JP6096141B2 - Transparent glass fiber film - Google Patents

Description

  The present invention relates to a surface-treated transparent glass fiber film and a method for producing a transparent glass fiber film.

  Along with the remarkable development of digital technology, there is an increasing demand for characteristics of printed circuit boards as a countermeasure for increasing the functionality of electronic devices such as personal computers and mobile phones. As one aspect of this printed board, one using glass fibers can be given. Among these glass fibers, E glass, which is commonly used, has a refractive index of 1.56. For example, when impregnating with a resin, the difference in refractive index between the glass fiber and the resin is ± 0.01 or less. If it exists, it is known that it will become transparent (patent document 1).

  Actually, a prepreg impregnated with an epoxy resin shown in Patent Document 1 or a glass fiber shown in Patent Documents 2 to 4 is impregnated with a low refractive index epoxy resin and further impregnated with a high refractive index epoxy resin. Transparent prepregs made and laminates using the same are known. In addition, a method of producing a low gas permeable multilayer substrate by sputtering Si or Al on an epoxy resin-containing transparent glass fiber film is also known. Furthermore, Patent Document 5 discloses a transparent resin molded body having high transparency using a thermoplastic resin. However, epoxy resins and thermoplastic resins are known to have poor thermal shock properties, and these are limited to use in electronic components with low heat generation among those used in electronic materials where high reliability is required. It was done.

  Silicone resins and cyanate ester resins (Patent Document 6) other than the above resins are disclosed as resins used for electronic materials that are required to have thermal shock properties. However, even those using these resins are not suitable for electronic materials that require high discoloration resistance and mechanical strength, heat resistance such as the above-mentioned transparency, mechanical strength, thermal shock, There has been a demand for a printed circuit board material that is excellent in all of the characteristics of discoloration resistance, electrical insulation, dimensional stability, and flexibility.

Japanese Patent No. 4117792 JP 2011-068019 A JP 2011-0668020 A JP 2013-028680 A JP 2010-037475 A Japanese Patent No. 502222265

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a transparent surface-treated glass fiber film having high transparency, high strength, excellent heat resistance, electrical insulation, dimensional stability, and flexibility.

To achieve the above object, the present invention provides:
A transparent glass fiber film containing one or more surface-treated glass fiber films laminated,
The value of the conventional bending rigidity of the surface-treated glass fiber film measured by the method described in JIS R 3420 is 3 to 100 times the value of the conventional bending rigidity of the untreated glass fiber film, and JIS K 7375 A transparent glass fiber film having a total light transmittance of 90% or more at a wavelength of 400 to 800 nm and a thickness of 500 μm or less measured by the method described in 1. is provided.

  With such a transparent glass fiber film, it is possible to obtain a film having high transparency, high strength, excellent heat resistance, electrical insulation, dimensional stability, and flexibility.

  Among these, it is preferable that the said surface treatment glass fiber film is a glass cloth surface-treated with the organosilicon compound.

  If such a surface-treated glass fiber film is used, the glass fiber is fixed with higher strength, and since it is a film that has been surface-treated with an organosilicon compound, it has excellent heat resistance and discoloration resistance. A glass fiber film can be obtained.

  Moreover, the refractive index difference of the sodium D line at 25 ° C. between the organosilicon compound and the glass cloth is −0.02 or more and +0.02 or less, and each refractive index value is 1.44 or more and 1.60 or less. It is preferable that

  If such a surface-treated glass fiber film is used, a transparent glass fiber film having higher transparency can be obtained.

  Furthermore, the glass cloth is preferably a quartz glass cloth.

  If such a surface-treated glass fiber film is used, a transparent glass fiber film having more excellent heat resistance and transparency can be obtained.

  The organosilicon compound is an alkoxysilane, polysilazane, silicone-modified varnish, a mixture of alkoxysilane and metal alkoxide, and a mixture of silica sol and alkoxysilane having an average particle diameter of 1 to 100 nm measured by a dynamic light scattering method. It is preferable that it is 1 type, or 2 or more types of compounds chosen from the group which consists of.

  If such a surface-treated glass fiber film is used, a transparent glass fiber film having more excellent electrical insulation, heat resistance, and weather resistance can be obtained.

The present invention also provides:
A semiconductor device using the transparent glass fiber film is provided.

  Such a semiconductor device is of high quality because the transparency, strength, heat resistance, electrical insulation, dimensional stability, and flexibility of the transparent glass fiber film are excellent.

Furthermore, the present invention provides
A protective film for a display using the transparent glass fiber film is provided.

