JP2019131739A - Resin composition and adhesive film or sheet - Google Patents

Abstract

To provide a curable resin composition suitable for a cured product having excellent transparency, heat resistance, and impact resistance, and its adhesive film or sheet.SOLUTION: This invention relates to an adhesive film or sheet that is obtained by combining a resin composition (A) containing a curable resin (a) and a silicone resin (b) with a glass fiber (C), with a difference in optical refractive indexes between the resin composition (A) and the glass fiber (C) being 0.02 or less..SELECTED DRAWING: None

Description

  The present invention relates to an adhesive film or sheet obtained by impregnating glass fibers with a curable resin and a silicone resin. The adhesive film or sheet of the present invention has excellent properties such as transparency, heat resistance, light resistance and impact resistance.

Fiber reinforced composite material consisting of glass fiber and epoxy resin is lightweight but has excellent mechanical properties and heat resistance such as strength, rigidity and fatigue resistance, and can be used as an adhesive film when uncured. Therefore, it is applied to fields such as display elements such as displays, illumination applications, and photoelectric conversion elements such as solar cells (Patent Documents 1 and 2).
However, these adhesive films are brittle in resin and have low impact resistance. In order to improve the brittleness of the resin, it has been studied to add an elastomer (Patent Document 3). However, since a synthetic rubber is used, there is a problem in light resistance and transparency is not sufficient.

Japanese Patent Application Laid-Open No. 2014-080587 JP 2005-170991 A Japanese Patent Laid-Open No. 2005-200621

  The present invention provides an adhesive film that is used when producing a transparent composite laminate having a thin thickness and excellent characteristics such as transparency, adhesion, impact resistance, temperature cycle resistance, and light resistance. It is.

  The present inventors have found that an adhesive film or sheet obtained by impregnating glass fiber with a curable resin and a silicone resin satisfies these characteristics.

That is, the present invention provides a resin composition (A) and a glass fiber (C) obtained by combining a resin composition (A) containing a curable resin (a) and a silicone resin (b) with a glass fiber (C). ) Is an adhesive film or sheet characterized in that the difference in optical refractive index is 0.02 or less.
Furthermore, the said resin composition (A) is related with the said adhesive film or sheet | seat characterized by including the polyfunctional epoxy resin which has an at least 2 or more epoxy group in 1 molecule.
Further, the present invention relates to the adhesive film or sheet, wherein the polyfunctional epoxy resin is at least one selected from an aliphatic epoxy resin and an aromatic epoxy resin.
Furthermore, the resin composition (A) relates to the adhesive film or sheet described above, wherein the resin composition (A) contains a polycarboxylic acid having at least two or more carboxy groups in one molecule, or an acid anhydride.
Further, the present invention relates to the adhesive film or sheet, wherein the polycarboxylic acid is a polycarboxylic acid obtained by reacting tricyclodecane dimethanol and methylhexahydrophthalic anhydride.
Furthermore, the silicone resin (b) has the functional group capable of reacting with at least one epoxy group in one molecule.
Furthermore, it is related with the said adhesive film or sheet | seat characterized by the total light transmittance of an adhesive film being 75% or more.
Furthermore, it is related with the said adhesive film or sheet | seat whose glass fiber (C) is a glass cloth (c).
Furthermore, the present invention relates to an adhesive film characterized in that the adhesive film does not have tackiness at room temperature, and the resin composition (A) is remelted by heating.
Furthermore, it is related with the adhesive film characterized by the reaction rate of a resin composition (A) being 5 to 80%.

The adhesive film of the present invention is an excellent adhesive film having high dimensions such as transparency, gas permeability, heat resistance, light resistance, impact resistance, and dimensional stability. Therefore, it can be preferably used as an adhesive material in applications that require a light transmitting function. For example, it is particularly suitable as an adhesive film for bonding and sealing an EL display, a light emitting element such as an illumination, a photoelectric conversion element such as a solar cell, a circuit board on which an organic semiconductor element or the like is mounted, and the lid material.
In addition, since the cured product of the adhesive film of the present invention has high dimensional stability and toughness at the adhesive part, taking advantage of these features, not only as an adhesive layer such as a panel, but also, for example, a printed material, a specimen, and a sign It can also be effectively used as a protective material such as an adhesive film for window materials.

  The curable resin (a) shown in the present invention refers to a resin that is cured by causing a reaction using heat as a trigger. In the present invention, the curable resin (a) is preferably colorless and transparent after curing.

  As the curable resin (a), those generally referred to as epoxy resin, urethane resin, (iso) cyanate resin, phenol resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, vinyl resin, amide resin, etc. are generally used. Any of these can be used in the present invention.

