JP5646932B2 - Optical adhesive and display device including the same - Google Patents

Description

  The present invention relates to an optical adhesive excellent in heat and light resistance and a display device using the same.

  As an optical adhesive for liquid crystal display devices and the like, a material having a low birefringence, a low photoelastic coefficient, and a high optical transparency is used. In the case of a material for a liquid crystal display device or the like, the material used in the manufacturing process needs high heat resistance. Various heat-resistant polymer materials have been used as materials that satisfy these requirements.

  Among these heat-resistant polymer materials, for example, in the case of a thermoplastic resin, introduction of an aromatic skeleton in order to express high heat resistance generally increases the birefringence and increases the photoelastic coefficient. And optical performance are difficult to achieve.

  In the case of a thermosetting resin, conventionally known thermosetting resins are generally colored and are not suitable for optical material applications. Furthermore, it generally has polarity, which is disadvantageous for optical performance. Therefore, for example, for use as a sealant for light-emitting diodes, a transparent epoxy resin using an acid anhydride-based curing agent has been widely used as a special thermosetting resin. However, such transparent epoxy resins also have low moisture resistance due to the high water absorption rate of the resin, or particularly low light resistance due to low light transmittance for light of low wavelengths, or are colored due to photodegradation. Had the disadvantages.

  In addition, thermosetting resins are generally brittle, and there has been a problem that cracking or peeling occurs when a thermal shock is applied to a cured product or a product prepared using the cured product.

  In recent years, for example, thermosetting resins mainly composed of a silicone composition have been developed. However, when the silicone composition is a major component, there is a drawback that adhesion to an organic material is low. Among silicone-based compositions, addition-type silicone-based compositions, in particular, have a small shrinkage during curing and are materials that support the reliability of display devices and the like.

However, with the recent enhancement of display performance of display devices and the like, problems such as occurrence of problems such as misalignment occur when substrates are bonded to each other (for example, Non-Patent Document 1).
In recent years, the demand for larger displays and higher performance has increased, and the functions of laminated films have been increasing. Adhesives used for bonding between films must be joined with polymers of various polarities. Is required. For example, in the PVC layer protective film used for the polarizing plate, there is a movement to replace the norbornene resin film from the triacetyl cellulose film, and even in the retardation film, the low polarity modified film of polycarbonate or the norbornene resin film can be used. Replacement is progressing. However, many of these films have a low polarity, and the adhesives that have been used conventionally have poor adhesion to the film surface, which may cause problems in durability (Patent Document 1).

  Therefore, there has been a demand for an optical adhesive that has excellent adhesive ability, small effect shrinkage, and excellent handling properties and heat and light resistance regardless of the type of film or substrate.

JP2010-1000085

ThreeBond Technical Report No.43, p.6

  The present invention has been made in view of the above-described present situation. For example, when used as a glass bonding adhesive in a display device, it is excellent in heat and light resistance and supports display device reliability without causing wrinkles or sink marks during curing. An object is to provide an optical adhesive.

  As a result of intensive studies by the present inventors, the thermosetting optical adhesive obtained by using a specific structure as a crosslinking component does not cause a problem even when two fixed substrates are bonded together. Furthermore, it was discovered that both the organic / inorganic materials have excellent adhesiveness, and the present invention has been completed. That is, the present invention has the following configuration.

1) An optical adhesive comprising a silicone-based curable composition comprising the following (A) to (D).
(A) Organosiloxane having two alkenyl groups in one molecule (B) Organosiloxane having two hydrosilyl groups in one molecule (C) (C-1) Organic compound having at least two alkenyl groups and (C -2) Three or more alkenyl groups and hydrosilyl groups in one molecule obtained by hydrosilylation reaction of a linear and / or cyclic organohydrogensiloxane having at least two hydrosilyl groups in one molecule (D) Hydrosilylation catalyst 2) The component (C) is 0.5 to 10 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B). An optical adhesive comprising the silicone-based curable composition according to (1).
3) The optical adhesive according to 1) or 2), wherein the curable composition has a viscosity of 700 centipoise or less.
4) The optical adhesive according to any one of 1) to 3), wherein the penetration of the cured product obtained by solidifying the curable composition is 65 or more according to JISK2220.
5) The component (C-1) is polybutadiene, vinylcyclohexane, cyclopentadiene, divinylbiphenyl, bisphenol A diarylate, and trivinylcyclohexane, and the following general formula (1)

(Wherein R1, R2, and R3 are all organic groups, and at least two of them are alkenyl groups), and are at least one compound selected from the group consisting of organic compounds 1) to 4) An optical adhesive comprising the silicone-based curable composition according to any one of items 1 to 4.
6) The component (C-1) is represented by the following general formula (2)

