JP2013082835A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic and inorganic hybrid type composition which provides a cured material having low refractive index and high hardness, strength and transparency.SOLUTION: The organic and inorganic hybrid type curable composition comprises (A) an organic compound having at least two carbon-carbon double bond having reactivity with SiH group in one molecule, (B) a silicon-containing compound having a three dimensional network structure comprising four functional structural unit expressed by SiO(1) as an essential structure, wherein the terminal of the essential structure has a structure blocked by a monofunctional structural unit expressed by RRSiO(2) and RSiO(3) (in the formula, Rexpresses alkenyl group and Rexpresses substituted or unsubstituted monovalent hydrocarbon group and each of them may be the equal to or different from each other) and the terminal of the essential structure further has a structure blocked by (2) at least two sites and having two alkenyl groups in one molecule, (C) a curing agent having at least two SiH groups in a molecule and (D) a hydrosilylating catalyst.

Description

  The present invention relates to an organic-inorganic hybrid curable composition that provides a resin layer exhibiting excellent light transmittance when used as, for example, a resin layer in contact with a glass substrate in a liquid crystal display panel.

  Many display devices including a liquid crystal display have a portion where a glass substrate and a polymer material are in contact (for example, Patent Document 1). In such a display device, for example, when light from a light source or the like passes through a portion where the glass substrate is in contact with the polymer material, the polymer material has a refractive index from the viewpoint of suppressing reflection of light at the interface. Low is required. As a material that satisfies these requirements, a silicone-based material that does not have a phenyl group has been proposed, but the silicone material has a lower resin strength than an organic polymer material typified by an epoxy resin, and the like. It is known that the adhesiveness is also inferior. Against this background, organic-inorganic hybrid resins have been proposed to give silicone-based materials the characteristics of organic polymer materials. However, when the refractive index is lowered, the characteristics of organic polymer materials are fully manifested. The problem that was not happened. On the other hand, among organic polymer materials, it is known that a fluorine-based resin or the like has a low refractive index, but the resin has a problem of low cohesive force and low adhesion to a substrate and resin strength. From the above, it has been desired to develop a material having a low refractive index similar to that of a silicone resin not having a phenyl group and having adhesiveness and resin strength similar to those of an organic polymer material.

Japanese Patent No. 3983316

  The present invention relates to an organic-inorganic hybrid composition that provides a cured product having a low refractive index and high hardness, high strength, and high transparency.

  The present invention has been made in view of such circumstances, and provides an organic-inorganic hybrid composition that provides a cured product having a low refractive index and high hardness, high strength, and high transparency.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific curable composition exhibits a low refractive index while maintaining the excellent characteristics of a hybrid resin, The present invention has been completed. That is, the present invention has the following configuration.

1). (A) Organic compound having at least two carbon-carbon double bonds having reactivity with SiH group in one molecule (B) General formula (1)
SiO _4/2 (1)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (2) and (3).
R ^a1 R ^a2 ₂ SiO _1/2 (2)
R ^a2 ₃ SiO _1/2 (3)
(Wherein R ^a1 is an alkenyl group, and R ^a2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
At least two alkenyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by the formula (II) and having at least two terminals of the main structure blocked with the general formula (2). An organic-inorganic hybrid curable composition comprising: a silicon-containing compound (C) having at least two SiH groups per molecule (D) and a hydrosilylation catalyst.

  2). The organic-inorganic hybrid curable composition according to 1), wherein a cured product obtained by curing the organic-inorganic hybrid curable composition has a refractive index of 1.475 or less at a wavelength of 588 nm.

  3). The organic-inorganic hybrid curable composition according to 1) or 2), wherein a Shore D hardness of a cured product obtained by curing the organic-inorganic hybrid curable composition is 60 or more.

  4). The number of carbon-carbon double bonds per unit weight of the component (B) is in the range of 3.0 mmol / g to 12 mmol / g, and the organic according to any one of 1) to 3) Inorganic hybrid curable composition.

  5). (A) component is (A) component is diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2, -tetraallyloxyethane Diarylidene pentaerythritol, triallyl cyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monomethyl isocyanurate, monoallyl dimethyl isocyanurate, 1,2,4-trivinylcyclohexane, divinyl biphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1 2) A ratio of 50 to 100%), at least one compound selected from the group consisting of an allyl ether of novolak phenol and an allylated polyphenylene oxide 1) to 4) Organic-inorganic hybrid curable composition.