  The resin composition (A) is cured by applying energy such as heat or ultraviolet rays, and used to form a composite with the glass fiber (C). In view of the purpose of use, a material that is colorless, highly transparent, and capable of obtaining a tough cured product is preferable.

  Representative compounds that are cured by heat include, for example, epoxy resins, phenol resins, urethane resins, and the like, and are colorless, transparent, and toughness is required. It is preferable.

  Preferred epoxy resins are polyfunctional epoxy resins, among which aromatic epoxy resins and aliphatic epoxy resins are preferred, and examples of aromatic epoxy resins include glycidyl ether compounds of aromatic phenols. In carrying out the present invention, a plurality of these may be used.

  For example, glycidyl ether compounds of aromatic phenols include phenyl glycidyl ether, cresol novolac type epoxy compounds, phenol novolac type epoxy compounds, biphenyl-phenol type epoxy compounds, novolak type epoxy compounds such as naphthol type epoxy compounds, and bisphenol A type. Epoxy compounds, bisphenol F type epoxy compounds, bisphenol type epoxy compounds such as bisphenol S type epoxy compounds, trisphenol methane type epoxy compounds, glyoxal type epoxy compounds, (4 (4 (1,1-bis (p-hydroxyphenyl)- And ethyl) α, α-dimethylbenzyl) phenol) type epoxy compounds. Among these, in the present invention, from the viewpoint of heat resistance and light resistance, bisphenol A type epoxy compound, (4 (4 (1,1-bis (p-hydroxyphenyl) -ethyl) α, α-dimethylbenzyl) phenol) Type epoxy compounds are preferred. These are available, for example, as NC-2000 series, NC-3000 series, NC-3100 series, NC-6000 series, EPPN-501 series (all manufactured by Nippon Kayaku).

  Examples of the aliphatic epoxy resin include an epoxy resin having an aliphatic cyclic structure and an epoxy resin having no aliphatic cyclic structure. The epoxy resin having an aliphatic side cyclic structure has at least one cyclic aliphatic structure in one molecule. For example, polycondensation of terpene diphenol and phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and aliphatic ring structure dienes (dicyclopentadiene, norbornadiene, hexahydroxyindene, etc.) Glycidyl etherified products derived from these products and modified products thereof, hydrogenated bisphenol (bisphenol A, bisphenol F) type epoxy compounds, alicyclic epoxy compounds, etc., compounds having a cyclohexyl structure or dicyclopentadiene structure in the molecule, Examples thereof include an epoxy resin having a triglycidyl isocyanurate structure. Specifically, for example, 1,2-cyclohexanediol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, 1,2-bis (hydroxymethyl) -1-butanol Examples include epoxy-4- (2-oxiranyl) cyclohexane adducts. These are available as, for example, EHPE series, Celoxide series, etc. (both manufactured by Daicel).

  Examples of the epoxy resin having no aliphatic cyclic structure include glycidyl ethers derived from linear or branched alcohols such as hexane diglycidyl ether.

  In addition, a modified epoxy compound such as a urethane-modified epoxy compound having a urethane bond, a rubber-modified epoxy compound containing butadiene or NBR can also be used.

  Among the epoxy resins, a polyfunctional epoxy resin containing two or more epoxy groups in at least one molecule is preferable because the toughness of the cured product is improved. As the epoxy resin used in the present invention, glycidyl ether compounds of aromatic phenols are preferable because of having heat resistance and toughness.

Moreover, in hardening of an epoxy resin, it is common to use other compounds that react with an epoxy group called a so-called curing agent in combination. Examples thereof include polycarboxylic acids, acid anhydrides, compounds containing amino groups, compounds containing phenolic hydroxyl groups, and the like.
Among these, in the adhesive film of the present invention, it is preferable to use polycarboxylic acid or acid anhydride in consideration of transparency, but a suitable one is used according to the curable resin to be used.

  The polycarboxylic acid preferably contains at least two carboxy groups in one molecule. More preferably, three or more are included. Thereby, a tougher adhesive film can be formed by the reaction of the resin composition (A). Specific examples include acrylic acid copolymers and acid anhydride adducts of hydroxyl group-containing compounds. In addition, the acid anhydride used for an acid anhydride adduct includes the acid anhydride mentioned later, and there is no special limitation.

  The hydroxyl group-containing compound is a compound having at least one hydroxyl group in one molecule. This is reacted with a compound containing an acid anhydride group, which will be described later, and esterified to produce a carboxy group at the same time, thereby obtaining an acid anhydride adduct of the hydroxyl group-containing compound.

