JP2013039777A - Method for manufacturing transparent composite substrate, transparent composite substrate and display element substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent composite substrate that is reduced in generation and adhesion of foreign objects, to provide a method of efficiently manufacturing the transparent composite substrate, and to provide a display element substrate of high reliability provided with the transparent composite substrate.SOLUTION: The method is provided for manufacturing the transparent composite substrate 1 that has a glass cloth 2, and resin materials 3 impregnated with the glass cloth 2. The method includes: a step of obtaining an impregnation body 101 by impregnating resin varnish 30 to the glass cloth 2; a step of obtaining a temporary cured body 102 by irradiating a part excluding the outer edge 12 of the impregnation body 101 (center part 13) with the ultraviolet and curing the uncured resin varnish 30 after piling up the sheet-like support members 71 on both sides of the impregnation body 101; a step of peeling off the support members 71 from the temporary cured body 102; and a step of obtaining this cured body (transparent composite substrate) by curing the uncured resin varnish 30 by irradiating the outer edge of the temporary cured body 102 with the ultraviolet.

Description

  The present invention relates to a method for producing a transparent composite substrate, a transparent composite substrate, and a display element substrate.

  Glass plates are widely used for color filter substrates used for display elements such as liquid crystal display elements and organic EL display elements, display element substrates such as active matrix substrates, and substrates for solar cells. However, in recent years, substrates made of plastic materials (plastic substrates) have been studied as substitutes for glass plates because they are easily broken, cannot be bent, and are not suitable for weight reduction.

  For example, Patent Document 1 discloses a resin sheet including an epoxy resin and a glass fiber cloth (glass cloth).

  Such a resin sheet is manufactured by, for example, impregnating a glass cloth with an epoxy resin and then curing the epoxy resin. However, if the glass fiber is exposed on the end face during continuous production of the long sheet, the portion becomes a dust generation source, and there is a possibility that the display quality may be lowered when used for, for example, a display body.

JP 2004-051960 A

  An object of the present invention is to provide a transparent composite substrate with less foreign matter generation and adhesion, a manufacturing method capable of efficiently manufacturing such a transparent composite substrate, and a highly reliable display element substrate including the transparent composite substrate. is there.

Such an object is achieved by the present inventions (1) to (15) below.
(1) A method for producing a transparent composite substrate comprising an aggregate of glass fibers and a resin material impregnated in the aggregate of glass fibers,
Impregnating the glass fiber aggregate with an uncured resin material to obtain an impregnated body;
After stacking a support member on at least one surface of the impregnated body, energy is applied to a portion excluding the outer edge portion of the impregnated body to cure the uncured resin material to obtain a temporary cured body;
Peeling the temporary cured body from the support member;
A step of applying energy to an outer edge portion of the temporary cured body to cure the uncured resin material remaining in the temporary cured body to obtain a main cured body. .

  (2) The method for producing a transparent composite substrate according to (1), wherein the aggregate of glass fibers has an elongated shape, and the outer edge portion of the impregnated body is at least outer edge portions of both end portions in the width direction. .

  (3) When the average thickness of the aggregate of glass fibers is t, the outer edge portion is in the range of 1 t to 500 t from the outer edge of the impregnated body to the inner side as described in (1) or (2) above. A method for producing a transparent composite substrate.

(4) Furthermore, a step of applying an uncured coating material to the surface of the main cured body to obtain a liquid film;
A step of superimposing a support member on the surface of the liquid film, applying energy to a portion excluding an outer edge of the liquid film to cure the uncured liquid material, and obtaining a temporary cured film;
Peeling the temporary cured film from the support member;
(1) including a step of applying energy to an outer edge portion of the temporarily cured film to cure the uncured coating material remaining on the temporarily cured film to obtain a coating layer covering the surface of the main cured body. Thru | or the manufacturing method of the transparent composite substrate in any one of (3).

(5) A method for producing a transparent composite substrate having a composite layer formed by impregnating a resin material into an aggregate of glass fibers, and a coating layer covering the surface of the composite layer,
Applying an uncured coating material to the surface of the composite layer to obtain a liquid film;
After superimposing a support member on the surface of the liquid film, applying energy to a portion excluding the outer edge of the liquid film to cure the uncured coating material, and obtaining a temporarily cured film;
Peeling the temporary cured film from the support member;
A method of producing a transparent composite substrate, comprising: applying energy to an outer edge portion of the temporary cured film to cure the uncured coating material remaining on the temporary cured film to obtain the coating layer. .

  (6) The method for producing a transparent composite substrate according to any one of (1) to (5), wherein the energy is thermal energy or light energy.

  (7) The manufacturing method of the transparent composite substrate in any one of said (1) thru | or (6) which provides energy in the state which shielded the said outer edge part.

(8) A transparent composite substrate having a composite layer formed by impregnating a resin material into an aggregate of glass fibers,
A transparent composite substrate, wherein an end face of the glass fiber is coated with the resin material.

  (9) The transparent composite substrate according to (8), wherein an average thickness of the resin material covering the end surface is 0.01d to 200d, where d is an average diameter of the glass fibers.

(10) Furthermore, it has a coating layer covering the surface of the composite layer,
The transparent composite substrate according to (8) or (9), wherein an end surface of the glass fiber is sequentially coated with the resin material and the coating layer.

(11) A transparent composite substrate having a composite layer formed by impregnating a resin material into an aggregate of glass fibers, and a coating layer covering the surface of the composite layer,
A transparent composite substrate, wherein the glass fiber has a side surface in which an end surface is coated with the coating layer.

  (12) The transparent composite substrate according to (11), wherein the ratio of the end surface covered with the coating layer is 70% or more of the total area occupied by the end surface of the glass fiber in the side surface.

  (13) The transparent composite substrate according to (11) or (12), wherein an average thickness of the coating layer covering the end surface is 0.01d to 200d, where d is an average diameter of the glass fiber.

  (14) The transparent composite substrate according to any one of (8) to (13), wherein the glass fiber aggregate has a long shape.

  (15) A display element substrate comprising the transparent composite substrate according to any one of (8) to (14).

  According to the present invention, since the glass fiber on the end face is coated with the resin when the transparent composite substrate is manufactured, the generation of foreign matters in the subsequent steps can be suppressed.

  Moreover, in the transparent composite substrate of this invention, since the end surface of glass fiber has the side surface covered with the resin material, it is hard to break a glass fiber in this side surface. For this reason, in the transparent composite substrate of the present invention, the broken glass fiber becomes a new foreign substance, or the foreign substance is prevented from adhering to the surface.

  In this way, by suppressing the generation of foreign matter, a display element substrate capable of realizing a highly reliable display element can be obtained.

It is sectional drawing which shows 1st Embodiment of the transparent composite substrate of this invention. It is the elements on larger scale of FIG. It is the elements on larger scale which show 2nd Embodiment of the transparent composite substrate of this invention. It is sectional drawing which shows 1st Embodiment of the manufacturing method of the transparent composite substrate of this invention. It is sectional drawing which shows 1st Embodiment of the manufacturing method of the transparent composite substrate of this invention. It is sectional drawing which shows 2nd Embodiment of the manufacturing method of the transparent composite substrate of this invention. It is sectional drawing which shows 2nd Embodiment of the manufacturing method of the transparent composite substrate of this invention.

  Hereinafter, the manufacturing method of the transparent composite substrate of this invention, a transparent composite substrate, and a display element substrate are demonstrated in detail based on suitable embodiment shown to an accompanying drawing.

  The method for producing a transparent composite substrate of the present invention comprises a glass fiber aggregate and a resin material impregnated in the glass fiber aggregate, and the resin material is impregnated into the glass fiber aggregate in a plate shape. This is a method for producing a transparent composite substrate formed and cured.