(Wherein R1, R2, and R3 are all organic groups, and at least two of them are alkenyl groups) 1) to 5) the silicone according to any one of the above An optical adhesive comprising a system curable composition.
7) The optical adhesive comprising the silicone-based curable composition according to any one of 1) to 6), wherein the component (A) has a molecular weight in the range of 750 to 100,000.
8) The optical adhesive comprising the silicone-based curable composition according to any one of 1) to 7), wherein the component (B) has a molecular weight in the range of 1,000 to 100,000.
9) A display device having an optical adhesive comprising the silicone-based curable composition according to any one of 1) to 8).
10) The display device according to 9), wherein among the display devices, at least one of the substrates bonded by the optical adhesive is a glass substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the optical adhesive excellent in adhesiveness and thermal stability can be given, and if the optical adhesive is used, reliability can be provided to a display device.

Details of the present invention will be described below.

<(A) Organosiloxane having two alkenyl groups in one molecule>
The component (A) in the present invention is not particularly limited as long as it is an organosiloxane having two alkenyl groups in one molecule, but a linear polydimethylsiloxane having an alkenyl group at the terminal from the viewpoint of operability of the composition. Is preferably used.

  Further, the alkenyl group contained in the component (A) is not particularly limited, but if it is intentionally exemplified, a vinyl group, an allyl group, a methallyl group, an acrylic group, a methacryl group, a 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, Examples include 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group, and the like.

  In addition, a functional group other than an alkenyl group may be bonded to the silicon atom in component (A), for example, an unsubstituted or substituted monovalent hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or a butyl group. Groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, dodecyl groups and other alkyl groups; cyclopentyl groups, cyclohexyl groups and other cycloalkyl groups; phenyl groups, tolyl groups, xylyl groups, naphthyl groups, etc. Aryl groups; aralkyl groups such as benzyl, 2-phenylethyl and 2-phenylpropyl groups; halogenated alkyl groups such as chloromethyl, 3,3,3-trifluoropropyl and 3-chloropropyl Is mentioned. Of these, 90% or more of the number of functional groups other than alkenyl groups is preferably a methyl group from the viewpoint of heat and light resistance. Preferable specific examples of such component (A) include polydimethylsiloxane blocked with dimethylvinylsiloxy group blocked at both ends of the molecular chain, polydimethylsiloxane blocked with methyldivinylsiloxy group blocked at both ends of the molecular chain, dimethylvinylsiloxy blocked dimethyl blocked at both ends of the molecular chain Examples include siloxane / methylphenylsiloxane copolymer. The organosiloxane of component (A) can be used alone or in combination of two or more having different viscosities.

  Moreover, it is preferable that the viscosity of (A) component exists in the range of 10-10000 cP from the viewpoint of the operativity of a composition, it is more preferable in the range of 10-5000 cP, and it is 10-1000 cP or less. Further preferred. Similarly, the molecular weight of the component (A) is preferably within the range of 750 to 100,000, more preferably within the range of 750 to 50,000, and within the range of 750 to 20000 from the viewpoint of operability of the composition. More preferably it is. If the viscosity or molecular weight is too high, for example, when the present invention is used as a bonding adhesive, it may be difficult to apply on the substrate, and if it is too low, for example, using a coating device on the substrate. In the case of application, the application amount may become difficult to stabilize. The molecular weight can be measured using, for example, GPC (manufactured by Tosoh Corporation, HLC-8220GPC).

<(B) Organosiloxane having two hydrosilyl groups in one molecule>
The component (B) in the present invention is not particularly limited as long as it is an organosiloxane having two hydrosilyl groups in one molecule. From the viewpoint of operability of the composition, a linear polydimethylsiloxane having a hydrosilyl group at the end. It is desirable to use

  In addition, a functional group other than hydrosilyl group may be bonded to the silicon atom in component (B), for example, an unsubstituted or substituted monovalent hydrocarbon group such as methyl group, ethyl group, propyl group, butyl group Groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, dodecyl groups and other alkyl groups; cyclopentyl groups, cyclohexyl groups and other cycloalkyl groups; phenyl groups, tolyl groups, xylyl groups, naphthyl groups, etc. Aryl groups; aralkyl groups such as benzyl, 2-phenylethyl and 2-phenylpropyl groups; halogenated alkyl groups such as chloromethyl, 3,3,3-trifluoropropyl and 3-chloropropyl Is mentioned. Of these, 90% or more of the number of functional groups other than hydrosilyl groups is preferably a methyl group from the viewpoint of heat and light resistance. Preferable specific examples of such component (B) include dimethylpolysiloxane blocked with dimethylhydrogensiloxy group at both ends of molecular chain, dimethylsiloxane / methylphenylsiloxane copolymer blocked with dimethylhydrogensiloxy group blocked at both ends of molecular chain, molecular chain Examples thereof include methylphenylpolysiloxane blocked with dimethylhydrodienesiloxy groups at both ends. The organosiloxane having two hydrosilyl groups as component (B) can be used alone or in combination of two or more.

