refractive index 1.61) 21 parts by mass and hardener (Rikacid MH700 (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30) (New Japan Physical and Chemical) (Stock), refractive index 1.49)) 32 parts by mass, diluted with 2-butanone to 50% by weight, and then stirred for 10 minutes with a magnetic stirrer. Then added O, O-diethylphosphorus as a hardening accelerator 0.8 parts by mass of Tetrabutylphosphonium O (O-Diethyl Phosphorodithioate) (Wako Pure Chemical Industries, Ltd.) was stirred by a magnetic stirrer for 5 minutes to prepare a monomer mixed solution.

The monomer mixed solution was immersed in an E glass fiber cloth (3313 53 S101S, manufactured by Nippon Seiko Co., Ltd., refractive index: 1.56), and heated at 130 ° C for 4 minutes to remove the solvent, and at the same time, the resin was semi-hardened to prepare a prepreg. . Then, one piece of this prepreg was placed on a surface-treated SUS plate, and it was mounted on a hot/cold press VH2-1630 (manufactured by Kitagawa Seiki Co., Ltd.), and heated to 200 ° C at 3 ° C / min. The mixture was kept at ° C for 1 hour for hardening to obtain a transparent layer 2.

A transparent epoxy adhesive KR-401 (made by ADEKA Co., Ltd.) was applied to a polycarbonate resin sheet (manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness: 700 μm) to a thickness of about 30 μm to prevent bubbles. The way to overlap the transparent layer 2. On the other surface, an adhesive was applied in the same manner, and the transparent layer 2 was superposed, and UV of 1000 mJ/cm ² was irradiated with a UV irradiation device, and then irradiated with a surface of 1000 mJ/cm ² to be hardened. Thereby, a three-layer transparent resin laminate of a transparent layer/transparent resin layer (PC)/transparent layer was formed, and a front panel for a display was produced. The thickness of the front panel for this display is 951 μm.

<Evaluation> The refractive index, total light transmittance, and Abbe number of the transparent layer or the glass fiber cloth were measured by the above-described evaluation method for the transparent resin laminate produced as described above; and the entire transparent resin laminate Light transmittance, light transmittance at 400 nm or 550 nm, and flexural modulus of elasticity.

【Table 2】

【table 3】

<Preparation of Transparent Resin Laminate> [Example B-1] A resin having a lower refractive index than that of the E glass fiber cloth used, that is, a tricyclodecane dimethanol diacrylate having an alkenyl group of an alicyclic resin ( Hereinafter, it is called A-DCP, which is manufactured by Shin-Nakamura Chemical Industry Co., Ltd., having a refractive index of 1.53), 83 parts by mass, and a refractive index higher than that of the E glass fiber cloth used. 17 parts by mass of benzyl-3,6-dithia-1,8-octanedithiol (hereinafter referred to as GST, manufactured by Mitsui Chemicals Co., Ltd.) was mixed with a magnetic stirrer for 5 minutes. Further, Irgacure 184 as a photopolymerization initiator was added in an amount of 0.5 part by mass based on the mass of the resin, and the mixture was stirred for 5 minutes with a magnetic stirrer to prepare a monomer mixture.

The monomer mixture liquid was placed in a tank, and an E glass fiber cloth (3313 53 S101S, manufactured by Nippon Seiko Co., Ltd., refractive index: 1.56) was immersed therein, and the above monomer mixture was immersed, and the mixture was subjected to release treatment. The ethylene terephthalate film is clamped. This was irradiated with ultraviolet light at 1000 mJ/cm ² using an ultraviolet light irradiation device (EDE ultraviolet curing device, manufactured by Eyegraphics Co., Ltd.), and then irradiated with a surface of 1000 mJ/cm ² to be hardened to obtain a transparent fiber-reinforced resin 1.

