JP5383250B2 - Curable resin composition and cured product - Google Patents

Description

  The present invention relates to a curable resin composition and a cured product. Specifically, a curable resin composition capable of obtaining a cured product useful as an optical material, a mechanical component material, an electrical / electronic component material, etc. for optical applications, optical device applications, display device applications, and the like, and obtained using the same. Relates to the cured product.

  Molded materials with cured resin are widely used, including machine parts materials, electrical / electronic parts materials, automotive parts materials, civil engineering and building materials, etc. Also, other than molded products, they are cured as various paints and adhesives. A resin composition containing a functional resin is used. Since these curable resin compositions can contain an inorganic substance, the coefficient of thermal expansion of the cured product can be lowered, and heat resistance and transparency can be improved. In particular, it is expected to be useful as an alternative to inorganic glass in electronic / electrical component materials. Specifically, since digital camera modules are being miniaturized, such as being mounted on mobile phones, and cost reduction is required, the use of plastic lenses such as PMMA / PC and polycycloolefin instead of inorganic glass has advanced. In addition, considering the use in a high-temperature exposure environment such as an in-vehicle camera, long-term heat resistance is required, and therefore further investigations on curable resin compositions are underway.

  As a curable resin composition such as these, a silicone resin composition capable of mainly obtaining a cured product having excellent heat resistance and transparency, and has a low curing shrinkage and good moldability compared to other curable resins. A curable epoxy resin composition etc. are mentioned. Among these, in the silicone resin composition, a method of adding a high-density siloxane compound such as a specific organopolysiloxane, for example, a polyfunctional cage-type silsesquioxane or a ladder-type silsesquioxane, in order to reduce the coefficient of thermal expansion. Has been proposed (see, for example, Patent Document 1). In addition, many resin compositions including those obtained by addition-curing a specific organopolysiloxane (such as a cage silsesquioxane) and a specific organohydrogenpolysiloxane have been reported (for example, Patent Documents 2 to 2). 4). On the other hand, in the curable epoxy resin composition, a method of adding an inorganic filler powder such as fumed silica for the purpose of improving mechanical properties and heat resistance (for example, see Patent Document 5), In addition to a method of adding inorganic particles as a silica sol, preferably a MEK sol (see, for example, Patent Documents 6 and 7), a method of adding colloidal silica surface-modified with a silane coupling agent (for example, Patent Document 8), etc. Proposed.

JP 2008-133442 A JP 9-316299 A JP 2006-131848 A JP 2008-248170 A JP-A-6-63502 Japanese Patent Laid-Open No. 2004-250521 JP 2002-327165 A JP-A-3-143915

  However, even if a composition containing a silicone resin can obtain a cured product excellent in heat resistance and heat discoloration, it causes shrinkage during the production of the cured product, and there is a problem in reproducibility in obtaining the cured product. There is. On the other hand, a composition containing an epoxy resin has low shrinkage at the time of curing and is excellent in moldability, but there is a problem in heat discoloration that an antimony-based curing catalyst used in combination causes yellowing at a high temperature. is there. These problems are not completely solved in various compositions that have been reported in the past.

  The present invention has been made in view of the current state of the curable resin composition, and is excellent in reproducibility of curing and processing characteristics in the production process of the cured product, and has a low curing shrinkage property that provides a cured product with stable quality. And a curable resin composition capable of obtaining a cured product having heat discoloration resistance, low thermal expansibility, and high transparency. It is an object to provide a cured product.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that, according to the curable resin composition containing a specific complex containing an organic component and an inorganic component, curing shrinkage and thermal discoloration. While solving the problems at the same time, it has been found that a resin composition can be obtained which is excellent in reproducibility of curing and processing characteristics and can obtain a cured product having low thermal expansion and high transparency. It came to be completed.

Accordingly, the present invention provides (A) an organic-inorganic composite having two or more aliphatic unsaturated bonds in one molecule and comprising a cage siloxane and an organic component, which is represented by the following formula (1):
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(However, R ¹ and R ² may be vinyl groups, allyl groups, alkyl groups, aryl groups, (meth) acryloyl groups, or groups having an oxirane ring, and may be the same or different from each other. aliphatic structure of 5 to 50 carbon atoms, group having 5 to 50 carbon atoms having an alicyclic structure, or any one of the groups having 5 to 50 carbon atoms having an aromatic structure, comprising two or more different from each other N, m and l each represent an average value, n is a number from 6 to 14, and m + l is from 2 to 2,000), and the weight average molecular weight is Mw = 5,000 to 1,000,000 at least one or more reactive functional groups selected from the group consisting of a vinyl group having an unsaturated double bond in one molecule, an allyl group, and a (meth) acryloyl group Organic-inorganic composite with two or more, (B) in one molecule An ethylenically unsaturated compound having at least two (meth) acrylic groups and (C) a curing catalyst as essential components, and (A) with respect to a total of 100 parts by weight of components (A), (B) and (C) A curable resin composition containing at least 30 parts by weight of an organic-inorganic composite as a main component.

  Moreover, this invention is a hardened | cured material obtained by hardening | curing said curable resin composition using a heat | fever, light, or both.