  As a compound that can be suitably used as the hydroxyl group-containing compound, a compound having one hydroxyl group in a molecule has, for example, a linear or branched structure such as methanol, ethanol, propanol, butanol, octanol, stearyl alcohol, etc. Aliphatic hydrocarbon alcohols, cyclohexanol, cyclohexane methanol, hydrocarbon alcohols having an alicyclic structure such as isobornyl alcohol, aromatic hydrocarbon alcohols such as benzyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl Examples thereof include alkylene glycol monoalkyl ethers such as ether, diethylene glycol monoethyl ether, and ethylene glycol monophenyl ether.

  Examples of the compound having two hydroxyl groups in one molecule include aliphatic hydrocarbon diols having a linear / branched structure such as ethylene glycol, propylene glycol, butanediol, hexanediol, nonanediol, and dodecanediol, cyclohexane Diol, cyclohexanedimethanol, dicyclopentadienedimethanol, tricyclodecanedimethanol, hydrocarbon-based diols having an alicyclic structure such as dioxane glycol, aromatic diols such as bisphenol A and bisphenol F, and addition of alkylene oxides thereof Products and cyclic ester adducts such as caprolactone.

Examples of the compound having three or more hydroxyl groups in one molecule include glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxyalkylmethyl 1,4-butanediol, and tris (2-hydroxyethyl) isocyanurate. And the like, triols such as ditrimethylolpropane and pentaerythritol, polyols such as dipentaerythritol and polyglycerol, and cyclic ester adducts such as alkylene oxide adducts and caprolactone.
Among these, it is preferable to use an aliphatic hydroxyl group-containing compound from the light resistance of the cured product and the ease of adjusting the optical refractive index, and further considering the heat resistance of the resin composition, the compound having an alicyclic structure is More preferred.

  The acid anhydride preferably has at least one acid anhydride group in one molecule. The acid anhydride group reacts with a hydroxyl group contained in the epoxy resin or a hydroxyl group generated by the carboxylation of the epoxy group first to generate a carboxy group. For this reason, the acid anhydride acts as a bifunctional compound as a curing reaction of the epoxy compound.

  Specific examples of the acid anhydride used in the present invention include aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, succinic anhydride, maleic anhydride, hexahydrophthalic anhydride, tetrahydro Fatty acid anhydrides such as phthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride, hexahydropyromellitic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride and the like can be mentioned. Among these, it is preferable to use an aliphatic acid anhydride from the light resistance of the cured product and the ease of adjusting the optical refractive index.

  The suitable ratio of the epoxy resin and the carboxylic acid curing agent is preferably 0.5 to 2 equivalents, more preferably 0.8 to 1.2 equivalents, of carboxy group to 1 equivalent of epoxy group. When the amount of the curing agent is less than this, the effect of the curing agent is not sufficiently exhibited, the curing reaction is delayed, and the adhesion with the substrate is deteriorated. On the other hand, when the curing agent is excessive, the curing reaction does not proceed sufficiently and a tough cured resin layer cannot be obtained.

  Examples of the compound that is cured by ultraviolet rays include acrylates, vinyl compounds, reactive monomers, and oligomers.

  Examples of acrylates that can be used include monofunctional (meth) acrylates and polyfunctional (meth) acrylates.

  Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, Examples include phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

  As polyfunctional (meth) acrylates, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, Diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogen Ε-Caprola of bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and neopent glycol hydroxybivalate Tone adduct di (meth) acrylate, poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone, trimethylolpropane tri (meth) acrylate, triethylolpropane tri ( (Meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and its ethylene oxide adduct, etc. Is mentioned.

  Examples of vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, and ethyl styrene. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

  Examples of reactive oligomers include urethane (meth) acrylates having (meth) acrylate groups and urethane bonds in the same molecule, as well as polyester (meth) acrylates and epoxy having (meth) acrylate groups and ester bonds in the same molecule. Examples include epoxy (meth) acrylates derived from resins and having (meth) acrylate groups in the same molecule, and reactive oligomers in which these bonds are used in combination. Examples of the epoxy (meth) acrylate include o-phenylphenol epoxy acrylate and tricyclodecane dimethanol diacrylate, and any epoxy (meth) acrylate may be used as long as the effect of the present invention is not affected. May be.

  The cation reactive monomer is not particularly limited as long as it is generally a compound having an epoxy group. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Union Carbide “Syracure UVR”) -6110 "), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as" ELR-4206 "manufactured by Union Carbide), limonene dioxide (" Celoxide 3000 manufactured by Daicel "). Etc.), allyl cyclohexylene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl) 5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (such as “Syracure UVR-6128” manufactured by Union Carbide), bis (3,4-epoxycyclohexyl) Methyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, and the like.

