KR20100097597A - Curable resin composition and cured product - Google Patents

Abstract

PURPOSE: A curable resin composition and a hardening material are provided to secure the excellent hardening and processing property, and to obtain the heat-resisting discoloration property and the low thermal expansibility of the hardening material. CONSTITUTION: A curable resin composition contains the following: an organic-inorganic composite formed with more than two aliphatic unsaturation bonds and cage type cage type siloxane; an ethylenically unsaturated compound with more than two (meth)acryl groups; and a curing catalyst. A hardening material is obtained by curing the curable resin composition using the heat or the light.

Description

Curable resin composition and hardened | cured material {CURABLE RESIN COMPOSITION AND CURED PRODUCT}

The present invention relates to a curable resin composition and a cured product. Specifically, it is related with the curable resin composition which can obtain hardened | cured material useful as optical materials, such as an optical use, an optical device use, a display device use, a mechanical component material, an electrical / electronic component material, etc., and the hardened | cured material obtained using this. .

Molding materials obtained by curing resins are widely used, including mechanical component materials, electrical and electronic component materials, automotive component materials, civil building materials, and the like, and resin compositions containing curable resins are used as various paints and adhesives in addition to moldings. By containing an inorganic substance in these curable resin compositions, the thermal expansion coefficient of hardened | cured material can be reduced, and heat resistance and transparency can also be improved, and in recent years, the usefulness is expected as a substitute for inorganic glass especially in an electronic and electrical component material. It is becoming. Specifically, since digital camera modules are being miniaturized such as being mounted on mobile phones, and cost reduction is required, plastic lenses such as PMMA, PC, and polycycloolefins are being used instead of inorganic glass. Considering use in a high-temperature exposure environment in a camera or the like, the examination of the curable resin composition is further progressed in that a long time heat resistance is required.

Examples of such curable resin compositions include silicone resin compositions capable of obtaining a cured product excellent in heat resistance and transparency, and curable epoxy resin compositions having low curing shrinkage and good moldability compared to other curable resins. Among these, in order to reduce thermal expansion coefficient in a silicone resin composition, the method of adding high density siloxane compounds, such as specific organopolysiloxane, for example, polyfunctional cage type silsesquioxane, ladder type silsesquioxane, is proposed ( For example, refer patent document 1). In addition, many resin compositions containing those obtained by additionally curing specific organopolysiloxanes (such as cage-type silsesquioxanes) and specific organohydrogenpolysiloxanes have been reported (see, for example, Patent Documents 2 to 4). On the other hand, in the curable epoxy resin composition, a method of adding inorganic filler powders such as fumed silica for the purpose of improving mechanical properties and heat resistance (see, for example, Patent Document 5), or organosilica sol for improving transparency, Preferably, the method of adding colloidal silica surface-modified by a silane coupling agent (for example, patent document 8) etc. other than the method of adding an inorganic particle as MEK sol (for example, refer patent document 6, 7) is also proposed. It is.

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

However, although the composition containing silicone resin can obtain the hardened | cured material excellent in heat resistance and heat discoloration resistance, there exists a problem in the reproducibility in obtaining hardened | cured material by generating hardening shrinkage at the time of hardened | cured material manufacture. On the other hand, a composition containing an epoxy resin has low moldability due to low shrinkage upon curing, but there is a problem in heat discoloration resistance that the antimony curing catalyst used in combination causes yellowing at a high temperature. These problems are not completely solved in the various compositions conventionally reported, respectively.

This invention is made | formed in view of the present state of curable resin composition, is excellent in the reproducibility of the hardening and processing characteristics in the manufacturing process of hardened | cured material, and is a resin composition provided with the low hardening shrinkage characteristic from which hardened | cured material with stable quality is obtained, Moreover, it aims at providing the curable resin composition which can obtain the heat discoloration resistance, low thermal expansion, and high transparency hardened | cured material, and also aims at providing the hardened | cured material obtained by this.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject, and according to the curable resin composition containing the specific composite containing an organic component and an inorganic component, hardening and processing characteristics, simultaneously solving the problem of a cure shrinkage and thermochromism, are solved. The resin composition which was excellent in the reproducibility of and which can obtain the low thermal expansion property and the high transparency hardened | cured material was obtained, and came to complete this invention.

Accordingly, the present invention provides an organic-inorganic composite comprising two or more aliphatic unsaturated bonds in one molecule (A) and a cage-type siloxane and an organic component, and (B) an ethylene having at least two (meth) acryl groups in one molecule. At least 30 weights of an organic-inorganic composite of (A) component as a main component with respect to a total of 100 weight part of (A), (B), and (C) component by making a unsaturated unsaturated compound and (C) hardening catalyst an essential component It is a curable resin composition characterized by containing more than a part.