  According to the curable resin composition of the present invention, it is possible to obtain a cured product having high heat discoloration and excellent in high transparency, low thermal expansibility and low cure shrinkage. In addition, the cured products obtained can be used in a wide range of applications such as optical materials, optical device applications, display device applications, etc., as well as various mechanical parts, automobile parts, civil engineering and building materials, paints, adhesives, etc. Applicable.

1 is a GPC chart of silanol group-containing cage-type siloxane (21) obtained in Synthesis Example 1. FIG. FIG. 2 is a ¹ H-NMR chart of silanol group-containing cage-type siloxane (21) obtained in Synthesis Example 1. FIG. 3 is a GPC chart of the organic-inorganic composite (22) obtained in Synthesis Example 1. FIG. 4 is a GPC chart of silanol group-containing cage-type siloxane (23) obtained in Synthesis Example 2. FIG. 5 is a GPC chart of the organic-inorganic composite (24) obtained in Synthesis Example 2. FIG. 6 is a GPC chart of silanol group-containing cage-type siloxane (25) obtained in Synthesis Example 3. FIG. 7 is a GPC chart of the organic-inorganic composite (26) obtained in Synthesis Example 3.

As a resin that can be suitably used as the organic-inorganic composite of component (A), the following formula (1)
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(However, R ¹ and R ² may be vinyl groups, allyl groups, alkyl groups, aryl groups, (meth) acryloyl groups, or groups having an oxirane ring, and may be the same or different from each other, and X is carbon aliphatic structure having 5 to 50, group having 5 to 50 ring carbon atoms having an alicyclic structure, or any one of the groups having 5 to 50 carbon atoms having an aromatic structure, also contain two or more different from each other Well, each of n, m, and l represents an average value, n is a number of 6 to 14, and m + 1 is 2 to 2,000.), And the weight average molecular weight Mw = 5,000 to 1 One or two or more types of reactivity selected from the group consisting of vinyl groups, allyl groups, and (meth) acryloyl groups having at least two unsaturated double bonds in one molecule. Mentioning organic-inorganic composites with functional groups it can.

（但し、Ｒ²は水素原子、ビニル基、アリル基、アルキル基、アリール基、（メタ）アクリロイル基又はオキシラン基であって互いに同じか異なるものであってもよい。）で表されるジクロロシランをシラノール基含有籠型シロキサン及び有機ジオールの合計モルに対して０．５〜５倍モル、好ましくは０．５〜３．０倍モルの範囲で添加して脱塩酸縮合させて式（１）で表される有機−無機複合体とすることができる。 As a preferable method for obtaining the organic-inorganic composite represented by the above formula (1), the following formula (2):
(R ¹ SiO _3/2 ) _n (HO _2/2 ) _k (2)
(However, R ¹ may be a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group or a group having an oxirane ring, and may be the same or different from each other, and n and k are average values. And n represents a number of 6 to 14, and k represents a number of 1 to 4.) and a silanol group-containing cage-type siloxane represented by the following formula (3):
HO-X-OH (3)
(Wherein, X is either a group having 5 to 50 carbon atoms and having a number 5 to 50 groups or aromatic structure, carbon having aliphatic structure having 5 to 50 carbon atoms, an alicyclic structure.) An organic diol compound represented by the following formula (4):

(Wherein R ² represents a hydrogen atom, a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group or an oxirane group, which may be the same or different from each other). Is added in a range of 0.5 to 5 times mol, preferably 0.5 to 3.0 times mol, with respect to the total mol of silanol group-containing cage-type siloxane and organic diol, and dehydrochlorination condensation is carried out to obtain the formula (1) It can be set as the organic-inorganic composite represented by these.

  Regarding specific reaction conditions for copolymerizing silanol group-containing cage-type siloxane of formula (2) and organic diol compound of formula (3) by dehydrochlorination using dichlorosilane of formula (4), Should be carried out under basic conditions. For example, a solution obtained by dissolving a silanol group-containing cage-type siloxane and an organic diol compound as a solvent and base in a mixed solution of pyridine or tetrahydrofuran and triethylamine, and dissolving dichlorosilane in pyridine at room temperature under an inert gas atmosphere such as nitrogen It is good to carry out stirring at room temperature for 2 hours or more after that. At this time, if the reaction time is short, the reaction is not completed. After completion of the reaction, toluene and water are added, and the organic-inorganic complex represented by the formula (1) is dissolved in toluene, and by-product hydrochloric acid and hydrochloride are dissolved and removed in the aqueous layer. Further, the organic layer is dried using a desiccant such as magnesium sulfate, and the used base and solvent are removed by concentration under reduced pressure.