  If it is such a protective film for displays, since the transparency, strength, heat resistance, electrical insulation, dimensional stability, and flexibility of the transparent glass fiber film are excellent, the quality is high.

  At this time, it is preferable that an antireflection layer, an antifouling layer, or both of them be provided on one side or both sides of the display protective film.

  The protective film for display of this invention can provide an antireflection layer or an antifouling layer on one side or both sides as needed.

  With the transparent glass fiber substrate of the present invention, it is possible to obtain a substrate having high transparency, high strength, excellent heat resistance, electrical insulation, discoloration resistance, dimensional stability, and flexibility. A semiconductor device or a protective film for display using such a transparent glass fiber film is of high quality.

It is sectional drawing of the semi-cylindrical housing | casing used in the case of the flexibility test in each Example and a comparative example.

  In the conventional transparent flexible substrate, the fiber film to be used has a problem such as “because mechanical strength is weak, so a separate support is required to place heavy parts. The thermal characteristics are poor.” . As a result of intensive studies, the present inventors have determined that a glass fiber film having a surface treatment having a specific conventional bending rigidity and total light transmittance has high transparency, high strength, electrical insulation, and heat resistance. , Found that the dimensional stability, discoloration resistance, weather resistance, flexibility, etc. are excellent, and found that the above problems can be solved by using this film as a material of a flexible substrate as a transparent glass fiber film, The present invention has been completed.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
The present invention
A transparent glass fiber film containing one or more surface-treated glass fiber films laminated,
The value of the conventional bending rigidity of the surface-treated glass fiber film measured by the method described in JIS R 3420 is 3 to 100 times the value of the conventional bending rigidity of the untreated glass fiber film, and JIS K 7375 A transparent glass fiber film having a thickness of 500 μm or less and a total light transmittance of 90% or more of the surface-treated glass fiber film at a wavelength of 400 to 800 nm measured by the method described in 1.

  In such a surface-treated glass fiber film, the value of the conventional bending stiffness of the cloth measured by the method defined in JIS R 3420 is 3 to 100 times the value of the conventional bending stiffness of the untreated fiber film. It is. This multiple is used as an index indicating the degree of change from the so-called “woven” state to the “film” state by surface treatment of the fiber film, preferably 5 to 60 times, more preferably 10 to 40 times.

  If the above value is less than 3 times, the intended dimensional stability and glass fiber fixation, that is, the effect of preventing opening and twisting are hardly obtained, and electrical insulation and heat resistance due to siloxane characteristics Insufficient weather resistance. Moreover, when it exceeds 100 times, the bending rigidity of the said surface treatment glass fiber film will become hard too much, the softness | flexibility as a flexible substrate will be impaired, and a crack etc. will generate | occur | produce.

  Moreover, it is preferable that a surface treatment glass fiber film is the glass cloth surface-treated with the organosilicon compound. Such a surface-treated glass fiber film is uniform without causing kinks or openings because part or all of the fibers (filaments) constituting the glass cloth are bound by surface treatment with an organosilicon compound. Excellent in homogeneity, no stress concentration at high temperature, low average linear expansion coefficient, and excellent dimensional stability even at high temperature.

  When glass cloth is used as the glass fiber film and an organosilicon compound is used for the surface treatment, in order to satisfy the above characteristics, the amount of the organosilicon compound attached to the fiber film is determined by the surface treated glass fiber film (fiber film after treatment). ) 2% by mass or more and 90% by mass or less is preferable with respect to 100% by mass, more preferably 5% by mass or more and 70% by mass or less, and further preferably 10% by mass or more and 60% by mass or less.

  An adhesion amount of 2% by mass or more is preferable because the above characteristics can be satisfied and, as a result, characteristics such as electrical insulation, heat resistance, dimensional stability, and self-supporting properties are improved. An adhesion amount of 90% by mass or less is preferable because electrical insulation, dimensional stability, and the like can be obtained without lowering heat resistance or impairing flexibility.

  When glass cloth is used in the present invention, it is also possible to use one that has been fiber-opened by a columnar flow or a water flow by a high-frequency vibration method. Furthermore, the glass fiber applied in the present invention can be any glass fiber such as E glass, A glass, D glass, and S glass. General-purpose E glass is preferred because of cost and availability, but quartz glass is preferred when higher properties are required (for example, low dielectric constant, high heat resistance, low impurities, etc.).

