TW201202336A - Resin composition, transparent composite substrate and display device substrate - Google Patents

Abstract

To provide a resin composition which can be used for manufacturing a transparent composite substrate in which deterioration of an optical anisotropy caused by an internal stress, which is evaluated by a reliability test such as a hyperthermic treatment, is suppressed, the transparent composite substrate manufactured by using the resin composition and a display device substrate. A resin composition of the present invention can be used for manufacturing a transparent composite substrate when the resin composition is cured to be formed into a composite substrate. It is preferred that the resin composition includes an epoxy resin, preferably a combination of a glycidyl-based epoxy resin and an alicyclic epoxy resin, a glass filler and a hindered phenol-based antioxidant. Further, a glass fiber cloth is preferably used for the glass filler, Furthermore, it is also preferred that the hindered phenol-based antioxidant is used together with a phosphorus-based antioxidant.

Description

201202336 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a resin composition, a transparent composite substrate, and a display element substrate. ... [Prior Art] A liquid crystal display element or a substrate (display element substrate) used in a display device for a light EL display device is widely used as a color plate substrate, a solar cell substrate, or the like. However, since the glass plate has the disadvantages of being cracked, not bendable, and not suitable for weight reduction, in recent years, a substrate made of a plastic material has been studied as a substitute material. For example, the transparent resin substrate for a liquid crystal display element described in the patent documents 1 and 2 is composed of a cured body obtained by curing an epoxy resin composition containing an epoxy resin, an acid anhydride-based curing agent, and a curing catalyst. By. However, these plastic materials used in the past for replacing glass have a larger coefficient of linear expansion than glass plates. Therefore, in particular, when the active matrix display element substrate is used, the warpage of the substrate and the consequent disconnection of the wiring are caused in this manufacturing step. Therefore, it is difficult to use in such applications. Therefore, in order to lower the coefficient of linear expansion, an inorganic filler such as glass frit or glass fiber is blended in a resin material to composite the material. However, since the refractive index of the resin material and the inorganic filler are different, when the light penetrating the resin material is scattered at the interface between the resin material and the inorganic filler, the transparency of the composite material is impaired. In order to solve the above problems, Patent Document 3 discloses a light-transmitting epoxy resin composition comprising a filler having substantially the same refractive index as an epoxy resin obtained by curing an acid anhydride. In such a resin composition 4/31 201202336, it is attempted to make the composite transparent by lowering the refractive index difference between the oxide resin and the filler. In the composite material as described above, even if the transparency is improved, optical anisotropy due to the structure of the composite material is generated. Specifically, since the thermal expansion coefficient of the resin material and the filler (filler) is different, "there is a slight internal stress in the interface between the two, and the molecular orientation of the resin material occurs, thereby generating optical Anisotropy. Such an optical anisotropy is difficult to achieve a clear display when a composite material is used to fabricate, for example, a display element substrate because the light penetrating the composite material causes a phase difference. In particular, in recent years, optical anisotropy in composite enamel has become a more important characteristic due to the progress of the refinement of display pixels. For example, in the display substrate, the reliability test was carried out under the harsh environment of the heat treatment, and the durability against the severe environment was obtained. Iron, but there is a problem of deterioration in the first test of the reliability test. [J] Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] The object of the present invention is to provide a tree core material, which is a material of the resin composition, which is provided with a transparent substrate, a plate. Providing a reliable composite substrate with a deterioration of optical anisotropy (〇pticalanis〇tr〇py) due to internal stress caused by the reliable 5/31 201202336. [Means for Solving the Problem] The object is achieved by the inventions of the following (1) to (12): (1) A resin composition' is a tree 爿曰 composition used in the manufacture of a transparent composite substrate The article is characterized by comprising an epoxy resin, a glass filler, and a hindered phenol antioxidant. (2) The resin composition of the above (丨), wherein the δ of the hindered phenol-based antioxidant wj is 质量·〇 1% by mass or more and 5% by mass or less. (3) The resin composition according to (1) or (2) above, wherein the melting point of the antioxidant group is 1 Å. (4) The resin composition according to any one of the above (1) to (3) wherein the hindered phenol-based antioxidant has a neopentane structure in the molecular structure. The resin composition according to any one of (1) to (4) further comprising a ruthenium-containing antioxidant in a ratio of from 3 to 3 parts by mass based on 100 parts by mass of the hindered phenol-based antioxidant. (6) The resin composition according to any one of the above (1) to (5), wherein the epoxy resin is an alicyclic epoxy resin and a glycidyl epoxy resin. (7) as described above (6) The resin composition of the present invention, wherein the alicyclic epoxy resin comprises an alicyclic epoxy resin represented by the following chemical formula (1) and a lipid-type poplar tree represented by the following chemical formula (2) At least one of them, 6/31 201202336