Following formula (2)
(R ¹ SiO _3/2 ) _n (HO _2/2 ) _k (2)
(However, R ¹ may be a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group or a group having an oxirane ring, and may be the same or different from each other, and n and k are average values. Yes, n represents a number of 6 to 14, and k represents a number of 1 to 4. For a preferable means for obtaining a silanol group-containing cage-type siloxane represented by the following formula (5):
R ¹ SiY ₃ (5)
(Wherein R ¹ is a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group or a group having an oxirane ring, and Y is selected from the group consisting of an alkoxy group, a halogen atom and a hydroxyl group. ¹ or 2 is used, and the basic catalyst is R ¹ SiY ₃ : basic catalyst = 3 to 7 mol: 1 mol of basic catalyst is present. In the process of hydrolysis (condensation of silanol groups) and cleavage (equilibrium), hydrolysis is performed in a polar solvent or nonpolar solvent or a mixed solvent thereof and the hydrolyzate is subjected to a condensation reaction. After the counter cation derived from the sex catalyst is bonded to the cleavage portion, it can be obtained by treating with an acid and converting the cleavage portion to a hydroxyl group. At this time, if the basic catalyst used is less than the above range, the condensation of the silanol group is prioritized and the silanol group is reduced. On the other hand, when the amount is larger than the above range, cleavage of the siloxane bond is given priority, and excess silanol groups are increased. From these facts, when the amount of the basic catalyst is out of the above range, the condensation reaction using the dehydrochlorination reaction of dichlorosilane with the organic compound in the next step causes insufficient reaction or gelation.

  The solvent used for obtaining the silanol group-containing cage-type siloxane represented by the above formula (2) is a solvent obtained by combining one or both of a nonpolar solvent and a polar solvent. Among these, examples of the nonpolar solvent include hydrocarbon solvents such as hexane, toluene, xylene, and benzene. Examples of the polar solvent include ether solvents such as diethyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol and 2-propanol, and ketone solvents such as acetone and methyl ethyl ketone. Among these, a two-phase system of 2-propanol and toluene is preferable from the viewpoint of reaction rate control. The volume ratio of 2-propanol / toluene is preferably 1/2. The preferred amount of the organic solvent used is such that the molar concentration (mol / liter: M) relative to the alkoxysilane of formula (5) is in the range of 0.01 to 10M, more preferably 0.01 to 1M. Is good.

About the reaction conditions at the time of synthesize | combining the silanol group containing cage-type siloxane of said Formula (2), 0-60 degreeC is preferable and 20-40 degreeC is more preferable. When the reaction temperature is lower than 0 ° C., the reaction rate becomes slow, resulting in a large amount of unreacted hydrolyzable groups and silanol groups remaining. On the other hand, when the temperature is higher than 60 ° C., the reaction rate is too high, so that a complicated condensation reaction proceeds, and as a result, high molecular weight is promoted. Although the reaction time varies depending on R ¹ a structure represented by the above formula (5), typically a few minutes to several hours, preferably good is 1-3 hours.

Specific examples of the silanol group-containing cage-type siloxane compound represented by the formula (2) are shown in the following structural formulas (6) to (12), respectively. Structural formula (6) is n = 6, k = 2, (7) is n = 7, k = 3, (8) -1 and (8) -2 are n = 8, k = 2, (9) is n = 9, k = 1, (10) is n = 10, k = 2, (11) is n = 12, k = 2, (12) is n = 14, k = 2. However, the structural unit represented by the formula (2) is not limited to those shown in the structural formulas (6) to (12). In Structural Formulas (6) to (12), R ¹ is the same as Formula (5).

  Examples of the silicon compound represented by the above formula (5) include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and n-propyltrimethoxysilane. Ethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, methacryloxymethyltrimethoxy Silane, methacryloxymethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Reethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexylethyl) trimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, Examples include p-styryltrimethoxysilane, p-styryltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Of these, phenyltrimethoxysilane, methyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and vinyltrimethoxysilane, which are easily available, are preferred.

  Examples of the basic catalyst used in the hydrolysis and condensation reaction of the above formula (5) include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide. And ammonium hydroxide salts such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide. Among these, tetramethylammonium hydroxide is preferably used because of its high catalytic activity.

  After completion of the synthesis reaction of the silanol group-containing cage-type siloxane, the reaction solution is neutralized with a weakly acidic solution. After neutralization or acidification, water or water-containing reaction solvent is separated. Thereafter, the organic layer is sufficiently washed with water or saturated saline. Then, it dries with drying agents, such as anhydrous magnesium sulfate. After removing the desiccant by filtration, the reaction product (silanol group-containing cage siloxane) can be recovered by concentration under reduced pressure. Concentration under reduced pressure is performed at 40 ° C or lower. If the temperature exceeds 40 ° C., the silanol groups produced by the reaction are condensed, resulting in a problem that the high molecular weight and gelation and the subsequent reaction do not proceed. Examples of the weakly acidic solution include sulfuric acid diluted solution, hydrochloric acid diluted solution, citric acid diluted solution, acetic acid, ammonium chloride aqueous solution, malic acid solution, oxalic acid solution and the like.

  Next, the siloxane siloxane and the organic component are obtained by copolymerizing the silanol group-containing cage siloxane obtained above and the organic diol compound of the formula (3) using dichlorosilane of the formula (4). An organic-inorganic composite consisting of

（但し、上記式（２０）のＲ³は炭素数５〜１０の脂肪族炭化水素及び／又は脂環式炭化水素であり、Ｍｗ＝５００〜２,０００である。）等を例示することができるが、これらに何ら制限されるものではない。またこれらを単独で使用してもよく、２種以上併用してもよい。 Here, as the organic diol compound represented by the formula (3), pentanediol, hexanediol, 1,9-nonanediol, the following formulas (13) to (20),

(However, R ³ in the above formula (20) is an aliphatic hydrocarbon and / or alicyclic hydrocarbon having 5 to 10 carbon atoms, and Mw = 500 to 2,000). Yes, but you are not limited to these. Moreover, these may be used independently and may be used together 2 or more types.

