WO2007119477A1 - Curable resin, curable resin compositions and moldings thereof - Google Patents

Abstract

A curable resin which exhibits strength, transparency, heat resistance and dimensional stability which are equivalent to those of inorganic glass respectively as well as high toughness and fabricability which are equivalent to those of plastics respectively. A curable resin having a molecular structure of the general formula (1) consisting of dense structural units (A) and thin structural units (B), in which the dense structural units (A) consist of a metal oxide having a Kp value of 0.68 to 0.8 and the thin structural units (B) have Kp values of less than 0.68 and comprises an organic substance and an organometallic oxide, with each Kp value being calculated by free volume fraction according to the formula (2), and which has an (A)/(B) weight ratio is 0.01 to 5.00, at least one unsaturated bond, and a number-average molecular weight of 800 to 60000: -{(A)-(B)m}n- (1), Kp=An Vw p/Mw (2) wherein An is Avogadro's number; Vw is van der Waals volume; p is density; and Mw is molecular weight.

Description

 Specification

 Curable resin, curable resin composition, and molded article thereof

 Technical field

 [0001] The present invention provides a molded article that can achieve both strength, transparency, heat resistance, and dimensional stability, such as inorganic glass, and high toughness and cacheability, such as plastic. It can be applied to optical applications such as lenses, optical discs, optical fibers, and flat panel display substrates, various transportation machines, window materials for houses, etc., and it is lightweight and has high impact strength. The present invention also relates to a curable resin capable of obtaining a molded body that can have transparency. Background art

 [0002] As a transparent material, inorganic glass has excellent heat resistance and dimensional stability, and is used in a wide range of industrial fields. The inorganic glass having such excellent characteristics is disadvantageous in that it is heavy with a force specific gravity of ¾.5 or more, has poor toughness and is susceptible to cracking, and is inferior in workability. The demand for transparent plastics such as polystyrene and PMMA (polymethyl methacrylate) as an alternative to glass is growing. Although these are lightweight and excellent in flexibility, they are organic, so they have heat resistance, light resistance, and dimensional stability. Etc. are significantly inferior to glass, and there is a problem that applications are limited.

 [0003] Not only glass and plastic, but generally homogeneous material systems, it is difficult to realize various physical properties such as heat resistance, impact resistance and mechanical strength at a high level. As a method for solving this problem, a polyalloy method represented by HIPS (no-impact polystyrene) with improved impact resistance without reducing the elastic modulus, strength, heat resistance, etc. as much as possible is known. However, when the refractive indexes of the resins to be mixed are different, there is a problem that the transparency is remarkably deteriorated. In addition, it is possible to reinforce the modulus of elasticity and dimensional stability by adding inorganic powder and fibers to the resin, but it is difficult to add while maintaining transparency, and blending of inorganic powder As a result, the resin viscosity increases, resulting in poor workability.

[0004] As a method for solving such a problem, a silicone resin that is superior in terms of heat resistance, weather resistance, and water resistance is promising due to the intermediate characteristics of the metal and nonmetal of the silicon atom. It is. However, there is no material that has both high strength and toughness in silicone resins. High-strength silicone resins are composed only of dense structural units that have a high crosslinking density and a low free volume fraction that suppresses molecular motion. It is difficult to mold to a brittle thickness, and its use is limited to coating agents. At present, only low-strength silicone rubbers composed of sparse structural units with a high free volume fraction, which suppresses the binding force of molecules with low crosslink density, are used for molding applications.

 Patent Document 1: Japanese Patent No. 3598749

 Patent Document 2: Japanese Patent Laid-Open No. 2006-22207

 Patent Document 3: Japanese Patent Laid-Open No. 2005-330455

 Disclosure of the invention

 Problems to be solved by the invention

[0005] Therefore, the object of the present invention is to provide a curability that can achieve both strength, transparency, heat resistance, and dimensional stability as in inorganic glass, and high toughness and cacheability as in plastic. It is in providing a resin and its composition.