As such a glass cloth, the fiber weave density is preferably 10 to 200/25 mm, more preferably 15 to 100/25 mm, and the mass is preferably 5 to 400 g / m ² , more preferably 10 to 10/25 mm. 300 g / m ² . If it is this range, binding by surface treatment will be performed effectively and characteristics, such as electrical insulation, heat resistance, dimensional stability, and self-supporting property, can be obtained easily.

  As a method of weaving such glass cloth, plain weave, satin weave, Nanako weave, or the like can be used. Moreover, the glass fiber woven with the glass fiber by which both or one side was textured may be sufficient. Further, the triaxially woven glass fiber has a higher strength and a highly reliable surface-treated glass fiber film. Further, a nonwoven fabric or a woven fabric in which long fibers are arranged in a certain direction can also be used. In addition, when the sizing agent is applied to the glass cloth, the treatment with the organosilicon compound may be hindered, so it is desirable to remove it beforehand.

  When the thickness of the surface-treated glass fiber film is 500 μm or less, it is a feature of the present invention that the total light transmittance measured by a method according to JIS K 7375 is 90% or more. The total light transmittance is preferably 92% to 100%, more preferably 95 to 100%. If it is less than 90%, the transparency that is important as a transparent material is lost.

  In the transparent glass fiber film, the difference in refractive index of sodium D-line at 25 ° C. between the glass cloth and the organosilicon compound may be −0.02 or more and 0.02 or less, preferably −0.015 or more, 0.0. It is 015 or less, More preferably, it is -0.01 or more and 0.01 or less. If the difference in refractive index between the glass cloth and the silicon-containing organic compound is within this range, a highly transparent surface-treated glass fiber film can be easily formed.

  Examples of the organosilicon compound used for the surface treatment of the glass cloth include alkoxysilane, polysilazane, silicone-modified varnish, a mixture of alkoxysilane and metal alkoxide, and an average particle size measured by a dynamic light scattering method of 1 to 1. There may be mentioned one or more compounds selected from the group consisting of a silica sol of 100 nm and a mixture of alkoxysilanes.

  For example, as the alkoxysilane, trimethylmethoxysilane, trimethylethoxysilane, phenylmethylvinylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethyldimethoxysilane, diphenyldimethyldiethoxy Silane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, 1,4-bis (methoxydimethylsilyl) Benzene, tetramethoxysilane, tetraethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, Ctyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-allylaminopropyltrimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltrieth Sisilane, 3-methacryloxypropyldiethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) ) 3-Aminopropyltriethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldiethoxysilane, N- (N-vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane and hydrochloric acid thereof Salt, N- (N-vinylbenzyl) -2-aminoethyl-3-aminopropylmethyldimethoxysilane and its hydrochloride, 3-isocyanatopropyltriethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureido Propyltriethoxysilane, 3-chloropre Examples include alkoxysilane compounds such as pyrtrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (trisethoxysilylpropyl) tetrasulfide, and one or a mixture of two or more thereof. May be. Moreover, it is not limited to these.

  Preferably, for adjusting the refractive index, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethyldimethoxysilane, diphenyldimethyldiethoxysilane, trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, naphthyltrimethoxysilane, Examples thereof include, but are not limited to, naphthyltriethoxysilane 1,4-bis (methoxydimethylsilyl) benzene.

  Moreover, you may use the 1 type, or 2 or more types of partial hydrolysis-condensation product of the said alkoxysilane. This partial hydrolysis-condensation product may be arbitrarily prepared by adding a known condensation catalyst, or a commercially available product may be used. Examples of commercially available products include epoxy group-containing alkoxysilane oligomer X-41-1059A (manufactured by Shin-Etsu Chemical Co., Ltd.), amino group-containing alkoxysilane oligomer X-40-2651 (manufactured by Shin-Etsu Chemical Co., Ltd.). Etc.

  As polysilazane, 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,1,3,3,5 , 5-hexamethylcyclotrisilazane and the like, but not limited thereto.

  As the silicone-modified varnish, various silicone-modified varnishes such as alkyd-modified varnish, polyester-modified varnish, epoxy-modified varnish, and acrylic-modified varnish are used, and may be selected depending on the end use and purpose.

  In the mixture of alkoxysilane and metal alkoxide, the alkoxysilane exemplified above is similarly used as the alkoxysilane, and examples of the metal alkoxide include aluminum isopropoxide, aluminum acetyl acetate, zirconium tetrabutoxide, tetraisopropyl titanate and the like. Is mentioned. The mixing ratio of the alkoxysilane and the metal alkoxide is preferably 100: 10 to 100: 100, particularly preferably 100: 20 to 100: 100, by mass ratio.