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

In this invention, the organic-inorganic composite of the said (A) component is a 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)

[In formula, R <^1> and R <^2> is a group which has a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group, or an oxirane ring, and may be same or different, and X is C5-C50 It is either an aliphatic structure, an alicyclic structure having 5 to 50 carbon atoms, an aromatic structure having 5 to 50 carbon atoms, or an -OCOO- bond, and may contain two or more different types, and n, m and l each represent an average value. , n is a number from 6 to 14, m + l is from 2 to 2,000.], a weight average molecular weight of Mw = 5,000 to 1,000,000, vinyl group, allyl group, ( It is a preferable aspect to have at least 2 sort (s) or 1 type (s) or 2 or more types of reactive functional groups chosen from the group which consists of a meta) acryloyl group.

(Effects of the Invention)

According to the curable resin composition of this invention, hardened | cured material excellent in high transparency, low thermal expansion, and low hardening shrinkage can be obtained, while being equipped with high heat discoloration resistance. Moreover, the obtained hardened | cured material can be applied to optical materials, such as an optical use, an optical device use, a display device use, and a wide range of uses, such as various mechanical parts, automobile parts, civil construction materials, paints, adhesives, etc. .

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

As resin which can be used suitably as an organic-inorganic composite of (A) component, 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)

[Wherein R ¹ and R ² are a group having a vinyl group, allyl group, alkyl group, aryl group, (meth) acryloyl group or oxirane ring and may be the same or different from each other, and X is an aliphatic carbon having 5 to 50 carbon atoms. It is either a structure, a C5-C50 alicyclic structure, a C5-C50 aromatic structure, or -OCOO- bond, and may contain 2 or more types different from each other, n, m, and l respectively represent an average value , n is a number of 6 to 14, m + l is 2 to 2,000.], a weight average molecular weight Mw = 5,000 to 1,000,000, at least two or more of the molecules have a vinyl group having an unsaturated double bond, And organic-inorganic complexes having one or two or more reactive functional groups selected from the group consisting of allyl groups and (meth) acryloyl groups.

As a preferable method for obtaining the organic-inorganic complex represented by said Formula (1), following formula (2)

(R ¹ SiO _3/2 ) _n (HO _2/2 ) _k (2)

[Wherein R ¹ is a group having a vinyl group, allyl group, alkyl group, aryl group, (meth) acryloyl group or oxirane ring and may be the same or different from each other, n and k are average values and n is 6 to The number of 14 and k represent the number of 1-4.] The silanol group containing cage-type siloxane shown by following formula, and following formula (3)

HO-X-OH (3)

Wherein X is any one of an aliphatic structure having 5 to 50 carbon atoms, an alicyclic structure having 5 to 50 carbon atoms, an aromatic structure having 5 to 50 carbon atoms, or an -OCOO- bond. (4)

The silanol group-containing k-dichlorosilane represented by [wherein R ² is a hydrogen atom, a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group or an oxirane group, and may be the same or different from each other. It can be made into the organic-inorganic complex represented by Formula (1) by adding in the range of 0.5-5 times mole, Preferably it is 0.5-3.0 times mole with respect to the total moles of topographic siloxane and organic diol, and dechlorinating-condensing.

The specific reaction conditions for copolymerizing the silanol group-containing cage siloxane of the formula (2) and the organic diol compound of the formula (3) by dehydrochloric acid using the dichlorosilane of the formula (4) are preferably basic. It is good to perform under conditions. For example, a silanol group-containing cage siloxane and an organic diol compound are dissolved in pyridine or a mixture of tetrahydrofuran and triethylamine as a solvent and base, and a solution of dichlorosilane in pyridine is dissolved in an inert gas atmosphere such as nitrogen. It is good to make it dripping at room temperature, and 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 to dissolve the organic-inorganic complex represented by formula (1) in toluene, and to remove and remove the hydrophobic hydrochloric acid and hydrochloride salt in the aqueous layer. In addition, the organic layer is dried using a drying agent such as magnesium sulfate, and the used base and the solvent are removed by concentration under reduced pressure.