  Moreover, it is preferable that the viscosity of (B) component exists in the range of 10-10000 cP from the viewpoint of the operativity of a composition, it is more preferable in the range of 10-5000 cP, and it is 10-1000 cP or less. Further preferred. Similarly, the molecular weight of the component (B) is preferably in the range of 1000 to 100,000, more preferably in the range of 1000 to 50000, and more preferably in the range of 1000 to 20000 from the viewpoint of operability of the composition. More preferably it is. If the viscosity or molecular weight is too high, for example, when the present invention is used as a bonding adhesive, it may be difficult to apply on the substrate, and if it is too low, for example, using a coating device on the substrate. In the case of application, the application amount may become difficult to stabilize. The molecular weight can be measured using, for example, GPC (manufactured by Tosoh Corporation, HLC-8220GPC).

<(C) (C-1) Hydrosilylation of an organic compound having at least two alkenyl groups and (C-2) a linear and / or cyclic organohydrogensiloxane having at least two hydrosilyl groups in one molecule Crosslinking agent having 3 or more alkenyl groups and hydrosilyl groups in one molecule obtained by reaction>
In the present invention, the component (C) is an organic compound (C-1) having at least two alkenyl groups and at least two hydrosilyl groups in one molecule from the viewpoint of compatibility with the components (A) and (B). A cross-linking agent having three or more alkenyl groups and hydrosilyl groups in one molecule obtained by hydrosilylation reaction of a linear and / or cyclic organohydrogensiloxane (C-2) having (C) It is preferable to use it.

  “With three or more alkenyl groups and hydrosilyl groups” means, for example, when there are 3 or more alkenyl groups in a molecule and 0 hydrosilyl groups, conversely 0 alkenyl groups and 3 or more hydrosilyl groups In addition, a case where two or more alkenyl groups are present and a hydrosilyl group is one is included.

  The component (C-1) is not particularly limited as long as it is an organic compound having at least two alkenyl groups. Specific examples of the component (C-1) include diallyl phthalate, triallyl trimellitate, diethylene glycol. Bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetraallyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2, 4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably having a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, Diallyl monoglycidyl isocyanurate , Diallyl ether of bisphenol A, diallyl ether of bisphenol S, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), novolak Examples include allyl ether of phenol, allylated polyphenylene oxide, and those in which a part or all of the glycidyl group of a conventionally known epoxy resin is replaced with an allyl group.

  As the component (C-1), low molecular weight compounds that are difficult to express separately as described above for the skeleton portion and the alkenyl group can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples thereof include aromatic cyclic polyene compound systems, and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene, vinylcyclohexene, and vinylnorbornene.

  The component (C-1) is preferably an organic compound having a heterocyclic skeleton. The organic compound having a heterocyclic skeleton is not particularly limited as long as it is a compound having a hetero element in the cyclic skeleton. However, those in which Si is contained in the atoms forming the ring are excluded. Further, the number of atoms forming the ring is not particularly limited and may be 3 or more. From availability, it is preferably 10 or less. Specific examples of the heterocyclic ring include epoxy, oxetane, furan, thiophene, pyrarole, oxazole, furazane, triazole, tetrazole, pyran, thiine, pyridine, oxazine, and thiazine. Type, pyridazine type, pyrimidine type, pyrazine type, piperazine type. Especially, since the effect of this invention is improved, isocyanurate is preferable as a heterocyclic ring, and specific examples of the component (C-1) include triallyl isocyanurate and diallyl monoglycidyl methacrylate.

  The component (C-2) used in the present invention is not particularly limited as long as it is an organohydrogensiloxane compound having at least two hydrosilyl groups in one molecule. For example, it is a compound described in International Publication WO96 / 15194, Those having at least two hydrosilyl groups in one molecule can be used.

  Among these, from the viewpoint of availability, a linear and / or cyclic organopolysiloxane having at least two hydrosilyl groups in one molecule is preferable, and from the viewpoint of good compatibility in the silicone-based curable composition. Is preferably a cyclic organopolysiloxane. Examples of the cyclic siloxane containing a hydrosilyl group include 1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetra. Siloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-trimethylcyclosiloxane, 1,3,5, 7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11 -Hexamethylcyclosiloxane and the like are exemplified. From the viewpoint of availability, 1,3,5,7-tetramethylcyclotetrasiloxane is preferable.

  The molecular weight of the component (C-2) is not particularly limited and any can be suitably used, but those having a low molecular weight are preferably used from the viewpoint of easier expression of fluidity. In this case, the lower limit of the preferable molecular weight is 58, and the upper limit of the preferable molecular weight is 100,000, more preferably 1,000, and still more preferably 700.