  In a mixture of silica sol and alkoxysilane, the silica sol is a silica sol having an average particle diameter measured by a dynamic light scattering method of 1 to 100 nm, preferably 1 to 50 nm, and the alkoxy silane exemplified above is used as the alkoxy silane. Silane is used as well. The mixing ratio of the silica sol and the alkoxysilane is preferably 100: 0.1 to 100: 10, particularly preferably 100: 0.1 to 100: 4, as the mass ratio of the solid content of the silica sol to the alkoxysilane.

  In the present invention, as long as the light transmittance is within a range of less than 90%, the glass fiber may be made of carbon fiber, ceramic fiber or other inorganic fiber, boron fiber, steel fiber, tungsten fiber or the like according to the required characteristics. A woven fabric in which fibers such as metal fibers, aramid, new heat-resistant fibers such as phenol are mixed can be used as the glass cloth.

  A general glass fiber processing method is applied to the method for producing the surface-treated glass fiber film of the present invention. As a method for applying the surface-treated glass fiber film of the present invention, a general glass fiber applying method is applied. Typical coating methods include direct gravure coater, chamber doctor coater, offset gravure coater, single roll kiss coater, reverse kiss coater, bar coater, reverse roll coater, slotter die, air doctor coater, forward rotation roll coater, blade coater. , Knife coaters, impregnation coaters, MB coaters, MB reverse coaters and the like. Among these, a direct gravure coater, an offset coater, and an impregnation coater coating method are preferable for producing the surface-treated glass fiber film of the present invention.

  Although the conditions vary depending on the organosilicon compound to be used, after the coating, for the purpose of drying and curing, heat treatment is performed at room temperature to 300 ° C, preferably 100 ° C to 250 ° C, more preferably 150 ° C to 230 ° C. It may be treated at a high temperature from the beginning, or the temperature may be raised in stages, but when it is first dried at room temperature to 100 ° C and then treated at a high temperature of 150 ° C to 200 ° C, voids caused by solvents, etc. are suppressed. This is particularly preferred because it can The treatment time is 1 minute to 24 hours, preferably 3 minutes to 4 hours, more preferably 5 minutes to 1 hour. These conditions may be set in consideration of productivity, cost, and workability, and the surface-treated glass fiber film of the present invention is produced by this heat treatment.

  The coating solution is obtained by diluting the organosilicon compound with a solvent. As examples of the solvent, water or organic solvents can be used alone or in admixture of two or more. Examples of organic solvents include alcohols such as methanol, ethanol, isopropanol and n-butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, glycol ethers such as ethylene glycol and propylene glycol, and fats such as hexane and heptane. And aromatic hydrocarbons such as toluene and xylene, ethers such as diethyl ether, diisopropyl ether and di n-butyl ether. In addition, pH adjusting agents such as organic acids such as formic acid, acetic acid, propionic acid, and oxalic acid, and aqueous ammonia, pigments, fillers, surfactants, thickeners, and the like can be added to the diluted solution.

  Further, an alkoxy group condensation catalyst may be added, and examples thereof include organometallic compounds such as organotin compounds, organotitanium compounds, and organic bismuth compounds, and amine compounds.

  Examples of organometallic compound-based condensation catalysts include dibutyltin dimethoxide, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin bis (acetylacetonate), dibutyltin bis (benzyl malate), dimethyltin dimethoxide, dimethyl Organotin compounds such as tin diacetate, dioctyltin dioctate, dioctyltin dilaurate, tin dioctate, and tin dilaurate, and tetraisopropyl titanate, tetranormal butyl titanate, tetra tertiary butyl titanate, tetra normal propyl titanate, tetra-2 -Ethylhexyl titanate, diisopropyl ditertiary butyl titanate, dimethoxy titanium bisacetylacetonate, diisopro Organic titanium compounds such as xititanium bisethylacetoacetate, ditertiary butoxytitanium bisethylacetoacetate, and ditertiary butoxytitanium bismethylacetoacetate, organic bismuth compounds such as bismuth tris (2-ethylhexanoate) or bismuth tris (neodecanoate), etc. Metallic Lewis acids such as zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate, zirconium dibutoxybis (ethylacetoacetate), zirconium tetra Zirconium such as acetylacetonate and zirconium tributoxy monostearate Compounds. The catalyst may be used alone or in combination of two or more. Examples of amine compounds include hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine, di-n-hexylamine, dicyclohexylamine, di-n-octylamine, hexamethoxymethylmelamine and the like. It is done.