  6). (A) Component is triallyl isocyanurate or diallyl monomethyl isocyanurate, The organic-inorganic hybrid curable composition according to any one of 1) to 5).

  7). (C) component (C-1) 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 The organic-inorganic hybrid curable composition as described in any one of 1) to 6) above, which is an organically modified silicone compound (C-3) obtained by a chemical reaction

  8). The component (C-1) is polybutadiene, vinylcyclohexane, cyclopentadiene, divinylbiphenyl, bisphenol A diarylate, and trivinylcyclohexane, and the following general formula (4)

(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) -7) The organic-inorganic hybrid curable composition according to any one of items 1 to 7).

  9). The component (C-1) is represented by the following general formula (5)

(Wherein R1, R2, and R3 are all organic groups, and at least two of them are alkenyl groups) 1) to 8) organic according to any one of the above Inorganic hybrid curable composition.

  10). The organic-inorganic hybrid curable composition according to any one of 1) to 9), wherein the component (C-2) is a cyclic polyorganosiloxane having at least two hydrosilyl groups in one molecule. object.

  11). 1) to 10) A cured product obtained by curing the organic-inorganic hybrid curable composition according to any one of items 1 to 10.

  12). 1) to 10) A laminate obtained by coating and baking the organic-inorganic hybrid curable composition according to any one of items 1 on quartz glass.

  13). The laminate according to 12), wherein the laminate has a light transmittance of 95% or more at a wavelength of 400 nm.

  By using the curable composition of the present invention, for example, the light extraction efficiency from the light source of the display element can be improved.

Hereinafter, the present invention will be described in detail. <Organic compound (A) having at least two carbon-carbon double bonds having reactivity with SiH group>
The component (A) in the present invention will be described. The component (A) is an organic compound composed of an organic skeleton having at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule. In the component (A), the structure is bonded to the skeleton part by a covalent bond (in some cases via a substituent having a valence of 2 or more) and has a reactivity with the SiH group. When divided into groups having a heavy bond (alkenyl group), the alkenyl group may be present anywhere in the molecule. The skeleton of the component (A) that is an organic compound is not particularly limited, and an organic polymer skeleton or an organic monomer skeleton may be used. Examples of organic polymer skeletons include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, polyacrylate, polyamide, phenol-formaldehyde (phenolic resin), and polyimide. A skeleton can be used. Examples of the monomer skeleton include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene, aliphatic hydrocarbons, and mixtures thereof. The alkenyl group of component (A) is not particularly limited as long as it has reactivity with the SiH group. As the component (A), 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, decadiene, cyclopentadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene, norbornadiene, triallyl isocyanurate, Examples include aliphatic cyclic polyene compound systems such as trivinylcyclohexane, and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene. As said (A) component, from a viewpoint that heat resistance can be improved more, 0.001 mol or more of carbon-carbon double bonds which have reactivity with SiH group are contained per 1 g of (A) component. Although what is necessary is just to contain 0.005 mol or more per gram, what contains 0.008 mol or more is especially preferable. Specific examples include butadiene, isoprene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, cyclohexadiene, decadiene, diallyl phthalate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, divinylbenzenes (purity 50-100% 1,3-diisopropenyl benzene, 1,4-diisopropenyl benzene, and oligomers thereof, 1,2-polybutadiene (1,2 ratio 10-100) %, Preferably 1,2 ratio of 50 to 100%), triallyl isocyanurate, trivinylcyclohexane, and the like. In addition, as the component (A), the component weight ratio in the component (A) of the aromatic ring is 50 wt% or less from the viewpoint of good optical properties such as a low refractive index and a low photoelastic coefficient. Are preferably 40 wt% or less, more preferably 30% or less. Most preferred are those that do not contain an aromatic ring. From the viewpoint that the resulting cured product is less colored and has high optical transparency and less light-resistant colorability, the component (A) includes vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate, and trivinylcyclohexane. Among them, triallyl isocyanurate and trivinylcyclohexane are more preferable.

<(B) component>
The component (B) in the present invention will be described.
The component (B) has the general formula (1)
SiO _4/2 (1)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (2) and (3).
R ^a1 R ^a2 ₂ SiO _1/2 (2)
R ^a2 ₃ SiO _1/2 (3)
(Wherein R ^a1 is an alkenyl group, and R ^a2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
At least two alkenyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by the formula (II) and having at least two terminals of the main structure blocked with the general formula (2). A silicon-containing compound.

  The alkenyl group is preferably a vinyl group, an allyl group, a butenyl group, or a hexenyl group, and more preferably a vinyl group from the viewpoints of availability, heat resistance, and light resistance.