 Means for solving the problem

 [0006] As a result of repeated studies to achieve the above-mentioned problems, the present inventors have found that a curable resin having a dense structural unit and a sparse structural unit having different free volume fractions in a molecular structure. The inventors have found that it is possible to provide a curable resin molded article that can be suitably used for an alternative use of inorganic glass having excellent transparency, and completed the present invention.

 [0007] That is, the present invention is a curable resin having a molecular structure composed of a dense structural unit (A) and a sparse structural unit (B) represented by the following general formula (1). The structural unit (A) is a sparse structural unit composed of a metal oxide having a packing coefficient Kp of 0.68 to 0.8 calculated by the following formula (2) calculated from the free volume fraction. The structural unit (Β) is a structural unit comprising the organic material and the organometallic oxide with the packing coefficient Kp of less than 0.68, and the weight ratio of the structural unit (A) Z (B). Is a curable resin having an organometallic structure, characterized by having an average molecular weight of 800 to 60000 having at least one unsaturated bond.

 -{(A)-(B)}-(1)

mn (However, m and n are integers of 1 or more.)

 Kp = An-Vwp / Mw (2)

(However, An = Avogadro number, Vw = Van der Waals volume, p = Density, Mw = Molecular weight, Vw = ∑ Va, Va = 4 π / R ³ -∑ 1/3 π hi ² (3Ra_hi), hi 2 Ra_ (Ra ² + di ² −Ri ² ) / 2di, Ra diatomic radius, Ri = bonding atomic radius, and di = interatomic distance. ]

Here, the dense structural unit (A) is composed of a metal oxide portion having a three-dimensional polyhedral structure skeleton excluding the organic matter portion of the following general formula (I), and the sparse structural unit (B) is It is a preferred embodiment of the curable resin of the present invention that it is composed of a chain unit composed of an organometallic oxide represented by the following general formula (II) and an organic part of the general formula (I).

 (RSiO) (MO) (RXSiO) (XMO) (I)

 3/2 w 2 x y 3/2 z

(R ³ R ⁴ R ⁵ SiO) (R ⁶ R ⁷ SiO) {R ⁶ R ⁷ XSiO} (II)

 1/2 j k 1/2 1

[However, R is indicated by (aH ^ -OCO-CR ^ CH, (b) -R ¹ -CR ² = CH or (c) _CH = CH

2 2 2 An unsaturated group, an alkyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a hydrogen atom, an alkoxyl group, or an alkylsiloxy group, and a plurality of R in formula (I) are different from each other However, at least one contains any of the above (a), (b) or (c), R ¹ represents an alkylene group, an alkylidene group or a phenylene group, and R ² represents hydrogen. Or represents an alkyl group. R ^{3 to} R ⁷ are (aH ^ -OCO-CR ^ CH, (b) -R ¹ -CR ² = CH or (c) _

 twenty two

 An unsaturated group represented by CH = CH, an alkyl group, a cycloalkyl group, a cycloalkenyl group,

2

A phenyl group, a hydrogen atom, an alkoxyl group, or an alkylsiloxy group. Further, M is a metal atom of silicon, germanium, titanium, or zirconium, X is a halogen atom, or an alkoxyl group, _w is an integer of 4 or more, and X, y, and z are w + x + y + It is an integer that satisfies z≥8. j, k, and 1 each represent an integer of 0 or more. ]

[0009] In addition, the general formula (I) is RSiX, MX or a mixture thereof (provided that R, M and X are general

 3 4

The same as in formula (I)), wherein the general formula (II) is R ³ R ⁴ R ⁵ Si X, R ⁶ R ⁷ SiX or a mixture thereof (provided that R ³ ˜R ⁷ and X are the same as in the general formula (Π).