  Among these condensation catalysts, it is preferable to use an organic titanium compound or a zirconium compound, and it is particularly preferable to use the ORGATIXX ZA series (manufactured by Matsumoto Fine Chemical Co., Ltd.), which is a zirconium-based catalyst having high discoloration resistance and high reactivity. preferable.

  The coating solution is preferably an aqueous coating solution in consideration of the influence on the coating environment. An amino group-containing silane coupling agent (commercial example: KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd.)) is a preferred organosilicon compound because of its excellent stability in water and good solubility.

  The transparent glass fiber film of the present invention includes a laminate obtained by laminating one or a plurality of the above-mentioned surface-treated glass fiber films. That is, one surface-treated glass fiber film can be used as it is, or a laminated plate obtained by bonding a plurality of surface-treated glass fiber films with an adhesive or the like can be used. Although it does not specifically limit as an adhesive agent which can be used at this time, What consists of thermosetting resins from a heat resistant and discoloration-resistant viewpoint is preferable.

  In the transparent glass fiber film of the present invention, the glass fiber film is surface-treated with an organosilicon compound or the like, and is excellent in transparency, heat resistance, electrical insulation, dimensional stability, discoloration, light resistance, weather resistance, and the like. Yes. In addition, by using a glass fiber film that has a refractive index close to that of glass cloth and an organic silicon compound, the glass fiber film has self-supporting properties that are not found in glass fibers, and the glass at the time of resin filling because the fibers are fixed. A uniform and homogeneous transparent glass fiber film that does not cause problems such as fiber twist and mesh opening can be obtained.

  From this, the transparent glass fiber film of this invention can be used suitably as a material of a semiconductor device, especially a material of an optical semiconductor device. In that case, the film can be used alone. It can also be used as a prepreg reinforcing substrate. Furthermore, it can be set as a metal-clad board | substrate by carrying out copper clad or copper plating on the surface, and can be used conveniently for a LED mounting board.

  Moreover, since the transparent glass fiber film of the present invention has high transparency and does not break like glass, it can be applied to a protective film for a display used in a thin PC, a tablet PC, a smartphone, and the like. When used as a protective film for a display, a film provided with an antireflection layer, an antifouling layer, or both on one or both sides of the protective film can be suitably used.

Among these, when using the transparent glass fiber film of the present invention as the protective film, the antireflection layer is applied to prevent or reduce reflection due to reflection of ambient light and improve visibility. Specifically, a thin film of TiO ₂ , ZrO, SiO ₂ , MgF or the like is preferably used, and more preferably a laminate of these.
In addition, the antifouling layer is a treatment for the surface of the protective film or antireflection layer, and prevents the surface from being attached with dirt from the human body such as fingerprints and sebum, making it easy to wipe off dirt, It is applied to make it inconspicuous. Therefore, it is desirable to have water and oil repellency, and in order to provide such performance, it is preferable to apply a fluorine-based silane coupling agent or an acrylic resin containing a fluorine-based acrylate. In particular, it is particularly preferable to use a perfluoropolyether group-containing treating agent as these fluorine-based treating agents because they are excellent in water and oil repellency and can provide high antifouling performance.

  In addition to the above, the transparent glass fiber film of the present invention may be used as a transparent reinforcing film for construction such as an explosion-proof or crime prevention window, or as a high-strength transparent reinforcing film such as for aviation windows and automobiles. Is also possible. In addition, since the transparency is high, the transparent glass fiber film of the present invention can be manufactured at a low cost by depositing a transparent conductive material such as ITO on the transparent glass fiber film. It can be used in various fields.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. The weight average molecular weight referred to in the present invention refers to a weight average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC) measured under the following conditions.

[Measurement condition]
Developing solvent: THF
Flow rate: 0.6mL / min
Detector: Differential refractive index detector (RI)
Column: TSK Guardcolom SuperH-L
TSKgel SuperH4000 (6.0 mm ID × 15 cm × 1)
TSKgel Super H3000 (6.0 mm ID × 15 cm × 1)
TSKgel SuperH2000 (6.0 mm ID × 15 cm × 2)
(Both manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 20 μL (0.5% by weight THF solution)

[Synthesis Example 1]
As an organic compound containing a silicon atom, 198.3 g (1.00 mol) of phenyltrimethoxysilane (KBM-103 manufactured by Shin-Etsu Chemical Co., Ltd.), diphenyldimethoxysilane (KBM-202 manufactured by Shin-Etsu Chemical Co., Ltd.) 224. 4 g (1.00 mol) and 600 g of isopropyl alcohol were added to the flask, 14 g of 25% tetramethylammonium hydroxide (TMAH) and 128 g of water were mixed, and the mixture was added to the flask and stirred for 3 hours. 400 g of toluene was added, washed with water, and the solvent was distilled off. The resulting alkoxysilane partially hydrolyzed condensate had a weight average molecular weight (Mw) of 1,500 and a refractive index of n _D ²⁵ = 1.551.