A transparent epoxy adhesive KR-401 (made by ADEKA Co., Ltd.) was applied to a polycarbonate resin sheet (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness: 800 μm) to a thickness of about 30 μm. The transparent fiber-reinforced resin 1 was superposed on the surface without bubbles, and ultraviolet light of 1000 mJ/cm ² was irradiated with an ultraviolet light irradiation device (EDY ultraviolet curing device, manufactured by Eyegraphics Co., Ltd.), and then irradiated with a surface of 1000 mJ/cm ² . Harden. Thereby, a three-layer transparent resin laminate of a transparent fiber-reinforced resin layer (transparent layer)/transparent resin layer (polycarbonate)/transparent fiber-reinforced resin layer (transparent layer) was formed. The thickness of this transparent resin laminate was 1080 μm. Further, when the light is irradiated from one side, the light also reaches the transparent layer on the other side, and the two adhesive faces of the transparent resin layer (PC) are simultaneously hardened, but for the sake of safety, the other side is illuminated.

[Comparative Example B-1] A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd., refractive index: 1.53) of a resin having a lower refractive index than that of the E glass fiber cloth used, that is, an alkenyl group-containing alicyclic resin. 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene, which is an aromatic resin having an alkenyl group having a refractive index higher than that of the E glass fiber cloth used (hereinafter, It is called A-BPEF, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., having a refractive index of 1.62) and mixed with 30 parts by mass, and stirred at 50 ° C for 30 minutes using a magnetic stirrer. Further, Irgacure 184 as a photopolymerization initiator was added in an amount of 0.5 part by mass based on the mass of the resin, and the mixture was stirred at 50 ° C for 5 minutes using a magnetic stirrer to prepare a monomer mixture.

The monomer mixture liquid was placed in a tank, and an E glass fiber cloth (3313 53 S101S, manufactured by Nippon Seiko Co., Ltd., refractive index: 1.56) was immersed therein, and the above monomer mixture liquid was immersed to be subjected to a release treatment. Cleaved on ethylene glycol film. This was irradiated with ultraviolet light at 1000 mJ/cm ² using an ultraviolet light irradiation device (EYE ultraviolet curing device, manufactured by Eyegraphics Co., Ltd.), and then irradiated with a surface of 1000 mJ/cm ² to be hardened to obtain a transparent fiber-reinforced resin 2.

A transparent epoxy adhesive KR-401 (made by ADEKA Co., Ltd.) was applied to a polycarbonate resin sheet (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness: 800 μm) to a thickness of about 30 μm. The transparent fiber-reinforced resin 2 is superposed on the surface without bubbles, and ultraviolet light of 1000 mJ/cm ² is irradiated with an ultraviolet light irradiation device (EDE ultraviolet curing device, manufactured by Eyegraphics Co., Ltd.), and then irradiated with a surface of 1000 mJ/cm ² . Harden. Thereby, a three-layer transparent resin laminate of a transparent fiber-reinforced resin layer (transparent layer)/transparent resin layer (polycarbonate)/transparent fiber-reinforced resin layer (transparent layer) was formed. The thickness of this transparent resin laminate was 1060 μm.

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

[Table 4] Table B1

【table 5】

<Preparation of Transparent Resin Laminate> [Example C-1] A resin having a refractive index lower than that of E glass cloth, that is, an epoxy resin having an epoxy group skeleton (Celloxide 2021P, Daicel) 51 parts by mass of a resin having an epoxy resin skeleton (Celloxide 2000Z, manufactured by Daicel Co., Ltd., refractive index: 1.50), 3 parts by mass, and a resin having a higher refractive index than the E glass cloth used, 51 parts by mass Neodymyl thiopropionate (hereinafter referred to as PETP, manufactured by Seiko Chemical Co., Ltd., refractive index 1.60) 43 parts by mass, 4-mercaptomethyl-3,6-dithia-1,8-octane Mercaptan (hereinafter referred to as GST, synthesized according to Japanese Patent No. 3048929, refractive index 1.70) was mixed in an amount of 3 parts by mass, and stirred by a magnetic stirrer for 5 minutes. Further, 1 part by mass of Tetrabutylphosphonium O (O-Diethyl Phosphorodithioate) (Wako Pure Chemical Industries, Ltd.) as a hardening accelerator was added and stirred with a magnetic stirrer. A monomer mixture was prepared for 5 minutes.