 2

And at least part of the organic moiety of the general formula (I) is bonded to the hydrolysis condensate to form the structural moiety (B) of the general formula (1). Is a preferred embodiment. [0010] In the present invention, the curable resin represented by the general formula (1) may be blended with a hydrosilylation catalyst, a radical initiator, or both to obtain a curable resin composition. Yo! Further, the curable resin composition may be blended with a hydrosilylatable compound having a hydrogen atom on at least one silicon atom, a compound having an unsaturated group, or both. Les.

 [0011] Hereinafter, the present invention will be described more specifically.

 The curable resin of the present invention has a molecular structure composed of a dense structural unit (A) and a sparse structural unit (B) as represented by the general formula (1), and has at least one unsaturated component. Have a bond. Here, the dense structural unit (A) is composed of a metal oxide having a packing coefficient Kp calculated by the above formula (2) of 0.68 to 0.8, and is a sparse structural unit ( Β) has a packing coefficient Kp of less than 0.68 and includes organic substances and organometallic oxides.

 The dense structural unit (A) is preferably composed of a metal oxide portion having a three-dimensional polyhedral structure skeleton, excluding the organic portion of the general formula (I). Here, the organic part is a part of R (organic group) in the general formula (I) that is bonded to a metal atom (that is, Si and M). In the general formula (I), at least one of R is preferably an organic group having an unsaturated group represented by the above formulas (a) to (c). Note that the plurality of R in the general formula (I) may not all be the same.

[0013] General formula (I) is a cage-type siloxane resin composed of a three-dimensional polyhedral structure skeleton and R. As an example, w in general formula (I) is 8, and X, y, and z If w is 0, w is 1 0 and X, y and z are 0, and w is 12 and X, y and z are 0, a specific example of the structure is represented by the following structural formula (3), Shown in (4) and (5). However, the structural unit represented by the general formula (I) is not limited to those represented by the structural formulas (3), (4) and (5). These structures are known and have been shown by X-ray crystal structure analysis for those having specific functional groups. (3;

In the general formula (I), one or more of the compounds represented by RSiX or MX

 3 4

It can be obtained by hydrolysis and condensation reaction in the presence of a medium. Here, R, X and M have the same meaning as R, X and M in formula (I). Among these, a part of R is preferably an unsaturated group represented by the above (a), (b) or (c). However, if a specific example of a preferable unsaturated group is shown, 3-metaatally Examples include a loxypropyl group, a 3-ataryloxypropyl group, an aryl group, a vinyl group, and a styryl group. X is a hydrolyzable group of a halogen atom or an alkoxyl group. Specific examples include chlorine, bromine, methoxy group, ethoxy group, n-propoxyl group, and i-propoxyl group. The [0015] Preferable examples of the compound represented by RSiX include trichlorosilane, methyloletrichlorosilane.

Three

 Lan, etyltrichlorosilane, isopropyltrichlorosilane, butyltrichlorosilane, t_butyltrichlorosilane, cyclohexyltrichlorosilane, phenyltrichlorosilane, vinylenotrichlorosilane, arinoletrichlorosilane, styryltrichlorosilane, cyclohexenyltrichlorosilane , Trimethoxysilane, methyltrimethoxysilane, etyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, allyltrimethoxysilane, styryltrimethoxysilane, cyclohexenyltri Methoxysilane, triethoxysilane, methyltriethoxysilane, etyltriethoxysilane, isopropyltriethoxysilane, butynoletriethoxysilane, t_Butinoretriethoxysilane, cyclohexylenetriethoxysilane, phenyltriethoxysilane, butyltriethoxysilane, allyltriethoxysilane, styryltriethoxysilane, cyclohexenyltriethoxysilane, tripropoxysilane, methyltripropoxysilane, Tiltripropoxysilane, isopropyltripropoxysilane, butyltripropoxysilane, t_butyltripropoxysilane, cyclohexyltripropoxysilane, phenyltripropoxysilane, butyltripropoxysilane, allyltripropoxysilane, styryltripropoxysilane Silane, cyclohexenyltripropoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxy

And lanthanum, 3-methacryloxypropyltriethoxysilane, 3-ataryloxypropyltrimethoxysilane, and 3-ataryloxypropyltrichlorosilane.