  Specifically, <1> a step of impregnating an uncured resin material into an aggregate of glass fibers to obtain an impregnated body, and a support member is stacked on at least one surface of the impregnated body, Applying energy to the portion excluding the step to cure the uncured resin material, obtaining a temporary cured body, removing the temporary cured body from the support member, and applying energy to the outer edge of the temporary cured body A step of curing the uncured resin material remaining in the temporarily cured body to obtain a main cured body, or <2> a composite layer of the glass fiber aggregate and the cured resin material, Applying a coating material, obtaining a liquid film, and after overlapping a support member on the surface of the liquid film, applying energy to a portion excluding the outer edge of the liquid film to cure the uncured coating material, A step of obtaining a temporary cured film and whether the temporary cured film is the support member A step of peeling, a step of applying energy to an outer edge portion of the temporarily cured film to cure the uncured coating material remaining on the temporarily cured film, and obtaining a coating layer covering the surface of the main cured body. Have.

  According to the present invention, since the glass fiber on the end face is coated with the resin during the production of the transparent composite substrate, the generation of foreign matters in subsequent processes can be suppressed, and the transparent composite with less foreign matter adhesion. A substrate can be manufactured.

  Moreover, since the obtained transparent composite substrate has a side surface in which the end surface of the glass fiber is covered with a resin material, the glass fiber is prevented from being broken by an external force on this side surface. As a result, the probability of occurrence of new foreign matter or surface adhesion of the generated foreign matter is reduced, and a transparent composite substrate with little foreign matter adhesion is obtained.

<Transparent composite substrate>
<< First Embodiment >>
First, a first embodiment of the transparent composite substrate of the present invention will be described.

  FIG. 1 is a sectional view showing a first embodiment of the transparent composite substrate of the present invention, and FIG. 2 is a partially enlarged view of FIG.

  A transparent composite substrate 1 shown in FIG. 1 has a composite layer 4 including a glass cloth (aggregate of glass fibers 21) 2 and a resin material (matrix resin) 3. Hereinafter, each component will be described.

(Glass cloth)
Examples of the glass cloth (aggregate of glass fibers 21) 2 used in the present invention include not only a bundle of glass fibers 21 but also a woven fabric and a nonwoven fabric containing the glass fibers 21. In FIG. 1, the case where the glass cloth 2 is a woven fabric is illustrated as an example.

  Examples of the inorganic glass material constituting the glass fiber 21 include E glass, C glass, A glass, S glass, T glass, D glass, NE glass, quartz, low dielectric constant glass, and high dielectric constant glass. Among them, E glass, S glass, T glass, and NE glass, which have few ionic impurities such as alkali metals and are easily available, are preferably used. In particular, S glass having an average linear expansion coefficient of 5 ppm or less at 30 ° C. to 250 ° C. Or T glass is used more preferably.

  Moreover, although the refractive index of an inorganic type glass material is suitably set according to the refractive index of the resin material to be used, it is preferable that it is about 1.4-1.6, for example, about 1.5-1.55. It is more preferable that Thereby, the transparent composite substrate 1 which shows the outstanding optical characteristic in a wide wavelength range is obtained.

  The average diameter d of the glass fibers 21 contained in the glass cloth 2 is preferably about 2 to 10 μm, and more preferably about 3 to 8 μm. Thereby, the transparent composite substrate 1 which can make mechanical characteristics, optical characteristics, and surface smoothness highly compatible is obtained. In addition, the average diameter d of the glass fiber 21 is calculated | required as an average value of the diameter of 100 glass fibers 21 measured from the observation image by observing the cross section of the transparent composite substrate 1 with various microscopes.

  On the other hand, the average thickness of the glass cloth 2 is preferably about 10 to 200 μm, and more preferably about 20 to 120 μm. By making the average thickness of the glass cloth 2 within the above range, the transparent composite substrate 1 can be made thin, and sufficient flexibility and translucency can be secured, while suppressing the deterioration of mechanical properties. it can.

  Further, when a bundle of a plurality of glass fibers 21 is woven into a woven fabric, the bundle preferably includes about 30 to 300 single fibers of glass fibers 21 and includes about 50 to 250 fibers. More preferably. Thereby, the transparent composite substrate 1 which can make mechanical characteristics, optical characteristics, and surface smoothness highly compatible is obtained.

  Such a glass cloth 2 is preferably subjected to a fiber opening treatment in advance. By the fiber opening process, a bundle made of a plurality of glass fibers 21 is widened, and the cross section of the bundle is formed into a flat shape. Also, the so-called basket hole becomes smaller. As a result, the smoothness of the glass cloth 2 is increased, and the smoothness of the surface of the transparent composite substrate 1 is also increased. Examples of the opening process include a process of spraying a water jet, a process of spraying an air jet, and a process of performing needle punching.

  Moreover, you may make it provide a coupling agent to the surface of the glass fiber 21 as needed. Examples of the coupling agent include a silane coupling agent and a titanium coupling agent, and a silane coupling agent is particularly preferably used. As the silane coupling agent, those containing an epoxy group, a (meth) acryloyl group, a vinyl group, an isocyanate group, an amide group or the like as a functional group are preferably used.

(Resin material)
Examples of the resin material 3 used in the present invention include epoxy resins, oxetane resins, isocyanate resins, acrylate resins, olefin resins, cycloolefin resins, diallyl phthalate resins, polycarbonate resins, and diallyl carbonate resins. Examples include resins, urethane resins, melamine resins, polyimide resins, aromatic polyamide resins, polystyrene resins, polyphenylene resins, polysulfone resins, polyphenylene oxide resins, silsesquioxane compounds, and the like. Of these, epoxy resins are preferably used, and more preferably various types of fats such as alicyclic polyfunctional epoxy resins, alicyclic epoxy resins having a hydrogenated biphenyl skeleton, and alicyclic epoxy resins having a hydrogenated bisphenol A skeleton. Cyclic epoxy resins are used.

  Specific examples of the alicyclic epoxy resin include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6. -Methylcyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro- (3,4-epoxy) cyclohexane-m-dioxane, 1,2: 8,9-diepoxy limonene, dicyclo Pentadiene dioxide, cyclooctene dioxide, acetal diepoxyside, vinylcyclohexane dioxide, vinylcyclohexylene monooxide 1,2-epoxy-4-vinylcyclohexane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3 4-epoxy-6 Tilcyclohexylmethyl) adipate, exo-exobis (2,3-epoxycyclopentyl) ether, 2,2-bis (4- (2,3-epoxypropyl) cyclohexyl) propane, 2,6-bis (2,3- Epoxypropoxycyclohexyl-p-dioxane), 2,6-bis (2,3-epoxypropoxy) norbornene, diglycidyl ether of linoleic acid dimer, limonene dioxide, 2,2-bis (3,4-epoxycyclohexyl) ) Propane, o- (2,3-epoxy) cyclopentylphenyl-2,3-epoxypropyl ether, 1,2-bis [5- (1,2-epoxy) -4,7-hexahydromethanoindanxyl] ethane , Cyclohexanediol diglycidyl ether and diglycidyl hexahydrofur Examples include esters of 3,4-epoxycyclohexylmethanol and 3,4-epoxycyclohexylcarboxylic acid on both ends of the rate and ε-caprolactone oligomer, epoxidized hexahydrobenzyl alcohol, etc. A seed or a mixture of two or more is used.

  In the present invention, an alicyclic epoxy resin having two or more epoxycyclohexane rings in the molecule is particularly preferably used. Among these, an alicyclic epoxy structure represented by the following chemical formula (1), (2), or (3) is particularly preferably used.

［上記式（１）中、−Ｘ−は−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）_２−を表す。］

[In the above formula (1), -X- is _{-O -, - S -, -} SO -, - SO 2 -, - CH 2 -, - CH (CH 3) -, or -C _{(CH 3) 2} -Represents. ]

  On the other hand, as the alicyclic epoxy resin having one epoxycyclohexane ring in the molecule, alicyclic epoxy resins represented by the following chemical formulas (4) and (5) are particularly preferably used.

  Since such an alicyclic epoxy resin is excellent in curability at low temperature, it can be cured at low temperature. Thereby, since it becomes unnecessary to make the resin material 3 high temperature at the time of hardening, even if it returns a hardened | cured material to room temperature after that, the variation | change_quantity of temperature can be suppressed. As a result, the transparent composite substrate of the present invention can suppress the generation of thermal stress accompanying a temperature change, and has excellent optical characteristics.