The monomer mixture liquid was placed in a tank, and an E glass cloth (3313 53 S101S, manufactured by Nitto Denko Co., Ltd., refractive index: 1.56) was impregnated therein to immerse the monomer mixture in a release treatment. The ethylene glycol diester film is clamped. This was placed in a forced air oven, and after holding at 40 ° C for 5 hours, the temperature was raised to 120 ° C at 0.5 ° C / min, and the temperature was kept at 120 ° C for 5 hours to be hardened to obtain a transparent layer. The total thickness of this transparent layer was 186 μm (single side: 93 μm).

A transparent epoxy adhesive KR-401 (made by ADEKA Co., Ltd.) was applied to a polycarbonate resin sheet (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness: 800 μm) to a thickness of about 20 μm. , the transparent layer is overlapped in a bubble-free manner. On the other hand, an adhesive was applied and the transparent layer was superposed thereon, and ultraviolet light of 1000 mJ/cm ² was irradiated with a UV irradiation device, and then irradiated with a surface of 1000 mJ/cm ² to be hardened. Thereby, a three-layer transparent laminate of a transparent layer/polycarbonate resin layer/transparent layer was formed. The thickness of this transparent laminate was 1020 μm. Further, when the light is irradiated from one side, the light also reaches the transparent layer 1 on the other side, and the two adhesive faces of the transparent resin layer (PC) are simultaneously hardened, but for the sake of safety, the other side is illuminated.

[Example C-2] The same procedure as in Example 1 except that 48 parts by mass of Celloxide 2021P, 6 parts by mass of Celloxide 2000Z, 43 parts by mass of PETP, and 3 parts by mass of GST were mixed to prepare a monomer mixture liquid. This was carried out to obtain a three-layer transparent laminate of a transparent layer/polycarbonate resin layer/transparent layer. The total thickness of the transparent layer was 178 μm (single side: 89 μm), and the thickness of the transparent laminate was 1028 μm.

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

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

[Example C-5] 27 parts by mass of Celloxide 2021P, 27 parts by mass of Celloxide 2000Z, 40 parts by mass of PETP, and 6 parts by mass of GST were mixed to prepare a monomer mixture, and Example C- 1 was carried out in the same manner, and a three-layer transparent laminate of a transparent layer/polycarbonate resin layer/transparent layer 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> For the transparent laminate produced in the above manner, the total light transmittance and the tensile modulus of the transparent layer were measured by the evaluation method described above; and the tensile modulus of the cured resin used for the transparent layer (B) And the flexural modulus of the transparent resin laminate.

Further, the tensile modulus of elasticity of the curable resin of the transparent layer was measured by the following method. A SUS frame (thickness: 1 mm) having a hole of 2 cm × 4 cm was placed on the release-treated glass plate, and each monomer mixture was filled in a hole to cover the release-treated glass plate, and a UV irradiation device was used. After irradiating UV at 1000 mJ/cm ² and then irradiating it at 1000 mJ/cm ² , it was hardened to obtain a curable resin test piece. With respect to the obtained curable resin test piece, the tensile modulus of elasticity was measured by the above method.

According to the following Table C1, the total light transmittance of the transparent layer of the examples was 80% or more.

