WO2013047382A1 - 透明複合基板および表示素子基板 - Google Patents
透明複合基板および表示素子基板 Download PDFInfo
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- WO2013047382A1 WO2013047382A1 PCT/JP2012/074260 JP2012074260W WO2013047382A1 WO 2013047382 A1 WO2013047382 A1 WO 2013047382A1 JP 2012074260 W JP2012074260 W JP 2012074260W WO 2013047382 A1 WO2013047382 A1 WO 2013047382A1
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- Prior art keywords
- glass
- transparent composite
- composite substrate
- glass fiber
- resin
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- 0 *(C1CC2OC2CC1)C1C*2OC2CC1 Chemical compound *(C1CC2OC2CC1)C1C*2OC2CC1 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/007—Impregnation by solution; Solution doping or molecular stuffing of porous glass
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
- B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D1/00—Woven fabrics designed to make specified articles
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/242—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
- D03D15/267—Glass
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/418—Refractive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/206—Organic displays, e.g. OLED
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
- D10B2101/06—Glass
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/02—Reinforcing materials; Prepregs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2041—Two or more non-extruded coatings or impregnations
- Y10T442/2098—At least two coatings or impregnations of different chemical composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2926—Coated or impregnated inorganic fiber fabric
- Y10T442/2951—Coating or impregnation contains epoxy polymer or copolymer or polyether
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2926—Coated or impregnated inorganic fiber fabric
- Y10T442/2992—Coated or impregnated glass fiber fabric
Definitions
- the present invention relates to 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, solar cell substrates, and the like.
- display element substrates such as active matrix substrates, solar cell substrates, and the like.
- substrates made of plastic materials plastic substrates
- 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.
- a glass fiber composite resin sheet for a printed circuit board has been proposed so far (for example, see Patent Document 1).
- the glass fiber composite resin sheet is obtained by impregnating a glass fabric containing glass fibers with a transparent resin material.
- the glass fiber composite resin sheet can particularly enhance mechanical properties (such as bending strength and low linear expansion coefficient).
- An object of the present invention is to provide a transparent composite substrate having excellent optical characteristics and a highly reliable display element substrate including the transparent composite substrate.
- Such an object is achieved by the present inventions (1) to (15) below.
- (1) having a composite layer comprising a glass fabric composed of an aggregate of glass fibers and a resin material impregnated in the glass fabric; A transparent composite substrate, wherein the glass fiber aggregate itself has a variation in refractive index, and a difference between a maximum value and a minimum value of the refractive index is 0.008 or less.
- the glass cloth weaves at least one first glass fiber bundle formed by bundling a plurality of glass fibers and at least one second glass fiber bundle formed by bundling the plurality of glass fibers.
- a glass woven fabric The ratio of the first ratio of the glass fibers in the cross section of the first glass fiber bundle per unit width to the second ratio of the glass fibers in the cross section of the second glass fiber bundle per unit width is 1.
- the transparent composite substrate according to (1) which is 04 or more and 1.40 or less.
- the first ratio and the second ratio are substantially equal;
- the at least one first glass fiber bundle includes a plurality of first glass fiber bundles, and the at least one second glass fiber bundle includes a plurality of second glass fiber bundles,
- the transparent composite according to (2) wherein a ratio of the number of the first glass fiber bundles per unit width to the number of the second glass fiber bundles per unit width is 1.02 or more and 1.18 or less. substrate.
- the transparent composite substrate according to (1) further comprising a surface layer provided on the composite layer and having at least transparency and gas barrier properties.
- the transparent composite substrate according to (7) further including an intermediate layer provided between the composite layer and the surface layer and made of a resin material.
- the water vapor permeability measured based on the method specified in JIS K 7129 B of the transparent composite substrate is 0.1 [g / m 2 / day / 40 ° C., 90% RH] or less.
- the transparent composite substrate according to (1) is 0.1 [g / m 2 / day / 40 ° C., 90% RH] or less.
- a display element substrate comprising the transparent composite substrate described in (1) above.
- a transparent composite substrate having uniform and excellent optical properties can be obtained by optimizing the refractive index of the glass fabric provided in the composite layer. Further, by providing a surface layer having at least transparency and gas barrier properties on the composite layer, the optical characteristics of the composite layer can be suppressed over time, so that the optical characteristics of the transparent composite substrate can be maintained over a long period of time. be able to.
- the surface layer is composed of an inorganic material containing a silicon compound having a specific composition, or the melting point of the inorganic material constituting the surface layer and the thermal decomposition temperature of the resin material impregnated into the glass fabric satisfy a predetermined correlation.
- FIG. 1 is a plan view showing a glass cloth according to an embodiment of the transparent composite substrate of the present invention.
- FIG. 2 is a cross-sectional view showing an embodiment of the transparent composite substrate of the present invention.
- the transparent composite substrate of the present invention has a composite layer containing a glass cloth composed of an aggregate of glass fibers and a resin material impregnated in the glass cloth.
- the transparent composite substrate of the present invention is characterized in that the glass fiber aggregate itself has a variation in refractive index, and the difference between the maximum value and the minimum value of the refractive index is 0.008 or less.
- the term “transparent” refers to a state having translucency, and may have a chromatic color, but is preferably colorless.
- the transparent composite substrate of the present invention can maintain uniform and excellent optical properties by optimizing the refractive index of the glass fabric contained in the composite layer.
- FIG. 1 is a plan view showing a glass cloth according to an embodiment of the transparent composite substrate of the present invention
- FIG. 2 is a cross-sectional view showing an embodiment of the transparent composite substrate of the present invention.
- the transparent composite substrate 1 shown in FIG. 2 is provided on the composite layer 4 so as to cover the composite layer 4 including the glass cloth (glass fabric) 2 and the resin material (matrix resin) 3 and the surface of the composite layer 4. And a gas barrier layer (surface layer) 5.
- each component will be described.
- Glass cloth examples of the glass cloth 2 used in the present invention include not only simple bundles of glass fibers, but also fabrics (aggregates of glass fibers) such as woven fabrics and nonwoven fabrics containing glass fibers.
- FIG. 1 the case where the glass cloth 2 is a woven fabric is illustrated as an example.
- a glass cloth 2 shown in FIG. 1 includes a longitudinal glass yarn (warp) 2a and a transverse glass yarn (weft) 2b.
- the longitudinal glass yarn 2a and the transverse glass yarn 2b are substantially orthogonal to each other.
- Examples of the woven structure of the glass cloth 2 include a plain weave, a woven weave, a satin weave, and a twill weave.
- Examples of the inorganic glass material constituting the glass fiber 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. .
- E glass, S glass, T glass, and NE glass are preferably used as inorganic glass materials because they have few ionic impurities such as alkali metals and are easily available, and particularly 30 ° C. to 250 ° C.
- S glass or T glass having an average linear expansion coefficient of 5 ppm or less is more preferably used.
- the refractive index of the inorganic glass material is appropriately set according to the refractive index of the resin material 3 to be used, but is preferably about 1.4 to 1.6, for example, 1.5 to 1.55. More preferred is the degree. Thereby, the transparent composite substrate 1 which shows the outstanding optical characteristic in a wide wavelength range is obtained.
- the average diameter of the glass fibers contained in the glass cloth 2 is preferably about 2 to 15 ⁇ m, more preferably about 3 to 12 ⁇ m, and even more preferably about 3 to 10 ⁇ m.
- the transparent composite substrate 1 which can make mechanical characteristics, optical characteristics, and surface smoothness highly compatible is obtained.
- the average diameter of glass fiber is calculated
- the average thickness of the glass cloth 2 is preferably about 10 to 200 ⁇ m, and more preferably about 20 to 120 ⁇ m.
- the glass yarn When a bundle (glass yarn) made of a plurality of glass fibers is woven to form a woven fabric, the glass yarn preferably contains about 30 to 300 single fibers of glass fiber, and about 50 to 250. More preferably it is included. 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 pre-opened.
- the fiber opening process the glass yarn is widened and the cross section is formed into a flat shape.
- a so-called basket hole formed in the glass cloth 2 is also reduced.
- the smoothness of the glass cloth 2 is increased, and the smoothness of the surface of the transparent composite substrate 1 is also increased.
- 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.
- a coupling agent may be applied to the surface of the glass fiber as necessary.
- the coupling agent include a silane coupling agent and a titanium coupling agent, and a silane coupling agent is particularly preferably used.
- 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.
- the content of such a coupling agent is preferably about 0.01 to 5 parts by mass, more preferably about 0.02 to 1 part by mass with respect to 100 parts by mass of the glass cloth. More preferably, it is about 02 to 0.5 parts by mass. If the content rate of a coupling agent is in the said range, the optical characteristic of the transparent composite substrate 1 can be improved. Thereby, for example, a transparent composite substrate 1 suitable as a display element substrate is obtained.
- the present inventor obtained the knowledge that the refractive index distribution in the glass cloth 2 is strongly involved in enhancing the optical characteristics of the transparent composite substrate 1. And the refractive index variation exists in itself, and the optical characteristics of the transparent composite substrate 1 can be greatly enhanced by using the glass cloth 2 whose difference between the maximum value and the minimum value of the refractive index is 0.008 or less. As a result, the present invention has been completed. That is, by using the glass cloth 2 having such a refractive index distribution, light interference associated with the refractive index difference can be suppressed, and the optical characteristics of the transparent composite substrate 1 can be particularly enhanced.
- the difference between the maximum value and the minimum value of the refractive index in the glass cloth 2 is preferably 0.005 or less.
- the lower limit value of the difference between the maximum value and the minimum value of the refractive index in the glass cloth 2 is not particularly limited, but is preferably 0.0001 or more, and more preferably 0.0005 or more. If it is in the said range, the productivity of the glass cloth 2 will improve.