  Examples of substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, phenyl groups, and tolyl groups. The same or different aryl groups or the same or different selected from chloromethyl group, trifluoropropyl group, cyanoethyl group, etc. in which part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups Of these, preferred are unsubstituted or substituted monovalent hydrocarbon groups having preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Among these, a methyl group is more preferable from the viewpoint of heat resistance and light resistance.

  Further, the component (B) preferably has a number of carbon-carbon double bonds per unit weight in the range of 3.0 mmol / g to 12.0 mmol / g, 4.0 mmol / g to 10.0 mmol / g. It is preferably in the range of g, more preferably in the range of 5.0 mmol / g to 9.0 mmol / g. When the number of carbon-carbon double bonds per unit weight is less than 3.0 mmol / g, the hardness of the cured product obtained by curing the organic-inorganic hybrid composition in the present invention may be low. When exceeding 12.0 mmol / g, the toughness of hardened | cured material may become low.

  Furthermore, the component (B) is preferably liquid at room temperature because it is easy to handle. The viscosity at room temperature is preferably 1000 Pa · s or less, and more preferably 100 Pa · s or less. .

  Furthermore, the component (B) is preferably 20 wt% to 70 Wt% in the composition, more preferably 30 wt% to 60 wt%, and even more preferably 40 wt% to 50 wt%. When the component (B) is less than 20 wt%, the refractive index of the cured product obtained by curing the organic-inorganic hybrid type composition in the present invention may not be effectively lowered. The toughness of the object may decrease.

  In addition to the component (B), a silicon-containing compound containing two or more alkenyl groups in one molecule can be partially added. Examples of the silicon-containing compound containing two or more alkenyl groups in one molecule include linear and cyclic silicon-containing compounds. These silicon compounds are also good as in the case of the component (B). From the viewpoint of providing a cured product having transparency, the number of carbon-carbon double bonds per unit weight is preferably in the range of 3.0 mmol / g to 12.0 mmol / g, and 4.0 mmol / g to 10 to 10. It is preferably in the range of 0.0 mmol / g, and more preferably in the range of 5.0 mmol / g to 9.0 mmol / g.

  Examples of linear silicon-containing compounds containing two or more alkenyl groups in one molecule include polysiloxanes terminated with dimethylvinylsilyl groups, dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy. Examples thereof include a copolymer with a unit.

  Examples of cyclic silicon-containing compounds containing two or more alkenyl groups in one molecule include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1 -Propyl-3,5,7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane Etc. can be exemplified.

  The addition amount of these linear and cyclic silicon-containing compounds is preferably in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the total of component (A), component (B), and component (C). , Preferably in the range of 1-15 parts by weight, more preferably in the range of 1-10 parts by weight. When the addition amount exceeds 20 parts by weight, the strength of the cured product may be reduced.

<Curing agent (C) having at least two SiH groups in one molecule>
The component (C) in the present invention will be described. Component (C) in the present invention is a curing agent having at least two SiH groups in one molecule.
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). It is preferable to use an organically modified silicone (C-3) obtained by hydrosilylation reaction of an organohydrogensiloxane (C-2) having two. 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 preferably in the range of 0.5 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, and even more preferably 0.5 to 5 parts by weight. 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.

<Hydrosilylation catalyst (D)>
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.

<Organic / inorganic hybrid curable composition>
The organic-inorganic hybrid composition in the present invention will be described. The organic-inorganic hybrid curable composition in the present invention is a curable composition comprising the component (A) that is an organic compound, the components (B) and (C) that are silicone compounds, and the component (D) that is a platinum catalyst. If it is a composition, it will not specifically limit, In addition to these each component, a various component can be added as an additional component. Specific examples of these additive components include polymer additives, adhesion-imparting agents, curing retarders and the like.
Specific examples of the polymer additive include epoxy resin, alkyd resin, silicone resin, bismaleimide triazine resin, polyamide resin, aramid resin, phenol resin, polyester resin, cellulose resin, polycarbonate resin, urea resin, urethane resin, poly An ether resin etc. are mentioned, These may be used independently or may use 2 or more types together. Of these polymer additives, an epoxy resin or a silicone resin is preferably used from the viewpoint of heat resistance, and a silicone resin is more preferably used from the viewpoint of heat resistance and light resistance.

  As specific examples of the adhesion imparting agent, a silane coupling agent, a boron-based coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, or the like can be used.

  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 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.