[Synthesis Example 2]
As an organic compound containing a silicon atom, phenyltrimethoxysilane (KBM-103 manufactured by Shin-Etsu Chemical Co., Ltd.) 198.3 g (1.00 mol), 1,4-bis (methoxydimethylsilyl) benzene 509.0 g (2. 00 mol) and 600 g of isopropyl alcohol were added to the flask, and the following operations were performed in the same manner as in Synthesis Example 1. Mw was 1,800 and the refractive index was n _D ²⁵ = 1.542.

[Synthesis Example 3]
As an organic compound containing a silicon atom, naphthyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 248.4 g (1.00 mol), diphenyldimethoxysilane (KBM-202 manufactured by Shin-Etsu Chemical Co., Ltd.) 224.4 g (1) 0.0000 mol) and 600 g of isopropyl alcohol were added to the flask, and the following operations were performed in the same manner as in Synthesis Example 1. Mw was 2,000, and the refractive index was n _D ²⁵ = 1.555.

[Example 1]
The resin of Synthesis Example 1 is made into a 10 wt% toluene solution and impregnated into glass cloth (for yarn: E250, density: warp yarn 59/25 mm, weft yarn 57/25 mm, thickness: 87 μm, mass: 95 g / m ² ). And dried by heating at 100 ° C. for 10 minutes. Thereafter, heat treatment was performed at 100 ° C. for 1 hour and 200 ° C. for 1 hour to prepare a surface-treated glass fiber film. The masses of the glass cloth before the treatment and the glass fiber film after the surface treatment were measured, and the adhesion amount of the organosilicon compound was calculated by the following formula.
Adhesion amount (mass%) = (mass of glass fiber film after treatment [g] −mass of glass cloth before treatment [g]) / mass of glass fiber film after treatment [g]
The results are shown in Table 1. Moreover, the following measurements were performed with respect to the surface-treated transparent glass-treated film.

-Mechanical characteristics The following mechanical characteristics were measured about the obtained surface treatment glass fiber treatment film.
1. Measurement was carried out by the method described in conventional bending rigidity JIS R 3420 (Glass Fiber General Test Method), and the measured value in the warp direction was used. The results are shown in Table 1.

·optical properties
2. Total light transmittance Based on JIS K7375, the total light transmittance in one surface treatment glass fiber film (thickness 100-150 micrometers) was measured.

[Examples 2 and 3]
The resin of Synthesis Examples 2 and 3 was made into a 10 wt% toluene solution, and glass cloth (yarn: E250, density: warp yarn 59/25 mm, weft yarn 57/25 mm, thickness: 87 μm, mass: 95 g / m ² ) And dried by heating at 100 ° C. for 10 minutes. Thereafter, heat treatment was performed at 100 ° C. × 1 hr and 200 ° C. × 1 hr to prepare a surface-treated glass fiber film, and the same measurement as in Example 1 was performed.

[Examples 4 to 6]
ORGATICS ZA-65 (tetrabutoxyzirconium n-butanol solution manufactured by Matsumoto Fine Chemical Co., Ltd.) is added to the resin of Synthesis Examples 1 to 3 with respect to 100 parts of resin, and then a 10 wt% solution is prepared with toluene. On the other hand, the same operation as in Example 1 was performed to produce a surface-treated glass fiber film, and the same measurement as in Example 1 was performed.

[Comparative Example 1]
Cyanate ester resin (Lonza “BADCy”, 52 parts by mass of 2,2-bis (4-cyanatophenyl) propane, epoxy resin containing 1,2-epoxy-4- (2-oxiranyl) cyclohexane (Daicel Chemical) 48 parts by mass of EHPE3150 manufactured by Kogyo Co., Ltd., 0.02 parts by mass of zinc octoate as a curing initiator, 50 parts by mass of toluene and 50 parts by mass of methyl ethyl ketone were added thereto, and the temperature was 70 ° C. A resin varnish was prepared by stirring and dissolving in 1. A prepreg was prepared through the steps shown in Example 1 using this varnish, and the same measurement as in Example 1 was performed.