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

[Table 6]

[Table 7]

<Preparation of Transparent Resin Laminate> [Example D-1] (Production of Transparent Layer (B-1)) The glass fiber cloth was made of E glass fiber cloth (3313 53 S101S, manufactured by Nitto Denko Co., Ltd.). A resin having a lower refractive index than the E glass fiber cloth used, that is, an epoxy resin having an epoxy group skeleton (Celloxide 2021P, manufactured by Daicel), 54 parts by mass, and a refractive index ratio of E glass used. The resin containing a sulfur compound is also a neopentyl thiopropionate (manufactured by Ding Chemical Co., Ltd., refractive index 1.60), 43 parts by mass, 4-mercaptomethyl-3,6-dithia-1 8-octanedithiol (hereinafter referred to as GST, synthesized according to Japanese Patent No. 3048929, refractive index 1.70) was mixed in an amount of 3 parts by mass, and stirred by a magnetic stirrer for 5 minutes. 1 part by mass of Tetrabutylphosphonium O (O-Diethyl Phosphorodithioate) (Wako Pure Chemical Industries, Ltd.) as a hardening accelerator, and stirred with a magnetic stirrer After 5 minutes, a curable resin composition was prepared.

The curable resin composition was placed in a bath, and an E glass fiber cloth was immersed therein, and the curable resin composition was immersed and held by a release-treated PET film. This was placed in a forced air oven, and after holding at 40 ° C for 5 hours, the temperature was raised to 120 ° C at 0.5 ° C / min, and the temperature was kept at 120 ° C for 5 hours and hardened to obtain a transparent layer (B-1) having a thickness of 113 μm. The transparent layer (B-1) has a tensile modulus of elasticity of 19 GPa.

(Adhesion of polycarbonate resin layer (A) and transparent layer (B-1)) on polycarbonate resin sheet (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness: 700 μm, bending elastic modulus: 2.6 GPa) The transparent epoxy-based adhesive KR-401 (made by Adeka Co., Ltd., tensile elastic modulus of 1593 MPa at a thickness of 1 mm) was coated with a coating bar to a thickness of about 30 μm, and the transparent layer was superposed without bubbles. -1). On the other hand, an adhesive was applied and the transparent layer (B-1) was superposed thereon, and ultraviolet light of 1000 mJ/cm ² was irradiated with a UV irradiation device, and then irradiated with a surface of 1000 mJ/cm ² to be hardened. Thereby, a three-layer transparent laminate of the transparent layer (B-1) / polycarbonate resin layer (A) / transparent layer (B-1) was formed. The thickness of this transparent laminate was 1013 μm. Further, when the light is irradiated from one side, the light also reaches the transparent layer (B-1) on the other side, and the two adhesive faces of the polycarbonate resin layer (A) are simultaneously hardened, but for the sake of safety, also from another On the one hand, the light is shining.

[Example D-2] (Production of Transparent Layer (B-2)) A glass fiber cloth was used in the same manner as in Example 1 (3313 53 S101S, Nitto Spin Co., Ltd.). a tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., refractive index 1.53) which is a resin having a lower refractive index than the E glass fiber cloth used, which is an alicyclic acrylate resin, and has a refractive index of 83 parts by mass. The ratio was mixed with 17 parts by mass of the resin GST having a higher refractive index than that of the E glass fiber cloth used, and stirred with a magnetic stirrer for 5 minutes. Further, 0.5 parts by mass of Irgacure 184 as a photopolymerization initiator was added, and the mixture was stirred for 5 minutes with a magnetic stirrer to obtain a curable resin composition. The curable resin composition was placed in a bath, and an E glass fiber cloth was immersed therein to impregnate the curable resin composition, and the film was sandwiched by a release-treated PET film. This was irradiated with UV of 1000 mJ/cm ² using a UV irradiation device, and then irradiated with a surface of 1000 mJ/cm ² and hardened to obtain a transparent layer (B-2) having a thickness of 119 μm. The transparent layer (B-2) has a tensile modulus of elasticity of 18 GPa.

(Adhesion of the polycarbonate resin layer (A) and the transparent layer (B-2)) The transparent layer (B-1) was changed to (B-2), and the adhesion was carried out in the same manner as in Example 1 to obtain a thickness of 1021 μm. Transparent laminate.