  Specific examples of the curing retardant include compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, and the like. It doesn't matter. 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.

<Hardened product obtained by curing organic-inorganic hybrid curable composition>
The hardened | cured material formed by hardening | curing the organic inorganic hybrid type curable composition in this invention is demonstrated. The cured product obtained by curing the organic-inorganic hybrid curable composition in the present invention is a curable composition obtained by baking the organic-inorganic hybrid curable composition. The cured product has a type D durometer hardness of 60 or more, preferably 70 or more, and more preferably 75 or more. When the hardness is less than 60, for example, when the cured product according to the present invention is diced, there is a risk of resin chipping.
From the same viewpoint, the cured product in the present invention preferably has a high resin strength. Any method for measuring the resin strength can be used, and an example is a die shear test method. A specific measurement method will be described below. The liquid composition after blending is stretched into a film shape with an applicator having a thickness of 100 μm, a 2 mm square glass die is brought into contact therewith, the liquid composition is adhered to one side of the die, glass epoxy and aluminum The test piece which carried out the thermosetting (adhesion) in steps in 80 degreeC * 2 hours, 100 degreeC * 1 hour, and 150 degreeC * 5 hours in the convection oven was created on each flat plate. Using this test piece, an adhesive strength between a glass epoxy flat plate and a glass die was evaluated using a universal bond tester 2400 manufactured by Daisy. A 10 kgf load cell was used and the test speed was 83 μm / sec. Measurement is performed at n = 5, and three average values excluding the maximum value and the minimum value are taken as the resin strength. The resin strength of the cured product in the present invention is preferably 8 kg · f or more, more preferably 12 kg · f or more, and further preferably 15 kg · f or more. When the resin strength is less than 8 kg · f, resin chipping or the like may occur.
Further, the cured product in the present invention preferably has a refractive index of 1.475 or less at a wavelength of 588 nm (D line), more preferably 1.472 or less, and further preferably 1.470 or less. When the refractive index exceeds 1.475, for example, the light transmittance of a laminate obtained by coating and baking the organic-inorganic hybrid composition in the present invention on a glass substrate may be lowered.

<Laminated body obtained by coating and baking organic / inorganic hybrid curable composition on glass substrate>
A laminate obtained by coating and baking the organic-inorganic hybrid curable composition of the present invention on a glass substrate will be described. The laminate formed by coating and baking the organic-inorganic hybrid curable composition on quartz glass according to the present invention is a laminate obtained by coating the organic-inorganic hybrid curable composition according to the present invention on a glass substrate by any method. -The laminated body obtained by baking is shown.
Any glass substrate may be used, and examples include soda lime glass, non-alkali glass, and quartz glass. From the viewpoint of application to optical devices, it is preferable to use quartz glass. Moreover, the glass substrate and the organic-inorganic hybrid composition only have to be in contact with a part of the surface of the glass substrate, and a concavo-convex structure may exist on the glass substrate by a photoresist material, metal wiring, or the like.
Similarly, the thickness of the glass substrate is preferably in the range of 0.1 mm to 1.5 mm, more preferably in the range of 0.5 mm to 1.2 mm, from the viewpoint of application to optical devices, and 0.7 mm. More preferably, it is in the range of -1.0 mm. When the thickness is less than 0.1 mm, the laminate may be warped. When the thickness exceeds 1.5 mm, for example, when the laminate of the present invention is used as an optical device, the light transmittance may decrease. is there.

<Light transmittance of laminate>
The light transmittance of the laminate in the present invention indicates the light transmittance when light having a wavelength of 400 nm is incident from the glass substrate direction of the laminate.
From the viewpoint of application to an optical device, the light transmittance of the laminate is preferably 95% or more, more preferably 97% or more, and even more preferably 99% or more at a wavelength of 400 nm. When the light transmittance is less than 95%, for example, when the laminate is applied to an optical device, the light extraction efficiency may be lowered. For the measurement of the light transmittance, for example, a visible ultraviolet spectrophotometer can be used.

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

(Creation of cured product)
The organic-inorganic hybrid curable composition of the present invention is poured into a mold prepared by sandwiching a 3 mm thick silicone rubber spacer between two glass substrates, and is 60 ° C./6 hours, 70 ° C./1 hour, 80 ° C. / A cured product for measurement (thickness 3 mm) was prepared by heating stepwise at 1 hour, 120 ° C./1 hour, 150 ° C./1 hour, and used for various tests.