  The silicone resin (b) used in the present invention refers to a resin having a siloxane skeleton, and is used for imparting impact resistance. As long as this silicone resin (b) has a siloxane skeleton, it can be used in any shape such as linear, cyclic, three-dimensional crosslinking, or a mixture thereof. From the viewpoint of transparency, the silicone resin (b) is preferably compatible with the curable resin (a) and is not clouded after curing.

Moreover, this silicone resin (b) has what has a reactive group in a side chain, and what does not have a reactive group in a side chain.
Specific examples of the silicone resin (b) having a reactive group include amino acids such as BY16-205, FZ-3760, BY16-891 manufactured by Toray Dow Corning, and KF-861 and KF-880 manufactured by Shin-Etsu Chemical Co., Ltd. Modified silicone oils, epoxy modified silicone oils such as BY16-839OIL, SF8411OIL, BY16-876 manufactured by Toray Dow Corning, KF-1001, KF-101 manufactured by Shin-Etsu Chemical Co., and BY16- manufactured by Toray Dow Corning Carboxols such as 880 and carboxy-modified silicone oil such as X-22-3710 manufactured by Shin-Etsu Chemical Co., Ltd., BY16-201 manufactured by Toray Dow Corning Co., Ltd., SF8427, KF-6000 manufactured by Shin-Etsu Chemical Co., Ltd., and KF-6001 Modified silicone oil, EP- manufactured by Toray Dow Corning 601 epoxy-modified silicone powder, methacryloxy-modified silicone powder EP-2720, etc. manufactured by Dow Corning Toray Co., include epoxy-modified silicone resin AY42-119 like manufactured by Toray-Dow Corning. In addition, a silicone resin having no reactive group may be epoxy-modified.
The silicone resin (b) having a reactive group is characterized by being difficult to bleed out after curing and having good compatibility with the curable resin (a).
Examples of the silicone resin (b) having no reactive group include alkyl-modified silicone oils such as BY16-606, BY16-846FLUID, SF-8419 FLUID manufactured by Toray Dow Corning, and KF-96, KF-412 manufactured by Shin-Etsu Chemical Co., Ltd. , Polyether modified silicone oils such as FZ-2203, FZ-2104, L-7604 manufactured by Toray Dow Corning, KF-351A, KF-945 manufactured by Shin-Etsu Chemical Co., Ltd., SH510- manufactured by Toray Dow Corning 100CS, SH550 FLUID, phenyl-modified silicone oils such as KF-50 and KF-54 manufactured by Shin-Etsu Chemical Co., Ltd., EP-5500 and EP-2600 manufactured by Toray Dow Corning Co., and KMP-600 and KMP manufactured by Shin-Etsu Chemical Co., Ltd. -590, silicone powder such as KMP-597, Examples include silicone resins such as FCA-107 and FCA-108 manufactured by Toray Dow Corning, and KR-480 and KR-114B manufactured by Shin-Etsu Chemical Co., Ltd.
The silicone resin (b) having no reactive group is characterized by further improving the impact resistance of the adhesive film or sheet of the present invention.

  The silicone resin (b) is usually 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the total curable resin in the resin composition (A). Used in part range. When used in a larger amount than this range, the refractive index difference from the glass fiber (C) becomes large and becomes cloudy, which is not preferable for applications requiring transparency. Moreover, when there is little usage-amount than the said range, the effect of impact resistance cannot fully be acquired.

  In these resin compositions (A), it is also possible to blend a solvent, a reaction catalyst, or a compound called a polymerization initiator according to each curing method. In addition to the above components, the resin composition (A) may contain other components. These other components include antioxidants, light stabilizers, ultraviolet absorbers and the like.

  Also when obtaining a resin composition (A), it can prepare by mixing and dissolving each component according to a conventional method. For example, the varnish of the resin composition (A) can be obtained by charging each component in a round bottom flask equipped with a stirrer and a thermometer and stirring at 40 to 80 ° C. for 0.5 to 6 hours. In this case, a method in which the resin varnish and the acid anhydride + reaction catalyst or additive varnish are separately prepared and mixed at the time of use is particularly preferable.

  In the present invention, both a thermosetting system and a photocuring system can be used, but the adhesive film has good adhesiveness and can be bonded to various substrates regardless of whether it is transparent or opaque. Therefore, the thermosetting system is preferable.