[Example D-3] A transparent layer (B) was obtained in the same manner as in Example D-1 except that GLX18-73N (manufactured by Gluelab (manufactured by Gluelab) having a tensile modulus of elasticity of 26 MPa) was used. -1) / Three-layer transparent laminate of polycarbonate resin layer (A) / transparent layer (B-1). The thickness of this transparent laminate was 1058 μm.

[Example D-4] The same procedure as in Example D-1 was carried out except that the adhesive was used in the same manner as in Example D-1 except that the adhesive was used in the use of World Rock HRJ-21 (manufactured by Kyoritsu Chemicals Co., Ltd., tensile modulus of elasticity at a thickness of 1 mm). A three-layer transparent laminate of a transparent layer (B-1) / a polycarbonate resin layer (A) / a transparent layer (B-1). The thickness of this transparent laminate was 1061 μm.

[Comparative Example D-1] A transparent epoxy-based adhesive KR-401 (ADEKA) was coated with a coating bar on a polycarbonate resin plate (Iupilon NF-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd., thickness: 700 μm). The film was formed into a thin film of about 30 μm, and a polyethylene terephthalate (PET) resin film (thickness: 100 μm) was laminated so as not to form bubbles. On the other hand, an adhesive was applied and the PET resin film was overlaid, and ultraviolet light of 1000 mJ/cm ² was irradiated with a UV irradiation device, and then irradiated with a surface of 1000 mJ/cm ² to be hardened. Thereby, a three-layer transparent laminate of a PET resin film/polycarbonate resin layer/PET resin film was formed. The thickness of this transparent laminate was 1014 μm.

For the sample prepared in the above manner, the total light transmittance and the bending elastic modulus of the transparent resin laminate were evaluated according to the evaluation method described above; the tensile modulus of the adhesive; and the tensile elasticity of the transparent layer (B) coefficient. Further, the tensile modulus of elasticity of the adhesive was measured by the following method.

(Measurement of Tensile Elastic Coefficient of Adhesive) A SUS frame (thickness: 1 mm) having a hole of 2 cm × 4 cm was placed on a glass plate subjected to release treatment so that each adhesive filled the hole to cover the separation. The glass plate of the type treated was irradiated with UV 1000 mJ/cm ² using a UV irradiation device, and then irradiated with a surface of 1000 mJ/cm ² and hardened. This was used as a sample for measuring the elastic modulus, and the tensile modulus of elasticity was measured by a viscoelasticity measuring device DMS6100 in the same manner as the method for measuring the tensile modulus of elasticity described above.

[Table 8]

As shown in Table D1, in the examples, the total light transmittance of the transparent layer was 80% or more. Further, as shown in Table D1, in Examples D-1 to 3, the transparent laminate had a flexural modulus of 5 GPa or more, and was used as a glass substitute for various covering materials, substrate materials, and front panels for displays. The ideal rigidity of the front panel material. From this, it was confirmed that the rigidity (flexural modulus of elasticity) of the laminate can be further improved by providing the transparent layer (B) with a tensile modulus of 10 GPa or more and using an adhesive having an elastic modulus of 1 MPa or more. Further, in Comparative Example D-1 in which a film having a tensile modulus of 10 GPa or less was used for the transparent layer (B), an adhesive having an elastic modulus of 1 MPa or less was used, but the flexural modulus of the transparent laminate was 5 GPa or less.

1‧‧‧Transparent resin layer (A)
2‧‧‧Transparent layer (B)
3‧‧‧Adhesive layer
4‧‧‧ Polyethylene terephthalate film layer
5‧‧‧ tablets
10‧‧‧Front panel for display
21‧‧‧glass cloth
22‧‧‧Resin composition

Fig. 1 is a schematic cross-sectional view showing a front panel for a display according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing a front panel for a display according to an embodiment of the present invention. Fig. 3 is a cross-sectional photograph of a transparent resin laminate according to an embodiment of the present invention, which is a cross-sectional photograph of a transparent resin laminate produced in Example A-2.

no

Claims (22)