  Examples of the dichlorosilane compound represented by the formula (4) include allyldichlorosilane, allylhexyldichlorosilane, allylmethyldichlorosilane, allylphenyldichlorosilane, methyldichlorosilane, dimethyldichlorosilane, divinyldichlorosilane, diethyldichlorosilane, Methylpropyldichlorosilane, diethoxydichlorosilane, butylmethyldichlorosilane, phenyldichlorosilane, diallyldichlorosilane, methylpentyldichlorosilane, methylphenyldichlorosilane, cyclohexylmethyldichlorosilane, hexylmethyldichlorosilane, phenylvinyldichlorosilane, 6-methyldichlorosilyl-2-norbornene, 2-methyldichlorosilylnorbornene, 3-methacryloxypropyldichloromethylsilane , Heptylmethylsilane, dibutyldichlorosilane, methyl-β-phenethyldichlorosilane, methyloctyldichlorosilane, t-butylphenyldichlorosilane, decylmethyldichlorosilane, diphenyldichlorosilane, dihexyldichlorosilane, dodecylmethyldichlorosilane, methyl Although octadecyl dichlorosilane etc. can be illustrated, it is not restrict | limited at all to these. Moreover, these may be used independently and may use 2 or more types together.

  The blending amount of the “organic-inorganic composite” of the component (A) is 30 parts by weight or more with respect to 100 parts by weight of the total of the components (A), (B) and (C). If it is less than 30 parts by weight, the heat discoloration will be lowered, the viscosity will be lowered, and the curing shrinkage will be increased, making it difficult to mold.

  In the curable resin composition of the present invention, the component (B) “ethylenically unsaturated compound having at least two (meth) acrylic groups in one molecule” acts as a diluent and a crosslinking agent. . (A) The viscosity of the “organic-inorganic composite” of component (A) is adjusted to an easily moldable viscosity, preferably 0.1 to 500 Pa · s, more preferably 1 to 200 Pa · s, or by highly cross-linking the cured product. Used for low thermal expansion and high strength.

  The blending amount of component (B) “ethylenically unsaturated compound having at least two (meth) acrylic groups in one molecule” is 100 parts by weight in total of components (A), (B) and (C). It should be less than 70 parts by weight. When it is 70 parts by weight or more, the heat discoloration is lowered, the viscosity is further lowered, and the curing shrinkage is increased, so that molding becomes difficult.

  Specific examples of the component (B) “ethylenically unsaturated compound having at least two (meth) acrylic groups in one molecule” include ethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, 1, 4 -Butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nandiol di (meth) acrylate, dimethylol-tricyclodecanedi (meta ) Acrylate, di (meth) acrylate ester of bisphenol A-type epoxy resin, trimethylolpropane tri (meth) acrylate, etc., but combined with an ethylenically unsaturated compound having one (meth) acryloyl group in one molecule You can also

  Moreover, about the curing catalyst of (C) component, a thermal polymerization initiator or a photoinitiator can be used. The addition amount may be 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the curable resin composition. If the added amount of the initiator is less than 0.01 parts by weight, curing is insufficient, and the strength and rigidity of the cured product are lowered. Conversely, if it exceeds 5 parts by weight, problems such as coloring may occur. Further, the thermal polymerization initiator or the photopolymerization initiator may be used alone, or both of them may be used in combination.

  Among these, as the thermal polymerization initiator, organic peroxides are preferable, and ketone peroxides, diacylalkyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and carbonates. Etc. Among these, dialkyl peroxide is preferable from the viewpoint of catalytic activity. Specifically, cyclohexanone peroxide, 1,1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t -Hexylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexanoate and the like can be exemplified, but are not limited thereto. Moreover, these may be used independently and may be used together 2 or more types.

  Examples of the photopolymerization initiator include alkylphenones, acetophenones, benzoins, benzophenones, thioxanthones, and acyl phosphooxides. Of these, alkylphenones are preferred from the viewpoint of catalytic activity. Specifically, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 1- [4- (2-hydroxyethoxy) -phenyl] -2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl- Propionyl) -benzyl] phenyl] -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-monophorinyl) phenyl] -1-butanone, etc. Illustrated However, it is not limited to these. Moreover, these may be used independently and may be used together 2 or more types.

  Further, in the curable resin composition of the present invention, as long as the transparency is not impaired, a conventionally known antioxidant, ultrafine silica such as Aerosil, and an inorganic filler matched to a resin whose refractive index is cured May be appropriately blended from the viewpoint of improving the mechanical strength and adjusting the thermal expansion coefficient.