Formula (2)

(R ¹ SiO _3/2 ) _n (HO _2/2 ) _k (2)

[Wherein R ¹ is a group having a vinyl group, allyl group, alkyl group, aryl group, (meth) acryloyl group or oxirane ring and may be the same or different from each other, n and k are average values and n is 6 to The number of 14 and k represent the number of 1-4. About the preferable means of obtaining the silanol-group containing cage type | mold siloxane shown by following formula (5)

R ¹ SiY ₃ (5)

[Wherein R ¹ is a group having a vinyl group, allyl group, alkyl group, aryl group, (meth) acryloyl group or oxirane ring, and Y is a hydrolyzable group selected from the group consisting of an alkoxy group, a halogen atom and a hydroxyl group Or a polar compound or a nonpolar solvent, or a basic catalyst in the presence of a basic catalyst in a range of R ¹ SiY ₃ : basic catalyst = 3-7 mol: 1 mol, using a single or plural silicon compounds represented by In addition to the hydrolysis in the mixed solvent, the hydrolyzate is condensed, and the counter cations derived from the basic catalyst are combined with the cleavage portion in the process of forming siloxane bonds (condensation of silanol groups) and cleavage (equilibrium). Can be obtained by converting the cleavage portion into a hydroxyl group. At this time, when the basic catalyst used is less than the said range, condensation of a silanol group will give priority and a silanol group will reduce. On the contrary, when more than the said range, the cleavage of a siloxane bond takes precedence and the excess silanol group will increase. Due to these points, when the amount of the basic catalyst is out of the above range, it causes a lack of reaction or gelation in the condensation reaction using the dechlorination reaction of dichlorosilane with the organic compound of the next step.

About the solvent used when obtaining the silanol-group containing cage type siloxane represented by said Formula (2), it is a solvent which combined one or both of a nonpolar solvent and a polar solvent. Among these, hydrocarbon solvents, such as hexane, toluene, xylene, benzene, are illustrated about a nonpolar solvent. Examples of polar solvents 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. do. Among these, the biphasic system of 2-propanol and toluene is preferable from a viewpoint of reaction rate control. It is preferable that the volume ratio of 2-propanol / toluene is 1/2. It is preferable that the molar concentration (mol / liter: M) with respect to the alkoxysilane of Formula (5) is the range of 0.01-10 M, and, as for the preferable usage-amount of an organic solvent, More preferably, it is 0.01-1 M.

About 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. If the reaction temperature is lower than 0 ° C, the reaction rate is slowed, resulting in a large amount of unreacted hydrolyzable groups and silanol groups remaining. On the contrary, if it is higher than 60 DEG C, the reaction rate is too fast, so that a complicated condensation reaction proceeds, and as a result, high molecular weight is promoted. In addition, although reaction time changes also with R <^1> of the structure represented by said Formula (5), it is usually several minutes-several hours, Preferably it is good that it is 1-3 hours.

Specific examples of the silanol group-containing cage siloxane compound represented by 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 Formula (2) is not limited to what is shown to Structural formulas (6)-(12). In addition, in Structural Formulas (6) to (12), R ¹ is the same as that of Formula (5).

Examples of the silicon compound represented by the formula (5) include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, n -Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, n-octyltrimethoxysilane, n-jade Tyltriethoxysilane, methacryloxymethyl trimethoxysilane, methacryloxymethyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl Trimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-glycidoxyoxytrimethoxysilane, 3-glycidoxyoxytriethoxysilane, 2- (3,4-epoxycyclohexylethyl) tri Methoxysilane, allyltrimethoxysilane, allyltriethoxysilane, p-styryltrimeth Oxysilane, p-styryl triethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, etc. are illustrated. Among them, phenyltrimethoxysilane, methyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxyoxytrimethoxysilane, and vinyltrimethoxysilane, which are readily available from raw materials, are preferable. .

As a basic catalyst used for the hydrolysis and condensation reaction of Formula (5), alkali metal hydroxides, such as potassium hydroxide, sodium hydroxide, and cesium hydroxide, or tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide Ammonium hydroxide salts, such as a lock seed, benzyl trimethylammonium hydroxide, and benzyl triethylammonium hydroxide, are illustrated. Among them, tetramethylammonium hydroxide is preferably used in view of high catalytic activity.

After completion of the synthesis reaction of the silanol group-containing cage siloxane, the reaction solution is neutralized with a weakly acidic solution. After approaching neutral or acidic, water or a water-containing reaction solvent are separated. Thereafter, the organic layer is sufficiently washed with water or saturated brine. Then, it dries with drying agents, such as anhydrous magnesium sulfate. The reaction product (silanol group-containing cage-type siloxane) can be recovered by filtration under reduced pressure and concentration under reduced pressure. Concentration under reduced pressure is performed at 40 degrees C or less. When it exceeds 40 degreeC, the silanol group produced | generated in reaction will condense, and the problem that high molecular weight and gelation and the next reaction will not progress will arise. Examples of the weakly acidic solution include sulfuric acid dilute solution, hydrochloric acid dilute solution, citric acid dilute solution, acetic acid, ammonium chloride aqueous solution, malic acid solution, oxalic acid solution, and the like.