- the glass cloth 2 used for this invention is a woven fabric
- the 2nd ratio which a glass fiber occupies in the cross section of the horizontal direction glass yarn (2nd glass fiber bundle) 2b per unit width is set to " 1 ”
- the ratio (relative value) of the first proportion of the glass fibers in the cross section of the longitudinal glass yarn (first glass fiber bundle) 2a per unit width is 1.04 to 1.40. Is more preferably 1.21 or more and 1.39 or less, and further preferably 1.25 or more and 1.35 or less.
- the uniformity of the linear expansion coefficient in the vertical direction and the linear expansion coefficient in the horizontal direction can be achieved, and the light transmittance of the transparent composite substrate 1 can be further improved.
- the longitudinal glass yarn 2a faces the MD direction (flow direction), and the transverse glass yarn 2b faces the TD direction (vertical direction). It is set in the manufacturing device so that it faces.
- equal force is not applied to both, but changes depending on the yarn feeding direction.
- the force applied to the longitudinal glass yarn 2a and the lateral glass yarn 2b is adjusted so that the ratio of the glass fibers (first ratio and second ratio) and the number of glass yarns are anisotropic.
- the glass cloth 2 has anisotropy as described above, anisotropy also occurs in dimensional changes due to changes in heat, humidity environment, etc., and depending on the type of inorganic glass material, the type of resin material 3, etc. There is a risk that the glass cloth 2 may be deformed.
- the gas barrier layer 5 by providing the gas barrier layer 5 on the composite layer 4, the dimensional change of the transparent composite substrate 1 can be suppressed. This effect is achieved when the gas barrier layer 5 is made of an inorganic material and the inorganic material is made of a silicon compound having a specific composition, or a predetermined relationship is satisfied between the inorganic material and the resin material 3. Sometimes particularly noticeable.
- the gas barrier layer 5 By providing the gas barrier layer 5 on the composite layer 4 in this way, it is possible to suppress the uneven distribution of internal stress that causes the dimensional change of the transparent composite substrate 1. This makes it possible to suppress the deterioration of the optical characteristics of the transparent composite substrate 1, the occurrence of warpage, deformation, and the like regardless of the type of inorganic glass material, the type of resin material 3, and the like. That is, by providing the gas barrier layer 5 on the composite layer 4, problems that may inevitably occur when the glass cloth 2 is a woven fabric can be solved.
- the “unit width” refers to a width of 1 inch in a direction substantially perpendicular to the longitudinal direction (length direction) of the glass fiber bundle.
- the twist numbers of the longitudinal glass yarn (first glass fiber bundle) 2a and the transverse glass yarn (second glass fiber bundle) 2b are each preferably 0.2 to 2.0 / inch. More preferably, it is 3 to 1.6 / inch. When the number of twists of the glass fiber bundle is in this range, the transparent composite substrate 1 having a small haze value can be obtained.
- the resin material 3 used in the present invention examples 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.
- the resin material 3 is preferably an epoxy resin or an acrylic resin (particularly, an alicyclic epoxy resin or an alicyclic acrylic resin).
- Examples of the epoxy resin used in the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, or hydrogenated products thereof, epoxy resin having a dicyclopentadiene skeleton, and triglycidyl isocyanurate.
- An epoxy resin etc. are mentioned, The 1 type (s) or 2 or more types of mixture of these epoxy resins can be used.
- the above-mentioned epoxy resin is a glycidyl ether type epoxy resin containing a glycidyl group and an ether bond, a glycidyl ester type epoxy resin containing a glycidyl group and an ester bond, and a glycidyl amine type epoxy resin containing a glycidyl group and an amino group.
- Type epoxy resins and alicyclic epoxy resins having an alicyclic epoxy group are particularly preferably used for the epoxy resin.
- the main component is various alicyclic epoxy resins such as alicyclic polyfunctional epoxy resins, alicyclic epoxy resins having a hydrogenated biphenyl skeleton, and alicyclic epoxy resins having a hydrogenated bisphenol A skeleton.
- Resin material 3 is used.
- alicyclic epoxy resins include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylene carboxylate, 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-methylcyclohexylmethyl) adipate, exo-exobis (2,3-epoxycyclopentyl) ether, 2,2-bis (4- (2,3-epoxypropyl) cyclohexyl) propane, 2,6-bis (2, 3-epoxypropoxycyclohexyl-p-di
- an alicyclic epoxy resin having one or more epoxycyclohexane rings in the molecule is particularly preferably used.
- an alicyclic epoxy structure represented by the following chemical formula (1), (2) or (3) is particularly preferably used.
- —X— represents —O—, —S—, —SO—, —SO 2 —, —CH 2 —, —CH (CH 3 ) —, or —C (CH 3 ) 2 -Represents.
- 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.
- the transparent composite substrate 1 obtained using the resin material 3 containing the alicyclic epoxy resin has a low coefficient of linear expansion after curing
- the glass cloth 2 and The interfacial stress at the interface with the resin material 3 is particularly small at room temperature.
- 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.
- the linear expansion coefficient is low, the transparent composite substrate 1 is prevented from being deformed such as warpage and swell.
- the resin material 3 is preferably a resin material mainly composed of an alicyclic epoxy resin.
- the main component means 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.
- a glycidyl type epoxy resin is preferably used together with an alicyclic epoxy resin.
- the refractive index of the resin material 3 can be easily adjusted while suppressing a decrease in optical properties 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.
- the addition amount of the glycidyl type epoxy resin is preferably about 0.1 to 10 parts by mass, more preferably about 1 to 5 parts by mass with respect to 100 parts by mass of the alicyclic epoxy resin.
- 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.
- a glycidyl type epoxy resin having a cardo structure is preferably used. That is, by adding a glycidyl type epoxy resin having a cardo structure to an alicyclic epoxy resin, a large number of aromatic rings derived from the bisarylfluorene skeleton are contained in the cured resin material 3. Therefore, the optical characteristics and heat resistance of the transparent composite substrate 1 can be further improved.
- the glycidyl type epoxy resin having such a cardo structure include Oncoat EX series (manufactured by Nagase Sangyo Co., Ltd.), Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.), and the like.
- a silsesquioxane compound is preferably used as the resin material 3 together with the alicyclic epoxy resin, and in particular, a silsesquioxane compound having a photopolymerizable group such as an oxetanyl group or a (meth) acryloyl group. Is more preferably used.
- the refractive index of the resin material 3 can be easily adjusted while suppressing a decrease in optical characteristics in the transparent composite substrate 1.
- the silsesquioxane-based compound having an oxetanyl group is highly compatible with the alicyclic epoxy resin, it is possible to uniformly mix them, and as a result, the refractive index of the composite layer 4 can be further increased.
- a transparent composite substrate 1 having excellent optical characteristics can be obtained while reliably adjusting.
- silsesquioxane compounds having an oxetanyl group examples include OX-SQ, OX-SQ-H, OX-SQ-F (all manufactured by Toagosei Co., Ltd.) and the like.
- the addition amount of the silsesquioxane-based compound is preferably about 1 to 20 parts by mass, more preferably about 2 to 15 parts by mass with respect to 100 parts by mass of the alicyclic epoxy resin. .
- alicyclic acrylic resin for example, tricyclodecanyl diacrylate, its hydrogenated product, dicyclopentanyl diacrylate, isobornyl diacrylate, hydrogenated bisphenol A diacrylate, cyclohexane-1,4- Examples include dimethanol diacrylate, and specifically, Hitachi Chemical's Optretz series, Daicel Cytec's acrylate monomer, and the like.
- the resin material 3 used in the present invention preferably has a glass transition temperature of 150 ° C. or higher, more preferably 170 ° C. or higher, and further preferably 180 ° 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 resin material 3 preferably has a heat distortion temperature of 200 ° C. or higher, and preferably has a coefficient of thermal expansion of 100 ppm / K or lower. Further, the refractive index of the resin material 3 is preferably as close as possible to the average refractive index of the glass cloth 2, and is preferably substantially the same refractive index. Specifically, the refractive index difference between the two is preferably 0.01 or less, and more preferably 0.005 or less. Thereby, the transparent composite substrate 1 with high light transmittance is obtained.
- the transparent composite substrate 1 may contain a filler in the resin material 3 in addition to the above.
- the filler examples include a glass filler composed of fiber pieces or particles of an inorganic glass material. Dispersion of the glass filler in the resin material 3 can improve the mechanical characteristics without inhibiting the light transmittance of the transparent composite substrate 1.
- the glass filler examples include glass chopped strands, glass beads, glass flakes, glass powder, and milled glass.
- 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.
- the diameter of a filler is 100 nm or less. Since such a filler hardly scatters at the interface, the transparency of the transparent composite substrate 1 can be maintained relatively high even when a large amount of filler is dispersed in the resin material 3.
- the coupling agent described above may be added to the resin material 3.
- the stress concentration described above can be further relaxed, and the optical characteristics of the transparent composite substrate 1 can be further enhanced.
- the addition amount is preferably about 0.01 to 5 parts by mass and about 0.05 to 2 parts by mass with respect to 100 parts by mass of the resin material. Is more preferable.
- a gas barrier layer 5 having transparency and gas barrier properties is provided on the composite layer 4.
- the gas barrier layer 5 By providing the gas barrier layer 5 on the composite layer 4, it is possible to prevent or suppress the gas such as oxygen and water vapor in the atmosphere from reaching the glass cloth 2. For this reason, it is possible to prevent these gases from acting on the glass cloth 2 over a long period of time and adversely affecting the glass cloth 2 to have an uneven refractive index. For this reason, the transparent composite substrate 1 in which the optical characteristics are prevented from decreasing with time, that is, the transparent composite substrate 1 having excellent optical characteristics over a longer period of time is obtained.
- the gas barrier layer 5 on the composite layer 4, it is possible to suppress the dimensional change itself of the glass cloth 2 due to moisture absorption. For this reason, the uniformity of the optical characteristics of the glass cloth 2 can be maintained even in a harsh environment, and the occurrence of anisotropy in the dimensional change of the glass cloth can be further reliably prevented. .