[Comparative Example 2]
Aronix M-315 (Trisacryloyloxyethyl isocyanurate, manufactured by Toagosei Co., Ltd.), Epoxy ester 3000A (Bisphenol A diglycidyl ether acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd.)), Kayarad HX220 (Caprolactone of neopentyl glycol hydroxypivalate) Addition (m + n = 2) diacrylate (Nippon Kayaku) 30 parts, Irgacure 369 (BASF Japan) 2 parts as curing catalyst, Kayacure ITX (Nippon Kayaku) 0.4 part, perbutyl O (t-butyl-) Add 1.5 parts of 2-ethylperhexanoate from Nippon Oil & Fats, stir and mix the prepared solution into a glass cloth (yarn: E250, density: warp 59 / 25mm, weft 57 / 25mm, thickness : 87 .mu.m, mass: impregnated into 95g / ^{m 2)} U Irradiated and cured. The following measurements were made as in Example 1.

The following measurements were performed on Examples 1 to 6 and Comparative Examples 1 and 2.
Each film and prepreg of the flexibility test were fitted on the outside of the casing shown in FIG. 1 to check for film breakage and breakage. The results are shown in Table 1.

  From the results of Table 1 and Table X, Examples 1 to 6 in which the value of the conventional bending rigidity magnification is between 3 times and 100 times showed good results in the flexibility test, but the values of the conventional bending rigidity magnification were In Comparative Examples 1 and 2, which exceeded 100 times, the results were that they were too elastic to bend.

[Example 7]
Two surface-treated transparent glass fiber films obtained in Example 1 were bonded together with an addition-type silicone resin adhesive (product name: KE-109, manufactured by Shin-Etsu Chemical Co., Ltd.), and a pressure of 2 MPa with a hot press. It was pressure-molded at 150 ° C. for 30 minutes, and further subjected to secondary curing at 150 ° C. for 1 hour to obtain a laminate. The following evaluation was performed about the obtained laminated board. The evaluation results are shown in Table 2.

[Example 8]
Using the glass fiber treated film obtained in Example 2, a laminate was obtained in the same manner as in Example 7. Using the obtained laminate, the appearance and heat resistance were evaluated in the same manner as in Example 7. The results are shown in Table 2.

[Example 9]
Using the glass fiber-treated film obtained in Example 3, a laminate was obtained in the same manner as in Example 7. Using the obtained laminate, heat resistance was evaluated in the same manner as in Example 7. The results are shown in Table 2.

[Example 10]
Using the glass fiber treated film obtained in Example 4, a laminate was obtained in the same manner as in Example 7. Using the obtained laminate, heat resistance was evaluated in the same manner as in Example 7. The results are shown in Table 2.

[Comparative Example 3]
Using the transparent prepreg obtained in Comparative Example 1, a laminate was obtained in the same manner as in Example 7 except that no adhesive was used. Using the obtained laminate, heat resistance was evaluated in the same manner as in Example 7. The results are shown in Table 2.

[Comparative Example 4]
Using the transparent prepreg obtained in Comparative Example 2, a laminate was obtained in the same manner as in Example 7 except that no adhesive was used. Using the obtained laminate, heat resistance was evaluated in the same manner as in Example 7. The results are shown in Table 2.

Heat resistance Each transparent laminate was subjected to a heat resistance test at 150 ° C. × 1000 hr to confirm the appearance.

Each of the transparent laminates of the flexibility test was fitted into the outer periphery of the case having a width of 10 cm shown in FIG. 1 to check for film breakage and breakage.

Thermal shock resistance test Table 2 shows the results of observation of cracks, peeling, discoloration and the like of the test pieces after 1000 cycles of -60 ° C x 1 minute ⇔ 150 ° C x 1 minute with a heat shock tester.

＊１ フィルム柔軟性
○良好（割れ、剥離なし） ×不良（割れ又は剥離あり）
＊２ 熱衝撃試験 外観
○ 良好（割れ、剥離なし） × 不良（割れ又は剥離あり）

* 1 Film flexibility
○ Good (no cracking or peeling) × Bad (with cracking or peeling)
* 2 Thermal shock test Appearance
○ Good (no cracking or peeling) × Bad (with cracking or peeling)

  In the laminates of Examples 7 to 10, since the laminate is produced without including epoxy resin or acrylic resin, it is possible to obtain a laminate that suppresses discoloration of the base material, which is a drawback of the conventional glass epoxy substrate. It becomes possible. In addition, since the conventional bending rigidity magnification of the surface-treated glass fiber film used is in the range of 3 to 10 times, a high-strength transparent substrate that maintains the flexibility of the film and has high thermal shock resistance is provided. be able to.