Subsequently, the organic-inorganic complex consisting of the cage-type siloxane and the organic component is copolymerized by copolymerizing the above-mentioned cage-type silanol-containing cage siloxane and the organic diol compound of the formula (3) with the dichlorosilane of the formula (4). You can get it.

Here, as an organic diol compound represented by Formula (3), a pentanediol, hexanediol, 1,9-nonanediol, following formula (13)-(20),

However, although R <^3> of said Formula (20) is a C5-C10 aliphatic hydrocarbon and / or an alicyclic hydrocarbon, Mw = 500-2,000. Etc. can be illustrated, It is not restrict | limited to these at all. In addition, these may be used independently and may be used together 2 or more types.

Examples of the dichlorosilane compound represented by formula (4) include allyldichlorosilane, allylhexyldichlorosilane, allylmethyldichlorosilane, allylphenyldichlorosilane, methyldichlorosilane, dimethyldichlorosilane, divinyldichlorosilane, diethyldichlorosilane, and methylpropyl. Dichlorosilane, diethoxydichlorosilane, butylmethyldichlorosilane, phenyldichlorosilane, diallyldichlorosilane, methylpentyldichlorosilane, methylphenyldichlorosilane, cyclohexylmethyldichlorosilane, hexylmethyldichlorosilane, phenylvinyldichlorosilane, 6-methyl Dichlorosilyl-2-norbornene, 2-methyldichlorosilylnorbornene, 3-methacryloxypropyldichloromethylsilane, heptylmethylsilane, dibutyldichlorosilane, methyl-β-phenethyldichlorosilane, methyloctyldichlorosilane, t -Butylphenyldichlorosilane, decylmethyldichlorosilane, diphenyldichlorosilane, dihexyldichloro Is, dodecyl can be mentioned, methyl dichlorosilane, methyl dichlorosilane, octadecyl, but it is not at all limited to these. In addition, these may be used independently and may use 2 or more types together.

The compounding quantity of the "organic-inorganic composite" of (A) component shall be 30 weight part or more with respect to a total of 100 weight part of (A), (B) and (C) component. If it does not reach 30 weight part, heat discoloration resistance will fall, a viscosity will fall, hardening shrinkage will become high, and molding will become difficult.

Moreover, in curable resin composition of this invention, (B) component "ethylenically unsaturated compound which has at least 2 (meth) acryl group in 1 molecule" acts as a diluent and a crosslinking agent. The viscosity of the "organic-inorganic composite" of the component (A) is easily adjusted to a viscosity, preferably 0.1 to 500 Pa · s, more preferably 1 to 200 Pa · s, or low thermal expansion due to high crosslinking of the cured product. Used for anger or high strength.

(B) Component "The ethylenically unsaturated compound which has at least two (meth) acryl groups in 1 molecule" compounding quantity may be less than 70 weight part with respect to a total of 100 weight part of (A), (B), and (C) component. Good to do. When the amount is 70 parts by weight or more, the heat discoloration resistance is lowered, the viscosity is lowered, the curing shrinkage increases, and molding becomes difficult.

As a specific example of "the ethylenically unsaturated compound which has at least 2 (meth) acryl group in 1 molecule" of (B) component, ethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, and 1, 4- butanediol di ( Meta) acrylate, neopentylglycoldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, 1,9-nonanedioldi (meth) acrylate, dimetholol-tricyclodecanedi (meth ), Di (meth) acrylate ester of bisphenol-A epoxy resin, trimetholpropane tri (meth) acrylate, etc. are mentioned, but ethylenic unsaturated which has one (meth) acryloyl group in 1 molecule You may use a compound together.

In addition, about the curing catalyst of (C) component, a thermal polymerization initiator or a photoinitiator can be used. It is preferable that it is 0.01-10 weight part with respect to a total of 100 weight part of curable resin composition, and, as for addition amount, it is preferable that it is 0.01-5 weight part. If the addition amount of the initiator is less than 0.01 part by weight, curing will be insufficient, resulting in low strength and rigidity of the cured product. On the contrary, when it exceeds 5 weight part, there exists a possibility that a problem, such as coloring, may arise. In addition, a thermal polymerization initiator or a photoinitiator may be used independently and may use both together.