  Moreover, since the alicyclic epoxy resin as described above has a low coefficient of linear expansion after curing, in the transparent composite substrate 1 obtained using a resin material containing the alicyclic epoxy resin, a glass cloth 2 and a resin are used. The interfacial stress at the interface with the material 3 is particularly small at room temperature. For this reason, the said transparent composite substrate 1 with a small interface stress can be obtained, and this transparent composite substrate 1 becomes a thing with small optical anisotropy. Furthermore, since the linear expansion coefficient is low, the transparent composite substrate 1 is prevented from being deformed such as warpage and swell.

  In addition, these alicyclic epoxy resins are excellent in transparency and heat resistance, and thus contribute to the realization of the transparent composite substrate 1 having excellent light transmittance and high heat resistance.

  The resin material 3 is preferably a resin material mainly composed of an alicyclic epoxy resin. The main component in this case refers to a component occupying more than 50% by mass of the resin material 3, and the content of the alicyclic epoxy resin in the resin material 3 is preferably 70% by mass or more, and 80% by mass. The above is more preferable.

  Examples of the resin material 3 other than the main component include epoxy resins other than alicyclic epoxy resins such as glycidyl type epoxy resins, oxetane resins, isocyanate resins, acrylate resins, olefin resins, and cycloolefin resins. Diallyl phthalate resin, polycarbonate resin, diallyl carbonate resin, urethane resin, melamine resin, polyimide resin, aromatic polyamide resin, polystyrene resin, polyphenylene resin, polysulfone resin, polyphenylene oxide resin, Examples thereof include silsesquioxane compounds.

  Among these, a glycidyl type epoxy resin is preferably used for the resin material 3 other than the main component. By using the glycidyl type epoxy resin together with the alicyclic epoxy resin, it is possible to easily adjust the refractive index of the resin material 3 while suppressing the deterioration of the optical characteristics in the transparent composite substrate 1. That is, the refractive index of the resin material 3 can be set to a desired value by appropriately adjusting the mixing ratio of the alicyclic epoxy resin and the glycidyl type epoxy resin. As a result, a transparent composite substrate 1 having a high light transmittance is obtained.

  In this case, the addition amount of the glycidyl type epoxy resin is preferably about 0.1 to 10 parts by mass and more preferably about 1 to 5 parts by mass with respect to 100 parts by mass of the alicyclic epoxy resin. .

  Examples of the glycidyl type epoxy resin include a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, and the like.

  Of the glycidyl type epoxy resins to be used, glycidyl type epoxy resins having a cardo structure are preferably used. That is, by adding a glycidyl type epoxy resin having a cardo structure to an alicyclic epoxy resin and using it, a large number of aromatic rings derived from the bisarylfluorene skeleton are included, so the optical characteristics of the transparent composite substrate 1 In addition, the heat resistance can be further increased.

  Examples of the glycidyl type epoxy resin having such a cardo structure include ONCOAT EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).

  Silsesquioxane compounds are also preferably used for the resin material 3 other than the main component, and among these, silsesquioxane compounds having a photopolymerizable group such as an oxetanyl group or a (meth) acryloyl group are more preferred. Preferably used. By using the silsesquioxane compound together with the alicyclic epoxy resin, it is possible to easily adjust the refractive index of the resin material 3 while suppressing a decrease in optical characteristics in the transparent composite substrate 1. Moreover, since the silsesquioxane-based compound having an oxetanyl group is rich in compatibility with the alicyclic epoxy resin, uniform mixing is possible, and as a result, the refractive index is more reliably adjusted, A transparent composite substrate 1 having excellent optical characteristics is obtained.

  Examples of such silsesquioxane compounds having an oxetanyl group include OX-SQ, OX-SQ-H, OX-SQ-F (all manufactured by Toagosei Co., Ltd.) and the like.

  In this case, the addition amount of the silsesquioxane-based compound is preferably about 1 to 20 parts by mass and more preferably about 2 to 15 parts by mass with respect to 100 parts by mass of the alicyclic epoxy resin. .

  Furthermore, the resin material 3 used in the present invention preferably has a glass transition temperature of 150 ° C. or higher, and more preferably 170 ° C. or higher. Thereby, even if various heat treatments are performed when the transparent composite substrate 1 is manufactured and then processed into a display element substrate, it is possible to prevent the transparent composite substrate 1 from being warped or deformed.

  The refractive index of the resin material 3 is preferably as close as possible to the refractive index of the glass cloth. Specifically, the difference in refractive index between the two is preferably 0.01 or less, and is 0.005 or less. Is more preferable. Thereby, the transparent composite substrate 1 with high light transmittance is obtained.

(Other ingredients)
The transparent composite substrate of the present invention may contain a filler in addition to the above.

  As a filler, the glass filler comprised, for example with the fiber piece or particle | grains, etc. of the inorganic type glass material is mentioned. Dispersing the glass filler in the resin material 3 can enhance the mechanical characteristics without inhibiting the light transmittance of the transparent composite substrate 1.

  Specific examples of the glass filler include glass chopped strands, glass beads, glass flakes, glass powder, and milled glass.

  As the inorganic glass material, the same material as that of the glass cloth described above is used.

  The content of the filler is preferably about 1 to 90 parts by mass, more preferably about 3 to 70 parts by mass with respect to 100 parts by mass of the glass cloth.

  In addition, it is preferable that the diameter of a filler is 100 nm or less. Since such a filler hardly causes scattering at the interface, the transparency of the transparent composite substrate 1 becomes relatively high.

  Further, the coupling agent described above may be added to the resin material 3. Thereby, the stress concentration described above can be further relaxed, and the optical characteristics of the transparent composite substrate 1 can be further enhanced. When adding a coupling agent in the resin material 3, it is preferable that the addition amount is about 0.01-5 mass parts with respect to 100 mass parts of resin materials, and is about 0.05-2 mass parts. Is more preferable.

(Coating layer)
You may make it provide the coating layer 5 as needed on the surface of the composite layer 4 with which the transparent composite substrate of this invention is provided. By providing the coating layer 5, the surface of the transparent composite substrate 1 can be smoothed and flattened.

  Examples of the constituent material of the covering layer 5 include an epoxy resin and an acrylic resin. Of the epoxy resins, alicyclic epoxy resins are preferably used. The average thickness of the coating layer is preferably about 0.1 to 30 μm, and more preferably about 0.5 to 30 μm.

  In addition, the composite layer 4 of the transparent composite substrate of the present invention has less foreign matter generation and adhesion as described above. For this reason, when the coating layer 5 is formed on the surface of the composite layer 4, it is possible to suppress the presence of foreign matter between the composite layer 4 and the coating layer 5, and to reduce the probability that the optical characteristics are deteriorated by the inclusion of the foreign matter. Can be lowered. Therefore, the transparent composite substrate 1 having excellent optical characteristics can be obtained.

(End face coating)
As shown in FIG. 2, the transparent composite substrate of the present invention has a side surface 11 configured such that the resin material 3 spreads so as to cover the end surface 210 of the glass fiber 21. That is, the resin material 3 is impregnated in the gaps of the glass cloth 2, and a part of the resin material 3 covers the end surface 210 of the glass fiber 21 on the side surface 11 of the transparent composite substrate 1. With this structure, the end surface 210 of the glass fiber 21 is prevented from being exposed on the side surface 11 of the transparent composite substrate 1, and the cut end of the glass fiber 21 is reinforced with the resin material 3. It becomes. As a result, even when an external force is applied to the transparent composite substrate 1, the cut end portion of the glass fiber 21 is prevented from being broken or chipped, and the generation (dropping off) of a foreign substance made of a glass fiber piece is prevented. . In the following description, the resin material 3 covering the end face 210 of the glass fiber 21 is particularly referred to as “end face covering portion 6”.

  Although the average thickness of the end surface covering portion 6 is not particularly limited, for example, when the average diameter of the glass fiber 21 is d, it is preferably about 0.01d to 200d, and about 0.02d to 100d. Is more preferable. By setting the average thickness of the end surface covering portion 6 within the above range, a sufficient reinforcing effect for preventing the glass fiber 21 from being broken is obtained, and the end surface covering portion 6 that has become too thick falls off. Can be prevented. That is, it is possible to prevent both the generation of foreign matter generated from the glass fiber 21 and the generation of foreign matter generated from the resin material 3.