  Moreover, it is not necessary for all of the alkenyl groups of the component (C-1) to react with the hydrosilyl group of the component (C-2). After reacting the components (C-1) and (C-2) The number of residual alkenyl groups derived from the component (C-1) and the number of residual hydrosilyl groups derived from the component (C-2) may be 3 or more, but if the number of alkenyl groups is too large, the heat resistance of the composition Light resistance may be reduced.

  Moreover, (C) component in this invention is (C) with respect to a total of 100 weight part of (A) component and (B) component from a viewpoint of reducing the stress at the time of hardening a silicone type curable composition, (C) ) Component is 0.5 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, 0.5 to 1 part by weight More preferably. If it is less than 0.5 part by weight, curing may be insufficient, and if it exceeds 10 parts by weight, the stress when cured increases, for example, the present invention is applied to a substrate bonding adhesive in a display device. When used as a display device, there is a possibility that a defect occurs in the display device.

<(D) Hydrosilylation catalyst>
The hydrosilylation catalyst in the present invention is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. For example, a platinum simple substance, a support made of alumina, silica, carbon black or the like on which solid platinum is supported, chloroplatinic acid , Complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (eg, Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ), Platinum-vinylsiloxane complexes (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complexes (for example, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum - phosphite complex _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me Methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers.), Dicarbonyldichloroplatinum, Karlstedt catalyst, and Ashby, USA And platinum-hydrocarbon complexes described in US Pat. Nos. 3,159,601 and 3,159,622, and platinum alcoholate catalysts described in US Pat. No. 3,220,972 to Lamoreaux. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. , Etc.

  Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

The addition amount of the catalyst is not particularly limited, but in order to have sufficient curability and keep the cost of the curable composition relatively low, it is 10 ⁻¹ to 10 ⁻⁸ mol relative to 1 mol of allyl group. The range is preferable, and more preferably in the range of 10 ⁻² to 10 ⁻⁶ mol.

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, amine compounds such as triethylamine, and the like. The amount of the cocatalyst added is not particularly limited, but is preferably in the range of 10 ⁻² to 10 ² mol, more preferably in the range of 10 ⁻¹ to 10 mol, with respect to 1 mol of the catalyst.

<Other additives>
In order to adjust the crosslinking density of the cured product obtained by solidifying the silicone-based curable composition in the present invention, a compound having three or more alkenyl groups or hydrosilyl groups can be added in one molecule. The structure of the compound is not particularly limited, but if it is intentionally exemplified, examples of the compound having 3 or more alkenyl groups in one molecule include triallyl isocyanurate, trivinylcyclohexane, trivinylbenzene, 2,3-divinyl- 1-pentene and the like can be mentioned, but from the viewpoint of light resistance of the optical adhesive in the present invention, triallyl isocyanurate or trivinylcyclohexane is preferably used, and from the viewpoint of heat resistance, triallyl isocyanurate is preferably used. Further preferred. Examples of the compound having three or more hydrosilyl groups in one molecule include linear dimethylhydrogenpolysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5. , 7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, , 3,5-trihydrogen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7, 9,11-Hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane is mentioned as an example, but it is linear from the viewpoint of operability of the composition. It is preferable to use dimethyl polysiloxane. Further, the addition amount of the additive is preferably 5 parts by weight or less with respect to a total of 100 parts by weight of the component (A) and the component (B) from the viewpoint of light resistance. More preferably, the amount is 1 part by weight or less.

<Silicone-based curable composition>
The silicone-based curable composition in the present invention is not particularly limited as long as it is a curable composition that causes a curing reaction by hydrosilylation and includes a compound containing a silicon atom as one of the components. A variety of organic and inorganic compounds can be used. The viscosity of the composition is preferably 700 cP or less, preferably 500 cP or less, and more preferably 300 cP or less, from the viewpoint of handling properties as an optical adhesive. When the viscosity exceeds 700 cP, for example, when the silicone composition in the present invention is thinly applied, it may be difficult to obtain a uniform coating.

<Curing retarder>
A curing retarder can be used for the purpose of improving the storage stability of the silicone-based curable composition of the present invention or adjusting the reactivity of the hydrosilylation reaction during the production process. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide and the like. Examples of nitrogen-containing compounds include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Of these curing retarders, benzothiazole, thiazole, dimethyl malate, and 3-hydroxy-3-methyl-1-butyne are preferred from the viewpoint of good retarding activity and good raw material availability.

The addition amount of the storage stability improving agent is preferably in the range of lower limit 10 ⁻¹ mol and upper limit 10 ³ mol, more preferably in the range of lower limit 1 mol and upper limit 50 mol, with respect to 1 mol of the hydrosilylation catalyst used.