  In addition, in order to promote the reaction by heat, a curing catalyst is generally added in order to accelerate the reaction in response to heat or to adjust the curing temperature. Any of these known materials can be used as long as they have the effect of promoting the curing reaction.

  Examples of the curing catalyst include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl- 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole ( 1 ′)) Ethyl-s-triazine, 2,4-diamino-6 (2′-me Ruimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethyl Various imidazoles such as imidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, terephthalic acid Acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, salts with polyvalent carboxylic acids such as succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5,4,0) undecene Diaza compounds such as 7 and their tetrafes Salts such as ruborate and phenol novolac, salts with the above polyvalent carboxylic acids or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, triphenylphosphine, tri (tolyl) phosphine Phosphines and phosphonium compounds such as tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, hexafluororostibin phosphonium salt, methyltributylphosphonium dimethyl phosphate, phenols such as 2,4,6-trisaminomethylphenol, octyl Tin oxide, cobalt octylate, zinc octylate, zirconium octylate, nickel octylate, cobalt naphthenate And organometallic compounds such as Furthermore, a microcapsule type curing catalyst in which a curing accelerator is used as a microcapsule can be used.

  Which of these curing catalysts is used should be appropriately selected depending on the properties required for the resin composition (A). A curing catalyst is normally used in 0.001-15 mass parts with respect to 100 mass parts of all the thermosetting resins in a resin composition (A).

The resin composition (A) may contain other components. These other components include antioxidants, light stabilizers, ultraviolet absorbers and the like.
In the resin composition of the present invention, in order to promote the reaction by heat, a curing catalyst is generally added in order to accelerate the reaction in response to heat or to adjust the curing temperature. Any of these known materials can be used as long as they have the effect of promoting the curing reaction.

  The antioxidant that can be used in the resin composition (A) is not limited as long as it is a known general one such as a phenol-based, sulfur-based, or phosphorus-based antioxidant. However, in view of the characteristics of the present invention, it is preferable to select a material that is colorless and difficult to be colored even when it is used for a long period of time as a circuit board after sealing or heat after curing.

  Examples of the phenolic antioxidant include monophenols, bisphenols, and high-molecular phenols.

  Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. .

  Examples of phosphorus antioxidants include phosphites and oxaphosphaphenanthrene oxides.

  These antioxidants can be used alone, but may be used in combination of two or more. The usage-amount of antioxidant is 0.008-1 mass part normally with respect to 100 mass parts of resin compositions of this invention, Preferably it is 0.01-0.5 mass part. In the present invention, a phosphorus-based antioxidant is preferable.

  As the light stabilizer that can be used in the resin composition (A), known general stabilizers can be used, and there is no particular limitation. However, in view of the characteristics of the present invention, it is preferable to select a material that is colorless and is difficult to be colored even when it is used for a long time or for heat during curing. Typical examples of these include hindered amines.

  As the ultraviolet absorber that can be used in the resin composition (A), known general absorbers can be used, and there is no particular limitation. Examples of ultraviolet absorbers include benzotriazoles and hydroxyphenyltriazines, and can be used in combination with the light stabilizer.

  In the present invention, it is preferable to use an ultraviolet absorber having a low colorability over time. For example, propanoic acid-2- [4- [4,6-bis ([1,1′-biphenyl] -4-yl) -1,3,5-triazin-2-yl] -3-hydroxyphenyl]- Isooctyl ester (for example, Tinuvin 479, manufactured by Ciba Japan Co., Ltd.) and the like can be mentioned.

  When improving the light resistance of this invention, a hydroxyphenyl triazine type ultraviolet absorber and a hindered amine light stabilizer are used together.

  The resin composition (A) includes a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, a polyamide resin, and a polyimide as long as the properties such as transparency and hardness are not impaired. A resin component such as a resin may be added as necessary.

  Further, fine particles having a primary particle size of 1 to 200 nm may be added to the resin composition (A). Examples of the fine particles include glass, silica, aluminum oxide, zirconium oxide, tin oxide, titanium oxide, zinc oxide, indium tin oxide, antimony oxide, selenium oxide, yttrium oxide, and the like. It can be obtained from the market and used as a dispersed colloidal solution. Moreover, these can be used 1 type or in mixture of 2 or more types. Each component of the composite resin composition of the present invention includes a dispersion solvent such as ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and dimethyldimethylacetamide, esters such as ethyl acetate and butyl acetate, and nonpolar solvents such as toluene and xylene. What is necessary is just to select and use what is dissolved.