  In addition, in the side surface 11 provided with the end surface covering portion 6, the area occupied by the end surface covering portion 6 is preferably 70% or more, and more preferably 80% or more, out of the total area occupied by the end surface 210 of the glass fiber 21. . Thereby, generation | occurrence | production of a foreign material can be suppressed effectively. Here, the ratio of the area occupied by the end face covering portion 6 out of the total area occupied by the end face 210 can be calculated as follows. For example, in the area of the end surface 210 of the 100 glass fibers 21 (cross-sectional area of the glass fiber 21), when the ratio of the area covered with the end surface covering portion 6 is 70%, the ratio is 70%.

This is expressed as follows.
(Area occupied by the end face covering portion 6) / (total area occupied by the end face 210 of the glass fiber 21) × 100 (%)

  The “end surface 210 of the glass fiber 21” described here refers to the end surface of the glass fiber extending in a direction perpendicular to the side surface 11, and is elliptical in the cross-sectional view shown in FIG. It refers to the end face of the bundle of glass fibers 21. This is because when the end face is not covered with the end face covering portion 6, the glass fiber 21 is bent, and the generation of foreign matters becomes significant.

  When the above-described coating layer 5 is provided on the surface of the composite layer 4, the end face 210 of the glass fiber 21 is not only covered with the resin material 3 but also covered with the coating layer 5. Is preferred. The end face covering portion 6 having such a multi-layer structure further enhances the effect of preventing the generation (dropout) of foreign substances made of glass fiber pieces. At the same time, when the coating layer 5 covers the end face 210 of the glass fiber 21, an anchor effect is exhibited, and a secondary effect that the coating layer 5 is difficult to peel is obtained.

  Further, the composite layer 4 (transparent composite substrate 1) is preferably long, and in this case, the side surface 11 having the end surface covering portion 6 is applied to at least the side surfaces of both ends in the width direction of the composite layer 4. preferable. Thereby, the composite layer 4 is particularly excellent in productivity when it is subjected to a mass production process for use in various applications. This is because when the transparent composite substrate 1 is subjected to various manufacturing processes, the long transparent composite substrate 1 can be supplied to the manufacturing process in a sequential manner, so that productivity is high. Further, when the coating layer 5 is formed on the surface of the composite layer 4 in the manufacturing process, the film can be formed in a long shape, and therefore, cutting work is performed at both ends in the width direction before the film formation. Therefore, the generation of foreign matter is prevented.

(Characteristics of transparent composite substrate)
The total light transmittance of the display element substrate at a wavelength of 400 nm is preferably 70% or more, more preferably 75% or more, and further preferably 78% or more. If the total light transmittance at a wavelength of 400 nm is less than the lower limit, the display performance of the display element may not be sufficient.

  Moreover, although the average thickness of a transparent composite substrate is not specifically limited, It is preferable that it is about 40-200 micrometers, and it is more preferable that it is about 50-100 micrometers.

  Moreover, it is preferable that the average linear expansion coefficient in 30 to 150 degreeC of the transparent composite substrate of this invention is 40 ppm or less, More preferably, it is 20 ppm or less, More preferably, it is 10 ppm or less. For example, when this transparent composite sheet is used for an active matrix display element substrate, if this upper limit is exceeded, problems such as warpage and disconnection of aluminum wiring may occur in the manufacturing process.

<< Second Embodiment >>
Next, a second embodiment of the transparent composite substrate of the present invention will be described.
FIG. 3 is a partially enlarged view showing a second embodiment of the transparent composite substrate of the present invention.

  Hereinafter, although 2nd Embodiment is described, it demonstrates centering around difference with 1st Embodiment, The description is abbreviate | omitted about the same matter.

The second embodiment is the same as the first embodiment except that the configuration of the composite layer 4 is different.
In the second embodiment, the end face 210 of the glass fiber 21 in the composite layer 4 is not covered with the resin material 3, but is covered with the covering layer 5. Therefore, in the first embodiment, the end face covering portion 6 has a laminated structure of the resin material 3 and the covering layer 5, whereas in the second embodiment, the end face covering portion 6 is configured only by the covering layer 5.

  Even in such a configuration, since the exposure of the end face 210 of the glass fiber 21 is prevented, the cut end portion of the glass fiber 21 is reinforced by the coating layer 5. As a result, the cut end portion of the glass fiber 21 is prevented from being broken or chipped, and the generation (dropping off) of a foreign substance consisting of a glass fiber piece is prevented.

<Display element substrate>
The transparent composite substrate of the present invention includes, for example, various display element substrates such as a liquid crystal display element substrate, an organic EL element substrate, a color filter substrate, a TFT substrate, an electronic paper substrate, and a touch panel substrate. In addition to the display element substrate, it is also applied to a solar cell substrate and the like.

  The display element substrate of the present invention includes the transparent composite substrate of the present invention, and has a functional layer formed on the surface of the transparent composite substrate as necessary.

  Examples of such a functional layer include a transparent conductive layer composed of indium oxide, tin oxide, an oxide of tin-indium alloy, a metal conductive layer composed of gold, silver, palladium, or an alloy thereof, silicon oxide, and the like. , Gas barrier layer composed of vinylidene chloride polymer, vinyl alcohol polymer, etc., smooth layer composed of epoxy resin, rubber-like or gel-like silicone cured product, polyurethane, epoxy resin, acrylic resin, polyethylene, polypropylene, Examples thereof include an impact buffer layer composed of polystyrene, vinyl chloride resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether sulfone, polysulfone and the like.

  Among these, the smooth layer preferably has heat resistance, transparency, and chemical resistance, and among the epoxy resins, the coating layer has the same composition as the alicyclic epoxy resin contained in the transparent composite material. More preferably used as a constituent material. The average thickness of the coat layer is preferably about 0.1 to 30 μm, and more preferably about 0.5 to 30 μm.

  In addition, as a layer configuration, a smooth layer is provided on at least one side of the transparent composite substrate, and an impact buffer layer is further provided thereon, or an impact buffer layer is provided on at least one side of the transparent composite substrate, and a smooth surface is further provided thereon. The structure etc. which provide a layer are mentioned.

  The display element substrate of the present invention is originally superior in impact resistance by a falling ball test than a glass substrate, but the impact resistance is further improved by providing the impact buffer layer as described above.

  As described above, since the transparent composite substrate of the present invention is less likely to generate and adhere to foreign matter, it is possible to suppress a decrease in optical characteristics due to these. For this reason, a display element substrate capable of realizing a high-quality and highly reliable display element is obtained.

<Method for producing transparent composite substrate>
<< First Embodiment >>
Next, 1st Embodiment of the manufacturing method of the transparent composite substrate of this invention is described.
4 and 5 are cross-sectional views showing a first embodiment of a method for producing a transparent composite substrate of the present invention.

  As described above, the first embodiment of the method for producing a transparent composite substrate includes a step of obtaining an impregnated body (impregnation step), a step of obtaining a temporary cured body (first curing step), and the temporary cured body from the support member. It has the process of peeling (1st peeling process), the process of obtaining this hardening body (2nd hardening process), and the process of forming a coating layer. Hereinafter, each process will be described sequentially.

[1]
First, a resin varnish containing a resin material to be impregnated into the glass cloth 2 is prepared. The resin varnish contains the above-mentioned uncured resin material, other components such as a filler, an organic solvent, and the like, and also contains a curing agent, an antioxidant, a flame retardant, an ultraviolet absorber, and the like as necessary.

(Curing agent)
Examples of such curing agents include acid anhydrides, crosslinking agents such as aliphatic amines, cationic curing agents, anionic curing agents, and the like, and one or a mixture of two or more thereof is used.

  Among these, a cationic curing agent is particularly preferably used. According to the cationic curing agent, since the epoxy resin can be cured at a relatively low temperature, it is not necessary to set the resin varnish to a high temperature at the time of curing, and generation of thermal stress accompanying a temperature change can be suppressed. As a result, a transparent composite substrate with low optical anisotropy is obtained.

  Further, by using a cationic curing agent, a transparent composite substrate having high heat resistance (for example, glass transition temperature) can be obtained. This is considered to be because the crosslinking density of the cured epoxy resin is increased by using a cationic curing agent.