Among these, as the thermal polymerization initiator, organic peroxides are preferable, and ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxy ketals, alkyl peresters, percarbonates, and the like can be given. Can be. Of these, dialkyl peroxides are preferred in view of catalytic activity. Specifically, cyclohexanone peroxide, 1,1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, di-t-butyl peroxide Although, t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexanoate, etc. can be illustrated, It is not restrict | limited to these at all. In addition, these may be used independently and may be used together 2 or more types.

Examples of the photopolymerization initiator include alkylphenones, acetophenones, benzoin, benzophenones, thioxanthones, acylphosphon oxides, and the like. Of these, alkylphenones are preferred in view of catalytic activity. Specifically 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1 -One, 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-propane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4- Although morpholinyl) phenyl] -1-butanone etc. can be illustrated, it is not restrict | limited to these at all. In addition, these may be used independently and may be used together 2 or more types.

In addition, in the curable resin composition of this invention, if it is a range which does not impair transparency, conventionally well-known antioxidant, ultrafine silica, such as aerosol, inorganic filler suited to resin which hardened refractive index, etc. improve the mechanical strength and coefficient of thermal expansion You may mix | blend suitably from a viewpoint to say.

Curable resin composition of this invention can be hardened using heat, light, or both. When hardening using a thermal polymerization initiator, it can harden | cure in a wide range from room temperature to around 200 degreeC according to selection of a thermal polymerization initiator and an accelerator. As needed, you may perform a postcure (additional heating). On the other hand, when hardening using a photoinitiator, hardened | cured material can be obtained by light irradiation, For example, the ultraviolet-ray of wavelength 100-400 nm and visible light of wavelength 400-700 nm are irradiated. Although the wavelength of the light to be used is not specifically limited, Especially near-ultraviolet rays with a wavelength of 200 to 400 nm are suitably used. Lamps used as UV generators include low pressure mercury lamps (output: 0.4 to 4 W / cm), high pressure mercury lamps (40 to 160 W / cm), ultra high pressure mercury lamps (173 to 435 W / cm), and metal halide lamps (80 to 160 W). / Cm), pulse xenon lamp (80 ~ 160W / cm), pulse xenon lamp (80 ~ 120W / cm), electrodeless discharge lamp (80 ~ 120W / 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 to be used. When using a thermal polymerization initiator and a photoinitiator together, it can harden | cure in order of light heat and hot light according to the said conditions. In particular, when thermal polymerization and photopolymerization differ, it can be hardened in a short time. Moreover, you may make hardened | cured material which has a predetermined shape by injection molding or compression molding the curable resin composition of this invention. At this time, the molding apparatus to be molded is not particularly limited.

Since the curable resin composition of this invention is excellent in heat discoloration resistance, low thermal expansion property, high transparency, and low hardening shrinkage property, the various materials of optical use, optical device use, display device use, the mechanical component material, Electrical and electronic component materials etc. can also be replaced by the molded object (cured product) which consists of curable resin composition of this invention. For example, because it has heat resistance to withstand solder reflow, such as a CCD with a lens mounted in a mobile phone, a digital camera, an in-vehicle camera, a CMOS sensor with a lens, an electronic device such as a camera module incorporating a lens and a semiconductor It can be applied to a part and can also be used for glass substitute materials, such as a diffraction grating, a polarizing part, and a reflector.

Example

Synthesis Example 1

14.3 g of tetramethylammonium hydroxide pentahydrate (manufactured by Kanto-Kagaku) was added as a basic catalyst to a reaction vessel equipped with a stirrer, a dropping lot, and a thermometer, dissolved in 17.0 g of water, and then 189 ml of toluene and 2-propanol 95 Ml was added. 46.8 g of vinyl trimethoxysilane (made by Shin-Etsu Chemical Co., Ltd .; KBM1003) was added to the dripping lot, and the vinyltrimethoxysilane was dripped over 3 hours at room temperature, stirring reaction container. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. After the stirring was completed, stirring was stopped, and the mixture was stopped for 1 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 three times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated to give 24.9 g (97%) of a colorless transparent viscous liquid silanol group-containing cage 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. It was confirmed from FIG. 1 that Mw = 1005 and Mw / Mn = 1.225. Among them, the peaks on the low molecular side, which occupy 70% of the area ratio, were Mw = 668 and Mw / Mn = 1.020. Next, it shows a result of measuring a ¹ H NMR in Figure 2. The peak integration ratio of the multiplet peak by the 5.8-6.2 ppm vinyl group and the 1.6 ppm silanol group was 0.174 of the silanol groups with respect to the vinyl group 1. Therefore, the compound approximately calculated from the low molecular side Mw and the integral ratio which are the main peaks is represented by the following formula.