- the constituent material of the gas barrier layer 5 is not particularly limited and may be either an inorganic material or an organic material, but is preferably an inorganic material.
- inorganic materials include at least one selected from the group consisting of Si, Al, Ca, Na, B, Ti, Pb, Nb, Mg, P, Ba, Ge, Li, K, Zr, Zn, and the like.
- the inorganic material preferably contains a plurality of types of oxides, and more preferably is composed of a glass material containing a plurality of types of oxides.
- the gas barrier property of the gas barrier layer 5 can be improved by a layer made of an amorphous and dense glass material.
- silicon oxide, aluminum oxide, magnesium oxide and boron oxide are preferably used, and among these, silicon oxide is particularly preferably used.
- silicon oxide is also preferable because of its high transparency.
- silicon oxide is a silicon compound represented by SiOxNy described later, and x is 1 ⁇ x ⁇ 2 and y is 0.
- the inorganic material preferably contains silicon nitride together with silicon oxide (hereinafter, those containing both are referred to as “silicon oxynitride”).
- silicon oxynitride By including silicon oxynitride, the gas barrier layer 5 has excellent surface hardness as well as gas barrier properties. That is, the gas barrier layer 5 can achieve both gas barrier properties and protective properties for the composite layer 4. Silicon oxynitride is also preferable because of its high transparency.
- Silicon oxynitride is a silicon compound represented by SiOxNy, and x and y preferably satisfy the relationship of 1 ⁇ x ⁇ 2 and y ⁇ 0 ⁇ y ⁇ 1, and 1.2 ⁇ x ⁇ 1.8. And it is more preferable to satisfy the relationship of 0.2 ⁇ y ⁇ 0.8.
- the gas barrier layer 5 composed of such silicon oxynitride can achieve both a high level of gas barrier properties and protective properties, and its refractive index is optimized with respect to the composite layer 4, so that the transparent composite substrate 1 This also contributes to the improvement of the light transmittance.
- x and y preferably satisfy a relationship of 0.3 ⁇ x / (x + y) ⁇ 1, and more preferably satisfy a relationship of 0.35 ⁇ x / (x + y) ⁇ 0.95. It is preferable that the relationship 0.4 ⁇ x / (x + y) ⁇ 0.9 is satisfied.
- the gas barrier layer 5 composed of such a silicon compound can achieve both gas barrier properties and surface protection properties. Therefore, moisture absorption and oxidation of the composite layer 4 can be suppressed, the optical characteristics of the transparent composite substrate 1 can be maintained uniformly over a long period of time, and the surface of the transparent composite substrate 1 can be reliably protected from scratches and the like. .
- the abrasion resistance is improved, and the transparent composite substrate 1 that can withstand use in a harsh environment is obtained.
- the refractive index of the gas barrier layer 5 is particularly optimized with respect to the composite layer 4, which contributes to the improvement of the light transmittance of the transparent composite substrate 1.
- the light transmittance and flexibility of the gas barrier layer 5 are lowered.
- x is “0” (that is, when the silicon compound is silicon nitride)
- the gas barrier layer Depending on the average thickness of 5, etc., the gas barrier property of the gas barrier layer 5 may be lowered.
- x exceeds the upper limit, depending on the value of y and the like, the surface protection of the gas barrier layer 5 may be lowered.
- y exceeds the said upper limit, there exists a possibility that the surface protection of the gas barrier layer 5 may fall.
- Such a transparent composite substrate 1 is rich in gas barrier properties by optimizing the properties between the inorganic material and the resin material 3, and also has surface protection properties. For this reason, moisture absorption, oxidation, warpage, deformation, etc. of the transparent composite substrate 1 are suppressed, the optical characteristics of the transparent composite substrate 1 are maintained uniformly over a long period of time, and the surface is reliably prevented from being scratched. Can do.
- the 5% weight reduction temperature Td is, for example, a temperature when a 5% weight reduction occurs in the main component included in the resin material 3 due to heating in the atmosphere by thermogravimetric analysis (TGA). Can be measured.
- TGA thermogravimetric analysis
- the starting temperature of the thermal decomposition can be set to the above Tm.
- the average thickness of the gas barrier layer 5 is not particularly limited, but is preferably about 10 to 500 nm. Within this range, the gas barrier layer 5 having sufficient gas barrier properties and protective properties and excellent flexibility can be obtained.
- the gas barrier layer 5 preferably has a water vapor permeability of 0.1 [g / m 2 / day / 40 ° C., 90% RH] or less as defined in JIS K 7129 B.
- the transparent composite substrate 1 has excellent optical characteristics over a long period of time by suppressing alteration and deterioration of the glass cloth 2 and the resin material 3 due to moisture absorption and suppressing the change in the refractive index associated therewith. Is obtained.
- the gas barrier layer 5 preferably has an oxygen permeability defined by JIS K 7126 B of 0.1 [cm 3 / m 2 / day / 1 atm / 23 ° C.] or less.
- the oxygen permeability is within the above range, the transparent composite substrate 1 having excellent optical characteristics over a long period of time can be obtained by suppressing alteration and deterioration of the resin material 3 due to oxidation and suppressing the change in the refractive index.
- An intermediate layer may be interposed between the composite layer 4 and the gas barrier layer 5 as necessary.
- the intermediate layer include a functional layer, which will be described later, and a layer composed of a resin material such as an epoxy resin or an acrylic resin is preferably used.
- the same material as the resin material 3 included in the composite layer 4 is used, and preferably the same material as the resin material 3 is used. Thereby, it becomes difficult to peel off the intermediate layer, and the adhesion between the composite layer 4 and the gas barrier layer 5 can be further improved.
- the gas barrier layer (surface layer) 5 only needs to have at least transparency and gas barrier properties, and may have other functions.
- the total light transmittance of the transparent composite substrate 1 as described above at a wavelength of 400 nm is preferably 70% or more, more preferably 75% or more, and further preferably 78% or more. There exists a possibility that the display performance in the display element using the transparent composite substrate 1 may not be enough that the total light transmittance in wavelength 400nm is less than a lower limit.
- the average thickness of the transparent composite substrate 1 is not particularly limited, but is preferably about 40 to 200 ⁇ m, and more preferably about 50 to 100 ⁇ m.
- the transparent composite substrate 1 has an average linear expansion coefficient at 30 ° C. to 150 ° C. of preferably 40 ppm or less, more preferably 20 ppm or less, still more preferably 15 ppm or less, and particularly preferably 10 ppm or less. Since the transparent composite substrate 1 having such an average linear expansion coefficient has a sufficiently small dimensional change due to a temperature change, it is possible to suppress a decrease in optical characteristics due to the dimensional change.
- the deterioration of the optical characteristics due to the dimensional change is, for example, peeling between the glass cloth 2 and the resin material 3 and the haze may be increased by peeling.
- the transparent composite substrate 1 can maintain uniform and excellent optical characteristics over a long period of time in a wide temperature range. Further, when the transparent composite substrate 1 having such an average coefficient of linear expansion is used for, for example, an active matrix display element substrate, various problems such as warpage and disconnection of wiring are unlikely to occur.
- the transparent composite substrate 1 preferably has a water vapor transmission rate defined in JIS K 7129 B of 0.1 [g / m 2 / day / 40 ° C., 90% RH] or less. If the water vapor permeability is within the above range, the amount of water vapor that permeates through the transparent composite substrate 1 is suppressed, and moisture absorption of the glass cloth 2 and the resin material 3 is suppressed. As described above, the glass cloth 2 has a small difference between the maximum value and the minimum value of the refractive index of 0.008 or less, and the microstructure is uniform. For this reason, the refractive index variation of the glass cloth 2 (composite layer 4) due to moisture absorption is also uniform, and the transparent composite substrate 1 can maintain uniform and excellent optical characteristics over a long period of time.
- a water vapor transmission rate defined in JIS K 7129 B of 0.1 [g / m 2 / day / 40 ° C., 90% RH] or less.
- the water vapor permeability is within the above range, the fluctuation of the linear expansion coefficient of the transparent composite substrate 1 due to moisture absorption is also suppressed. For this reason, the fall of the optical characteristic of the transparent composite substrate 1 accompanying a dimension change can also be suppressed reliably. Furthermore, when the water vapor permeability is within the above range, when the transparent composite substrate 1 is used as a display element substrate, deterioration of the display element due to moisture absorption can be suppressed and high reliability of the display element can be maintained over a long period of time. it can.
- the transparent composite substrate 1 preferably has an oxygen permeability specified by JIS K 7126 B of 0.1 [cm 3 / m 2 / day / 1 atm / 23 ° C.] or less.
- the oxygen permeability is within the above range, when the transparent composite substrate 1 is used as a display element substrate, deterioration of the display element due to oxidation can be suppressed, and high reliability of the display element can be maintained over a long period of time.
- the transparent composite substrate 1 includes 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 (the display element of the present invention). In addition, 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 1 and has a functional layer formed on the surface of the transparent composite substrate 1 as necessary.
- 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, or an epoxy resin.
- Smooth layer composed of acrylic resin, rubber or gel cured silicone, polyurethane, epoxy resin, acrylic resin, polyethylene, polypropylene, polystyrene, vinyl chloride resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether
- An impact buffer layer composed of sulfone, polysulfone or the like can be used.
- the smooth layer preferably has heat resistance, transparency, and chemical resistance, and, for example, a material having the same composition as that of the resin material 3 included in the composite layer 4 is preferably used.
- the average thickness of the smooth layer is preferably about 0.1 to 30 ⁇ m, and more preferably about 0.5 to 30 ⁇ m.
- a smooth layer is provided on at least one side of the transparent composite substrate 1 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 1 and further thereon.