  The cationic curing agent releases a substance that initiates cationic polymerization by heating, for example, an onium salt cationic curing agent, an aluminum chelate cationic curing agent, or a substance that initiates cationic polymerization by active energy rays. For example, an onium salt cationic curing agent. Among these, a photocationic curing agent is preferable. Thereby, the presence or absence of hardening can be easily selected only by selecting the irradiation region of light.

  The cationic photocuring agent is not particularly limited as long as it can cause a polycationic cationically polymerizable compound and a monofunctional cationically polymerizable compound to undergo a cationic photopolymerization reaction. For example, Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid And onium salts such as sulfonium salts. Specifically, boron difluoride phenyldiazonium salt, phosphorus hexafluoride diphenyliodonium salt, antimony hexafluoride diphenyliodonium salt, arsenic hexafluoride tri-4-methylphenylsulfonium salt, antimony tetrafluoride And tri-4-methylphenylsulfonium salt.

  On the other hand, examples of the thermal cationic curing agent include aromatic sulfonium salts, aromatic iodonium salts, ammonium salts, aluminum chelates, and boron trifluoride amine complexes.

  Although content of such a cationic hardening | curing agent is not specifically limited, It is preferable that it is about 0.1-5 mass parts with respect to 100 mass parts of alicyclic epoxy resins, and 0.5-3 weight part is especially preferable. Is preferred. If the content is less than the lower limit, the curability may be lowered, and if the content exceeds the upper limit, the transparent composite substrate may become brittle.

  In the case of photocuring, a sensitizer, an acid proliferating agent, and the like can be used together to accelerate the curing reaction as necessary.

(Antioxidant)
As the antioxidant, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like are used, and a hindered phenol-based antioxidant is particularly preferably used.

In addition, the resin varnish may contain an oligomer or a monomer agent of a thermoplastic resin or a thermosetting resin as necessary as long as the characteristics are not impaired. In addition, when using these oligomers and monomers, the composition ratio is appropriately set so that the overall refractive index matches the refractive index of the glass cloth.
The resin varnish is obtained by mixing the above components.

  Thereafter, the resin varnish 30 obtained as shown in FIG. When impregnating the resin varnish 30 into the glass cloth 2, for example, a method of immersing the glass cloth 2 in the resin varnish 30, a method of applying the resin varnish 30 to the glass cloth 2, or the like is used. Moreover, after impregnating the resin varnish 30 in the glass cloth 2, after the resin varnish 30 is uncured or cured, the resin varnish 30 may be further applied thereon.

  Thereafter, the resin varnish 30 is defoamed as necessary. Thereby, the impregnated body 101 is obtained.

  In addition, as the glass cloth 2, a long thing is used preferably. This is because the long glass cloth 2 can be wound up in a roll shape, so that the resin varnish 30 can be continuously impregnated by sequentially feeding it out.

[2]
[2-1] Next, as shown in FIG. 4B, sheet-like support members 71 are stacked on both surfaces of the obtained impregnated body 101. Thereby, the resin varnish 30 contained in the impregnated body 101 is flattened and smoothed by the sheet-like support member 71 and pressed so as to penetrate into the glass cloth 2. As a result, a part of the resin varnish 30 protrudes outward from the end of the glass cloth 2.

  A polyester film, a polyimide film, or the like is used for the sheet-like support member 71.

  When the sheet-like support member 71 is pressed against the impregnated body 101, the pressure does not deform the glass cloth 2 more than necessary, and the impregnated body 101 is compressed until it is about the same as the thickness of the glass cloth 2. Adjusted to obtain pressure. This pressure varies depending on the thickness and width of the glass cloth 2, the viscosity of the resin varnish 30, and the surrounding environment (temperature, etc.). As an example, the applied pressure per unit length is 0.05 to 5 kg / cm. Is preferably about 0.1 to 2 kg / cm.

  In addition, the sheet-like support member 71 is preferably transparent (including translucent and colored transparency) since it is necessary to transmit light when light energy is used in a process described later.

  Note that the support member 71 stacked on the impregnated body 101 is preferably stacked on both surfaces of the impregnated body 101, but may be only one surface.

  [2-2] Next, energy is applied to the impregnated body 101 in a state where the sheet-like support members 71 are stacked on both surfaces of the impregnated body 101. In FIG. 4C, energy is applied to a portion of the impregnated body 101 excluding the outer edge portion 12 and a portion outside the outer edge portion 12 in plan view, that is, a portion from the center in plan view to the inner edge of the outer edge portion 12. Hereinafter, this portion is referred to as “central portion 13”. By applying energy, the resin varnish 30 in the central portion 13 of the impregnated body is cured to obtain a temporarily cured body 102 (first curing step).

  The energy to be applied is appropriately selected according to the composition of the curing agent and the resin material contained in the resin varnish 30, and may be an electron beam, an X-ray, or the like, but is generally light energy or thermal energy. When light energy is applied, light such as ultraviolet light, visible light, and infrared light is irradiated. These are preferably used in this step because the irradiation region can be easily selected using a photomask or the like. On the other hand, when applying thermal energy, the central portion 13 can be selectively heated by using a locally heatable heater or the like. In this case, the non-heated area can be easily insulated using a heat insulating material or the like.

  As the light energy, for example, ultraviolet light having a wavelength of about 200 to 400 nm is used (see FIG. 4C), and a UV lamp, UV-LED, UV laser, or the like is used as a light source.

Light energy applied (integrated quantity of light) is preferably at 5 mJ / cm ² or more 1000 mJ / cm ² or less, more preferably 10 mJ / cm ² or more 800 mJ / cm ² or less. If the integrated light quantity is within the above range, it can be cured uniformly and reliably without unevenness.

The irradiation intensity is preferably at 10 mW / cm ² or more 2000 mW / cm ² or less, more preferably 20 mW / cm ² or more 1500 mW / cm ² or less.

  On the other hand, when heating the central portion 13, the heating condition is set to a condition in which the resin-like varnish 30 is cured and the sheet-like support member 71 is not denatured. Preferably, the heating temperature is about 50 to 300 ° C., and the heating time is The heating temperature is set to about 0.5 to 10 hours, more preferably the heating temperature is set to about 170 to 270 ° C., and the heating time is set to about 1 to 5 hours.

  Moreover, you may make it change heating temperature on the way. For example, it may be initially heated at about 50 to 100 ° C. for about 0.5 to 3 hours, and then heated at about 200 to 300 ° C. for about 0.5 to 3 hours.

  As a result of selectively heating the central portion 13 as described above, the resin varnish 30 in the central portion 13 is cured, and the outer edge portion 12 and the resin varnish 30 outside the central portion 13 are maintained in an uncured state. Such a state is referred to as the temporary cured body 102 described above (see FIG. 4D).

  Here, in the obtained temporary cured body 102, the resin varnish 30 of the outer edge portion 12 is uncured and the resin varnish 30 of the central portion 13 is cured.

  The term “curing” here refers to a state in which a curing reaction has started, and the curing rate (reaction rate) is not particularly limited. That is, it includes a semi-cured state and a fully cured state. On the other hand, “uncured” means that the resin monomer is in an unreacted state.

  Note that the reaction rate of the central portion 13 in the temporary cured body 102, that is, the mass ratio of the resin monomers subjected to the curing reaction among all the resin monomers in the central portion 13, is preferably 50% or more, and 80% or more. It is more preferable that Thereby, the resin material 3 and the glass cloth 2 in the center part 13 can be reliably integrated, and the effects and effects as described above can be reliably exhibited.