[R ¹ SiO _3/2 ] _n [HO _1/2 ] _k (2)

When it was assumed as, it was suggested that n is 8 and k is 2 (R ¹ is a vinyl group).

IR was measured in order to confirm the presence of the silanol group of the colorless transparent viscous liquid silanol group containing cage-type siloxane (21) obtained above. As a result, the existence of a silanol group was confirmed from having a broad peak derived from a silanol group at 3100-3400 cm <^-1> . From the above result, the structure of the colorless transparent viscous liquid represented by said Formula (2) was judged as silanol-group containing cage-type siloxane.

Table 1 shows the results of electrospray ionization mass spectrometry (ESI-MS) of the silanol group-containing cage silsesquioxane 21 obtained above. Table 1 shows the main peaks detected by mass spectrometry and numerical values suitable for n and k. The peak (m / z) detected is the value which ammonium ion (Mw = 18) was added to the molecular weight of the silanol group containing cage-type siloxane 21. Also from the result of this mass spectrometry, it is shown that a part of the siloxane bond which forms cage structure becomes a structure which has a silanol group in a terminal part.

23.7 g of the silanol group-containing cage siloxane (21) obtained above in a reaction vessel equipped with a stirrer and a dropping lot, and the following formula (19)

19.3 g of the epoxy acrylate (manufactured by Kyoeisha Chemical Co., Ltd .; 3002M) was weighed in and substituted with nitrogen to dissolve in 60 ml of pyridine. 19.2 g of diphenyldichlorosilane and 76 ml of pyridine were put into the dropping lot, and it was dripped over 2 hours at room temperature. After completion of the dropwise addition, 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 three times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated to give 52.1 g (yield 97%) of an organic-inorganic composite 22 of a colorless transparent viscous liquid.

The result of measuring the GPC of the organic-inorganic composite 22 of the colorless transparent viscous liquid obtained above is shown in FIG. It was Mw = 8035 and Mw / Mn = 2.755 from FIG. 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 consists of Formula (19)], and it confirmed that n was 6-14 and m + l = 5.

Synthesis Example 2

14.3 g of tetramethylammonium hydroxide pentahydrate was added as a basic catalyst to the reaction vessel provided with a stirrer, a dropping lot, and a thermometer, dissolved in 17 g of water, and then 189 ml of toluene and 95 ml of 2-propanol were added thereto. 23.4 g of vinyl trimethoxysilane (made by Shin-Etsu Chemical Co., Ltd .; KBM1003) and 23.7 g of ethyl trimethoxysilane (made by Shin-Etsu Chemical Co., Ltd .; LS-890) are added to the dropping lot, and reaction is carried out. The liquid mixture of vinyl trimethoxysilane and ethyl trimethoxysilane was dripped over 3 hours at room temperature, stirring a container. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. After the end of stirring, stirring was stopped and it stopped for 1 day. Subsequently, Dean-Stark and a cooling tube were provided in the reaction vessel, 95 ml of toluene was added, and 2-propanol and methanol produced during hydrolysis were removed at 90 ° C using an oil bath. . Then, the temperature of the oil bath was set to 120 degreeC, toluene was superheated and refluxed, removing water, and the recondensation reaction was performed. After toluene reflux, after stirring for 3 hours, the reaction was 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 three times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated to give 25.5 g (98%) of a colorless transparent viscous liquid silanol group-containing cage siloxane (23).

The result of having measured the GPC of the colorless transparent viscous liquid silanol group containing cage-type 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, which occupy 70% of the area ratio, were Mw = 650 and Mw / Mn = 1.032. Next, as a result of measuring ¹ H-NMR, the peak integration ratio of 5.8-6.2 ppm vinyl group, peak peak of 0.4-1.2 ppm ethyl group, and 1.6 ppm silanol group were integrated into vinyl group 1. Ethyl group 1 and silanol group were 0.189. Therefore, the compound approximately calculated from the low molecular side Mw and the integral ratio which are the main peaks is represented by the following formula (2).

[R ¹ SiO _3/2 ] _n [HO _1/2 ] _k (2)

When assumed as, n was 8 and k was 2 (R ¹ is a vinyl group: ethyl group = 1: 1).

20.0 g of the silanol group-containing cage-type silsesquioxane compound (23) obtained above and 4.4 g of cyclohexanedimethanol (manufactured by Tokyo Kasei Co., Ltd.) were weighed into a reaction vessel equipped with a stirrer and a dropping lot, and nitrogen. Substituted and dissolved in 61 ml of pyridine. 19.2 g of diphenyldichlorosilane and 76 ml of pyridine were put into the dropping lot, and it was dripped over 2 hours at room temperature. After completion of the dropwise addition, 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 three times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated to give 35.3 g (yield 92%) of an organic-inorganic composite (24) of a colorless transparent viscous liquid.