  The resin composition (A) includes carbon fiber, casein fiber, peanut protein fiber, corn protein fiber, soybean protein fiber, algin fiber, chitin fiber, mannan fiber, rubber fiber, cellulose fiber, nylon fiber, polyvinylidene chloride fiber, Fibers such as polyvinyl chloride fiber, polyester fiber, polyacrylonitrile fiber, modacrylic fiber, polyethylene fiber, polypropylene fiber, polystyrene fiber, polyetherester fiber, and polyurethane fiber can also be used. These can be used alone or in combination of two or more.

  A silane coupling agent, a release agent, a leveling agent, a surfactant, a dye, a pigment, an organic light diffusion filler, a diluting solvent, and the like can also be added to the resin composition (A).

  A known general metal salt may be added to the resin composition (A). For example, carboxylic acid metal salts (zinc salts such as 2-ethylhexanoic acid, stearic acid, behenic acid, myristic acid, tin salts, zirconium salts) and phosphoric acid ester metal salts (zinc salts such as octyl phosphoric acid and stearyl phosphoric acid) And metal compounds such as alkoxy metal salts (such as tributylaluminum and tetrapropylzirconium) and acetylacetone salts (such as acetylacetonezirconium chelate and acetylacetonetitanium chelate). These may be used alone or in combination of two or more. By adding a metal salt, the heat resistance and light resistance of the present invention can be improved.

  The resin composition (A) is obtained by uniformly mixing each component by a method similar to a conventionally known method. For example, an epoxy resin, an acid anhydride curing agent and, if necessary, a curing accelerator and other components are mixed thoroughly until uniform using an extruder, kneader, roll, etc., if necessary, to obtain a resin composition ( A) is obtained. When obtaining a cured product, there is a technique in which if the resin composition (A) is highly viscous or solid at room temperature, it is melted, then molded using a casting or transfer molding machine, and further cured by heating. . If the resin composition (A) is liquid at room temperature, a method of molding using a casting or transfer molding machine, and further curing by heating can be used.

  Resin composition (A) is composed of toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, It can be diluted with a solvent such as propylene glycol monomethyl ether acetate and used as a varnish. Since the resin composition (A) is usually solid at normal temperature, it is more preferable to use it after diluting in a solvent.

  The glass fiber (C) shown in this invention refers to what consists of what melt | dissolved and pulled glass and made it fiber shape. More preferably, it is spun and further made into a cloth. By combining this with a curable resin, high toughness and dimensional stability can be imparted to the resulting adhesive film.

  In order to make it into a cloth shape, a known general method such as weaving, knitting or making into a nonwoven fabric can be used, but the glass cloth woven into a cloth shape by weaving the spun glass fiber has toughness, dimensional stability, and after heating. From the standpoint of preventing penetration, it can be most suitably used in the present invention.

There is no limitation in particular as a kind of glass which comprises the glass fiber (C) used suitably in this invention, A well-known general glass can be used. For example, so-called E-glass, S-glass, T-glass, D-glass, UN-glass, NE-glass, Q-glass and the like can be mentioned.
Among these, E-glass is easy to obtain and has few alkali metal oxides, and is suitable for use in the present invention as an alkali-free glass. Further, although there are cost problems, S-glass and T-glass also have excellent characteristics from the viewpoint of dimensional stability. Moreover, what processed the glass fiber for controlling adhesiveness with resin and surface tension with a silane coupling agent can be used suitably.

  The diameter of the glass fiber suitable for the present invention is preferably small in consideration of transparency and the like, and preferably 10 μm or less.

  The optical refractive index of the resin composition (A) and the glass fiber (C) is preferably substantially the same in the stage after curing, and the difference is 0.02 or less, preferably 0.01 or less, more preferably 0. 0.005 or less is preferable. This is because the adhesive film obtained can be made transparent by setting the optical refractive index to substantially the same value. When it exceeds this range, the transparency of the adhesive film is lost.

  Therefore, the kind of glass which comprises glass fiber (C), and the structure of a resin composition (A) have a close relationship, for example, E-glass (about 1.54-1.57) which is comparatively easy to obtain. The glass cloth (c) made of has a high refractive index. For this reason, an aliphatic curable resin and an aromatic curable resin are used for the resin composition (A) in accordance with the intended refractive index. On the other hand, when S-glass and T-glass having excellent dimensional stability are used, since the optical refractive index is low (about 1.51 to 1.53), an aliphatic curable resin is mainly used.

  The mass ratio of the preferred resin composition (A) and glass fiber (C) is 20 to 80, preferably 55 to 75% by mass as indicated by (A) / ((A) + (C)). . If the amount of resin is larger than this value, the distortion of transmitted light due to the deformation of the resin due to heat during curing increases, and if the amount of resin is small, the substrate and the glass fiber (C) are in direct contact, The glass fiber may be seen locally.