- the structure etc. which provide a smooth 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.
- the transparent composite substrate 1 is less likely to generate and adhere to foreign matter, it is possible to suppress a decrease in optical characteristics caused by these. For this reason, a display element substrate capable of realizing a display element with high quality and high reliability can be obtained.
- the transparent composite substrate 1 is obtained by impregnating the glass cloth 2 with the uncured resin material 3 and molding (shaping) it into a plate shape in this state, and then curing the resin material 3.
- the transparent composite substrate 1 is obtained by impregnating a glass cloth with a resin varnish, curing the resin varnish while molding (shaping), and obtaining a composite layer 4 and covering the surface of the composite layer 4 And a step of forming a gas barrier layer 5 on the composite layer 4.
- the manufacturing process will be described in detail.
- a coupling agent is applied to the glass cloth 2 to perform surface treatment.
- the coupling agent is applied by, for example, a method of immersing the glass cloth 2 in a liquid containing the coupling agent, a method of applying the liquid to the glass cloth 2, a method of spraying the liquid on the glass cloth 2, and the like. . This step may be performed as necessary, and may be omitted.
- the resin varnish contains the above-described uncured resin material 3, 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 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 of these curing agents is used.
- a cationic curing agent is particularly preferably used as the curing agent.
- the resin material can be cured at a relatively low temperature. For this reason, it is not necessary to heat the resin varnish to a high temperature at the time of curing, and generation of thermal stress accompanying a temperature change can be suppressed when the cured product of the resin material 3 is returned to normal temperature (room temperature). As a result, a transparent composite substrate 1 with low optical anisotropy is obtained.
- the transparent composite substrate 1 having high heat resistance (for example, glass transition temperature) can be obtained. This is considered to be because the crosslinking density of the cured product of the resin material 3 (for example, 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.
- an onium salt cationic curing agent for example, an onium salt cationic curing agent.
- a photocationic curing agent is preferable as the cationic curing agent. Thereby, it is possible to easily select whether or not to cure the resin material 3 only by selecting the light irradiation region.
- the photocationic curing agent may be any one that can react a polyfunctional cation polymerizable compound and a monofunctional cation polymerizable compound by photocationic polymerization.
- Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid Examples include onium salts such as sulfonium salts of acids.
- the photocationic curing agent examples include phenyldiazonium salt of boron tetrafluoride, diphenyliodonium salt of phosphorous hexafluoride, diphenyliodonium salt of antimony hexafluoride, tri-4-methylphenylsulfonium of arsenic hexafluoride Salt, tri-4-methylphenylsulfonium salt of antimony tetrafluoride, and the like.
- a radical photocuring agent such as Irgacure series (manufactured by Ciba Japan Co., Ltd.) is also used.
- thermal cationic curing agent examples include aromatic sulfonium salts, aromatic iodonium salts, ammonium salts, aluminum chelates, and boron trifluoride amine complexes.
- the content of such a cationic curing agent is not particularly limited, but is preferably about 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin material 3 (eg, alicyclic epoxy resin), particularly 0 .5 to 3 parts by weight is preferred. If the content is less than the lower limit value, the curability of the resin material 3 may be reduced, and if the content exceeds the upper limit value, the transparent composite substrate 1 may become brittle.
- a sensitizer, an acid proliferating agent, and the like can be used as necessary.
- 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.
- examples of the hindered phenol antioxidant include BHT, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and the like.
- the content of the antioxidant in the resin varnish is preferably 0.01% by mass to 5% by mass, and more preferably about 0.1% by mass to 3% by mass.
- the weight average molecular weight of the antioxidant is preferably 200 to 2000, more preferably 500 to 1500, and still more preferably 1000 to 1400.
- the weight average molecular weight of the antioxidant is within the above range, the volatilization of the antioxidant is suppressed and compatibility with the resin material 3 (for example, alicyclic epoxy resin) is ensured.
- the resin material 3 for example, alicyclic epoxy resin
- Such an antioxidant can remain in the transparent composite substrate 1 even after a reliability test such as wet heat treatment, and can realize a transparent composite substrate that can suppress deterioration of optical anisotropy.
- phenolic antioxidants other than hindered phenolic antioxidants include, for example, semi-hindered phenolic antioxidants in which one of the substituents located so as to sandwich the hydroxyl group is substituted with a methyl group or the like. And a hindered phenolic antioxidant in which both of two substituents sandwiching a hydroxyl group are substituted with a methyl group or the like. These are added to the resin varnish in an amount less than that of the hindered phenol antioxidant.
- phosphorus antioxidants include tridecyl phosphite and diphenyl decyl phosphite.
- the amount of the antioxidant (particularly phosphorus antioxidant) other than the hindered phenol antioxidant is preferably about 30 to 300 parts by mass with respect to 100 parts by mass of the hindered phenol antioxidant. More preferably, it is about 50 to 200 parts by mass.
- a hindered phenolic antioxidant and other antioxidants can exhibit each effect without burying (cancelling), and can bring about a synergistic effect.
- the resin varnish may contain an oligomer, a monomer, or the like of a thermoplastic resin or a thermosetting resin as necessary as long as the characteristics are not impaired.
- the composition ratio of each component of the resin varnish is appropriately set so that the refractive index of the cured resin composition 3 is substantially equal to the refractive index of the glass cloth 2. .
- the resin varnish is obtained by mixing the above components.
- the obtained resin varnish is impregnated into the glass cloth 2.
- a method of immersing the glass cloth 2 in the resin varnish a method of applying the resin varnish to the glass cloth 2 or the like is used.
- the resin varnish may be further applied from above the resin varnish in an uncured state or after the resin varnish is cured. Thereafter, if necessary, the resin varnish is subjected to defoaming treatment. Furthermore, the resin varnish is dried as necessary.
- the glass cloth 2 impregnated with the resin varnish is heated while being formed into a plate shape.
- the resin material 3 is hardened and the composite layer 4 is obtained.
- the heating conditions are preferably a heating temperature of about 50 to 300 ° C. and a heating time of about 0.5 to 10 hours, more preferably a heating temperature of about 170 to 270 ° C. and a heating time of about 1 to 5 hours. Is done.
- the heating temperature may be changed midway. For example, initially (initial), the resin varnish may be heated at about 50-100 ° C. for about 0.5-3 hours, and then heated at about 200-300 ° C. for about 0.5-3 hours. .
- a polyester film or a polyimide film is used for molding the resin varnish.
- the surface of a resin varnish can be smooth
- the resin material 3 (resin varnish) is cured by irradiating ultraviolet rays having a wavelength of about 200 to 400 nm.
- Light energy applied 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, the resin material 3 can be cured uniformly and reliably without unevenness.
- the gas barrier layer 5 is formed on both surfaces of the composite layer 4.
- various liquid phase film forming methods such as a sol-gel method
- various vapor phase film forming methods such as a vacuum deposition method, an ion plating method, a sputtering method, and a CVD method are used.
- a vapor deposition method is preferably used, and a sputtering method or a CVD method is more preferably used.
- the gas barrier layer 5 containing silicon oxynitride is formed by using an RF sputtering method using silicon oxide and silicon nitride as raw materials, a silicon-containing target, oxygen, nitrogen, or the like during the process.
- a DC sputtering method or the like in which a reactive gas is introduced is used.
- the transparent composite substrate 1 is obtained as described above.
- the present invention is not limited to this.
- an arbitrary component may be added to the transparent composite substrate and the display element substrate.
- the glass cloth 2 is comprised with the woven fabric which weaves the several vertical glass yarn 2a and the several horizontal glass yarn 2b, it is one vertical glass yarn. 2a and a plurality of transverse glass yarns 2b, a woven cloth comprising a plurality of longitudinal glass yarns 2a and a transverse glass yarn 2b, and a longitudinal glass yarn. It may be a woven fabric formed by weaving 2a and one horizontal glass yarn 2b.
- the transparent composite substrate of the present invention may not have a surface layer.
- Example 1A Production of transparent composite substrate (Example 1A)
- a glass cloth a 100 mm square NE glass-based glass cloth (average thickness 95 ⁇ m, average wire diameter 9 ⁇ m) was prepared. After this was immersed in benzyl alcohol (refractive index 1.54), acetoxyethoxyethane (refractive index 1.406) was added to the benzyl alcohol little by little. Each time the refractive index of benzyl alcohol was changed, the glass cloth was held over a fluorescent lamp to check whether the glass cloth became substantially transparent. Moreover, the refractive index of the liquid mixture when the part which became substantially transparent appeared in the glass cloth was measured.
- the number of MD yarns in the MD direction (longitudinal direction) per inch width was 58, and the number of TD direction (lateral directions) glass yarns per inch width was 50. That is, when the number of TD direction glass yarns per inch width was “1”, the ratio (relative value) of the number of MD direction glass yarns per inch width was 1.16.
- the ratio of the glass fiber in the cross section of the TD direction glass yarn per inch width is “1”
- the ratio of the glass fiber in the cross section of the MD direction glass yarn per inch width is The ratio (relative value) was 1.35.
- the number of twists of the glass fiber bundle of the glass cloth was 1.0 per 1 inch length in the MD direction and 1.0 per 1 inch length in the TD direction.
- the refractive index of the matrix resin was measured as follows. First, after applying a resin varnish to a release-treated glass plate to form a liquid film, the same release-treated glass plate is placed on the liquid film, and the liquid film is sandwiched between two glass plates. It is. At this time, spacers having a thickness of 200 ⁇ m were arranged on the four sides between the glass plates. And after irradiating 1100 mJ / cm ⁇ 2 > of ultraviolet-ray with this high voltage
- the glass cloth impregnated with the resin varnish in this way was sandwiched between two glass plates subjected to a release treatment, and irradiated with ultraviolet rays of 1100 mJ / cm 2 with a high-pressure mercury lamp. Furthermore, the composite layer of average thickness 97micrometer (glass cloth content 63 mass%) was obtained by heating at 250 degreeC for 2 hours.