<Adhesive agent>
To the silicone-based curable composition of the present invention, an adhesion-imparting agent can be added as an additive for the purpose of improving the adhesion to an adherend, such as a silane coupling agent, a boron-based coupling agent, titanium It is possible to use a system coupling agent, an aluminum coupling agent, or the like.

  Examples of the silane coupling agent include at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group in the molecule, and a silicon atom-bonded alkoxy group. A silane coupling agent having a group is preferred. About the said functional group, an epoxy group, a methacryl group, and an acryl group are especially preferable in a molecule | numerator from the point of sclerosis | hardenability and adhesiveness especially.

  Specifically, as the organosilicon compound having an epoxy functional group and a silicon atom-bonded alkoxy group, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxy) And cyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

  Examples of the organosilicon compound having a methacryl group or an acryl group and a silicon atom-bonded alkoxy group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acrylonitrile. Examples include, but are not limited to, loxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

  Examples of the boron-based coupling agent include trimethyl borate, triethyl borate, tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, Examples include, but are not limited to, tri-butyl borate, tri-sDE-butyl borate, tri-tDrt-butyl borate, triisopropyl borate, tri-propyl borate, triallyl borate, and boron methoxyethoxide.

  Examples of the titanium coupling agent include tetra (n-butoxy) titanium, tetra (i-propoxy) titanium, tetra (stearoxy) titanium, di-i-propoxy-bis (acetylacetonate) titanium, i- Propoxy (2-ethylhexanediolate) titanium, di-i-propoxy-diethylacetoacetate titanium, hydroxy-bis (lactate) titanium, i-propyltriisostearoyl titanate, i-propyl-tris (dioctylpyrophosphate) titanate, Tetra-i-propyl) -bis (dioctyl phosphite) titanate, tetraoctyl-bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) et Renchitaneto, i- propyl trioctanoyl titanate, but i- propyl dimethacrylate -i- stearoyl titanate is exemplified, but not limited thereto.

  Examples of the aluminum coupling agent include, but are not limited to, aluminum butoxide, aluminum isopropoxide, aluminum acetylacetonate, aluminum ethylacetoacetonate, and acetoalkoxyaluminum diisopropylate.

  The adhesiveness imparting agent in the present invention may be used alone or in combination of two or more. The addition amount is preferably 5 parts by weight or less with respect to 100 parts by weight as a total of the component (A) and the component (B). In addition, depending on the type or addition amount of the adhesion-imparting agent, there are those that inhibit the hydrosilylation reaction, so the influence on the hydrosilylation reaction must be considered.

<Physical properties of cured product>
The silicone-based curable composition in the present invention cures the curable composition from the viewpoint of reducing stress generation due to curing shrinkage, for example, when used as a bonding adhesive in a display device on which a substrate is fixed. It is preferable that the cured product obtained in this way is soft.
As a specific example, the penetration specified in JIS K 2220 can be cited as an example. The cured product obtained by curing the curable composition of the present invention has a penetration of 60 or more, preferably 70 or more, and more preferably 80 or more. When the penetration is less than 60, the cured product becomes hard. For example, when the present invention is used as a substrate bonding adhesive in a display device, there are cases where sinks, wrinkles, etc. are generated and the display device is defective. is there.

  The silicone-based curable composition according to the present invention can be used as various optical adhesives. For example, bonding adhesives between various circuit boards, bonding adhesives between circuit boards and coverlay films, bonding adhesives for copper-clad films for bonding polyimides and copper foils, bonding adhesives between glass substrates Agent, a bonding adhesive between polarizing films, a flexible display panel bonding adhesive, and the like.

  Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

(Glass substrate bonding test)
Attach a 20 μm-thick polyimide tape (cut into 2 cm squares) to each end of a slide glass (width 26 mm × length 76 mm × thickness 1.2 to 1.5 mm, hereinafter referred to as glass substrate 1), This was used as a spacer. Further, an epoxy adhesive (made by Cemedine) was applied to the center of the slide glass in a square shape of about 1.5 cm ± 0.2 mm square. The curable composition was poured into the epoxy resin dam thus produced, and another slide glass (hereinafter referred to as a glass substrate 2) was pressed from above, and the temperature was set at 1 at 150 ° C. in a convection oven. Cured for hours. The state of the curable composition after curing is visually observed. If no defective mode occurs, ◎, if slightly sink or wrinkle is observed, but if a large defective mode is not observed, ○, sink or If the wrinkles were severe and the defective mode was clearly observed, it was judged as Δ, and if the sinks and wrinkles further progressed and cracks were generated, it was judged as x.