[0016] Further, M is silicon, germanium, titanium, or zirconium. Where MX is the table

 4) Preferred examples of the compound are tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrachromate germane, tetramethoxygermane, tetraethoxygermane, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium yubutoxide, Titanium isobutoxide, zirconium ethoxide, zirconium propoxide, zirconium isopropoxide, zirconium butoxide, zirconium isobutoxide and the like can be mentioned.

[0017] Next, the sparse structural unit (B) is a three-dimensional polyhedron in the structural unit represented by the general formula (I). The organic structure (silicone compound) having a chain unit as represented by the above general formula (Π) and the organic part (or substituent) which is a residue other than the body structure skeleton . In other words, it consists of the structural unit represented by the above general formula (I) except the dense structural unit (A) and the structural unit represented by the general formula (Π). More specifically, as described ^{below, R¾ 4R 5 SiX, R 6} R 7 SiX or a mixture thereof (wherein, R ³ to R ⁷ and X are the same as those in the general formula ([pi)

 2

 A chain structure of an organometallic oxide of the general formula (ii) consisting of a hydrolysis condensate of (a) and an organic moiety of the general formula (I) [ie, in the structural unit represented by the general formula (I) Or a residue (or substituent)] or at least a part of X is preferably bonded to form the structural site (B) of the general formula (1). That is, a part of the organic part of the general formula (1) may be bonded to the general formula (II), or the whole organic part of the general formula (1) may be bonded to the general formula (式). ,. The organic part of the general formula (I) bonded to the general formula (Π) is incorporated into the chain unit of the general formula (II).

[0018] The structural unit represented by the general formula (Π) is a compound represented by R ³ R ⁴ R iX or R ⁷ SiX.

 2

One or more compounds can be obtained by hydrolysis and condensation reactions in the presence of an acid or base catalyst. Here, R ^{3 to} R ⁷ have the same meaning as R ^{3 to} R ^{7 in} formula (II). In the case where a part of R ^{3 to} R ⁷ is an unsaturated group, preferred specific examples include a 3-methatalyloxypropyl group, a 3-aryloxypropyl group, an aryl group, a bier group and a styryl group. X is a halogen atom or an alkoxy group, and specific examples include chlorine, bromine, methoxy group, ethoxy group, n-propoxyl group, and i-propoxyl group.

Preferred examples of the compound represented by R ³ R ⁴ R iX include trimethylchlorosilane, vinylenodimethylchlorosilane, dimethylchlorosilane, phenyldimethylchlorosilane, phenolinochlorosilane, trietinorechlorosilane, and trivininorechlorosilane. , Methino Resinino Lecro mouth

Methoxy silane, butyl dimethyl methoxy silane, dimethyl methoxy silane, phenyl dimethyl methoxy silane, phenyl methoxy silane, triethyl methoxy silane, tribyl methoxy silane, methyl divinyl methoxy silane, allyl dimethyl methoxy silane, 3-methataryloxy Tyryldimethylmethoxysilane, trimethylethoxysilane, butyldimethylethoxysilane, dimethinoreethoxysilane, pheninoresimethinoreethoxysilane, phenenoreethoxysilane, trichinoleethoxysilane, trivininoreethoxysilane, methinoresininoreethoxy Silane, aryl dimethyl ethoxy silane, 3_meta acryloxy propyl dimethyl ethoxy silane, 3-acryloxy propyl dimethyl ethoxy silane, styryl dimethyl ethoxy silane, trimethyl propoxy silane, butyl dimethyl propoxy silane, dimethyl propoxy silane, phenol Dimethylpropoxysilane, phenylpropoxysilane, triethylpropoxysilane, tribylpropoxysilane, methyldibutylpropoxysilane, Dimethylpropoxysilane, 3-methatalyloxypropyldimethylpropoxysilane, 3-Atalyloxypropyldimethyldimethylpropoxysilane, Styryldimethylpropoxysilane, Trimethylisopropoxysilane, Butyldimethylisopropoxysilane, Dimethylisopropoxysilane, Phenyldimethylisopropoxysilane , Phenyl isopropoxy silane, triethyl isopropoxy silane, tribyl isopropoxy silane, methyl dibutyl isopropoxy silane, allyl dimethyl isopropoxy silane, 3-meta atyloxy propyl dimethyl isopropoxy silane, 3-ataryloxy propyl dimethyl iso Examples include propoxysilane and styryldimethylisopropoxysilane.