  In general, the adhesive film or sheet of the present invention is a liquid resin composition (A) as it is, and in the case of a high viscosity or solid resin composition (A), it is diluted with a solvent or the like to form a solution. A so-called varnish is prepared, glass fiber such as glass cloth is immersed in the varnish, and the solvent is evaporated and dried.

  What is obtained by drying and curing the prepreg of the resin composition (A) is also the adhesive film or sheet of the present invention. The prepreg of the resin composition (A) is used at least in a state where the curing reaction is not completed, that is, a completely uncured or semi-cured state. At this time, the preferable reaction rate (that is, the value indicated by the reaction amount of the prepreg / the reaction amount when the curing reaction is completed) is 5 to 80%, preferably 10 to 50%. The prepreg does not have tackiness and is remelted by heating to return to the resin composition (A).

  The production of the prepreg of the resin composition (A) can be performed by a known general method, and is not particularly limited. For example, the glass fiber (C) is impregnated with the resin composition (A) dissolved in the solvent, and then the solvent is volatilized, or the glass fiber (C) is impregnated with the heat-melted resin composition (A). Thereafter, a method of cooling, a method of applying pressure or the like to a non-cured resin composition (A) molded into a flat shape using a roll or the like, a glass fiber (C) being placed in a mold and heated there Examples thereof include a method of pouring the resin composition (A) using a transfer molding machine or the like.

  The curing temperature and time of the resin composition (A) are 80 to 200 ° C. and 0.5 to 200 hours. As a curing method, it can be cured at a high temperature at a stretch, but may be cured at a low temperature of 150 ° C. or lower for a long time. For example, initial curing may be performed at 80 to 150 ° C., and post-curing may be performed at 100 to 200 ° C., and the curing reaction may be promoted by increasing the temperature stepwise.

  The total light transmittance of the adhesive film or sheet of the present invention is 75% or more, preferably 85% or more in view of its transparency. The same applies to the laminated board bonded to the base material.

  The haze value of the adhesive film or sheet of the present invention is 5 or less, preferably 3 or less, more preferably 1.5 or less in view of its transparency. The same applies to the laminated board bonded to the base material.

  Next, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited at all by the following examples. In the synthesis example, the reaction was terminated when the disappearance of the raw material alcohols was confirmed by gel permeation chromatography (hereinafter referred to as “GPC”).

Synthesis Example 1-1 Synthesis of Carboxylic Acid Curing Agent A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while 228 g of methyl ethyl ketone (hereinafter, MEK), 196 g of tricyclodecane dimethanol, methyl Add 336 g of hexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH; hereinafter referred to as H1), react at 50 ° C. for 2 hours, and then heat and stir at 70 ° C. for 4 hours for carboxylic acid curing agent 760 g of MEK solution was obtained. The resulting solution was colorless and the concentration was 70% by mass.

Example 1 and Comparative Example 1: Preparation of Curable Resin The components shown in Table 1 were heated and mixed at 70 ° C. to obtain a resin composition and a resin composition for a comparative example.

Hardener listed in Table 1: Synthesis Example 1-1
Curing agent 2: Isophoronediamine epoxy resin 1: Aliphatic epoxy resin EHPE-3150: Made by Daicel, Epoxy equivalent 181
Epoxy resin 2: Aromatic epoxy resin NC-3000: Made by Nippon Kayaku, biphenyl polyfunctional epoxy resin, epoxy equivalent 275, total chlorine content 550ppm
Silicone resin 1: KR-480 epoxy-modified product: Shin-Etsu Chemical, epoxy-modified silicone resin silicone resin 2: KR-480: Shin-Etsu Chemical, high phenyl type silicone resin silicone resin 3: BY16-876: Toray Dow Corning Epoxy-modified silicone oil silicone resin 4: KMP-600: Shin-Etsu Chemical Co., Ltd., silicone powder epoxy acrylate 1: Nippon Kayaku, tricyclodecane dimethanol diacrylate epoxy acrylate 2: Nippon Kayaku, o-phenylphenol Epoxy acrylate photopolymerization initiator: Irgacure 184: manufactured by BASF, 1-hydroxy-cyclohexyl-phenyl-ketone catalyst: zinc octoate dilution solvent: methyl ethyl ketone

Example 2 and Comparative Example 2: Evaluation of reaction rate of prepreg The resin composition obtained in Example 1 and Comparative Example 1 was impregnated in E-glass cloth (equivalent to IPC spec 106), and then the solvent was added in an oven at 150 ° C. for 10 times. The prepreg having a thickness of 50 μm was obtained by drying for a minute. Table 2 below shows the results obtained by calculating the reaction rate of the prepreg from the reaction heat amount by DSC (differential scanning calorimeter).