(Adhesion test for plastic substrates)
In the above glass substrate bonding test, the same test as described above was performed except that an Amodel board was used instead of the glass substrate 2. If the Amodel board was completely adhered, ◎, some wrinkles and sink marks occurred. The case was evaluated as ◯, the case where slight peeling was observed from the Amodel board due to wrinkles and sink marks, and the case where it was completely peeled off from the Amodel board.

(Thermal stability test)
500 mg of the obtained silicone-based curable composition was applied onto a glass substrate using a dropper. This was cured by heating in a convection oven at 150 ° C. for 1 hour, and the obtained cured product was further heated in a convection oven at 100 ° C. for 100 hours to perform a thermal stability test. The state of the cured product after heating is visually observed, ◎ if there is no change from before the test, ○ if the surface is slightly colored, △ if the entire cured product is colored, colored When a failure mode such as an upper crack occurred, it was judged as x.

(Viscosity measurement)
The viscosity of the obtained silicone-based curable composition was measured with an E-type viscometer.

(Penetration test)
The obtained silicone-based curable composition was filled into a mold and cured in a convection oven at 150 ° C. for 5 hours to prepare a sample having a length of 35 mm, a width of 5 mm, and a thickness of 2 mm. A penetration test was conducted on the cured product thus obtained according to JIS K2220.

(Synthesis Example 1)
A stirrer, a condenser, and a dropping funnel were set in a 1 L four-necked flask. Into this flask, 190 g of toluene, 48 mg of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum), 236.2 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and heated and stirred at 70 ° C. in an oil bath. did. To this solution, a 10 g toluene solution of 20.0 g 1,2,4-trivinylcyclohexane was added dropwise over 1 hour. The obtained solution was heated and stirred in an oil bath at 70 ° C. for 90 minutes. 9.2 mg of 1-ethynyl-1-cyclohexanol was added. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ^{According to 1} H-NMR, this is a product in which a part of the hydrosilyl group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with 1,2,4-trivinylcyclohexane (hereinafter referred to as modified product A). I found out. The modified product A thus obtained was used as the component (C) in Examples 1, 3, 4, and 5.

(Synthesis Example 2)
A stirrer, a condenser, and a dropping funnel were set in a 5 L two-necked flask. To this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and the mixture was heated and stirred in an oil bath at 120 ° C. To this solution, 200 g of triallyl isocyanurate, 200 g of toluene and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) were added dropwise over 50 minutes. The resulting solution was stirred for 6 hours as it was. After adding 2.95 mg of 1-ethynyl-1-cyclohexanol, unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain 724 g of a product. ^{From 1} H-NMR, it is understood that this is a product in which a part of the hydrosilyl group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with triallyl isocyanurate (hereinafter referred to as modified product B). It was. The modified product B thus obtained was used as the component (C) in Examples 2, 6, 7, and 8.

Example 1
22 mg of modified product A obtained in Synthesis Example 1, 1 g of MVD8MV (manufactured by Clariant) having a alkenyl group at both ends, and DMS-H11 (manufactured by Gelest) having a siloxane compound having hydrosilyl groups at both ends 1.28 g, 0.3% xylene solution of platinum vinylsiloxane complex (containing 0.5 wt% as platinum), and 1-ethynyl-1-cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing retarder 10.1 μL of a 10% xylene solution was mixed to obtain a silicone-based curable composition, which was used for various tests.

(Example 2)
22 mg of the modified product B obtained in Synthesis Example 2, 1 g of MVD8MV (manufactured by Clariant) having alkenyl groups at both ends, and DMS-H11 (manufactured by Gelest) having siloxane compounds having hydrosilyl groups at both ends 1.28 g, 0.3% xylene solution of platinum vinylsiloxane complex (containing 0.5 wt% as platinum), and 1-ethynyl-1-cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing retarder 10.1 μL of a 10% xylene solution was mixed and used as a silicone-based curable composition for various tests.

Example 3
24 mg of the modified product A obtained in Synthesis Example 1, MVD8MV (manufactured by Clariant), which is a siloxane compound having alkenyl groups at both ends, 1.00 g, DMS-V31 (manufactured by Gerest) having alkenyl groups at both ends, 2.00 g 1.35 g of DMS-H11 (Gerest Co., Ltd.), a siloxane compound having hydrosilyl groups at both ends, 10.7 μL of a 0.3% xylene solution of platinum vinylsiloxane complex (containing 0.5 wt% as platinum), and further curing As a retarder, 6.2 μL of a 10% xylene solution of 1-ethynyl-1-cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed and used for various tests to obtain a silicone-based curable composition.