The result of measuring GPC of the organic-inorganic complex 24 obtained above is shown in FIG. It was Mw = 13937 and Mw / Mn = 4.369 from FIG. 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 vinyl group: ethyl group = 1: 1, R <^2> consists of a phenyl group and X is cyclohexane dimethanol), and it confirmed that n was 6-14 and m + l = 11.

Synthesis Example 3

14.3 g of tetramethylammonium hydroxide pentahydrate was added as a basic catalyst to the reaction vessel provided with a stirrer, a dropping lot, and a thermometer, dissolved in 17 g of water, and then 189 ml of toluene and 95 ml of 2-propanol were added thereto. 78.4 g of 3-methacryloxypropyl trimethoxysilane (made by Shin-Etsu Chemical Co., Ltd .; LS-3380) is added to the dripping lot, and 3-methacryloxypropyl trimeth is added at room temperature, stirring reaction container. The oxysilane was dripped over 3 hours. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. After the end of stirring, stirring was stopped and it stopped for 1 day. Next, the reaction vessel was equipped with a Dean Stark and a cooling tube, 95 ml of toluene was added, and 2-propanol and methanol produced at the time of hydrolysis were removed at 90 degreeC using the oil bath. Then, the temperature of the oil bath was set to 120 degreeC, toluene was superheated and refluxed, removing water, and the recondensation reaction was performed. After toluene reflux, after stirring for 3 hours, the reaction was 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 three 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 siloxane (25).

The result of measuring 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, which occupy 70% of the area ratio, were Mw = 1480 and Mw / Mn = 1.028. Subsequently, as a result of measuring ¹ H-NMR, the peak integration ratio of the peak by 5.4-6.2 ppm methacryl group and the 1.6 ppm silanol group was 0.189 of the silanol groups with respect to methacryl group 1. Therefore, the compound approximately calculated from the low molecular side Mw and the integral ratio which are the main peaks is represented by the following formula (2).

[R ¹ SiO _3/2 ] _n [HO _1/2 ] _k (2)

When assumed as, it was suggested that n is 8 and k is 2 (R ¹ is a 3-methacryloxypropyl group).

20.0 g of the silanol group containing cage-type silsesquioxane compound (25) obtained above to the reaction container provided with the stirrer and the dropping lot, and following formula (20)

(However, R ³ is-(CH ₂ ) _6- , 13.8 g of an organic diol compound represented by Asahi Kasei Co., Ltd. (ETERNACOLL UH-100) having Mw = 1000; Dissolved in. 8.7 g of diphenyl dichlorosilanes and pyridine were put into the dropping lot, and it was dripped over 2 hours at room temperature. After completion of the dropwise addition, 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 three times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated to give 40.1 g (yield 95%) of an organic-inorganic composite 26 of a colorless transparent viscous liquid.

The result of measuring GPC of the organic-inorganic complex 26 obtained above is shown in FIG. From FIG. 7, Mw was 28164 and Mw / Mn was 7.277. Therefore, the obtained organic-inorganic composite 26 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)

[R <^1> is a 3-methacryloxypropyl group, R <^2> is a phenyl group and X consists of said Formula (20). ", It confirmed that n was 6-14 and m + l = 10.

Example 1

70 parts by weight of the organic-inorganic composite (22) obtained in Synthesis Example 1 as the component (A), and (B) the following formula (27)

30 weight part of compounds represented by (Kyosei Chemical Co., Ltd .; DCP-A) are mixed, and following formula (28) which is (C) component

1 weight part of the curing catalyst represented by (the Nippon Oil Chemical Industries, Ltd .; percumyl D) is mixed with respect to a total of 100 weight part of (A) and (B) component, it is stirred well, and the curable resin composition of Example 1 Prepared.

[Example 2]

Instead of the organic-inorganic composite 22, the curable resin composition according to Example 2 was prepared 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). Prepared.

Example 3

70 weight part of organic-inorganic composites (26) obtained by the said Synthesis Example 3 which is (A) component, and 30 weight part of said formula (27) which is (B) component are mixed, and it is following formula (29) which is (C) component

 The curing catalyst represented by (Ciba Japan Co., Ltd .; Irgacure184) was mixed with 1 weight part with respect to a total of 100 weight part of (A) and (B) component, it was stirred well, and it prepared as the curable resin composition of Example 3. .