p Ο) 〇

(2) [In the above formula [2], -X- represents ·〇_, -S-, -SO-, -S02-, _CH _, -CH(CH3)- 2-' or -C(CH3)2 -]. (8) The resin composition according to the above (6) or (7), wherein the content of the glycidyl type epoxy resin is from 0.5 to 丨〇 by mass based on 100 parts by mass of the alicyclic epoxy resin . (9) The resin composition according to any one of (1) to (8) above, wherein the glass filler is a glass fiber cloth. (10) The resin composition according to any one of the above (1) to (9), wherein the resin composition is substantially at least two times after the temperature of TC is heated for 丨 minutes to detect the antioxidant or (1) A transparent composite substrate characterized by being a cured product of the resin composition according to any one of the above (1). (12) A display element substrate, the characteristics of which are The composite substrate is as described above. [Effect of the Invention] According to the present invention, a resin composition can be obtained, and the resin can provide a transparent composite substrate, and the _ lipid group can be reduced when it is hardened into a substrate. Optical entanglement from internal stress (4), providing a transparent composite substrate that can replace the glass substrate. As a display substrate, the long-term reliability of the transparent composite substrate is necessary. Therefore, it is necessary to seek In the reliability test, there is no or a small number of transparent composite substrates having deteriorated characteristics. According to the present invention, it is possible to obtain a transparent composite substrate which is less susceptible to deterioration in photonic anisotropy in reliability, and which is small in optical properties. [Brief Description of the Invention] [Embodiment] The resin composition, the transparent composite substrate, and the display element substrate of the present invention will be described in detail with reference to preferred embodiments shown in the drawings. The resin composition of the invention is formed by forming and hardening the composite of the invention, which comprises a Wei resin, a glass-filled age-resistant antioxidant, and the transparent composite substrate of the invention is composed of the above resin composition. In the shape and hardening, it has a small optical anisotropy, and is a plate: and the display element substrate of the present invention includes the above-mentioned transparent composite plate, and the optical anisotropy is small and can be clearly displayed. Soil <Resin Composition> First, the description of the tree of the present invention is explained. The glass filler is a resin composition comprising a ring and a hindered phenol-based antioxidant. (Epoxy resin) The epoxy resin can be used as a resin, the double IF type epoxy resin, the second type A compound, the product having the dicyclopentane quinone bismuth, or the oxygen of the nitrogen-based iso-cyanide. Ethylene wax with a triglycidyl milk tree, a skeleton with Cardo (a combination of various benzene rings and 8/31 201202336), an epoxy resin with polycaxane structure, and an alicyclic polyfunctional An epoxy resin, an alicyclic type oxy-resin having a hydrogenated double-branched skeleton, an alicyclic resin having a gasified double-A skeleton, a recording resin, or the like may be used, and one or a mixture of two or more of these epoxy resins may be used. 'The above epoxy resins can be roughly classified into: glycidyl ether type epoxy resins containing glycidyl groups and ether bonds, glycidol type epoxy resins containing glycidyl groups and ester bonds, glycidyl groups and amine groups. a glycidyl type epoxy resin of a glycidylamine type epoxy resin; and an alicyclic epoxy resin having a lipid oxime type epoxy group, but in the present invention, in particular, the use of a molecule like a ring-like ring The thief's rotary epoxy resin is preferred. Further, it is preferable to use a hydrogenated biphenyl type epoxy ring structure represented by the following chemical formula (1) or an alicyclic epoxy structure represented by the following chemical formula (2).

[In the above formula [2], -X- represents _〇_, each, _S0_, _s〇 -CH(CH3)-2_, or -C(CH.3)2_]. Such an alicyclic epoxy resin can be hardened at a low temperature because of its excellent hardenability at low temperatures. By this, it is not necessary to set the resin composition to be hardened at a high temperature, and therefore, the amount of change due to temperature can be suppressed even if the resin is composed of 2 to 1 room temperature. As a result, the transparent composite substrate obtained by using the resin composition of the present invention can suppress the generation of thermal stress accompanying the change of the degree of 19/31 201202336, and can suppress the optical anisotropy such as the above-mentioned alicyclic epoxy. Resin, because of the expansion of the material after hardening, therefore, in the preparation of the substrate containing the ring of light oxygen (4), the interface stress in the interface between the glass filler and the epoxy tree is almost the temperature of the system close to the chamber. temperature. Therefore, the dream is obtained by using the resin composition of ^: to obtain the above-mentioned interface transparent complex &amp; substrate' (10) optical phase of the composite

Moreover, since the coefficient of expansion is low, the deformation of the composite substrate is curved or curved. I. Because of the excellent transparency and stagnation resistance of these alicyclic epoxy resins, it is helpful for the excellent and resistant to the high-tech composite substrate and the 'inventive tree of the present invention, epoxy It is preferred that the resin is used in combination with a fat-based type of oxyhydrogen glycerin type epoxy. Thereby, the permeability of the oxygen resin can be confirmed, and the compatibility of the epoxy glycerol with the antioxidant can be improved. As a result, a translucent substrate having high transmittance and low optical anisotropy was obtained. Further, since the oxidation resistance of the epoxy tree is improved, the antioxidant resistance can be suppressed, and the heat resistance of the transparent composite substrate can also be improved. - At this time, the amount of &amp; water Gan's type, the amount of oxygen resin added, relative to the alicyclic synthetic grease HK) parts by mass, preferably from about G to 1G f parts, to]