Example 3, Comparative Example 3: Refractive Index of Resin Composition (A) In order to measure the optical refractive index, thermosetting resin compositions (Examples 3-1 to 7, Comparative Examples 3-1 and 2) Example 2 was heat-cured at 150 ° C. for 24 hours to prepare a test piece. About the photocurable resin composition (Example 3-8), the resin was cured by irradiating ultraviolet rays from the top so as to be 300 mJ / cm ² , thereby preparing test pieces.
Using these test pieces, the refractive index at 589 nm was measured by the A method shown in JIS K7142: 2014 and shown in Table 3.
In addition, since the refractive index at 589 nm of the E-glass cloth used in this example is 1.555, the curable resin of Comparative Example 2-2 has a low refractive index.

Example 4 and Comparative Example 4: Production and Evaluation of Laminated Plate In the thermosetting transparent laminated plates (Examples 4-1 to 7 and Comparative Examples 4-1 and 2), the prepreg produced in Example 2 was used. Cut into 15 cm square, sandwiched both by 15 cm square polycarbonate plate (Sumitomo Bakelite Co., Ltd .: EC-105, thickness 1.5 mm), overlapped, then cut into 20 cm square for the purpose of preventing contamination of the press plate A fluororesin film (Aflex, manufactured by Asahi Glass Co., Ltd.) was further stacked up and down, and cured at 110 ° C. for 24 hours under vacuum with a vacuum press at 1 MPa to obtain a transparent laminate.

In the photocurable transparent laminate (Example 4-8), the prepared prepreg prepared in Example 2 was cut into 15 cm square, and a 15 cm square polycarbonate plate (Sumitomo Bakelite Co., Ltd .: EC-105, After sandwiching both layers with a thickness of 1.5mm) and stacking them together, a fluororesin film (Aflex, manufactured by Asahi Glass Co., Ltd.) cut into 20cm squares for the purpose of preventing contamination of the press plate is further stacked up and down, and then a vacuum press machine The pressure was applied at 40 ° C. for 5 minutes while applying pressure at 0.2 MPa under vacuum to defoam and homogenize the surface.
Thereafter, a curing reaction was performed through a conveyor type ultraviolet irradiation device equipped with a 300 mJ / cm ² metal halide lamp to obtain a transparent laminate.

The obtained laminated plate was evaluated for impact resistance with a large-scale high-speed impact compression tester (IM10T-30 manufactured by IMATEK) in accordance with JIS K7211-2: 2006. The test speed was 4.5 m / s, the striker diameter was Φ20 mm, the tip shape was hemispherical, and the hole diameter of the holding jig was Φ100 mm, and the impact energy at that time was measured.
◎: 140J or more ○: 130J or more and 139J or less △: 120J or more and 129J or less × 119J or less

Moreover, the measurement of the total light transmittance was measured based on JISK7361-1: 2008.
◎: 85% or more ○: 75% or more and 84% or less △: 65% J or more and 74% or less ×: 64% or less

  From the above results, it was shown that the adhesive film or sheet of the present invention has good properties. In particular, the film to which the silicone resin (b) was added showed excellent impact resistance. Moreover, in the case of using a prepreg composed of a resin composition (A) and glass cloth not optically considered, the transparency was insufficient.

Claims (8)

An optical refractive index of the resin composition (A) and the glass fiber (C) obtained by combining the resin composition (A) containing the curable resin (a) and the silicone resin (b) with the glass fiber (C). An adhesive film or sheet having a difference of 0.02 or less. The adhesive film or sheet according to claim 1, wherein the resin composition (A) contains a polyfunctional epoxy resin having at least two epoxy groups in one molecule. The adhesive film or sheet according to claim 1, wherein the resin composition (A) contains at least two or more carboxy groups or one or more acid anhydrides in one molecule. The adhesive film or sheet according to claim 1, wherein the silicone resin (b) has a functional group capable of reacting with at least one epoxy group in one molecule. The adhesive film or sheet according to claim 1, wherein the adhesive film has a total light transmittance of 75% or more. The adhesive film or sheet according to claim 1, wherein the glass fiber (C) is a glass cloth (c). The adhesive film according to claim 1, wherein the adhesive film does not have tackiness at room temperature, and the resin composition (A) is remelted by heating. The reaction rate of the resin composition (A) of Claim 1 is 5 to 80%, The adhesive film characterized by the above-mentioned.