  The curable resin composition of the present invention can be cured using heat, light, or both. When curing is performed using a thermal polymerization initiator, curing can be performed in a wide range from room temperature to around 200 ° C. depending on the selection of the thermal polymerization initiator and the accelerator. You may make it perform post-cure (additional heating) as needed. On the other hand, when hardening using a photoinitiator, hardened | cured material can be obtained by light irradiation, for example, ultraviolet rays with a wavelength of 100-400 nm and visible light with a wavelength of 400-700 nm are irradiated. The wavelength of the light to be used is not particularly limited, but near ultraviolet light having a wavelength of 200 to 400 nm is particularly preferably used. As a lamp used as an ultraviolet generator, a low-pressure mercury lamp (output: 0.4 to 4 W / cm), a high-pressure mercury lamp (40 to 160 W / cm), an ultra-high pressure mercury lamp (173 to 435 W / cm), a metal halide lamp (80 ˜160 W / cm), pulse xenon lamp (80 to 160 W / cm), pulse xenon lamp (80 to 120 W / cm), electrodeless discharge lamp (80 to 120 W / cm), and the like. Since each of these ultraviolet lamps is characterized by its spectral distribution, it is selected according to the type of photoinitiator used. When a thermal polymerization initiator and a photopolymerization initiator are used in combination, curing can be performed sequentially in the order of photothermal and thermal light in accordance with the above conditions. In particular, when the thermal polymerizability and the photopolymerizability are different, it can be cured in a short time by using it efficiently. Furthermore, you may make it obtain the hardened | cured material which has a predetermined shape by carrying out injection molding or compression molding of the curable resin composition of this invention. At this time, the molding apparatus for molding is not particularly limited.

  The curable resin composition of the present invention is excellent in heat discoloration, low thermal expansion, high transparency, and low curing shrinkage, so that optical applications, optical device applications, and display device applications in which glass was primarily used were originally used. It is also possible to replace these various materials, mechanical component materials, electrical / electronic component materials, and the like with moldings (cured products) made of the curable resin composition of the present invention. For example, because it has heat resistance that can withstand solder reflow, it is a camera module that integrates a semiconductor and a lens, such as a CCD with a lens and a CMOS sensor with a lens that are mounted on a mobile phone, a digital camera, an in-vehicle camera, etc. The present invention can also be applied to electronic components such as diffraction gratings, polarizing components, reflectors, and other glass substitute materials.

[Synthesis Example 1]
To a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 14.3 g of tetramethylammonium hydroxide pentahydrate (manufactured by Kanto Chemical) as a basic catalyst is added and dissolved in 17.0 g of water, followed by 189 mL of toluene and 95 mL of 2-propanol were added. 46.8 g of vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .; KBM1003) was added to the dropping funnel, and vinyltrimethoxysilane was added dropwise at room temperature over 3 hours while stirring the reaction vessel. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After completion of the stirring, the stirring was stopped and the mixture was left for one day. Thereafter, the reaction solution was neutralized with 82.9 g of a 10% aqueous citric acid solution. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 24.9 g (97%) of a colorless and transparent viscous liquid silanol group-containing cage-type siloxane (21).

The result of having measured GPC of the colorless transparent viscous liquid silanol group containing cage-type siloxane (21) obtained above is shown in FIG. From FIG. 1, it was confirmed that Mw = 1005 and Mw / Mn = 1.225. Among them, the peaks on the low molecular side occupying 70% of the area ratio were Mw = 668 and Mw / Mn = 1.020. Next, the result of measuring H ¹ NMR is shown in FIG. The peak integration ratio of the multiplet peak due to the vinyl group of 5.8 to 6.2 ppm and the silanol group of 1.6 ppm was 0.174 with respect to the vinyl group 1. Therefore, the compound estimated from the low molecular side Mw that is the main peak and the integration ratio is the following formula:
[R ¹ SiO _3/2 ] _n [HO _1/2 ] _k (2)
It was suggested that n is 8 and k is 2 (R ¹ is a vinyl group).

In order to confirm the presence of the silanol group of the colorless and transparent viscous liquid silanol group-containing cage-type siloxane (21) obtained above, IR was measured. As a result, it had a broad peak derived from silanol groups at 3100 to 3400 cm ⁻¹ , so the presence of silanol groups was confirmed. From the above results, the structure of the colorless and transparent viscous liquid represented by the above formula (2) was determined to be silanol group-containing cage-type siloxane.

  Table 1 shows the results of electrospray ionization mass spectrometry (ESI-MS) of the silanol group-containing silsesquioxane (21) obtained above. Table 1 below summarizes the main peaks detected by mass spectrometry and the numerical values applicable to n and k. The detected peak m / z is a value obtained by adding ammonium ions (Mw = 18) to the molecular weight of the silanol group-containing cage-type siloxane (21). From the result of mass spectrometry, it is shown that a part of the siloxane bond forming the cocoon structure is cleaved to have a structure having a silanol group at the terminal portion.

で表されるエポキシアクリレート（共栄社化学株式会社製；３００２Ｍ）１９．３ｇをはかり込み窒素置換し、ピリジン６０ｍＬに溶解した。滴下ロートにジフェニルジクロロシラン１９．２ｇ及びピリジン７６ｍＬを入れ、室温で２時間かけて滴下した。滴下終了後、室温で２時間撹拌した。２時間撹拌後、トルエン１４０ｍＬ、蒸留水７０ｍＬを加えた。水層をトルエンで抽出し、有機層を蒸留水で３回洗浄した。有機層を無水硫酸マグネシウムで乾燥、ろ別し、濃縮することで無色透明粘性液体の有機−無機複合体（２２）を５２．１ｇ（回収率９７％）得た。 In a reaction vessel equipped with a stirrer and a dropping funnel, 23.7 g of the silanol group-containing cage-type siloxane (21) obtained above and the following formula (19)

19.3 g of epoxy acrylate represented by (Kyoeisha Chemical Co., Ltd .; 3002M) was weighed in and purged with nitrogen, and dissolved in 60 mL of pyridine. Into the dropping funnel, 19.2 g of diphenyldichlorosilane and 76 mL of pyridine were added and dropped at room temperature over 2 hours. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 140 mL of toluene and 70 mL of distilled water were added. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 52.1 g (97% recovery rate) of an organic-inorganic composite (22) as a colorless transparent viscous liquid.