= 5 parts by weight left red. Thereby, it is possible to achieve a high degree of compatibility between light transmission and optical anisotropy. S It is also preferable to use a glycidyl type epoxy resin having a poison of c in the use of the glycidyl type epoxy resin. That is, by adding a glycidyl type epoxy resin having an eardG structure to the alicyclic ring=resin to form a plurality of aromatic rings derived from a bisaryl (tetra) frame, 10/31 201202336 can suppress the transparent composite substrate. The optical anisotropy can further improve transparency and heat resistance. Examples of the glycidyl type epoxy resin having a cardo structure include 〇n-C〇at EX series (manufactured by Nagase Industrial Co., Ltd.), 〇gs〇丨 (manufactured by Osaka Gas Chemical Co., Ltd.), and the like. (Hardener) The resin composition of the present invention may contain a hardener of an epoxy resin. Examples of the hardening agent include (IV) anthracene such as an acid anhydride or an aliphatic amine, a cationic hardening agent, and an anionic curing agent. These may be used, or a mixture of two or more thereof may be used. Among the X 4 , a cationic hardener is particularly preferably used. The use of a cationic hardening agent can harden the epoxy resin at a lower temperature. Therefore, the resin composition can be set at a high temperature in a more stable manner, and the thermal stress of the coating can be used. Production is inhibited. Thus, light can be obtained;:: A transparent composite substrate having low lusity. ΐ ΐ ' ' By using a cationic hardener, heat resistance can be obtained (for example, a high-ionic substrate with a high ion content. This can be considered to be a hardening of a nuclear oxygen resin by using a positive electrode. The cation-eliminating agent with increased cross-linking density can be exemplified by: releasing the priming agent by heating; hard:; hardening agent, _ 払 払 払 由 化 化 由 由 由 由" " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " " "绮 salt, aromatic 201202336 锵 salt, ammonium salt, Ilu chelating agent, tri-negative fossilamine complex, etc. Specific and 5, for example, as the aromatic salt-salting Sanxin chemical industry manufacturing%601 ^S1_80L, ST_]00L, §ρ_66' manufactured by Asahi Kasei Industrial Co., Ltd., or hexafluoroantimonate of Team, etc.; ethyl acetoacetate ethylaluminum diisopropylate (al_inum ethy丨acetoacetate d as aluminum chelating agent)丨is〇pr〇py丨), aluminum tris(acetate ethyl acetate), etc., as a boron trifluoride amine complex can be enumerated The trifluoride pentaethylamine complex, the trifluorocarbon pentazone complex, the Sanhuahua County bite complex, etc. Further, examples of the photocationic hardener include, for example, SP manufactured by Asahi Kasei Industrial Co., Ltd. -ΠΟ, etc. ', such a cationic hardening _ content is not _ (four), but for example, using the upper rail to cut) the ring (10) correction, relative to the epoxy resin 〇〇 mass parts 'm to 5 parts by mass Preferably, it is preferably 5 to 3 parts by mass, and if the content does not reach the above-mentioned τ limit, there is a case where the hardening property is low, and when the above upper limit is exceeded, the transparent composite substrate may be easily broken. When curing the light, a sensitizer, an acid amplifier, or the like for promoting the hardening reaction may be used in combination as needed. (Glass filler) ★ The glass filler is made of an inorganic glass material. A filler (filler) composed of fibers, particles, etc. Specifically, a glass fiber cloth such as glass cloth or glass non-woven fabric; glass fllament; glass fiber stranded (6) chopped strand) Glass beads; glass flakes; broken glass Grinding glass, etc. 'Where' is also a high-strength effect of the linear expansion system and the number of the substrate, so glass fiber fiber and glass fiber cloth are suitable, especially glass fiber 12/31 201202336 cloth is more suitable. Examples of the glass material include E glass, c glass, A glass, S glass, T glass, D glass, NE glass, quartz (glass), low dielectric glass, high dielectric glass, and the like, wherein alkali is used. E glass, S glass, T glass, and N glass, which are easy to obtain ionic impurities such as metal, are preferable, and S glass or T glass having an average linear expansion coefficient of 5 ppm or less in 30 t to 250 t: good. The content of the glass filler is preferably from 90% by mass in the transparent composite substrate, more preferably from 10 to 80% by mass, and is from 3 Å to 70% by mass. /. The amount is even better. When the content of the glass filler is within this range, it is easy to rise and the effect of reducing the linear expansion due to the compositing. Further, if the amount of the glass filler is large, the uniformity of the stress is improved, so that the uniformity of the amount of the resin per unit volume is improved. When the uniformity is improved, the bending of the transparent substrate becomes small. The diameter of the glass fiber fiber and the glass fiber cloth is preferably 100 nm or less. Such a glass fiber fiber and a glass fiber cloth are less likely to cause scattering at the interface due to the difference between the refractive index of the resin and the refractive index of the epoxy resin. Therefore, the transparency of the transparent composite substrate becomes high. Conversely, when the diameter exceeds 丨 00 nm, the difference from the refractive index of the epoxy resin should be considered. In this case, among the glass materials constituting the glass fiber yarn and the glass fiber cloth, those having a refractive index of 丨4 to 丨6 are suitable, and those of 5, 5 to 丨.55 are more suitable. Thereby, a transparent transparent composite Wei having a wide wavelength range can be obtained. ~ &lt; In addition, the average particle diameter of glass fiber strands, glass beads, glass flakes, glass matte powder, ground glass, etc. is preferably 10 Å or less, and more preferably 8 〇〇 or less. 13/31 C. 201202336 (Antioxidant) As a hindered phenolic antioxidant, for example, BHT, 2,2'-methylenebis(4-methyl-6-third-butylene), neopenta Tetrahydrin tetra||3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,3',3",5,5',5"-hexa-t-butyl -α, α', α" - (mesitylene-2,4,6-triyl)trisylphenol, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) Propionate, :l,3,5-tri[(4-tert-butyl-3-hydroxy-2,6-diphenyl)methyl; μ,3,5-triazine-2,4 ,6-(1Η,3Η,5Η)-5,, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2, 4,6-(1 where 31-丨,5-trione, diethylbis[{3,5-bis(],1-didecylethyl)-4-hydroxyphenyl}indenyl]phosphoric acid Calcium, bis(2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-didecylphenyl)ethane, hydrazine, Ν'-hexane-1,6-di One or a mixture of two or more of these may be used as the hindered phenol-based antioxidant such as fluorenyl bis[3-(3,5-di-t-butyl)-4-hydroxyphenyl-propionamide.