Example 4
24 mg of the modified product A obtained in Synthesis Example 1, MVD8MV (manufactured by Clariant), which is a siloxane compound having alkenyl groups at both ends, 1.00 g, DMS-V31 (manufactured by Gerest), 1.00 g having alkenyl groups at both ends , 1.31 g of DMS-H11 (Gerest Co., Ltd.), a siloxane compound having hydrosilyl groups at both ends, 10.4 μL of a 0.3% xylene solution of platinum vinylsiloxane complex (containing 0.5 wt% as platinum), and further curing As a retarder, 6.1 μL of a 10% xylene solution of 1-ethynyl-1-cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed and used in various tests to obtain a silicone-based curable composition.

(Example 5)
23 mg of the modified product A obtained in Synthesis Example 1, MVD8MV (manufactured by Clariant), which is a siloxane compound having alkenyl groups at both ends, 1.00 g, 0.7 g of DMS-V31 (manufactured by Gerest) having alkenyl groups at both ends 1.30 g of DMS-H11 (manufactured by Gerest), a siloxane compound having hydrosilyl groups at both ends, 10.4 μL of a 0.3% xylene solution of platinum vinylsiloxane complex (containing 0.5 wt% as platinum), and further curing As a retarder, 6.1 μL of a 10% xylene solution of 1-ethynyl-1-cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed and used in various tests to obtain a silicone-based curable composition.

(Example 6)
24 mg of the modified product B obtained in Synthesis Example 2, MVD8MV (manufactured by Clariant), which is a siloxane compound having alkenyl groups at both ends, 1.00 g, DMS-V31 (manufactured by Gerest) having alkenyl groups at both ends, 2.00 g 1.35 g of DMS-H11 (Gerest Co., Ltd.), a siloxane compound having hydrosilyl groups at both ends, 10.7 μL of a 0.3% xylene solution of platinum vinylsiloxane complex (containing 0.5 wt% as platinum), and further curing As a retarder, 6.2 μL of a 10% xylene solution of 1-ethynyl-1-cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed and used for various tests to obtain a silicone-based curable composition.

(Example 7)
24 mg of the modified product B obtained in Synthesis Example 2, MVD8MV (manufactured by Clariant), which is a siloxane compound having alkenyl groups at both ends, 1.00 g, DMS-V31 (manufactured by Gerest), which has alkenyl groups at both ends, 1.00 g , 1.31 g of DMS-H11 (Gerest Co., Ltd.), a siloxane compound having hydrosilyl groups at both ends, 10.4 μL of a 0.3% xylene solution of platinum vinylsiloxane complex (containing 0.5 wt% as platinum), and further curing As a retarder, 6.1 μL of a 10% xylene solution of 1-ethynyl-1-cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed and used in various tests to obtain a silicone-based curable composition.

(Example 8)
23 mg of the modified product B obtained in Synthesis Example 2, MVD8MV (manufactured by Clariant), which is a siloxane compound having alkenyl groups at both ends, 1.00 g, DMS-V31 having a alkenyl group at both ends (manufactured by Gerest), 0.7 g 1.30 g of DMS-H11 (manufactured by Gerest), a siloxane compound having hydrosilyl groups at both ends, 10.4 μL of a 0.3% xylene solution of platinum vinylsiloxane complex (containing 0.5 wt% as platinum), and further curing As a retarder, 6.1 μL of a 10% xylene solution of 1-ethynyl-1-cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed and used in various tests to obtain a silicone-based curable composition.

Example 9
6.5 mg of the modified product B obtained in Synthesis Example 2, 5 g of DMS-V25 (manufactured by Gelest) having a siloxane group having an alkenyl group at both ends, and DMS-H11 (gelest) having a compound having a hydrosilyl group at the terminal. 232 mg, HMS-301 (Gerest Co., Ltd.) 28 mg which is a compound having 3 or more hydrosilyl groups in one molecule as an additive, 0.3% xylene solution of platinum vinylsiloxane complex (0.5 wt% as platinum) 1.4 μL, and further, 2.4 μL of 10% xylene solution of 1-ethynyl-1-cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing retarder was mixed to obtain a silicone-based curable composition. Used for.

(Example 10)
6.5 mg of the modified product B obtained in Synthesis Example 2, 5 g of DMS-V25 (manufactured by Gelest) having a siloxane group having an alkenyl group at both ends, and DMS-H11 (gelest) having a compound having a hydrosilyl group at the terminal. 204 mg, 43 mg of HMS-301 (manufactured by Gerest), a compound having 3 or more hydrosilyl groups in one molecule as an additive, 0.3% xylene solution of platinum vinylsiloxane complex (0.5 wt% as platinum) 1.4 μL, and further, 2.4 μL of 10% xylene solution of 1-ethynyl-1-cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing retarder was mixed to obtain a silicone-based curable composition. Used for.