The result of having measured GPC of the organic-inorganic composite (22) of the colorless and transparent viscous liquid obtained above is shown in FIG. From FIG. 3, it was Mw = 8035 and Mw / Mn = 2.755. Therefore, the obtained organic-inorganic composite (22) has the following formula (1):
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(R ¹ is a vinyl group, R ² is a phenyl group, and X is composed of the formula (19)). It was confirmed that n was 6 to 14 and m + 1 = 5.

[Synthesis Example 2]
To a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 14.3 g of tetramethylammonium hydroxide pentahydrate as a basic catalyst is added and dissolved in 17 g of water, followed by 189 mL of toluene and 95 mL of 2-propanol. Put. To the dropping funnel, 23.4 g of vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .; KBM1003) and 23.7 g of ethyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .; LS-890) are added, and the reaction vessel is stirred. Then, a mixed solution of vinyltrimethoxysilane and ethyltrimethoxysilane was added dropwise at room temperature over 3 hours. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After completion of the stirring, the stirring was stopped and the mixture was left for one day. Next, the reaction vessel was equipped with a Din Stark and a cooling tube, 95 mL of toluene was added, and 2-propanol and methanol generated during hydrolysis were removed at 90 ° C. using an oil bath. Thereafter, the temperature of the oil bath was set to 120 ° C., and toluene was heated to reflux while removing water to perform a recondensation reaction. After refluxing toluene, the mixture was stirred for 3 hours and then returned to room temperature to complete the reaction. The reaction solution was neutralized with 82.9 g of 10% aqueous citric acid solution. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 25.5 g (98%) of a colorless and transparent viscous liquid silanol group-containing cage-type siloxane (23).

The result of having measured GPC of the colorless transparent viscous liquid silanol group containing cage type | mold siloxane (23) obtained above is shown in FIG. From the figure, it was confirmed that Mw = 863 and Mw / Mn = 1.195. Among them, the peaks on the low molecular side occupying 70% of the area ratio were Mw = 650 and Mw / Mn = 1.032. Next, as a result of measuring ¹ H-NMR, a multiplet peak due to a vinyl group of 5.8 to 6.2 ppm, a multiplet peak due to an ethyl group of 0.4 to 1.2 ppm, and a silanol group of 1.6 ppm The peak integration ratio was 1 for ethyl group and 0.189 for silanol group relative to 1 vinyl group. Therefore, the compound estimated from the low molecular side Mw which is the main peak and the integration ratio is represented by the following formula (2).
[R ¹ SiO _3/2 ] _n [HO _1/2 ] _k (2)
It was suggested that n is 8 and k is 2 (R ¹ is vinyl group: ethyl group = 1: 1).

  In a reaction vessel equipped with a stirrer and a dropping funnel, 20.0 g of the silanol group-containing cage-type silsesquioxane compound (23) obtained above and 4.4 g of cyclohexanedimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) are weighed. The solution was purged with nitrogen and dissolved in 61 mL of pyridine. Into the dropping funnel, 19.2 g of diphenyldichlorosilane and 76 mL of pyridine were added and dropped at room temperature over 2 hours. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 140 mL of toluene and 70 mL of distilled water were added. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated to obtain 35.3 g (recovery rate: 92%) of an organic-inorganic composite (24) as a colorless transparent viscous liquid.

The result of having measured GPC of the organic-inorganic composite (24) obtained above is shown in FIG. From FIG. 5, it was Mw = 13937 and Mw / Mn = 4.369. Therefore, the obtained organic-inorganic composite (24) has the following formula (1):
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(R ¹ is represented by vinyl group: ethyl group = 1: 1, R ² is composed of phenyl group and X is composed of cyclohexanedimethanol), and n was confirmed to be 6 to 14 and m + 1 = 11.

[Synthesis Example 3]
To a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 14.3 g of tetramethylammonium hydroxide pentahydrate as a basic catalyst is added and dissolved in 17 g of water, followed by 189 mL of toluene and 95 mL of 2-propanol. Put. To the dropping funnel, 78.4 g of 3-methacryloxypropyltrimethoxyxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .; LS-3380) was added, and 3-methacryloxypropyltrimethoxysilane was added at room temperature while stirring the reaction vessel. It was added dropwise over time. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After completion of the stirring, the stirring was stopped and the mixture was left for one day. Next, the reaction vessel was equipped with a Din Stark and a cooling tube, 95 mL of toluene was added, and 2-propanol and methanol generated during hydrolysis were removed at 90 ° C. using an oil bath. Thereafter, the temperature of the oil bath was set to 120 ° C., and toluene was heated to reflux while removing water to perform a recondensation reaction. After refluxing toluene, the mixture was stirred for 3 hours and then returned to room temperature to complete the reaction. The reaction solution was neutralized with 82.9 g of 10% aqueous citric acid solution. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 47.4 g (98%) of a colorless transparent viscous liquid silanol group-containing cage-type siloxane (25).