  [3] Next, as shown in FIG. 5A, the temporarily cured body 102 is peeled from the support member 71 (first peeling step). When the temporary cured body 102 is gradually peeled off, the cured resin material 3 is integrated in a state in which the glass cloth 2 is impregnated in the central portion 13 so that it is peeled off from the support member 71 together with the glass cloth 2. Since the resin varnish 30 is not cured, the resin varnish 30 not impregnated in the glass cloth 2 remains on the support member 71 side. This is because, in the resin varnish 30 close to the glass cloth 2, interaction such as interfacial tension works between the glass cloth 2. It is surmised that it does not work and is left behind on the support member 71 side. Accordingly, the uncured resin varnish 30 impregnated in the glass cloth 2 is peeled from the support member 71 together with the glass cloth 2 in the outer edge portion 12, and the uncured resin varnish 30 not impregnated in the glass cloth 2, that is, In the impregnation step, the resin varnish 30 protruding from the end of the glass cloth 2 remains on the support member 71 side. As a result, the excess resin varnish 30 is naturally removed in this peeling step, and the process of finally cutting and removing the excess resin material 3 becomes unnecessary. Therefore, according to this invention, generation | occurrence | production and adhesion of the foreign material accompanying cutting are prevented.

  It should be noted that a thin layer of the resin varnish 30 is formed so as to cover the end surface 210 of the glass fiber 21 by removing the excess resin varnish 30 as described above on the side surface of the temporarily cured body 102 due to the above interaction. Adhere to. This thin layer finally becomes the end surface covering portion 6.

  Here, the width of the outer edge portion 12, that is, the distance from the outer edge to the inner edge of the outer edge portion 12, is preferably in the range of 1t to 500t, where t is the average thickness of the glass cloth 2, and is in the range of 10t to 300t. It is more preferable that By setting it as this range, the said end surface coating | coated part 6 which can suppress a dust generation source is producible. Accordingly, the resin varnish 30 protruding from the glass cloth 2 is reliably prevented from being peeled off from the support member 71 together with the glass cloth 2, and the resin varnish 30 impregnated in the glass cloth 2 is not intended to support the support member 71. It can also be prevented from remaining on the side.

  [4] Next, as shown in FIG. 5B, energy is applied to the temporarily cured body 102 peeled from the support member 71. Thereby, the uncured resin varnish 30 remaining in the temporarily cured body 102 is cured to obtain a main cured body 103 shown in FIG. 5C (second curing step).

  The energy to be applied is the same as the energy in the first curing step, and for example, light energy or heat energy is used.

In this step, it is sufficient if energy is applied to the outer edge portion 12 and energy may not be applied to the central portion. However, in this step, energy is also applied to the central portion in two steps. Therefore, the curing of the resin varnish at the center can be made uniform.
The main cured body 103 obtained as described above becomes the composite layer 4.

  In addition, the obtained hardened | cured body 103 means the state which the hardening reaction has started in the whole including the outer edge part 12 and the center part 13, and the hardening rate (reaction rate) is not specifically limited. That is, it includes a semi-cured state and a fully cured state. In order that the main cured body 103 is in a semi-cured state and is completely cured in a short time, thermal energy may be further applied as necessary.

[5] After that, as shown in FIG. 5D, the coating layer 5 is formed on the surface of the composite layer 4.
The coating layer 5 is formed by, for example, a method of immersing the composite layer 4 in a liquid containing the raw material of the coating layer 5, a method of applying the liquid to the composite layer 4, a method of spraying the liquid on the composite layer 4, Various vapor deposition methods are used.

  The covering layer 5 formed on the surface of the composite layer 4 is also formed on the end face covering portion 6 described above. As a result, the end surface covering portion 6 has a multi-layer structure, and as described above, the generation (dropping off) of foreign matters can be more reliably prevented. In order to reliably manufacture the end surface covering portion 6 having such a multilayer structure, it is preferable to form the covering layer 5 according to a second embodiment described later. Thereby, the transparent composite substrate 1 shown in FIGS.

  As a liquid containing the raw material of the coating layer 5, what melt | dissolved the resin monomer in the solvent is mentioned, For example, it can prepare similarly to the resin varnish 30 mentioned above.

<< Second Embodiment >>
Next, 2nd Embodiment of the manufacturing method of the transparent composite substrate of this invention is described.
6 and 7 are cross-sectional views showing a second embodiment of the method for producing a transparent composite substrate of the present invention.

  In the second embodiment of the manufacturing method of the transparent composite substrate, energy is applied to the step of applying the liquid coating 51 covering the surface of the composite layer 4 (application step), and the portion of the liquid coating 51 excluding the outer edge portion 14 is temporarily cured. A process of obtaining the film 52 (third curing process), a process of peeling the temporary cured film 52 from the support member 72 (second peeling process), and applying energy to the outer edge portion 14 of the temporarily cured film 52 to cover the coating layer 5 (Step 4). Hereinafter, each process will be described sequentially.

[1] First, the coating layer 5 is formed on the surface of the composite layer 4.
[1-1] The composite layer 4 used in this step may be manufactured by any method, but here it is manufactured by a conventional method. That is, the entire impregnated body is cured in the first curing step of the first embodiment, and then the outer edge portion is cut and removed. In such a composite layer 4, the end surface 210 of the glass fiber 21 is exposed on the side surface.

  [1-2] An uncured coating material is applied so as to cover the surface of the composite layer 4, and a liquid film 51 is obtained as shown in FIG. 6A (application process). This step is the same as the film forming method for the coating layer 5 described above. Moreover, as a coating material, the same thing as the above-mentioned resin varnish 30 can be used.

[2]
[2-1] Next, as shown in FIG. 6B, a sheet-like support member 72 is overlaid on the surface of the obtained liquid film 51. Thereby, the liquid coating 51 is flattened and smoothed by the sheet-like support member 72. As a result, a part of the liquid coating 51 spreads outside.

  [2-2] Next, energy is applied to the portion of the liquid coating 51 excluding the outer edge portion 14, that is, the portion from the center in plan view to the inner edge of the outer edge portion 14 (see FIG. 6C). Hereinafter, this portion is referred to as “central portion 15”. By applying energy, the liquid coating 51 in the central portion 15 of the liquid coating 51 is cured to obtain a temporarily cured film 52 shown in FIG. 6D (third curing step).

  [3] Next, as shown in FIG. 7A, the composite layer 4 on which the temporarily cured film 52 is formed is peeled from the support member 72 (second peeling step). When the temporary cured film 52 and the support member 72 are gradually peeled off, the cured coating material is integrated in a state of being in close contact with the composite layer 4 in the central portion 15, and thus peels off from the support member 72 together with the composite layer 4. Since the coating material is not cured at the outer edge portion 14, the coating material that is not in close contact with the composite layer 4 remains on the support member 72 side. As a result, the extra coating material is naturally removed in this peeling step, and the process of finally cutting and removing the extra coating layer 5 becomes unnecessary. Therefore, according to this invention, generation | occurrence | production and adhesion of the foreign material accompanying cutting are prevented.

  In addition, on the side surface of the composite layer 4, a thin layer of the coating material is attached so as to cover the end surface 210 of the glass fiber 21 by removing the excess coating material as described above. This thin layer finally becomes the end surface covering portion 6.

[4] Next, as shown in FIG. 7B, energy is applied to the temporarily cured film 52 peeled from the support member 72. Thereby, the uncured coating material remaining on the temporarily cured film 52 is cured, and the coating layer 5 shown in FIG. 7C is obtained (fourth curing step).
The transparent composite substrate 1 shown in FIG. 3 is obtained as described above.

  Although the present invention has been described above, the present invention is not limited to this. For example, an arbitrary component may be added to the transparent composite substrate and the display element substrate. Moreover, the process of arbitrary objectives may be added to the manufacturing method of a transparent composite substrate.

  In addition, the composite layer 4 having the end surface covering portion 6 as described above is manufactured by a manufacturing method involving one curing process and a cutting process in addition to the manufacturing method of the transparent composite substrate of the present invention involving two curing processes. Can also be manufactured.

  That is, in the first embodiment of the method for producing a transparent composite substrate of the present invention, as described above, in the first curing step, the resin varnish in the portion from the center in plan view to the inner edge of the outer edge portion 12 in the impregnated body 101. 30 is first cured, whereas in the manufacturing method involving one curing process, the entire impregnated body 101 is cured, and then the excess resin varnish 30 is removed by a cutting process, so that the end face covering portion 6 is removed. The composite layer 4 can be manufactured.