(Create laminate)
1.5 cc of the organic-inorganic hybrid composition of the present invention is dropped on a 10 cm x 10 cm size quartz glass substrate (0.7 mm thick), and a coating is produced under the following rotation conditions using a spin coater. did.
Rotation condition: reach 500 rpm over 5 seconds → maintain at 500 rpm for 10 seconds → reach 1000 rpm over 5 seconds → maintain 1000 rpm for 30 seconds → stop over 5 seconds.
The cured product thus obtained was baked on a hot plate heated to 160 ° C. for 5 minutes to obtain a laminate and used for various tests.

(Refractive index measurement)
The cured product obtained above was measured for refractive index at a wavelength of 588 nm using a prism coupler.

(Hardness measurement)
According to the method described in JIS K6253, measurement was performed using a durometer HD-1120 manufactured by Ueshima Seisakusho. The average value of the measurement values of five measurements was adopted. As the test piece, the cured product obtained above was conditioned in advance at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5% for 24 hours or more before the test.

(Light transmittance measurement)
The light transmittance of the laminate obtained above was measured with a visible ultraviolet spectroscopic hardness meter, and the light transmittance at a wavelength of 400 nm was evaluated. In the measurement, measurement light was incident from the glass substrate side.

(Dicing test)
The cured product obtained above was subjected to a dicing test with a blade having a blade thickness of 0.3 mm using an ISOMET diamond cutter manufactured by BUEHCER. The section after the test was visually observed, and it was evaluated as “◯” when no resin chipping, cracking, or the like occurred, and “X” when resin chipping, cracking, or the like occurred.

(Resin strength test: Die shear test method)
An organic-inorganic hybrid curable composition is stretched into a film shape with an applicator having a thickness of 100 μm, a 2 mm square glass die is brought into contact therewith, and the liquid composition is adhered to one side of the die, and then made of glass epoxy. And the test piece which carried out the thermosetting (adhesion) stepwise on the conditions of 80 degreeC * 2 hours, 100 degreeC * 1 hour, 150 degreeC * 5 hours in the convection oven was put on each flat plate made from aluminum. Using this test piece, an adhesive strength between a glass epoxy flat plate and a glass die was evaluated using a universal bond tester 2400 manufactured by Daisy. A 10 kgf load cell was used and the test speed was 83 μm / sec. Measurement was performed at n = 5, and three average values excluding the maximum value and the minimum value were adopted.

(Synthesis Example 1)
A 3L four-necked flask was set with a sales expansion device, a condenser tube, and a dropping funnel. To this flask was added 300 g of toluene, 300 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and 7.5 ml of a toluene solution of platinum vinylsiloxane complex (containing 0.03 wt% as platinum) at 100 ° C. The mixture was heated and stirred in an oil bath. A solution obtained by dissolving 50 g of 1,3,5,7-tetramethylcyclotetrasiloxane in 240 g of toluene was dropped into this solution over 2 hours. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain 150 g of a product. ^{From 1} H-NMR, this is a product in which a part of the hydrosilyl group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with 1,3-divinyl-1,1,3,3-trimethyldisiloxane. (Hereinafter referred to as modified product B1). The modified product B1 thus obtained was used in Example 2.

(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 heated and stirred as it was for 6 hours. 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 was found that this was a product in which a part of the hydrosilyl group of 1,3,5,7-tetramethylcyclotetrasiloxane was reacted with triallyl isocyanurate (hereinafter referred to as modified product C1). It was. The modified product C1 thus obtained was used as the component (C) in Examples 1 to 3 and Comparative Examples 1 and 2.

(Synthesis Example 3)
A stirrer, a condenser tube, 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 C2 thus obtained was used as the component (C) in Example 4.

(Examples 1-3 and Comparative Examples 1-3)
By blending each component at the blending ratio shown in Table 1, a curable silicone composition part was obtained, and cured products for various evaluations were obtained under predetermined curing conditions, and each evaluation was performed. The details of the components (A) to (C) shown in Table 1 other than the components obtained in the above synthesis examples are shown below.