Specifically, for example, 1RGANOX 1330, IRGANOX 1010, 丨RGANOX 1076, IRGANOX 3114 (above is manufactured by Ciba Fine Chemical Co., Ltd.); SUMIL1ZER BHT, SUMILIZER BP-101 (above), YOSH1NOX BHT, YOSHINOX 250 , TOTOMOX SS, TOM1NOX TT, YOSHINOX 314, GSY-242 (above AH-Corp.); ADKSTABAO-50, Mark AO-50, ADKSTAB AO-60, ADKSTAB AO-20 (above ADEKA) . The content of the hindered phenol-based antioxidant is preferably 0.01% by mass or more and 5% by mass or less based on the resin composition, and more preferably 5% by mass or less, and more preferably 0.1% by mass or more and 3% by mass or less. It’s better and better. When the content of the antioxidant is within the above range, a transparent composite substrate having low optical anisotropy can be obtained, and a transparent composite having a small deterioration in optical anisotropy even in the reliability test 14/31 201202336 can be obtained. Substrate. Medium ====::=-: One reason for the composite substrate is that the hindered part and the epoxy are listed as the starting point of the elimination or protection of the epoxy resin. Deterioration. Moreover, since the resistance is increased by the _ part =::: j, the virginity is increased, that is, the result is suppressed, and the deterioration of the optical anisotropy is lowered. An optical omnidirectional two and a achievable substrate were obtained even in the reliability test. 〃, f 生...'s small transparent complex and 'blocking material, antioxidant melting point boots are better. If the melting point is better in the upper (4) prevention, it is better to have + P; only when the fat composition is hardened = there is a retaining agent, so that the above optical stability can be improved. Basin; drought-to-the-point melting point of the anti-oxidant, that is, the opposite sex: chemical: penetration = reliability test coffee optical direction 2_ and is;:, == ==, to hindered phenol Seven live and again 丨 _ to 1400 is especially good. If the weight average molecular weight is within the above range, it can be volatile and can ensure the compatibility with Wei. The two sub-system antioxidants even worsened the anisotropy of the Wei (four) filament anisotropy after the reliability test of the heat treatment such as the diameter heat treatment, and the antioxidants were in the molecular structure of the system to have a new 15/31 201202336 It is better to construct a pentylene structure or a hetero-cyanate structure. Since these structures are all three-dimensional or planar enlarged structures, most of the binding sites (e.g., hydroxyl groups) are distributed over a wide area. Therefore, the resistance (the interaction) of the anti-oxidant and the epoxy resin having such a structure is improved, and the state of bonding between the anti-oxidation agent and the epoxy resin can be surely maintained. As a result, when the resin composition is cured, it is possible to prevent the volatilization of the hindered phenol-based antioxidant device or the decrease in the dependence of the transparent composite substrate. Further, the neopentyl structure is preferably contained in the block. The action and effect are more remarkable in the other parts. In addition, as a molecular structure, the oxidizing agent of the Shin-Yuan structure is included, and the following chemical formula (3) = IRGANOX 1010, etc.), f-Bu HO-ί-Βϋ -ch2ch2co〇ch2- Contains differences in molecular structure