Example 4

80 parts by weight of the organic-inorganic composite (24) obtained in Synthesis Example 2 as the component (A), and (B) the following formula (30)

 20 parts by weight of the trimetholpropane tri (meth) acrylate (manufactured by Kyoeisha Chemical Co., Ltd .; TMPTA) represented by the above is mixed, and the curing catalysts of the formulas (28) and (29) as the (C) component are 1 weight part of each was mixed, it stirred well, and it prepared as curable resin of Example 5.

Comparative Example 1

To 100 parts by weight of the silanol group-containing cage-type siloxane (21) prepared in Synthesis Example 1, 1 part by weight of the curing catalyst of the formula (28) of component (C) is mixed and stirred well to prepare the composition of Comparative Example 1. did.

Comparative Example 2

1 weight part of said curing catalysts of said Formula (28) of (C) component were mixed with respect to 100 weight part of compounds represented by said Formula (27) which is (B) component, it stirred well, and the composition of Comparative Example 2 was prepared. .

Using the compositions prepared in the above Examples and Comparative Examples, poured into a mold mounted on a glass plate to a thickness of 2 mm, and for [Examples 1, 2] and [Comparative Examples 1, 2] at 120 ° C. for 1 hour, It was formed by heating at 150 ° C. for 1 hour and 2 hours at 180 ° C., respectively. For Example 3, molding was performed at an integrated exposure amount of 2000 mJ / cm 2 using a high-pressure mercury lamp of 30 W / cm. After hardening by the integrated exposure amount of 2000mJ / cm <2> using the high pressure mercury lamp of 30W / cm, it heated at 200 degreeC for 1 hour, and obtained the test molding of 50mm * 25mm * thickness 2mm, respectively.

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

<Viscosity>

The viscosity at 24 degreeC and rotational speed D = 1 / s was evaluated by the R / S rheometer (the Brookfield company made in USA). When the viscosity was 20 Pa · s or more, the measuring jig of RC-25-1 was used, and when less than 20, the jig of RC50-1 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 curable resin composition.

<Cure shrinkage rate>

Specific gravity before and after curing was measured to calculate volume shrinkage. The specific gravity of curable resin composition was calculated | required by the picnometer method (JIS K 7112), and the hardened | cured material by the underwater substitution method (JlS K 7112).

Curing shrinkage ratio = (specific gravity of resin before 1-curing / specific gravity of resin after curing) × 100

<Coefficient of thermal expansion>

Based on the thermomechanical analysis method, it calculated | required on the conditions of a temperature increase rate of 5 degree-C / min, and a compression load of 0.1N.

<Transmittance>

The transmittance | permeability of the hardened | cured material in wavelength 450nm was evaluated using the light absorber (The Shimadzu Corporation make, spectrophotometer UV-3100). Moreover, the transmittance | permeability after holding hardened | cured material in 260 degreeC and a 10 minute drier was also evaluated.

<Refractive index>

It evaluated using the refractive index meter (the Atago company make, DR-M2). Moreover, the refractive index after holding hardened | cured material in 260 degreeC and a 10-minute drier was also evaluated.

<Turbidity>

The haze of hardened | cured material was evaluated using (NDH2000 by Nippon Denshoku Co., Ltd.).

<State of hardened | cured material after hardening>

Visually confirmed the cracking.

Claims (3)

(A) an organic-inorganic complex having two or more aliphatic unsaturated bonds in one molecule and further comprising a cage-type siloxane and an organic component,
(B) an ethylenically unsaturated compound having two or more (meth) acryl groups in one molecule, and
(C) A curing catalyst is an essential component, and it contains 30 weight part or more of organic-inorganic composites of (A) component as a main component with respect to a total of 100 weight part of (A), (B), and (C) component. Curable resin composition. The organic-inorganic composite of claim 1, wherein the organic-inorganic composite of component (A) 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)
[Wherein R ¹ and R ² are a group having a vinyl group, allyl group, alkyl group, aryl group, (meth) acryloyl group or oxirane ring and may be the same or different from each other, and X is an aliphatic carbon having 5 to 50 carbon atoms. Any one of a structure, an alicyclic structure having 5 to 50 carbon atoms, an aromatic structure having 5 to 50 carbon atoms, or an -OCOO- bond, and may contain two or more different species, and 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 a weight average molecular weight is Mw = 5,000 to 1,000,000, and vinyl group, allyl group, (meth) having an unsaturated double bond in 1 molecule. Curable resin composition characterized by having 2 or more types of 1 or 2 or more reactive functional groups chosen from the group which consists of acryloyl group. Hardened | cured material obtained by hardening | curing curable resin composition of Claim 1 or 2 using heat, light, or both.

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