  Specifically, in this manufacturing method, first, the entire impregnated body 101 is cured in the first curing step. Thereby, the resin varnish 30 which protruded from the edge part of the glass cloth 2 will also harden | cure in that state. Then, only the protruding cured product of the resin varnish 30 is cut and removed so as not to cut the glass cloth 2. As a result, a state in which the end face 210 of the glass fiber 21 is covered with the resin material 3 is formed, and the end face covering portion 6 is formed.

  For example, a laser processing method, a mechanical processing method, or the like is used to cut the protruding cured product of the resin varnish 30. Moreover, in order not to cut | disconnect the glass cloth 2, for example, the position of the outer edge of the glass cloth 2 is memorize | stored, the method of cut | disconnecting based on the position, the light of a predetermined wavelength is incident, glass cloth A method of determining the cutting position by utilizing the difference in transmittance between the cured product of the resin varnish 30 and the resin varnish 30 can be employed.

  In addition, the process which piles up the supporting member 71 on the impregnation body 101 should just be performed as needed, and can also be abbreviate | omitted.

Next, specific examples of the present invention will be described.
1. Production of transparent composite substrate (Example 1)
In Example 1, a composite layer was obtained by the method shown in FIGS.

Specifically, first, a long NE glass-based glass cloth (average thickness 95 μm, average wire diameter 9 μm) has a structure represented by the following chemical formula (1), and “—X—” is “—CH ( CH ₃ ) — ”, an alicyclic epoxy resin (E-DOA manufactured by Daicel Chemical Industries, Ltd.), a silsesquioxane-based oxetane (manufactured by Toagosei Co., Ltd., OX-SQ-H), and initiation of photocationic polymerization An agent (SP-170, manufactured by Ciba Japan) was mixed at a ratio shown in Table 1 to prepare a resin varnish. In addition, after using this example, when E-DOA was used as the alicyclic epoxy resin, methyl isobutyl ketone was used in combination so that the resin concentration of the resin varnish was 80% by mass.

  Subsequently, the glass cloth was immersed in the obtained resin varnish, and then defoaming was performed. Thereby, an impregnated body was obtained.

  Next, a long PET film (average thickness 125 μm, width 500 mm, length 3500 mm) was prepared, and after the silicone release treatment was performed on the surface, the impregnated body was sandwiched between two PET films, A sandwich was obtained. Then, the pressing area was moved in the longitudinal direction of the PET film at a speed of 0.1 m / min while pressing the holding body in the thickness direction at a linear pressure of 0.5 kg / cm.

  At the same time, the clamping body immediately after pressing was irradiated with ultraviolet rays (wavelength 365 nm) irradiated from a UV lamp, and the first curing process was performed. In addition, the irradiated area | region was made into the part (central part) except the both ends (1 mm from an outer edge) of the longitudinal direction of a clamping body, and the both ends (1 mm from an outer edge) of the width direction of a clamping body. Thereby, the resin varnish of the center part was hardened and the temporary hardening body was obtained. The outer edge portion was shielded from being exposed to ultraviolet rays by a photomask.

  Next, the temporarily cured body was peeled from the PET film. And the ultraviolet-ray (wavelength 365nm) was again irradiated with respect to the temporary hardening body, and the 2nd hardening process was performed. In this step, the entire surface of the temporarily cured body was irradiated with ultraviolet rays. Thereby, the whole temporary hardening body was hardened and it was set as the main hardening body (composite layer).

Subsequently, a coating layer was obtained by the method shown in FIGS.
Specifically, first, E-DOA and a photocationic polymerization initiator (manufactured by Ciba Japan, SP-170) are mixed on the surface of the composite layer so as to have a mass ratio of 100: 1, and a coating material is prepared. Prepared.

Next, a coating material was applied to both surfaces of the composite layer by a dipping method to obtain a liquid film.
Next, a long PET film (average thickness 125 μm, width 500 mm, length 3500 mm) was prepared, and a silicone-based release treatment was performed on the surface, and then a liquid film was formed with two PET films. The composite layer was sandwiched to obtain a sandwiched body. Then, the pressing area was moved in the longitudinal direction of the PET film at a speed of 0.1 m / min while pressing the holding body in the thickness direction at a linear pressure of 0.5 kg / cm.

  At the same time, the sandwich body immediately after pressing was irradiated with ultraviolet rays (wavelength 365 nm) irradiated from a UV lamp, and a third curing step was performed. In addition, the irradiated area | region was made into the part (central part) except the both ends (1 mm from an outer edge) of the longitudinal direction of a clamping body, and the both ends (1 mm from an outer edge) of the width direction of a clamping body. As a result, the coating material at the center was cured to obtain a temporarily cured film. The outer edge portion was shielded from being exposed to ultraviolet rays by a photomask.

  Next, the temporarily cured film was peeled from the PET film. And the ultraviolet-ray (wavelength 365nm) was again irradiated with respect to the temporary hardening film, and the 4th hardening process was performed. In this step, the entire surface of the temporarily cured film was irradiated with ultraviolet rays. As a result, the entire temporarily cured film was cured to form a coating film. A transparent composite substrate was obtained as described above. Table 1 shows the manufacturing conditions of the transparent composite substrate described above. In addition, the end surface coating | coated part formed by laminating | stacking the layer formed from the resin varnish and the layer formed from the coating material was formed in the side surface of the obtained transparent composite substrate. Here, in the vicinity of the side surface of the obtained transparent composite substrate, among 100 glass fibers, the cross-sectional area where the end face covering portion was formed was observed with an electron microscope, and the ratio covered by calculation was calculated. %Met.

(Examples 2-9)
A transparent composite substrate was obtained in the same manner as in Example 1 except that the production conditions were changed as shown in Table 1 and below. In addition, the width | variety of the outer edge part in the 3rd hardening process of each Example was made the same as the width | variety of the outer edge part in a 1st hardening process.

  Moreover, the hydrogenated biphenyl type alicyclic epoxy resin (made by Daicel Chemical Industries, E-BP) used in Examples 2, 3, 4, 7, and 9, Example 10 described later, and Comparative Examples 2 and 3, It has the structure of the following chemical formula (2). Further, the dicyclopentadiene skeleton acrylic resin (manufactured by Daicel-Cytec, IRR-214K) used in Example 5, Example 11 described later, and Comparative Example 4 has a structure represented by the following chemical formula (6).

  Further, the long T glass-based glass cloth used in Examples 3, 9, 10 and Comparative Example 3 has an average thickness of 95 μm and an average wire diameter of 9 μm.

  Moreover, the heater used in Examples 3, 7, 8 and Comparative Example 3 was an electric heater capable of local heating.

  Further, SI-100L manufactured by Sanshin Chemical Co., Ltd. was used as the thermal cationic polymerization initiator used in Examples 3, 7, 8 and Comparative Example 3.

  Further, Irgacure 184 manufactured by Ciba Japan was used as the photoradical polymerization initiator used in Example 5, Example 11 described later, and Comparative Example 4.

  Moreover, the coating material used for the coating layer used in Example 8 and Comparative Example 4 is a mixture of YX-8000 (manufactured by Mitsubishi Chemical), which is a glycidyl type epoxy resin, and SP-170 in a mass ratio of 100: 1. It was prepared.

  Moreover, in the vicinity of the side surface of the obtained transparent composite substrate, the ratio of the cross-sectional area in which the end surface covering portion was formed out of 100 glass fibers was 97 to 99% in Examples 2 to 9.

(Example 10)
After the entire impregnated body was cured in the first curing process, the outer edge in the width direction was cut off with a dicing machine, and the second curing process was omitted, and the composite was performed in the same manner as in Example 1. A layer was obtained. In the obtained composite layer, the end face of the glass fiber was exposed on the side surface in the width direction.

  Next, in the same manner as in Example 1, a coating layer was formed on the surface of the composite layer by the method shown in FIGS. 6 and 7 to obtain a transparent composite substrate. In the obtained transparent composite substrate, the surface and the side surface in the width direction were covered with the coating layer.

  In the vicinity of the side surface of the obtained transparent composite substrate, the ratio of the cross-sectional area in which the end surface covering portion was formed out of 100 glass fibers was 92%.

(Example 11)
In the same manner as in Example 1, a cured product (composite layer) was obtained. Thereafter, no coating layer was formed, but in the obtained transparent composite substrate, the side surfaces in the width direction were covered with the cured resin used in the composite layer.