Shape Change Test Using the glass cloth obtained in Example 1, Example 2, Example 4, and Example 5 and the transparent prepreg obtained in Comparative Example 1, the following comparative evaluation test was performed.

  In advance, cresol novolac type epoxy resin (trade name: EPICRON N-695, manufactured by DIC Corporation) 10 parts by mass, phenol novolac resin (trade name: PHENOLITE TD-2090, manufactured by DIC Corporation) 5 parts by mass, imidazole series A slurry of a high filler-containing epoxy resin composition comprising 0.1 part by mass of a catalyst (trade name: 1B2PZ, manufactured by Shikoku Kasei Co., Ltd.) and 50 parts by mass of a MEK solvent was prepared.

[Example 11]
The glass fiber film obtained in Example 1 was impregnated with the above-mentioned epoxy resin composition slurry, dried at 100 ° C. for 10 minutes, then placed in a mold with two sheets stacked, temperature: 200 ° C., pressure: 2 MPa, applied Pressing time: 70 minutes to obtain a laminate. Then, the opening of the film and the glass cloth, kinking, etc. were observed visually. The results are shown in Table 3.

[Example 12]
Using the glass fiber film obtained in Example 2, a laminate was obtained in the same manner as in Example 11. Using the obtained laminated plate, the opening of the film and glass cloth, kinking, and the like were visually observed in the same manner as in Example 11. The results are shown in Table 3.

[Example 13]
Using the glass fiber film obtained in Example 4, a laminate was obtained in the same manner as in Example 11. Using the obtained laminated plate, the opening of the film and glass cloth, kinking, and the like were visually observed in the same manner as in Example 11. The results are shown in Table 3.

[Example 14]
Using the glass fiber film obtained in Example 5, a laminate was obtained in the same manner as in Example 11. Using the obtained laminated plate, the opening of the film and glass cloth, kinking, and the like were visually observed in the same manner as in Example 11. The results are shown in Table 3.

[Comparative Example 5]
A laminate was obtained in the same manner as in Example 11 using the transparent prepreg obtained in Comparative Example 1. Using the obtained laminated plate, the opening of the film and glass cloth, kinking, and the like were visually observed in the same manner as in Example 11. The results are shown in Table 3.

＊３ 形状変化
○ 良好（目開きなし） × 不良（目開きあり、縒れあり）

* 3 Shape change ○ Good (no opening) × Poor (opening and twisting)

  From the results in Table 3, in the laminated plates of Examples 11 to 14, since the glass fiber film of the present invention is used, unlike the conventional silane coupling agent-treated glass cloth, there is little shape change at the time of pressing and dimensional stability. We were able to provide an excellent substrate. For this reason, the substrate is twisted and warped due to the inherent stress, and can be applied as a highly reliable material at high temperatures.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  DESCRIPTION OF SYMBOLS 1 ... Surface treatment glass fiber film, 2 ... Semi-cylindrical housing.

Claims (7)

A transparent glass fiber film containing one or more surface-treated glass fiber films laminated,
The value of the conventional bending rigidity of the surface-treated glass fiber film measured by the method described in JIS R 3420 is 3 to 100 times the value of the conventional bending rigidity of the untreated glass fiber film, and JIS K 7375 der those total light transmittance of 90% or more of the surface-treated glass fiber film at a wavelength of 400~800nm below thickness 500μm as measured by the method described in is,
The transparent glass fiber film, wherein the surface-treated glass fiber film is a glass cloth surface-treated with an organosilicon compound . The refractive index difference of the sodium D line at 25 ° C. between the organosilicon compound and the glass cloth is −0.02 or more and +0.02 or less, and the respective refractive index values are 1.44 or more and 1.60 or less. The transparent glass fiber film according to claim 1 . The transparent glass fiber film according to claim 1 or 2 , wherein the glass cloth is a quartz glass cloth. The organosilicon compound is composed of alkoxysilane, polysilazane, silicone-modified varnish, a mixture of alkoxysilane and metal alkoxide, and a mixture of silica sol and alkoxysilane having an average particle diameter measured by dynamic light scattering method of 1 to 100 nm. transparent glass fiber film as claimed in any one of claims 3, characterized in that one or more compounds selected from the group. Wherein a claim 1 in which using a transparent glass fiber film according to any one of claims 4. A protective film for a display, comprising the transparent glass fiber film according to any one of claims 1 to 4 . The protective film for a display according to claim 6 , wherein the protective film for a display is provided with an antireflection layer, an antifouling layer, or both on one surface or both surfaces thereof.

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