C (3) Polycyanate structure 抗 抗 抗 抗 抗 抗 抗 抗 抗 AD AD AD AD AD AD AD AD AD AD 聚 聚 AD 聚 AD AD 抗 AD 抗 AD 抗 抗 AD 抗 下述 AD 下述 抗 下述 下述 下述 AD AD AD AD AD AD AD AD AD AD AD AD AD AD AD AD AD AD ΑΟ-20, etc.) 16/31 201202336

OH

Further, in the resin composition of the present invention, other antioxidants may be contained in addition to the hindered g-separation antioxidant H. Other oxidizing agents may be listed as materials other than antioxidants, antioxidants, scaly antioxidants, and sulfur-based antioxidants. The phenolic antioxidant other than the phenol-resistant antioxidant may be a semi-blocking phenolic antioxidant in which one of the substituents sandwiching the hydroxyl group is substituted with a methyl group or the like, or two hydroxy groups interposed therebetween. A phenol-based antioxidant having a less hindered type in which both of the substituents are substituted with a thiol group or the like. These are added in an amount less than the amount of the antioxidant that is blocked. Examples of the dish-based antioxidants include, for example, tridecyl sulphate, diphenyl decyl phosphite, and tetrakis(2,4-di-t-butylphenyl) [1, 〗-biphenyl; _4,4,-di-bromobisphosphate, bis[2,4-bis(1,1-didecylethyl)-6-fluorenylphenyl]ethyl oxalate, bis[2,4 - Di-tert-butylphenyl) pentaerythritol di-saltate or the like, or a mixture of these or a mixture of two or more kinds can be used. Specifically, for example, GSY-P101, T0MIH0S (above, API-Corp.); Mark 2112, ADKSTAB PEP-36, ADKSTAB PEP-24 'ADKSTAB PEP-45, ADKSTAB HP_10 (above, manufactured by ADEKA); SUMILIZERGP (above 17/31 201202336 manufactured by Sumitomo Chemical Co., Ltd.). In addition, by using the combination of the anti-oxidant and the (4) antioxidant, it is possible to synergistically effect the oxidation resistance of the epoxy resin and the optical anisotropy of the transparent composite substrate. This is considered to be because the anti-oxidation mechanism of the anti-oxidant and the phosphorus-based antioxidant is different, so that the two independently act and produce a multiplication effect. Examples of the thioindigo antioxidants include dilauroyl thiodipropionate and thiodipropionic acid, and the like, and the like, or the like, or a mixture of two or more kinds thereof. Specifically include such as: DLTPyashit〇mi, LMTPyashitomi, DS1 Pyashitomi, DTTPyashitomi (. Api_c〇rp manufactured as above) 'ADKSTAB ΑΟ · 23 (manufactured by ADEKA Corporation); SUMILIZER TPL ·, SUMTLIZER TPM, SUMILIZER TPS, SUMILIZER TL, SUΜ丨LIZER TP-D (above), manufactured by Sumitomo Chemical Co., Ltd., etc. The amount of the antioxidant (especially the phosphorus-based antioxidant) other than the hindered phenol-based antioxidant is preferably from about 30 to 300 parts by mass based on the mass of the hindered phenol-based antioxidant. It is better to set it around 50 to 200 Berry. Thereby, the hindered g-dividing antioxidant and the other antioxidant are not buried, and the respective effects can be exerted, and the multiplication effect can be exerted. Further, the resin composition of the present invention may contain an oligomer or a monomer of a thermoplastic resin or a thermosetting resin as required, or may contain a coupling agent or the like, insofar as it does not impair the properties of the resin. Further, when such oligomers or monomers are used, the composition ratios can be appropriately set so that the overall refractive index coincides with the refractive index of the glass filler. Further, the resin composition of the present invention contains ultraviolet absorbers, dyes, pigments, and potting fillers, etc., as needed in the range of non-destructive properties and properties 18/31 201202336. y. The resin composition of the present invention is obtained by mixing the above epoxy resin, glass filler, hindered phenol antioxidant, and the like. Ya, the best surface of the tree ribs of this (four) is in. c Wen Lu has been heated! After a minute, the gas of the above-mentioned antioxidant: / knife component was not substantially detected. As described above, the tree test product is obtained by volatilizing an antioxidant at the time of hardening, and the obtained cured product is also low in anisotropy and high in transparency. The detection of helium gas is preferably carried out by gas chromatography or gas chromatography mass spectrometry (GC-MSh, in which the latter can be obtained from the chromatogram ffi]i^(4)" = easy identification of gas components, that is, By evaluating whether or not the antioxidant or its decomposition component is extracted, it can be judged that the antioxidant a touches the so-called body that does not substantially detect the above-mentioned antioxidant or its decomposition component, and the peak cannot be recognized in the mass spectrum. &lt;Transparent Composite Substrate and Display Element Substrate&gt; The