(Comparative Example 1)
240 mg of modified product A obtained in Synthesis Example 1, 1 g of MVD8MV (manufactured by Clariant) having alkenyl groups at both ends, and DMS-H11 (manufactured by Gelest) having siloxane compounds having hydrosilyl groups at both ends ) 1.28 g, 0.3% xylene solution of platinum vinylsiloxane complex (containing 0.5 wt% as platinum), 1-ethynyl-1-cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) as curing retarder A 10% xylene solution of 10.1 μL was mixed to obtain a silicone-based curable composition, which was used in various tests.

(Comparative Example 2)
240 g of the modified product B obtained in Synthesis Example 2, 1 g of MVD8MV (manufactured by Clariant) having a alkenyl group at both ends, and DMS-H11 (manufactured by Gelest) having a siloxane compound having hydrosilyl groups at both ends ) 1.28 g, 0.3% xylene solution of platinum vinylsiloxane complex (containing 0.5 wt% as platinum), 1-ethynyl-1-cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd.) as curing retarder A 10% xylene solution of 10.1 μL was mixed to obtain a silicone-based curable composition, which was used in various tests.

(Comparative Example 3)
22 mg of 1,3,5,7-tetramethylcyclotetrasiloxane, 1 g of MVD8MV (manufactured by Clariant), which is a siloxane compound having alkenyl groups at both ends, and DMS-H11, which is a siloxane compound having hydrosilyl groups at both ends (Guerest) 1.28 g, platinum vinylsiloxane complex 0.3% xylene solution (containing 0.5 wt% as platinum) 5.9 μL, further 1-ethynyl-1-cyclohexanol (Wako Pure Chemical Industries) as a retarder 10% xylene solution (manufactured by Kogyo Co., Ltd.) was mixed to obtain a silicone-based curable composition, which was used for various tests.
Various test results are shown in Table 1.

  From Table 1, in Examples 1 and 2, good results were obtained in any of the tests. On the other hand, if too much component (C) was used as in Comparative Examples 1 and 2, the stress at the time of curing was increased, resulting in sink marks. And defective modes such as cracks occur. Moreover, when Example 1 and 2 are compared, in Example 1, although it shows a little coloring in a thermal stability test, since Example 2 does not have coloring, it is an isocyanuric ring as a compound which has an alkenyl group of (C-1) component. It can be seen that it is preferable to use. Furthermore, when Examples 3-8 are compared, even if it is a composition which has the same structural component, it turns out that the one where a viscosity is lower does not produce a malfunction at the time of a glass bonding test.

  Further, as in Comparative Example 3, a system that does not contain any organic compound has a problem in adhesion to a plastic substrate. From the above, it can be seen that the silicone-based curable composition of the present invention is a compound having excellent properties as an optical adhesive.

Claims (9)

The following (A) to (D) :
(A) an organosiloxane having two alkenyl groups in one molecule ;
(B) a hydrosilyl group and two chromatic per molecule, linear polydimethylsiloxanes having hydrosilyl groups at both ends of the molecular chain,
(C) (C-1) from the hydrosilation reaction and at least hydrosilyl group two Yusuke that ring-shaped organohydrogensiloxane to alkenyl groups of at least two organic compounds having a (C-2) in a molecule a crosslinking agent having three or more heat Doroshiriru groups in one molecule obtained by, and,
(D) Hydrosilylation catalyst
An optical adhesive comprising a silicone-based curable composition containing 0.5 to 3 parts by weight of the component (C) with respect to 100 parts by weight of the total of the components (A) and (B). The optical adhesive according to claim 1, wherein the curable composition has a viscosity of 700 centipoise or less. The optical adhesive according to claim 1 or 2 , wherein the penetration of the cured product obtained by solidifying the curable composition is 65 or more as measured according to JISK2220. The component (C-1) is polybutadiene, vinylcyclohexane, cyclopentadiene, divinylbiphenyl, bisphenol A diarylate, and trivinylcyclohexane, and the following general formula (1)

(Wherein R1, R2, and R3 are all organic groups, and at least two of them are alkenyl groups), and are at least one compound selected from the group consisting of organic compounds An optical adhesive comprising the silicone-based curable composition according to any one of claims 1 to 3 . The component (C-1) is represented by the following general formula (2)

(Both wherein R1, R2, R3 is an organic group, at least two of which are alkenyl groups) silicones according to any one of claims 1-4, characterized by being represented by An optical adhesive comprising a system curable composition. The optical adhesive comprising the silicone-based curable composition according to any one of claims 1 to 5 , wherein the component (A) has a molecular weight in the range of 750 to 100,000. (B) Component is in the range of molecular weight 1000-100000, The optical adhesive consisting of the silicone type curable composition of any one of Claims 1-6 characterized by the above-mentioned. Claim 1-7 display device having an optical adhesive comprising a silicone-based curable composition according to any one. The display device according to claim 8 , wherein at least one of the substrates to be bonded by the optical adhesive is a glass substrate.