- the shutter provided between the target and the composite layer was opened, and the film formation of the gas barrier layer composed of SiOxNy was started. Thereafter, when the average thickness of the gas barrier layer reached 100 nm, the shutter was closed to complete the film formation.
- the chamber was opened to the atmosphere to obtain a manufactured transparent composite substrate.
- Examples 2A to 9A and Comparative Examples 1A to 5A A transparent composite substrate was obtained in the same manner as in Example 1A, except that the production conditions were changed as shown in Tables 1 and 2. The average thickness of the composite layer is shown in Tables 1 and 2.
- Examples 2A, 3A, 4A, 8A, 9A and Comparative Example 2A a hydrogenated biphenyl type alicyclic epoxy resin (manufactured by Daicel Chemical Industries, Ltd., E-BP, Tg:> 250 ° C.) used as a resin monomer. ) Has the structure of the following chemical formula (2). The refractive index after crosslinking of E-BP was 1.522.
- T glass-based glass cloth (average thickness 95 ⁇ m, average wire diameter 9 ⁇ m) was used as the glass cloth
- examples 5A and Comparative Examples 3A, 4A glass was used.
- an S glass-based glass cloth (average thickness 95 ⁇ m, average wire diameter 9 ⁇ m) was used.
- the average refractive index of the glass cloth used, the difference in refractive index, and the MD fiber glass yarn per inch width when the ratio of the glass fiber in the cross section of the TD glass yarn per inch width is “1”.
- the ratio (relative value) of the ratio of the glass fibers in the cross section is as shown in Tables 1 and 2.
- Example 3A, 7A, and 8A and Comparative Example 2A a thermal cationic polymerization initiator (manufactured by Sanshin Chemical Industry Co., Ltd., SI-100L) was used as a curing agent. Then, the glass cloth impregnated with the resin varnish was sandwiched between two glass plates subjected to release treatment, heated at 80 ° C. for 2 hours, and further heated at 250 ° C. for 2 hours to obtain a composite layer.
- a thermal cationic polymerization initiator manufactured by Sanshin Chemical Industry Co., Ltd., SI-100L
- Example 5A and Comparative Examples 3A and 4A the alicyclic acrylic resin (IRR-214K, manufactured by Daicel Cytec Co., Ltd.) used as the resin monomer has a structure represented by the following chemical formula (6).
- the refractive index after crosslinking of IRR-214K was 1.529.
- Example 5A and Comparative Examples 3A and 4A when the resin varnish was cured, the glass cloth impregnated with the resin varnish was irradiated with ultraviolet rays having a wavelength of 365 nm. Moreover, the radical photopolymerization initiator (the Ciba Japan Co., Ltd. make, Irgacure 184) was used as a polymerization initiator. Moreover, the average thickness of the gas barrier layer in Example 2A was 50 nm, and the average thickness of the gas barrier layer in Example 9A was 250 nm.
- the radical photopolymerization initiator the Ciba Japan Co., Ltd. make, Irgacure 184
- the average thickness of the gas barrier layer in Example 2A was 50 nm
- the average thickness of the gas barrier layer in Example 9A was 250 nm.
- Example 1B a transparent composite substrate was obtained in the same manner as in Example 1A, except that the glass cloth content in the composite layer was 57 mass%.
- Example 2B to 10B and Comparative Examples 1B to 6B transparent composite substrates were obtained in the same manner as Example 1B, except that the production conditions were changed as shown in Tables 3 and 4. The average thickness of the composite layer is shown in Tables 3 and 4.
- T glass-based glass cloth (average thickness 95 ⁇ m, average wire diameter 9 ⁇ m) was used as the glass cloth.
- glass was used as the cloth.
- S glass-based glass cloth (average thickness 95 ⁇ m, average wire diameter 9 ⁇ m) was used.
- the ratio (relative value) of the proportion of glass fibers in the cross section and the number of twists of the glass fiber bundle are as shown in Tables 3 and 4.
- Example 5B and Comparative Examples 3B and 4B when the resin varnish was cured, the glass cloth impregnated with the resin varnish was irradiated with ultraviolet rays having a wavelength of 365 nm.
- Examples 3B and 7B and Comparative Examples 2B, 5B, and 6B a glass cloth impregnated with a resin varnish was sandwiched between two glass plates subjected to a release treatment, heated at 80 ° C. for 2 hours, and then 250 A composite layer was obtained by further heating at 2 ° C. for 2 hours.
- the average thickness of the gas barrier layer in Example 2B was 50 nm
- the average thickness of the gas barrier layer in Example 8B was 250 nm.
- Example 1C a transparent composite substrate was obtained in the same manner as in Example 1A, except that the content of the glass cloth in the composite layer was 60% by mass.
- Example 2C to 10C and Comparative Examples 1C to 6C transparent composite substrates were obtained in the same manner as Example 1C, except that the production conditions were changed as shown in Tables 5 and 6. The average thickness of the composite layer is shown in Tables 5 and 6.
- Td The 5% weight reduction temperature of the alicyclic epoxy resin or alicyclic acrylic resin, which is the main component contained in the resin material, is Td [° C.], and the melting point of the inorganic material constituting the gas barrier layer is Tm [° C.]. Tm ⁇ Td was calculated and shown in Tables 5 and 6.
- T glass-based glass cloth (average thickness 95 ⁇ m, average wire diameter 9 ⁇ m) was used as the glass cloth.
- glass was used as the cloth.
- S glass-based glass cloth (average thickness 95 ⁇ m, average wire diameter 9 ⁇ m) was used.
- the ratio (relative value) of the proportion of the glass fibers in the cross section and the number of twists of the glass fiber bundle are as shown in Tables 5 and 6.
- Example 5C and Comparative Examples 3C and 4C when the resin varnish was cured, the glass cloth impregnated with the resin varnish was irradiated with ultraviolet rays having a wavelength of 365 nm.
- Examples 3C and 7C and Comparative Examples 2C, 5C, and 6C a glass cloth impregnated with a resin varnish was sandwiched between two glass plates subjected to a release treatment, heated at 80 ° C. for 2 hours, and then 250 A composite layer was obtained by further heating at 2 ° C. for 2 hours.
- the average thickness of the gas barrier layer in Example 2C was 50 nm
- the average thickness of the gas barrier layer in Example 8C was 250 nm.
- Example 1D a transparent composite substrate was obtained in the same manner as Example 1A, except that the glass cloth content in the composite layer was 65% by mass.
- Example 2D to 9D and Comparative Examples 1D to 6D transparent composite substrates were obtained in the same manner as Example 1D, except that the production conditions were changed as shown in Tables 7 and 8. The average thickness of the composite layer is shown in Tables 7 and 8.
- Td The 5% weight reduction temperature of the alicyclic epoxy resin or alicyclic acrylic resin, which is the main component contained in the resin material, is Td [° C.], and the melting point of the inorganic material constituting the gas barrier layer is Tm [° C.]. Tm ⁇ Td was calculated and shown in Tables 7 and 8.
- Example 3D and Comparative Examples 2D and 6D T glass-based glass cloth (average thickness 95 ⁇ m, average wire diameter 9 ⁇ m) was used as the glass cloth, and in Example 5D and Comparative Examples 3D and 4D, the glass cloth was used. , S glass-based glass cloth (average thickness 95 ⁇ m, average wire diameter 9 ⁇ m) was used.
- the ratio (relative value) of the proportion of the glass fibers in the cross section and the number of twists of the glass fiber bundle are as shown in Tables 7 and 8.
- Example 5D and Comparative Examples 3D and 4D when the resin varnish was cured, the glass cloth impregnated with the resin varnish was irradiated with ultraviolet rays having a wavelength of 365 nm.
- Examples 3D and 7D and Comparative Examples 2D, 5D, and 6D a glass cloth impregnated with a resin varnish was sandwiched between two glass plates subjected to a release treatment, heated at 80 ° C. for 2 hours, and then 250 A composite layer was obtained by further heating at 2 ° C. for 2 hours.
- the average thickness of the gas barrier layer in Example 2D was 50 nm
- the average thickness of the gas barrier layer in Example 8D was 250 nm.
- Comparative Example 7D a resin film was produced using the same material as in Example 1D except that no glass cloth was used.
- the glass plate by which the mold release process was similarly carried out on the liquid film
- the liquid film was sandwiched between glass plates. At this time, spacers having a thickness of 100 ⁇ m were arranged on the four sides between the glass plates.
- the liquid film was irradiated with ultraviolet rays of 1100 mJ / cm 2 with a high-pressure mercury lamp, and then heated at 250 ° C. for 2 hours to obtain a resin film having an average thickness of 105 ⁇ m.
- the transparent composite substrate obtained in each example had a small haze, and even when subjected to moisture treatment, the haze change rate was small.
- the transparent composite substrate obtained in each Example had a small anisotropy of dimensional change depending on the weaving direction. Furthermore, the gas barrier properties were relatively good.
- the transparent composite substrate obtained in each example has excellent optical characteristics and can maintain excellent optical characteristics over a long period even in a harsh environment. Moreover, the transparent composite substrate obtained in each Example was relatively excellent in surface wear resistance.
- the transparent composite substrates obtained in Comparative Examples 1A and 4A had a large cross-sectional area ratio per unit width of yarn, but the dimensional change due to moisture absorption was larger than expected from the cross-sectional area.
- the glass cloth used by Comparative Example 1A, 2A, 4A has a large refractive index difference, it turned out that the haze change rate by moisture absorption is large compared with each Example. The reason for this is that when the cross-sectional area ratio per unit width of the glass yarn or the difference in the refractive index of the glass cloth is large, it is more susceptible to changes in physical properties due to humidity, which may cause a difference more than expected. .