The result of having measured GPC of the colorless transparent viscous liquid silanol group containing cage-type siloxane (25) obtained above is shown in FIG. From the figure, it was confirmed that Mw = 2156 and Mw / Mn = 1.092. Among them, the peaks on the low molecular side occupying 70% of the area ratio were Mw = 1480 and Mw / Mn = 1.028. Next, as a result of measuring ¹ H-NMR, the peak integration ratio of 5.4 to 6.2 ppm methacryl group and 1.6 ppm silanol group was 0.189 with respect to methacryl group 1. there were. Therefore, the compound estimated from the low molecular side Mw which is the main peak and the integration ratio is represented by the following formula (2).
[R ¹ SiO _3/2 ] _n [HO _1/2 ] _k (2)
It was suggested that n is 8, and k is 2 (R ¹ is a 3-methacryloxypropyl group).

（但し、Ｒ³は−(ＣＨ₂)₆−、Ｍｗ＝１０００である旭化成株式会社製；ＥＴＥＲＮＡＣＯＬＬ ＵＨ−１００）で表される有機ジオール化合物１３．８ｇをはかり込み窒素置換し、ピリジン６１ｍＬに溶解した。滴下ロートにジフェニルジクロロシラン８．７ｇ、及びピリジン７６ｍＬを入れ、室温で２時間かけて滴下した。滴下終了後、室温で２時間撹拌した。２時間撹拌後、トルエン１４０ｍＬ、蒸留水７０ｍＬを加えた。水層をトルエンで抽出し、有機層を蒸留水で３回洗浄した。有機層を無水硫酸マグネシウムで乾燥、ろ別し、濃縮することで無色透明粘性液体の有機−無機複合体（２６）を４０．１ｇ（回収率９５％）得た。 In a reaction vessel equipped with a stirrer and a dropping funnel, 20.0 g of the silanol group-containing cage silsesquioxane compound (25) obtained above and the following formula (20)

(However, R ³ is — (CH ₂ ) ₆ —, Mw = 1000, manufactured by Asahi Kasei Co., Ltd .; ETERNACOLL UH-100). did. Into the dropping funnel, 8.7 g of diphenyldichlorosilane and 76 mL of pyridine were added and dropped at room temperature over 2 hours. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 140 mL of toluene and 70 mL of distilled water were added. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 40.1 g (recovery rate: 95%) of an organic-inorganic composite (26) as a colorless transparent viscous liquid.

The result of having measured GPC of the organic-inorganic composite (26) obtained above is shown in FIG. From FIG. 7, it was Mw = 28164 and Mw / Mn = 7.277. Therefore, the obtained organic-inorganic composite (26) has the following formula (1):
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(R ¹ is a 3-methacryloxypropyl group, R ² is a phenyl group, and X is composed of the above formula (20)), and n was confirmed to be 6 to 14 and m + 1 = 10.

（共栄社化学株式会社製；ＤＣＰ−Ａ）で表される化合物３０重量部を混合し、(Ｃ)成分である下記式（２８）

（日本油脂株式会社製；パークミルＤ）で表される硬化触媒を(Ａ)、(Ｂ)成分の合計１００重量部に対して１重量部混合し、よく撹拌し、実施例１の硬化性樹脂組成物を調製した。 [Example 1]
70 parts by weight of the organic-inorganic composite (22) obtained in Synthesis Example 1 as component (A), and the following formula (27) as component (B)

30 parts by weight of a compound represented by (Kyoeisha Chemical Co., Ltd .; DCP-A) is mixed, and the following formula (28) which is the component (C)

1 part by weight of the curing catalyst represented by (Nippon Yushi Co., Ltd .; Park Mill D) is mixed with 100 parts by weight of the total of the components (A) and (B), stirred well, and the curable resin of Example 1 A composition was prepared.

[Example 2]
Implementation was conducted in the same manner as in Example 1 except that 70 parts by weight of the organic-inorganic composite (24) obtained in Synthesis Example 2 was used as the component (A) instead of the organic-inorganic composite (22). A curable resin composition according to Example 2 was prepared.

（チバ・ジャパン株式会社製；Irgacure184）で表される硬化触媒を(Ａ)、(Ｂ)成分の合計１００重量部に対して１重量部混合し、よく撹拌し、実施例３の硬化性樹脂組成物として調製した。 [Example 3]
70 parts by weight of the organic-inorganic composite (26) obtained in Synthesis Example 3 as the component (A) and 30 parts by weight of the formula (27) as the component (B) are mixed. The following formula (29)

1 part by weight of a curing catalyst represented by (Ciba Japan Co., Ltd .; Irgacure184) is mixed with 100 parts by weight of the total of components (A) and (B), stirred well, and the curable resin of Example 3 Prepared as a composition.