  In the vicinity of the side surface of the obtained transparent composite substrate, the ratio of the cross-sectional area in which the end surface covering portion was formed out of 100 glass fibers was 95%.

(Comparative Example 1)
After the entire impregnated body was cured in the first curing step, the outer edge portion in the width direction of the cured body was cut off with a dicing machine, and the subsequent second curing step was omitted. Similarly, a transparent composite substrate was obtained. In the obtained transparent composite substrate, the end surface of the glass fiber was exposed on the side surface in the width direction.

(Comparative Example 2)
After the entire impregnated body was cured in the first curing step, a coating material was applied to the surface of the obtained cured body to form a liquid film. Subsequently, the obtained liquid film was irradiated with ultraviolet rays to be cured entirely, and a cured film was obtained. Subsequently, a transparent composite substrate was obtained in the same manner as in Example 1 except that the outer edge in the width direction of the cured film was cut off with a dicing machine and the subsequent second curing step was omitted. In the obtained transparent composite substrate, the end surface of the glass fiber was exposed on the side surface in the width direction.

(Comparative Example 3)
A transparent composite substrate was obtained in the same manner as in Comparative Example 2 except that the production conditions were changed as shown in Table 1.

(Comparative Example 4)
A transparent composite substrate was obtained in the same manner as in Comparative Example 2 except that the production conditions were changed as shown in Table 1.

2. 2.1 Evaluation of Transparent Composite Substrate 2.1 Evaluation of the Number of Foreign Objects The transparent composite substrate obtained in each Example and each Comparative Example is first a belt for simulating the case where it is used in the display element manufacturing process. 10m was conveyed on the conveyor.

  Subsequently, about the surface of the transparent composite substrate after conveyance, a 1 square cm area | region was observed with the optical microscope, respectively. And the number of the foreign materials with a diameter of 1 micrometer or more adhering to the surface of a coating layer was measured, and the measurement result was evaluated according to the following evaluation criteria. In the evaluation, the measurement value for the transparent composite substrate obtained in Comparative Example 1 was set to 1, and the relative value for the transparent composite substrate obtained in each Example and each Comparative Example was calculated.

<Evaluation criteria for foreign matter>
A: The relative value of the number of foreign matters is less than 0.2 B: The relative value of the number of foreign matters is 0.2 or more and less than 0.4 C: The relative value of the number of foreign matters is 0.4 or more and 0.6 D: The relative value of the number of foreign substances is 0.6 or more and less than 0.8 E: The relative value of the number of foreign substances is 0.8 or more and less than 1 F: The relative value of the number of foreign substances is 1 or more Is

2.2 Evaluation of the end face covering portion Of the transparent composite substrates obtained in the respective Examples and Comparative Examples, the cross sections of the side surfaces of the one end portion in the width direction were observed with an electron microscope. And the average thickness of the end surface coating | coated part which has covered the end surface of glass fiber from the observed image was measured. In addition, when the end surface covering portion has a multilayer structure of the resin material and the covering layer, the sum of the layers is defined as the thickness of the end surface covering portion. Subsequently, the measured average thickness of the end surface covering portion was evaluated according to the following evaluation criteria.

<Evaluation criteria for the average thickness of the end face covering portion>
A: 100 μm or more and less than 400 μm B: 50 μm or more and less than 100 μm C: 10 μm or more and less than 50 μm D: Less than 10 μm E: No end face covering (0 μm)

2.3 Evaluation of parallel light transmittance The parallel light transmittance at a wavelength of 550 nm was measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV2400PC).
The above evaluation results are shown in Table 1.

  As is clear from Table 1, the transparent composite substrates obtained in each example had fewer foreign substances attached than the transparent composite substrates obtained in the comparative examples. For this reason, it became clear that the transparent composite substrate obtained by each Example can be used suitably for the use as which the optical characteristic is calculated | required like a display element substrate.

  Moreover, it became clear that all the transparent composite substrates obtained in the respective examples have end face covering portions. On the other hand, it became clear that the transparent composite substrate obtained in each comparative example did not have an end face covering portion.

DESCRIPTION OF SYMBOLS 1 Transparent composite substrate 11 Side surface 12, 14 Outer edge part 13, 15 Center part 2 Glass cloth 21 Glass fiber 210 End surface 3 Resin material 30 Resin varnish 4 Composite layer 5 Coating layer 51 Liquid film 52 Temporary cured film 6 End surface coating part 71, 72 Support member 101 Impregnated body 102 Temporarily cured body 103 Completely cured body

Claims (15)

A method for producing a transparent composite substrate comprising an aggregate of glass fibers, and a resin material impregnated in the aggregate of glass fibers,
Impregnating the glass fiber aggregate with an uncured resin material to obtain an impregnated body;
After stacking a support member on at least one surface of the impregnated body, energy is applied to a portion excluding the outer edge portion of the impregnated body to cure the uncured resin material to obtain a temporary cured body;
Peeling the temporary cured body from the support member;
A step of applying energy to an outer edge portion of the temporary cured body to cure the uncured resin material remaining in the temporary cured body to obtain a main cured body. .   2. The method for producing a transparent composite substrate according to claim 1, wherein the aggregate of glass fibers has an elongated shape, and the outer edge portion of the impregnated body is at least the outer edge portions of both end portions in the width direction.   3. The method for producing a transparent composite substrate according to claim 1, wherein when the average thickness of the aggregate of glass fibers is t, the outer edge portion is in the range of 1 t to 500 t inward from the outer edge of the impregnated body. . Furthermore, a step of applying an uncured coating material to the surface of the main cured body to obtain a liquid film;
A step of superimposing a support member on the surface of the liquid film, applying energy to a portion excluding an outer edge of the liquid film to cure the uncured liquid material, and obtaining a temporary cured film;
Peeling the temporary cured film from the support member;
A process of applying energy to an outer edge portion of the temporarily cured film to cure the uncured coating material remaining on the temporarily cured film to obtain a coating layer covering a surface of the main cured body. 4. The method for producing a transparent composite substrate according to any one of 3 above. A method for producing a transparent composite substrate comprising: a composite layer formed by impregnating a resin material into an aggregate of glass fibers; and a coating layer covering the surface of the composite layer,
Applying an uncured coating material to the surface of the composite layer to obtain a liquid film;
After superimposing a support member on the surface of the liquid film, applying energy to a portion excluding the outer edge of the liquid film to cure the uncured coating material, and obtaining a temporarily cured film;
Peeling the temporary cured film from the support member;
A method of producing a transparent composite substrate, comprising: applying energy to an outer edge portion of the temporary cured film to cure the uncured coating material remaining on the temporary cured film to obtain the coating layer. .   The method for producing a transparent composite substrate according to claim 1, wherein the energy is thermal energy or light energy.   The manufacturing method of the transparent composite substrate in any one of Claim 1 thru | or 6 which provides energy in the state which shielded the said outer edge part. A transparent composite substrate having a composite layer formed by impregnating a glass fiber aggregate with a resin material,
A transparent composite substrate, wherein an end face of the glass fiber is coated with the resin material.   The transparent composite substrate according to claim 8, wherein the average thickness of the resin material covering the end surface is 0.01 d to 200 d, where d is the average diameter of the glass fibers. Furthermore, it has a coating layer covering the surface of the composite layer,
The transparent composite substrate according to claim 8 or 9, wherein an end face of the glass fiber is sequentially coated with the resin material and the coating layer. A transparent composite substrate having a composite layer formed by impregnating a resin material into an aggregate of glass fibers, and a coating layer covering the surface of the composite layer,
A transparent composite substrate, wherein the glass fiber has a side surface in which an end surface is coated with the coating layer.   The transparent composite substrate according to claim 11, wherein in the side surface, a ratio of the end surface covered with the coating layer is 70% or more in a total area occupied by the end surface of the glass fiber.   The transparent composite substrate according to claim 11 or 12, wherein an average thickness of the coating layer covering the end face is 0.01d to 200d, where d is an average diameter of the glass fibers.   The transparent composite substrate according to claim 8, wherein the aggregate of glass fibers has a long shape.   A display element substrate comprising the transparent composite substrate according to claim 8.

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