(A) component triallyl isocyanurate (Evonik Degusza Japan)
Component (B) MQV7: Vinyl group-containing polysiloxane having a three-dimensional structure (manufactured by Clariant, trade name MQV-7, number of carbon-carbon double bonds per unit weight = 3.5 mmol / g)
DMS-V03: vinyldimethylsilicone polymer at both ends (manufactured by Gelest, trade name DMS-V03, number of carbon-carbon double bonds per unit weight = 4 mmol / g)
DMS-V41: both ends vinyl dimethyl silicone polymer (manufactured by Gelest, trade name DMS-V03, number of carbon-carbon double bonds per unit weight = 0.05 mmol / g)
Component (C) MQH5: Hydrosilyl group-containing polysiloxane having a three-dimensional structure (manufactured by Clariant, trade name MQH-5, number of hydrosilyl groups per unit weight = 2.3 mmol / g)
MQH8: Hydrosilyl group-containing polysiloxane having a three-dimensional structure (manufactured by Clariant, trade name MQH-8, number of hydrosilyl groups per unit weight = 7.5 mmol / g)

Table 2 shows various evaluation results. From Table 2, when Examples 1 to 3 and Comparative Examples 1 and 2 are compared, each cured product has a low refractive index, but Comparative Example 1 has a low number of carbon-carbon double bonds per unit weight ( It can be seen that since the component B) is used, the hardness is low, and the compatibility between the component (B) and other components is low and the light transmittance is low. When Example and Comparative Example 3 are compared, it can be seen that Comparative Example 3, which is not an organic-inorganic hybrid composition, is brittle and has low resin strength, although the hardness can be maintained high. Moreover, when Example and Comparative Example 2 are compared, although all have high hardness, resin strength, and light transmittance, it turns out that Comparative Example 2 has many organic frame | skeletons and the refractive index is high.
From the above, it was found that the refractive index can be lowered without impairing the advantages of the hybrid resin by the presence of the component (B) having a specific structure.

Claims (13)

(A) Organic compound having at least two carbon-carbon double bonds having reactivity with SiH group in one molecule (B) General formula (1)
SiO _4/2 (1)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (2) and (3).
R ^a1 R ^a2 ₂ SiO _1/2 (2)
R ^a2 ₃ SiO _1/2 (3)
(Wherein R ^a1 is an alkenyl group, and R ^a2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
At least two alkenyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by the formula (II) and having at least two terminals of the main structure blocked with the general formula (2). An organic-inorganic hybrid curable composition comprising: a silicon-containing compound (C) having at least two SiH groups per molecule (D) and a hydrosilylation catalyst. The organic-inorganic hybrid curable composition according to claim 1, wherein the cured product obtained by curing the organic-inorganic hybrid curable composition has a refractive index of 1.475 or less at a wavelength of 588 nm. The organic-inorganic hybrid curable composition according to claim 1 or 2, wherein a Shore D hardness of a cured product obtained by curing the organic-inorganic hybrid curable composition is 60 or more. The number of carbon-carbon double bonds per unit weight of (B) component exists in the range of 3.0 mmol / g-12 mmol / g, The organic of any one of Claims 1-3 characterized by the above-mentioned. Inorganic hybrid curable composition. (A) component is (A) component is diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2, -tetraallyloxyethane Diarylidene pentaerythritol, triallyl cyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monomethyl isocyanurate, monoallyl dimethyl isocyanurate, 1,2,4-trivinylcyclohexane, divinyl biphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1 2 to 50%), at least one compound selected from the group consisting of allyl ethers of novolak phenols and allylated polyphenylene oxides. Organic-inorganic hybrid curable composition. The organic-inorganic hybrid curable composition according to any one of claims 1 to 5, wherein the component (A) is triallyl isocyanurate or diallyl monomethyl isocyanurate. (C) component (C-1) 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 The organic-inorganic hybrid curable composition according to any one of claims 1 to 6, which is (C-3) an organically modified silicone compound obtained by a reaction of hydration. The component (C-1) is polybutadiene, vinylcyclohexane, cyclopentadiene, divinylbiphenyl, bisphenol A diarylate, and trivinylcyclohexane, and the following general formula (4)

(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 The organic-inorganic hybrid curable composition according to any one of claims 1 to 7. The component (C-1) is represented by the following general formula (5)

(Wherein R1, R2, and R3 are all organic groups, and at least two of these are alkenyl groups), and the organic according to any one of claims 1 to 8, Inorganic hybrid curable composition. The organic-inorganic hybrid curable composition according to any one of claims 1 to 9, wherein the component (C-2) is a cyclic polyorganosiloxane having at least two hydrosilyl groups in one molecule. object. Hardened | cured material formed by hardening | curing the organic-inorganic hybrid curable composition of any one of Claims 1-10. A laminate obtained by coating and baking the organic-inorganic hybrid curable composition according to any one of claims 1 to 10 on quartz glass. The laminate according to claim 12, wherein the laminate has a light transmittance of 95% or more at a wavelength of 400 nm.