permeation substrate (4) of the present invention is a product of the present invention. That is, the permeation substrate of the present invention is formed into a plate shape by the invention of the invention. And the method of hardening it. 3. The method can be solved as follows: Newly used as the green of the sacred, and the method of reading the sap of the tree is read in the solvent and then washed. Another example is the use of broken glass = cloth? In the case of the filler, the components other than the glass filler are impregnated with the glass fiber cloth and the resin composition. The curing conditions of the resin composition in which the τ is formed into a fine plate shape are at a heating temperature of 5 (rc to 3 ah left 19/31 201202336 right and plus The time is preferably from about 0.5 to about 1 hour, the heating temperature is from about 17 Å to about 25 〇 ° C, and the heating time is from about 1 to about 5 hours. The transparent composite substrate of the present invention is suitably used, for example, for a substrate for a liquid crystal display element. Various transparent substrates such as a substrate for an organic EL device, a substrate for a filter, a substrate for an electronic paper, a substrate for a solar cell, and a substrate for a touch panel. The average thickness of the transparent composite substrate is not particularly limited, but is 4 〇 to 2 〇. 〇#m is better than 5' to 〇〇# ηι is better. Moreover, the transparent composite substrate of the present invention is used at 30 ° C to 15 〇. (: The average linear expansion coefficient is 40 叩m The following is preferable, and it is more preferably 2 〇 ppm or less, and most preferably 〇 ppm or less. For example, when the transparent composite sheet is used for a substrate for an active matrix display device, if it exceeds the upper limit, the manufacturing is performed. In the step, there is a problem that warp or aluminum wiring is broken. The transparent composite substrate of the present invention can be applied to the above-mentioned transparent substrate (display element substrate) for various display elements. In this case, the display element substrate is at wavelength 4 〇〇 The total light transmittance in nm is preferably 80% or more, preferably 85% or more, and more preferably 88% or more. When the total light transmittance in the wavelength 400 nm does not reach the lower limit value, the performance in the display element may be displayed. Further, when the transparent composite substrate of the present invention is applied to a display element substrate, it can be provided with a coating layer for a substrate having a flat surface, and the resin used as the coating layer is excellent, for example. It is preferable that the resin is the same as the epoxy resin used in the transparent composite substrate, and the coating thickness is about 3.] to about 3G front. Preferably, the transparent composite substrate of the present invention is applied to the display element substrate and can be provided to suppress the damage of the substrate due to impact from the outside. 20/31 201202336 Buffer layer . The layer structure may be, for example, a smooth layer provided on a side of the transparent composite substrate, and a shock buffer layer may be provided thereon, or an impact buffer layer may be provided on at least one side of the transparent composite substrate, and then disposed thereon. The structure of the smoothing layer, etc. That is, the shock absorbing layer can be provided at any position of the plurality of layers. Further, the display element substrate of the present invention is superior to the glass substrate in the impact resistance of the ball drop impact test, and the impact resistance can be further improved by providing such an impact buffer layer. The above description of the resin composition, the transparent composite substrate, and the display element substrate of the present invention is not limited thereto, and for example, any structure may be added to the transparent composite substrate and the display element substrate. [Embodiment] Next, a specific embodiment of the present invention will be described. 1. Production of Transparent Composite Substrate (Example 1) First, a hydrogenated biphenyl type alicyclic epoxy resin having a structure of the following chemical formula (1) (manufactured by Daicel Chemical Industry Co., Ltd.; E-BP, Tg: &gt; 250. 〇, gasification double-seeking type A 哀 oxygen tree 爿 a (made by Nippon Oxygen Resin Co., Ltd.; γχ_8〇〇〇, Tg ·]〇3 C), Fangxiang ethnic dredging heat 13⁄4 ion hardener (Sanxin Chemical The company manufactures; S1-100L) and the blocked anti-deuteration agent (manufactured by Ciba Fine Chemical Co., Ltd.; IRGANOX 1010, weight average molecular weight 丨178) are mixed in the ratio shown in Table , to prepare a resin material.