- the refractive index difference of the glass cloth in the composite layer is 0.008 or less, and by providing gas barrier layers on both sides of this composite layer, the optical properties of the transparent composite substrate are maintained well over a long period of time. It became clear that it was possible.
- the transparent composite substrate obtained in each example had a small haze, and even when the moisture treatment was performed, the haze change rate was small. Moreover, the difference (anisotropy) of the dimensional change by the weaving direction was small in the transparent composite substrate obtained in each Example. Furthermore, the gas barrier properties were relatively good. It was also found that the wear resistance can be improved by optimizing the abundance ratio of oxygen atoms and nitrogen atoms in the silicon compound constituting the gas barrier layer.
- the transparent composite substrate obtained in each example has excellent optical characteristics and can maintain excellent optical characteristics over a long period even in a harsh environment. It was also revealed that the transparent composite substrate obtained in each example was resistant to rubbing and the like and excellent in surface wear resistance.
- the transparent composite substrate obtained in each comparative example contained a large haze. Moreover, the thing whose haze changes a lot with moisture treatment was also included. Furthermore, it has been clarified that the transparent composite substrates obtained in the respective comparative examples are rapidly deteriorated by performing an accelerated test such as moisture treatment even if the haze is small immediately after production. The reason for this is that when the refractive index difference of the glass cloth is large, the deterioration rate with respect to moisture is remarkably high, which causes a change in haze.
- the transparent composite substrates obtained in the respective comparative examples included those having a large difference in dimensional change depending on the weaving direction, and also included those having a low gas barrier property and surface wear resistance.
- the refractive index difference of the glass cloth in the composite layer is 0.008 or less, and by providing gas barrier layers made of silicon compounds of a specific composition on both sides of the composite layer, a harsh environment It was revealed that the optical characteristics of the transparent composite substrate can be maintained well over a long period even under the above conditions.
- the transparent composite substrate obtained in each Example had a small haze, and even when the moisture treatment was performed, the haze change rate was small. Moreover, the difference (anisotropy) of the dimensional change by the weaving direction was small in the transparent composite substrate obtained in each Example. Furthermore, the gas barrier properties were relatively good. It was also recognized that the wear resistance was high. Therefore, it became clear that the above characteristics are satisfied by optimizing the relationship between Tm and Td.
- the transparent composite substrate obtained in each comparative example contained a large haze. Moreover, the thing whose haze changes a lot with moisture treatment was also included. Furthermore, it has been clarified that the transparent composite substrates obtained in the respective comparative examples are rapidly deteriorated by performing an accelerated test such as moisture treatment even if the haze is small immediately after production. The reason for this is that when the refractive index difference of the glass cloth is large, the deterioration rate with respect to moisture is remarkably high, which causes a change in haze.
- the transparent composite substrates obtained in the respective comparative examples included those having a large difference in dimensional change depending on the weaving direction, and also included those having a low gas barrier property and surface wear resistance.
- the difference in refractive index of the glass cloth in the composite layer is 0.008 or less, and a gas barrier layer made of an inorganic material is provided, and the 5% weight reduction temperature of the main component contained in the resin material
- the transparent composite substrate obtained in each example had a small haze, and even when the moisture treatment was performed, the haze change rate was small.
- the transparent composite substrate obtained in each Example had a small anisotropy of dimensional change depending on the weaving direction.
- the gas barrier properties were relatively good. It was also found that the wear resistance can be improved by optimizing the abundance ratio of oxygen atoms and nitrogen atoms in the silicon compound constituting the gas barrier layer. Therefore, it became clear that the transparent composite substrate obtained in each example was resistant to rubbing and the like and was excellent in surface wear resistance.
- the transparent composite substrate obtained in each comparative example contained a large haze. Moreover, the thing whose haze changes a lot with moisture treatment was also included. Furthermore, it has been clarified that the transparent composite substrates obtained in the respective comparative examples are rapidly deteriorated by performing an accelerated test such as moisture treatment even if the haze is small immediately after production. The reason for this is that when the refractive index difference of the glass cloth is large, the deterioration rate with respect to moisture is remarkably high, which causes a change in haze.
- the transparent composite substrates obtained in the respective comparative examples included those having a large difference in dimensional change depending on the weaving direction, and also included those having a low gas barrier property and surface wear resistance.