A transparent resin laminate having a transparent layer (B) disposed on both surfaces of a transparent resin layer (A), the transparent layer (B) comprising a glass fiber cloth and a resin composition containing a sulfur compound. The transparent resin laminate according to the first aspect of the invention, wherein a transparent layer (B) is disposed on both surfaces of the transparent resin layer (A), the transparent layer (B) being composed of a glass fiber cloth and containing a mercaptan The base compound (a) is formed with a resin composition of the alkenyl group-containing compound (b). The transparent resin laminate according to claim 1 or 2, wherein a transparent layer (B) is disposed on both surfaces of the transparent resin layer (A), and the transparent layer (B) is made to have a thickness of 1 mm. The resin composition of the curable resin having a tensile modulus of 10 MPa or more is impregnated into a glass fiber cloth. The transparent resin laminate according to claim 1 or 2, wherein an adhesive layer containing a transparent adhesive is provided between the transparent resin layer (A) and the transparent layer (B). The transparent resin laminate according to claim 4, wherein the adhesive layer has a thickness of from 1 μm to 100 μm. The transparent resin laminate according to claim 4, wherein the transparent adhesive is cured to a thickness of 1 mm and has a tensile modulus of elasticity of 1 MPa or more. The transparent resin laminate according to the first or second aspect of the invention is a transparent adhesive-bonding transparent layer having a tensile modulus of elasticity of 1 MPa or more when the thickness of the transparent resin layer (A) is 1 mm or less. In the case of the transparent layer (B), the resin composition containing the curable resin is impregnated into the glass fiber cloth and cured to have a tensile modulus of elasticity of 10 GPa or more. The transparent resin laminate according to claim 4, wherein the transparent adhesive is selected from the group consisting of an acrylic adhesive, an epoxy adhesive, and an urethane adhesive. At least one. The transparent resin laminate according to claim 1 or 2, wherein the transparent resin laminate has a bending elastic modulus of 5 GPa or more. The transparent resin laminate according to claim 1 or 2, wherein the transparent resin layer (A) has a thickness of from 100 μm to 2000 μm, and the transparent layer (B) has a thickness of from 20 μm to 300 μm. The transparent resin laminate of claim 1 or 2 has a total light transmittance of 80% or more. The transparent resin laminate according to claim 1 or 2, wherein a difference between the Abbe number after curing of the resin composition of the transparent layer (B) and the Abbe number of the glass cloth is 15 or less. The transparent resin laminate according to claim 1 or 2, wherein a difference between a refractive index of the resin composition of the transparent layer (B) and a refractive index of the glass cloth is 0.01 or less. The transparent resin laminate according to claim 1 or 2, wherein the resin composition of the transparent layer (B) contains a polymer of a thiol compound and an epoxy resin. The transparent resin laminate according to claim 1 or 2, wherein the glass fiber cloth of the transparent layer (B) has a refractive index greater than 1.55. The transparent resin laminate according to claim 1 or 2, wherein the glass fiber cloth of the transparent layer (B) is an E glass cloth. The transparent resin laminate according to claim 1 or 2, wherein the resin component of the transparent resin layer (A) is selected from the group consisting of polycarbonate, polyethylene terephthalate, and polyparaphenylene. At least one of the group consisting of butylene dicarboxylate and polymethyl methacrylate. The transparent resin laminate according to claim 17, wherein the resin component of the transparent resin layer (A) contains polycarbonate. The transparent resin laminate according to claim 1 or 2, wherein a polyethylene terephthalate film layer is disposed on at least one of the outer sides of the transparent layer (B). The transparent resin laminate according to claim 19, wherein a hard coat layer is disposed on at least one of the outer sides of the polyethylene terephthalate film layer. The transparent resin laminate according to claim 19, wherein a transparent conductive film layer is disposed on at least one of the outer sides of the polyethylene terephthalate film layer. A front panel for a display, which is a transparent resin laminate according to any one of claims 1 to 21.