Q (1) 0 201202336 Next, the obtained resin material was impregnated with a glass cloth (thickness 95; refractive index mo; manufactured by Nitto Textile Co., Ltd.). Thereby, a resin composition was prepared. The glass cloth (resin composition) impregnated with such a resin material was sandwiched between two glass plates subjected to mold release treatment at 8 inches. After heating for 2 hours under the armpits, 'at 250'. (: Further heating for 2 hours, a transparent composite substrate having a thickness of 97 # m (glass filler content of 63% by mass) was obtained. (Examples 2 to 22) In addition to changing the composition of the resin composition to the table, 2 The same procedure as in Example 1 was carried out to obtain a transparent composite substrate. The alicyclic epoxy resin (Daicd Chemical Industry Co., Ltd.; EHPE 3150) used in Examples 20 and 21 was 2,2- 1,2-decyloxy-4-(2-oxiranyl)cyclohexane adduct of bis(hydroxymethyl)-1- 1 -butanol (molecular weight 2234) (5) indicates.

[In the above formula (5), R is an organic group; η is an integer of the above] and the alicyclic epoxy resin used in Example 22 (manufactured by Daicei Chemical Industry Co., Ltd.; E-DOA, Tg: &gt; 250 °C) is an alicyclic epoxy resin having the structure of the following chemical formula (2), and "-X-" is "_CH(CH3y". 22/31 (2) 201202336 ο

(Example 23) The material was replaced with a (four) cloth, and the glass powder and the resin material Lu Li 2 were synthesized into a resin composition, and the same treatment as in Example ’ was carried out to serve as a transparent composite substrate. (Comparative Example 1) The same procedure was carried out except that the use of the antioxidant was omitted, and a transparent composite substrate was obtained. (Comparative Example 2) The same treatment as in Example 1 was carried out in the same manner as in Example 1 except that the dish-based antioxidant in Table 2 and Table 2 was replaced with the same treatment as in Example 1 to obtain transparency (Comparative) Example 3) The same treatment as in Example! was carried out on the transparent composite substrate in the amount of the less-receiving antioxidant indicated by the resistance. (Comparative Example 4) In addition to the use of the glass frit, The glass frit was mixed with a resin material to form a resin composition, and the same treatment as in Comparative Example 2 was carried out to form a transparent composite substrate. (Comparative Example 5) In addition to using a smashed powder, the glass frit and the resin were used. The materials were mixed together to form a resin composition, and the same treatment as in Comparative Example 3 was carried out to obtain a transparent composite substrate. 23/31 201202336 Further, the hindered phenol-based melting points used in the respective examples and comparative examples are as follows. . IRGANOX 1010: 110 to 125〇C ADKSTAB AO-20: 220〇C SUM1UZERBHT: 69 to 73 ° C IRGANOX 1076 ·· 50 to 55 ° C 2. evaluation of the transparent substrate of the composite 2.1 evaluation of the obtained optically anisotropic transparent The composite substrate is respectively subjected to the following The wet heat treatment of the second stage is shown. &lt;Condition of the first wet heat treatment&gt; • Treatment temperature: 85 ° C • Treatment humidity: 85% RH • Treatment time: 1061 hours &lt; Conditions of the second wet heat treatment &gt; • Treatment Temperature: 85 ° C • Treatment humidity: 85 ° / 0 RH • Treatment time: 30 丨 5 hours No method for measuring optical anisotropy. Details of this measurement,