で表されるトリメチロールプロパントリ（メタ）アクリレート（共栄社化学株式会社製；ＴＭＰＴＡ）２０重量部を混合し、(Ｃ)成分である上記式（２８）及び（２９）の硬化触媒をそれぞれ１重量部混合し、よく撹拌し、実施例５の硬化性樹脂として調製した。 [Example 4]
80 parts by weight of the organic-inorganic composite (24) obtained in Synthesis Example 2 as component (A), and the following formula (30) as component (B)

20 parts by weight of trimethylolpropane tri (meth) acrylate (manufactured by Kyoeisha Chemical Co., Ltd .; TMPTA) represented by the formula (1) is mixed with each of the curing catalysts of the above formulas (28) and (29) as component (C) Part of the mixture was mixed and stirred well to prepare a curable resin of Example 5.

[Comparative Example 1]
1 part by weight of the curing catalyst of the above formula (28) as the component (C) is mixed with 100 parts by weight of the silanol group-containing cage-type siloxane (21) prepared in Synthesis Example 1 and stirred well. A composition was prepared.

[Comparative Example 2]
1 part by weight of the curing catalyst of the above formula (28) as the component (C) is mixed with 100 parts by weight of the compound represented by the above formula (27) as the component (B), and stirred well. A composition was prepared.

Using the compositions prepared in the above Examples and Comparative Examples, it was poured into a mold incorporated in a glass plate so as to have a thickness of 2 mm, and [Examples 1 and 2] and [Comparative Examples 1 and 2] were at 120 ° C. Molded by heating for 1 hour, 150 ° C for 1 hour, and 180 ° C for 2 hours, respectively, and for [Example 3], a 30 W / cm high-pressure mercury lamp was used and molded with an integrated exposure of 2000 mJ / cm ^2. [Example 4] was cured with an integrated exposure amount of 2000 mJ / cm ² using a 30 W / cm high-pressure mercury lamp, and further heated at 200 ° C. for 1 hour, 50 mm × 25 mm × thickness 2 mm, respectively. A molded product for the test was obtained.

  With respect to the viscosity of the curable resin composition and the obtained molded product, the curing shrinkage rate, the thermal expansion coefficient, the heat resistance after the reflow test, and the transparency were evaluated by the following methods. The results are shown in Table 2.

<Viscosity>
The viscosity at 24 ° C. and rotational speed D = 1 / s was evaluated with an R / S rheometer (manufactured by Brookfield, USA). When the viscosity was 20 Pa · s or more, an RC-25-1 measuring jig was used, and when the viscosity was less than 20, an RC50-1 jig was used. About the thing which cannot measure the viscosity at the time of D = 1 / s, the value of D = 5-100 / s was extrapolated and evaluated as the viscosity of a curable resin composition.

<Curing shrinkage>
The specific gravity before and after curing was measured and the volume shrinkage was calculated. The specific gravity of the curable resin composition was determined by a pycnometer method (JIS K 7112), and the cured product was determined by an underwater substitution method (JIS K 7112).
Curing shrinkage = (1-specific gravity of resin before curing / specific gravity of resin after curing) × 100

<Coefficient of thermal expansion>
Based on the thermomechanical analysis method, it calculated | required on conditions with a temperature increase rate of 5 degree-C / min and a compressive load of 0.1N.

<Transmissivity>
The transmittance of the cured product at a wavelength of 450 nm was evaluated using an absorptiometer (manufactured by Shimadzu Corporation, spectrophotometer UV-3100). Moreover, the transmittance | permeability after hold | maintaining a hardened | cured material in a dryer at 260 degreeC for 10 minutes was also evaluated.

<Refractive index>
Evaluation was performed using a refractometer (DR-M2 manufactured by Atago Co., Ltd.). Moreover, the refractive index after hold | maintaining hardened | cured material in a dryer at 260 degreeC for 10 minutes was also evaluated.

<Turbidity>
(Nippon Denshoku make, NDH2000) was used and the haze of hardened | cured material was evaluated.

<State of cured product after curing>
The crack was visually confirmed.

Claims (2)

(A) An organic-inorganic composite having two or more aliphatic unsaturated bonds in one molecule and comprising a cage siloxane and an organic component, which is represented by the following formula (1)
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(However, R ¹ and R ² may be vinyl groups, allyl groups, alkyl groups, aryl groups, (meth) acryloyl groups, or groups having an oxirane ring, and may be the same or different from each other. aliphatic structure of 5 to 50 carbon atoms, group having 5 to 50 carbon atoms having an alicyclic structure, or any one of the groups having 5 to 50 carbon atoms having an aromatic structure, comprising two or more different from each other N, m and l each represent an average value, n is a number from 6 to 14, and m + l is from 2 to 2,000), and the weight average molecular weight is Mw = 5,000 to 1,000,000 at least one or more reactive functional groups selected from the group consisting of a vinyl group having an unsaturated double bond in one molecule, an allyl group, and a (meth) acryloyl group An organic-inorganic composite having two or more,
(B) an ethylenically unsaturated compound having at least two (meth) acrylic groups in one molecule, and
(C) A curing catalyst is an essential component, and the organic-inorganic composite of component (A) is contained as a main component in an amount of at least 30 parts by weight based on 100 parts by weight of components (A), (B) and (C) A curable resin composition characterized by comprising: The curable resin composition according to claim 1 Symbol placement, heat, light, or cured product obtained by curing using both.

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