- the difference in the refractive index of the glass cloth in the composite layer is 0.008 or less, and the water vapor permeability measured based on the method defined in JIS K 7129 B of the transparent composite substrate is 0. 1 [g / m 2 / day / 40 ° C., 90% RH] or less, it became clear that the optical properties of the transparent composite substrate can be maintained well over a long period even under harsh environments. .
- the glass fiber assembly itself has a composite layer including a glass fabric composed of a glass fiber aggregate and a resin material impregnated in the glass fabric, and the glass fiber aggregate itself has a refractive index variation.
- the difference between the maximum value and the minimum value of the refractive index is 0.008 or less, thereby providing a transparent composite substrate having excellent optical characteristics and a highly reliable display element substrate including the transparent composite substrate. Can do. Therefore, the present invention has industrial applicability.
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Abstract
Description
しかしながら、従来のガラス繊維複合樹脂シートは、プリント基板用途に特化して最適化されてきたため、上述したような用途に適した光学特性を備えていないという問題がある。
(1) ガラス繊維の集合体で構成されたガラス布帛と、前記ガラス布帛に含浸された樹脂材料とを含む複合層を有し、
前記ガラス繊維の集合体自体に屈折率のバラつきが存在し、その屈折率の最大値と最小値との差が0.008以下であることを特徴とする透明複合基板。
単位幅当たりの前記第2ガラス繊維束の断面において前記ガラス繊維が占める第2割合に対する前記単位幅当たりの前記第1ガラス繊維束の断面において前記ガラス繊維の占める第1割合の比は、1.04以上1.40以下である上記(1)に記載の透明複合基板。
前記少なくとも1本の第1ガラス繊維束は、複数本の前記第1ガラス繊維束を含み、前記少なくとも1本の第2ガラス繊維束は、複数本の前記第2ガラス繊維束を含み、
前記単位幅当たりの前記第2ガラス繊維束の本数に対する前記単位幅当たりの前記第1ガラス繊維束の本数の比は、1.02以上1.18以下である上記(2)に記載の透明複合基板。
また、少なくとも透明性およびガスバリア性を備える表面層を複合層上に設けることにより、複合層の光学特性の経時的な低下を抑制することができるので、透明複合基板の光学特性を長期にわたって維持することができる。
また、本発明によれば、上記のような透明複合基板を備えたことにより、信頼性の高い表示素子基板が得られる。
本発明の透明複合基板は、ガラス繊維の集合体で構成されたガラス布帛と、このガラス布帛に含浸された樹脂材料とを含む複合層を有している。そして、本発明の透明複合基板は、ガラス繊維の集合体自体に屈折率のバラつきが存在し、その屈折率の最大値と最小値との差が0.008以下であることに特徴を有する。
本発明の透明複合基板は、複合層中に含まれるガラス布帛の屈折率を最適化することにより、均一で優れた光学特性を維持し得るものとなる。
まず、本発明の透明複合基板の実施形態について説明する。
図1は、本発明の透明複合基板の実施形態に係るガラスクロスを示す平面図、図2は、本発明の透明複合基板の実施形態を示す断面図である。
本発明に用いられるガラスクロス2としては、ガラス繊維を単に束ねたものの他、ガラス繊維を含む織布や不織布等の布帛(ガラス繊維の集合体)が挙げられる。図1では、ガラスクロス2が織布である場合を例に図示している。図1に示すガラスクロス2は、縦方向ガラスヤーン(経糸)2aおよび横方向ガラスヤーン(緯糸)2bで構成されており、縦方向ガラスヤーン2aと横方向ガラスヤーン2bとは略直交している。ガラスクロス2の織組織としては、図1に示す平織りの他、ななこ織り、朱子織り、綾織り等が挙げられる。
なお、ガラスクロス2における屈折率の最大値と最小値との差の下限値は、特に限定されないが、0.0001以上であるのが好ましく、0.0005以上であるのがより好ましい。上記範囲内であれば、ガラスクロス2の生産性が向上する。
なお、本明細書において、上記の「単位幅」とは、ガラス繊維束の長手方向(長さ方向)にほぼ垂直な方向における1インチ幅を言う。
本発明に用いられる樹脂材料3には、例えば、エポキシ系樹脂、オキセタン系樹脂、イソシアネート系樹脂、アクリレート系樹脂、オレフィン系樹脂、シクロオレフィン系樹脂、ジアリルフタレート系樹脂、ポリカーボネート系樹脂、ジアリルカーボネート系樹脂、ウレタン系樹脂、メラミン系樹脂、ポリイミド系樹脂、芳香族ポリアミド系樹脂、ポリスチレン系樹脂、ポリフェニレン系樹脂、ポリスルホン系樹脂、ポリフェニレンオキサイド系樹脂、シルセスキオキサン系化合物等が挙げられる。これらの中でも、樹脂材料3には、好ましくはエポキシ樹脂またはアクリル樹脂(特に、脂環式エポキシ樹脂または脂環式アクリル樹脂)が用いられる。
なお、樹脂材料3は、脂環式エポキシ樹脂が主成分であるものが好ましい。本発明において主成分とは、樹脂材料3の50質量%超を占める成分のことをいい、樹脂材料3における脂環式エポキシ樹脂の含有率は70質量%以上であるのが好ましく、80質量%以上であるのがより好ましい。
グリシジル型エポキシ樹脂としては、例えば、グリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂等が挙げられる。
このようなカルド構造を有するグリシジル型エポキシ樹脂としては、例えば、オンコートEXシリーズ(長瀬産業社製)、オグソール(大阪ガスケミカル社製)等が挙げられる。
この場合、シルセスキオキサン系化合物の添加量は、脂環式エポキシ樹脂100質量部に対して、1~20質量部程度であるのが好ましく、2~15質量部程度であるのがより好ましい。
また、樹脂材料3の屈折率は、ガラスクロス2の平均屈折率にできるだけ近い方がよく、実質的に同一の屈折率であるのが好ましい。具体的には、両者の屈折率差は0.01以下であるのが好ましく、0.005以下であるのがより好ましい。これにより、光透過性の高い透明複合基板1が得られる。
透明複合基板1は、樹脂材料3中において上記のもの以外にフィラー等を含んでいてもよい。
無機系ガラス材料としては、前述したガラスクロスの構成材料と同様のものが用いられる。
なお、フィラーの直径は100nm以下であるのが好ましい。このようなフィラーは、界面での散乱が生じ難いので、樹脂材料3中に多量のフィラーが分散した場合でも、透明複合基板1の透明性を比較的高く維持することができる。
複合層4上には、透明性およびガスバリア性を備えるガスバリア層5が設けられている。かかるガスバリア層5を複合層4上に設けることにより、大気中の酸素、水蒸気等のガスがガラスクロス2に達するのを防止または抑制することができる。このため、これらのガスが長期にわたってガラスクロス2に作用して悪影響を及ぼし、ガラスクロス2の屈折率が不均一となることを阻止することができる。このため、光学特性の経時的な低下が防止された透明複合基板1、すなわち、より長期にわたって優れた光学特性を有する透明複合基板1が得られる。
なお、ガスバリア層(表面層)5は、少なくとも透明性およびガスバリア性を有していればよく、それ以外の機能を有していてもよい。
以上のような透明複合基板1の波長400nmにおける全光線透過率は、70%以上であるのが好ましく、より好ましくは75%以上であり、さらに好ましくは78%以上である。波長400nmにおける全光線透過率が下限値未満であると、透明複合基板1を用いた表示素子における表示性能が十分でないおそれがある。
また、透明複合基板1の平均厚さは、特に限定されないが、40~200μm程度であるのが好ましく、50~100μm程度であるのがより好ましい。
また、透明複合基板1は、JIS K 7126 Bに規定の酸素透過度が0.1[cm3/m2/day/1atm/23℃]以下であるのが好ましい。酸素透過度が前記範囲内にあると、透明複合基板1を表示素子基板として用いた場合、酸化による表示素子の劣化を抑制し、表示素子の高い信頼性を長期にわたって維持することができる。
透明複合基板1は、例えば、液晶表示素子用基板、有機EL素子用基板、カラーフィルター用基板、TFT用基板、電子ペーパー用基板、タッチパネル用基板のような各種表示素子基板(本発明の表示素子基板)に適用され、その他、太陽電池用基板等にも適用される。
かかる機能層としては、例えば、酸化インジウム、酸化スズ、スズ-インジウム合金の酸化物等で構成される透明導電層、金、銀、パラジウムまたはこれらの合金等で構成される金属導電層、エポキシ樹脂、アクリル樹脂等で構成される平滑層、ゴム状またはゲル状のシリコーン硬化物、ポリウレタン、エポキシ樹脂、アクリル樹脂、ポリエチレン、ポリプロピレン、ポリスチレン、塩化ビニル樹脂、ポリアミド樹脂、ポリカーボネート樹脂、ポリアセタール樹脂、ポリエーテルスルフォン、ポリスルフォン等で構成される衝撃緩衝層等が挙げられる。
また、本発明の表示素子基板は、元々ガラス基板よりも落球試験による耐衝撃性が優れているが、上記のような衝撃緩衝層を設けることにより、さらに耐衝撃性が向上する。
透明複合基板1は、前述したようにガラスクロス2に未硬化の樹脂材料3を含浸させ、この状態で板状に成形(整形)された後、樹脂材料3を硬化させてなるものである。
かかる硬化剤としては、酸無水物、脂肪族アミン等の架橋剤、カチオン系硬化剤、アニオン系硬化剤等が挙げられ、これらの硬化剤の1種または2種以上の混合物が用いられる。
また、樹脂材料3(樹脂モノマー)の種類によっては、イルガキュアシリーズ(チバ・ジャパン株式会社製)のような光ラジカル硬化剤も用いられる。
光硬化させる場合は、樹脂材料3の硬化反応を促進させるため、必要に応じて、増感剤、酸増殖剤等も併せて用いることができる。
酸化防止剤としては、例えば、フェノール系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤等が用いられるが、特にヒンダードフェノール系酸化防止剤が好ましく用いられる。
ヒンダードフェノール系酸化防止剤としては、例えば、BHT、2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)等が挙げられる。
リン系酸化防止剤としては、例えば、トリデシルホスファイト、ジフェニルデシルホスファイト等が挙げられる。
樹脂ワニスは、以上のような成分を混合して得られる。
その後、必要に応じて、樹脂ワニスに脱泡処理を施す。さらには、必要に応じて、樹脂ワニスを乾燥させる。
加熱条件としては、好ましくは加熱温度が50~300℃程度、加熱時間が0.5~10時間程度とされ、より好ましくは加熱温度が170~270℃程度、加熱時間が1~5時間程度とされる。
付与される光エネルギー量(積算光量)は、5mJ/cm2以上1000mJ/cm2以下であるのが好ましく、10mJ/cm2以上800mJ/cm2以下であるのがより好ましい。積算光量が前記範囲内であれば、ムラなく均一かつ確実に樹脂材料3を硬化させることができる。
ガスバリア層5の成膜には、例えば、ゾル・ゲル法のような各種液相成膜法、真空蒸着法、イオンプレーティング法、スパッタリング法、CVD法のような各種気相成膜法等が用いられる。このうち、気相成膜法が好ましく用いられ、スパッタリング法またはCVD法がより好ましく用いられる。
以上のようにして透明複合基板1が得られる。
また、前記実施形態では、ガラスクロス2は、複数本の縦方向ガラスヤーン2aと複数本の横方向ガラスヤーン2bとを織り込んでなる織布で構成されているが、1本の縦方向ガラスヤーン2aと複数本の横方向ガラスヤーン2bとを織り込んでなる織布、複数本の縦方向ガラスヤーン2aと1本の横方向ガラスヤーン2bとを織り込んでなる織布、1本の縦方向ガラスヤーン2aと1本の横方向ガラスヤーン2bとを織り込んでなる織布であってもよい。