24/31 Next, for the wet heat treatment, the L tilting button is imaged by the observation portion of mm below (pixel 64〇X converts this into a black and white image with each pixel having a 〇 level of 201202336 (gradation). The layer of each pixel in the image is subjected to the evaluation value of the optical anisotropy after the first wet heat treatment. Next, the transparent composite substrate subjected to the first wet heat treatment is again subjected to the wet heat treatment, and the treatment is performed until the accumulation. The treatment time is the condition of the wet heat treatment of the above second. Then, a black-and-white image is obtained by the same method as described above, and the gradation of each pixel in the obtained black-and-white image is obtained to prepare the optical anisotropy after the second wet heat treatment. the evaluation value. the evaluation results are shown in the above table 2.1 1,2. 25/31 02 2 20 26/31 c »V CH- antioxidant hard glass filler left foot dagger optical anisotropy less hindered epoxy catalyst Phenolic antioxidants Phosphorus-based antioxidants are anti-oxidant glass powder glass cloth cationic hardening catalyst glycidyl epoxy resin: 1 alicyclic epoxy resin 3015 small 1061 hour SUMILIZBR AO-80 ADKSTAB , PEP-36 IRGAN0X 1076 SUM1LIZER ! BHT ADKSTAB ! AO-20 IRGAN0X 1010 Aromatic thermal cation hardening catalyst 〇crc V) 〇_ YX-8000 E-DOA EHPE3150 E-BP X 〇 X parts by mass 1 part by mass parts mass parts mass parts mass parts by mass 1 part by mass 1 ί parts by mass 1 part by mass 1 1 part by mass parts by mass 1 part by mass mass parts 1 3.59 1_2 ^ 9_ 0.01 Os - Ln ο Example 1 3.12 N·) Lr&gt; p Os — ο Example 2 2.89 1 2.39 On — ο Example 3 2.61 ro UJ — Os UJ — Example 4 2.52 2.27 U) Os — ο Example 5 2.48 2.25 Private ON — Ln ο Embodiment 6 2.48 ! 2.24 ON U) - ο Embodiment 7 3.06 2.81 ON - ο Embodiment 8 2.71 2.45 U&gt; ON OJ - S ο Example 9 | 2.60 | 1 2.36 U) ON U) One - ο Example 10 2.55 2.32 Os OJ — K&gt; ο Example: 11 - 2.55 2.33 Os) On U) A 5 ο Example 12 | 2.74 I 2.53 U) ON U 1) Example 13 &gt;1] 201202336 [(Nd tbfe example 5 S IT) - r*~t 8 ΓΛ 3.93 tbl example 4 8 iTi - rn oc rn 4.09 Mm 3 S m — 3.02 3.90 Mm 2 S iTi —〇! S */Ί A R 4.74 Example 23 8 — 3 234 2.56 Example 22 8 - 2.78 3.07 Example 21 8 in a «Ν - Example 20 S iTi — 2.44 2.73 Example 19 S — ΓΟ S 3.14 If Example 18 8 IT) — r·) 229 3.13 Example 17 S m - 3 Γ *-1 235 3.07 Example 16 8 - 2 228 2.47 Example 15 SV) — \〇 2.19 Example 14 8 Vi * Ί n parts (N • mass parts mass parts mass parts mass parts mass parts i mass parts mass parts mass parts mass parts mass parts mass parts mass parts mass parts mass XX E-BP CHPF3I50 H-DOA YX-8000 O ^ ol aromatic Family ^ Thermal cation hardening catalyst glass cloth glass powder IRGANOX 1010 ADKSTABAa20 SUMlLIZIZRBiri' [ ' IRGANOX1076 AI] KSTABPEI)-36 SUM1LIZ HRAO80 1061 hour 3015 hours alicyclic epoxy resin glycidyl epoxy resin cationic hard solvent bribery anti-oxidation bismuth phosphate pit oxidant less resistant age system chemical agent optical anisotropic ring fine fat hard _ medium glass spine Green anti-oxidation enthalpy evaluation result 201202336 It can be understood from Tables 1 and 2 that the optical anisotropy of the transparent composite sense obtained by each of the examples is higher than that of the transparent composite substrate obtained by each comparative example. The transparent composite substrate was evaluated using a gas chromatography mass spectrometer _ degassing. At the same time, the evaluation environment is set to 3〇〇〇c to heat the shovel. As a result, the transparent composite substrate obtained in each of the examples was incapable of seeing volatilization of a component derived from a hindered antioxidant. Fig. 1 (a) shows the degassing evaluation (mass spectrometry) of the hindered phenol-based anti-air monomer used in Example 7, and (b) the degassing of the transparent composite substrate of the wire transfer 7 A chart of the evaluation results (mass spectrometry). As can be understood from Fig. 1(a), the hindered antagonist used in Example 7 has its monomer volatilized by heating of C, and a peak A' is detected on the mass spectrum. The transparent composite substrate obtained in 7 can be whitened by the drawing (b), and the peak a cannot be detected even after heating by 3 (8)c. From this, it was confirmed that the transparent composite substrate obtained in Example 7 can inhibit oxidation-oxidation even at a high temperature which is volatilized as long as it interacts with the anti-suppressant antioxidant. Antioxidants remain in place. (4) In the transparent composite substrate obtained in each of the comparative examples, it was confirmed that the components of the human oxidizing agent were volatilized. From this, it was confirmed that the transparent stone substrates were heated to release the antioxidant. At the same time, it can be considered that "the acceleration of the optical heterogeneous characteristics is deteriorated by the explanation. 28/31 201202336 [Simplified description of the drawings] Fig. (a) shows the hindered phenol-based antioxidant monomer used in Example 7. The evaluation results of the degassing (mass spectrometry) and (b) are the graphs showing the evaluation results (mass spectrometry) of degassing of the transparent composite substrate obtained in Example 7. ' [Main component symbol description] 'A wave peak 29/31

Claims (1)

201202336 VII. Patent application scope: 1. The compound of the full-day composition is a resin used in the manufacture of the transparent substrate, and the product includes: epoxy resin, glass filler and hindered phenol. It is an antioxidant. 2. ^申β专#] The purpose of the first item is to prevent the content of the antioxidant from being _f% or more and 5% by mass or less. 3. The resin composition of item 丨 or item 2 of the scope of application, wherein the melting point of the above-mentioned hindered phenol-based antioxidant is l〇 (above TC. 4. Resin composition as in any of the scope of claims _ to 3) The material in which the upper sputum is blocked and the antioxidant is in the molecular construction towel has a new smoldering structure. ^中中(4) The resin composition of any one of the items 4 to 4, which is related to the cross-resistance The antioxidant is further contained in a ratio of 30 to 300 parts by mass of the antioxidant. The resin composition of any one of the above-mentioned items, wherein the resin contains an alicyclic ring. The resin composition of the sixth aspect of the invention, wherein the above-mentioned anthraquinone type oxygen-containing surface comprises an alicyclic epoxy represented by the following chemical formula (1): 2) at least one of the alicyclic epoxy resins shown, (1) [In the above formula [2], -X- represents _〇-, -S-, -SO-, (2) S〇r, -CH: 30/31 201202336 -CH(CH3)-, tC(CH3) 2-] 〇8. The alicyclic epoxy _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ For example, the patent scopes 1 to 2 will be applied. The above glass filler is a resin composition of the glass fiber cloth, wherein the patent composition is the same as the scope of the patent application! In the resin composition pot of any one of the items 9, the resin composition is substantially not detected by the above-mentioned antioxidant or its decomposition component after heating for 30 minutes at a temperature of TC. 11. A transparent composite substrate And characterized in that it is composed of a cured product of a resin composition according to any one of claims 1-10 to 12. 12. A display element substrate characterized by having transparency as disclosed in the scope of claim U Composite substrate. 31/31