また、本発明の透明複合基板は、表面層を有していなくてもよい。
1.透明複合基板の製造
(実施例1A)
(1)ガラスクロスの用意
まず、ガラスクロスとして、100mm四方のNEガラス系ガラスクロス(平均厚さ95μm、平均線径9μm)を用意した。これをベンジルアルコール(屈折率1.54)に浸漬した後、そのベンジルアルコールにアセトキシエトキシエタン(屈折率1.406)を少量ずつ添加した。そして、ベンジルアルコールの屈折率を変化させる度に、ガラスクロスを蛍光灯にかざし、ガラスクロスが実質的に透明になったか否かを確認した。また、ガラスクロスに実質的に透明になった部分が現れた際の混合液の屈折率を測定した。
また、ガラスクロスのガラス繊維束の撚り数は、MD方向1インチ長さ当たり1.0、TD方向1インチ長さ当たり1.0であった。
次に、樹脂モノマーとして、下記化学式(1)の構造を有し、式中の「-X-」が「-CH(CH3)-」である脂環式エポキシ樹脂(ダイセル化学工業株式会社製、E-DOA、Tg:>250℃)およびシルセスキオキサン系オキセタン(東亞合成株式会社製、OX-SQ-H)と、硬化剤として、光カチオン重合開始剤(株式会社ADEKA製、SP-170)と、溶剤として、メチルイソブチルケトンとを、表1に示す割合で混合し、樹脂ワニスを調製した。なお、E-DOAの架橋後の屈折率は1.513であり、OX-SQ-Hの架橋後の屈折率は1.47であった。
まず、離型処理されたガラス板に樹脂ワニスを塗布して液膜を形成した後、同じく離型処理されたガラス板をその液膜の上に載せ、液膜を2枚のガラス板で挟み込んだ。なお、この際、ガラス板の間には、四辺に厚み200μmのスペーサーを配置した。そして、この液膜に対して高圧水銀灯にて1100mJ/cm2の紫外線を照射した後、250℃で2時間加熱することにより、厚さ200μmの樹脂フィルム(マトリックス樹脂)を得た。その後、アッベ屈折計(株式会社アタゴ製DR-A1)を用いて、この樹脂フィルムの589nmにおける屈折率を測定した。その結果を表1に示す。
次いで、得られた樹脂ワニスをガラスクロスに含浸させ、その後、脱泡処理を施し、さらに樹脂ワニスを乾燥させた。
上記化学式(1)の構造を有し、式中の「-X-」が「-C(CH3)2-」である脂環式エポキシ樹脂(ダイセル化学工業株式会社製、E-DOA、Tg:>250℃)100質量部と、光カチオン重合開始剤(株式会社ADEKA製、SP-170)1質量部とを混合し、被覆材料を調製した。次いで、バーコーターにより複合層の両面に塗布した後、高圧水銀灯にて1100mJ/cm2の紫外線を照射した。さらに、250℃で2時間加熱することにより、平均厚さ5μmの平滑層を成膜した。
次いで、平滑層を成膜した複合層をRFスパッタリング装置のチャンバー内に載置した。そして、チャンバー内を減圧した後、Arガスを0.5Pa、O2ガスを0.005Paの分圧で導入した。続いて、チャンバー内に載置されたSi3N4ターゲットと複合層との間に0.3kWのRF電力を印加して放電させた。
製造条件を表1および2に示すように変更した以外は、それぞれ実施例1Aと同様にして透明複合基板を得た。なお、複合層の平均厚さは表1および2に示す。
また、実施例2Aにおけるガスバリア層の平均厚さは50nm、実施例9Aにおけるガスバリア層の平均厚さは250nmであった。
実施例1Bでは、複合層におけるガラスクロスの含有量を57質量%とした以外は、実施例1Aと同様にして透明複合基板を得た。また、実施例2B~10Bおよび比較例1B~6Bでは、製造条件を表3および4に示すように変更した以外は、それぞれ実施例1Bと同様にして透明複合基板を得た。なお、複合層の平均厚さは、表3および4に示す。
また、実施例3B、7Bおよび比較例2B、5B、6Bでは、樹脂ワニスを含浸させたガラスクロスを、離型処理を施した2枚のガラス板に挟み込み、80℃で2時間加熱後、250℃でさらに2時間加熱することにより複合層を得た。
また、実施例2Bにおけるガスバリア層の平均厚さは50nm、実施例8Bにおけるガスバリア層の平均厚さは250nmであった。
実施例1Cでは、複合層におけるガラスクロスの含有量を60質量%とした以外は、実施例1Aと同様にして透明複合基板を得た。また、実施例2C~10Cおよび比較例1C~6Cでは、製造条件を表5および6に示すように変更した以外は、それぞれ実施例1Cと同様にして透明複合基板を得た。なお、複合層の平均厚さは、表5および6に示す。
また、実施例3C、7Cおよび比較例2C、5C、6Cでは、樹脂ワニスを含浸させたガラスクロスを、離型処理を施した2枚のガラス板に挟み込み、80℃で2時間加熱後、250℃でさらに2時間加熱することにより複合層を得た。
また、実施例2Cにおけるガスバリア層の平均厚さは50nm、実施例8Cにおけるガスバリア層の平均厚さは250nmであった。
実施例1Dでは、複合層におけるガラスクロスの含有量を65質量%とした以外は、実施例1Aと同様にして透明複合基板を得た。また、実施例2D~9Dおよび比較例1D~6Dでは、製造条件を表7および8に示すように変更した以外は、それぞれ実施例1Dと同様にして透明複合基板を得た。なお、複合層の平均厚さは表7および8に示す。
また、実施例3D、7Dおよび比較例2D、5D、6Dでは、樹脂ワニスを含浸させたガラスクロスを、離型処理を施した2枚のガラス板に挟み込み、80℃で2時間加熱後、250℃でさらに2時間加熱することにより複合層を得た。
また、実施例2Dにおけるガスバリア層の平均厚さは50nm、実施例8Dにおけるガスバリア層の平均厚さは250nmであった。
比較例7Dでは、ガラスクロスを使用しない以外は、実施例1Dと同様の材料を使用し、樹脂フィルムを作製した。なお、製造方法は、調整した樹脂ワニスを、離型処理されたガラス板に塗布してその樹脂組成物の液膜を形成した後、同じく離型処理されたガラス板をその液膜の上に乗せ、液膜をガラス板で挟み込んだ。なお、この際、ガラス板の間には、四辺に厚み100μmのスペーサ-を配置した。そして、この液膜に高圧水銀灯にて1100mJ/cm2の紫外線を照射した後、250℃で2時間加熱することにより、平均厚さ105μmの樹脂フィルムを得た。
2.1 湿度による寸法変化の評価
各実施例および各比較例で得られた透明複合基板から100mm×100mmのサンプルを切り出し、非接触画像測定機(株式会社ミツトヨ製、S-QVH606)にて、25℃/50%RHの環境下でサンプルの四辺の寸法を測定した。次いで、25℃/90%RH/24時間の条件でサンプルを処理後、同じく四辺の寸法を測定し、吸湿処理に伴うサンプルの寸法変化を測定した。なお、寸法変化の測定は、ガラスクロスの織組織にならい、MD方向とTD方向のそれぞれについて行った。以上の測定結果を表1~8に示す。
各実施例および各比較例で得られた透明複合基板について、100mm×100mmのサンプルを切り出し、サンプルの均一に分散した9点を選択し、各点について、それぞれ濁度計(日本電色工業製、NDH2000)を用いて、25℃/50%RHの環境下、JIS K 7136に準拠した条件でヘイズを測定した。測定されたヘイズの平均値を表1~表8に示す。
次いで、25℃/90%RH/24時間の条件でサンプルを処理後、2.2に記載された測定点と同じ部分のヘイズを2.2記載の方法で測定し、2.2で測定したヘイズとの差を求めた。
次いで、2.2で求めたヘイズに対する、求めたヘイズ差の割合を変化率として算出し、これを以下に示す評価基準にしたがって評価した。
A:0.5%未満
B:0.5%以上1%未満
C:1%以上2%未満
D:2.0%以上
表1および2にはヘイズ変化率の評価結果を示し、表3~8にはヘイズ変化量を示す。
各実施例および各比較例で得られた透明複合基板について、JIS K 7129 Bに規定の水蒸気透過度およびJIS K 7126 Bに規定の酸素透過度を測定した。 なお、測定条件は、表1~8に示す通りである。
各実施例および各比較例で得られた透明複合基板について、JIS K 5600-5-4に規定の塗膜の機械的性質の試験方法(引っかき硬度(鉛筆法))に準拠して耐摩耗性を評価した。なお、耐摩耗性の評価は、測定された強度を以下の評価基準にしたがって評価した。
A:引っかき硬度が2Hより硬い
B:引っかき硬度がFまたはHである
C:引っかき硬度がBより軟らかい
以上の評価結果を表1~8に示す。
各実施例1D~9Dおよび各比較例1D~6Dで得られた透明複合基板、および、比較例7Dで得られた樹脂フィルムから、それぞれサンプルを切り出し、このサンプルを熱応力歪測定装置(セイコー電子株式会社製、TMA/SS120C型)にセットした。次に、窒素雰囲気下、無荷重で雰囲気温度を30℃から150℃まで5℃/分の昇温速度で上昇させた後、一旦0℃まで冷却した。そして、サンプルに5gの荷重をかけて、サンプルを引っ張りながら、雰囲気温度を30℃から150℃まで5℃/分の昇温速度で上昇させ、平均線膨張係数の測定を行った。なお、ここでは、サンプルのMD方向の線膨張係数を測定した。
この測定結果を表7および8に示す。
Claims (15)
- ガラス繊維の集合体で構成されたガラス布帛と、前記ガラス布帛に含浸された樹脂材料とを含む複合層を有し、
前記ガラス繊維の集合体自体に屈折率のバラつきが存在し、その屈折率の最大値と最小値との差が0.008以下であることを特徴とする透明複合基板。 - 前記ガラス布帛は、複数の前記ガラス繊維を束ねてなる少なくとも1本の第1ガラス繊維束と、複数の前記ガラス繊維を束ねてなる少なくとも1本の第2ガラス繊維束とを織り込んでなるガラス織布であり、
単位幅当たりの前記第2ガラス繊維束の断面において前記ガラス繊維が占める第2割合に対する前記単位幅当たりの前記第1ガラス繊維束の断面において前記ガラス繊維の占める第1割合の比は、1.04以上1.40以下である請求項1に記載の透明複合基板。 - 前記第1割合と前記第2割合とは、実質的に等しく、
前記少なくとも1本の第1ガラス繊維束は、複数本の前記第1ガラス繊維束を含み、前記少なくとも1本の第2ガラス繊維束は、複数本の前記第2ガラス繊維束を含み、
前記単位幅当たりの前記第2ガラス繊維束の本数に対する前記単位幅当たりの前記第1ガラス繊維束の本数の比は、1.02以上1.18以下である請求項2に記載の透明複合基板。 - 前記第1ガラス繊維束および前記第2ガラス繊維束の撚り数は、それぞれ0.2~2.0/インチ以下である請求項2に記載の透明複合基板。
- 前記樹脂材料は、脂環式エポキシ樹脂または脂環式アクリル樹脂を主成分とする請求項1に記載の透明複合基板。
- 前記樹脂材料は、脂環式エポキシ樹脂を主成分とし、さらにシルセスキオキサン系化合物を含む請求項1に記載の透明複合基板。
- さらに、前記複合層上に設けられ、少なくとも透明性およびガスバリア性を備える表面層を有する請求項1に記載の透明複合基板。
- 前記表面層は、無機材料で構成されている請求項7に記載の透明複合基板。
- 前記表面層の前記無機材料の融点をTm[℃]とし、前記複合層の前記樹脂材料に含まれる主成分の5%重量減少温度をTd[℃]としたとき、1200<(Tm-Td)<1400の関係を満足する請求項8に記載の透明複合基板。
- 前記無機材料は、SiOxNyで表され、xおよびyが1≦x≦2および0≦y≦1の関係を満足するケイ素化合物を含む請求項8に記載の透明複合基板。
- 前記ケイ素化合物において、xおよびyがy>0かつ0.3<x/(x+y)≦1の関係を満足する請求項10に記載の透明複合基板。
- さらに、前記複合層と前記表面層との間に設けられ、樹脂材料で構成された中間層を有する請求項7に記載の透明複合基板。
- 当該透明複合基板のJIS K 7129 Bに規定された方法に基づいて測定される水蒸気透過度が、0.1[g/m2/day/40℃、90%RH]以下である請求項1に記載の透明複合基板。
- 当該透明複合基板の30~150℃での平均線膨張係数が、40ppm以下である請求項1に記載の透明複合基板。
- 請求項1に記載の透明複合基板を備えることを特徴とする表示素子基板。
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JP2010146831A (ja) * | 2008-12-18 | 2010-07-01 | Hiraoka & Co Ltd | 曲面発光性に優れた可撓性面発光シート |
Cited By (1)
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CN104139571A (zh) * | 2013-05-07 | 2014-11-12 | 徐林波 | 一种可折弯的安全复合玻璃 |
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KR20140066772A (ko) | 2014-06-02 |
CN103842172A (zh) | 2014-06-04 |
TW201320836A (zh) | 2013-05-16 |
US20140242865A1 (en) | 2014-08-28 |
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