In addition, preferable examples of the compound represented by R ⁶ R ⁷ SiX include dimethyldichlorosilane,

 2 Tildichlorosilane, methylphenyldichlorosilane, methylethyldichlorosilane, ethyl

Styrylethyl dichlorosilane, 3-metaataryloxypropylmethyldichlorosilane, dimethyldimethoxysilane, butylmethyldimethoxysilane, dibutyldimethoxysilane, allylmethyldimethoxysilane, methyldimethoxysilane, methylphenyldimethoxysilane, methyl

Cypropylmethyldimethoxysilane, dimethyljetoxysilane, butylmethyljetoxysilane, divininoletoxysilane, arlinolemethinolegoxysilane, methinolegoxysilane, methylphenyljetoxysilane, methylethyljetoxysilane, Etilbinini Diethoxysilane, Ethylaryljetoxysilane, Styrylmethyljetoxysilane, Styrylethyljetoxysilane, 3-Methataryloxypropylmethyljetoxysilane, Dimethyldipropoxysilane, Bulmethyldipropoxysilane, Di Burdipropoxysilane, allylmethyldipropoxysilane, methyldipropoxysilane, methylphenyldipropoxysilane, methinorethinoresipropoxysilane, ethinolevininoresipropoxysilane, ethylaryldipropoxysilane, styrylmethyldi Propoxy silane, styryl ethyl dipropoxy silane, 3-methataryloxypropyl methyl dipropoxy silane, dimethyl diisopropoxy silane, butyl methyl diisopropoxy silane, dibul diisopropoxy , Arylmethyldiisopropoxysilane, methyldiisopropoxysilane, methylphenyldiisopropoxysilane, methylethyldiisopropoxysilane, ethylbutyldiisopropoxysilane, ethylaryldiisopropoxysilane, Examples include styrylmethyl diisopropoxysilane, styrylethyl diisopropoxysilane, and 3-metaatyl mouthpiece pyrmethyldiisopropoxysilane.

 [0021] The curable resin of the present invention can be obtained by reacting a force-type siloxane resin represented by the general formula (I) with a silicone compound represented by the general formula (I). However, the obtained curable resin has a molecular structure in which the unsaturated bonds of the structural units represented by the general formula (I) and the general formula (Π) are condensed by crosslinking or hydrolysis condensation. This curable resin is composed of a dense structural unit (A) having a packing coefficient calculated from a free volume fraction of 0.68 to 0.8 and a sparse structural unit (B) having a packing coefficient of less than 0.6 · 68. ) And at least one unsaturated bond.

 [0022] The packing coefficient Kp used in the present invention is calculated by the following calculation formula (2).

 Kp = AnVw p / Mw (2)

 (However, An = Avogadro number, Vw = Van der Waals volume, p = Density, Mw = Molecular weight.)

 Vw = ∑Va

Va = 4 π / R ³ -∑ΐ / 3 π hi ² (3R_hi)

hi = R- (R ² + di ² -Ri ² ) / 2di

の鎖状構造をとるオタタメチルトリシ口 キサンの密度は 0. 820gん m³であり、そのパッキング係数は 0. 521となる。すなわち、 ケィ素原子が 3つ以上の酸素原子と結合した三次元多面体構造を有する金属酸化 物のパッキング係数は 0. 69以上となり、本発明における密な構造単位となる。また環 状および鎖状構造をとる化合物のパッキング係数は 0. 576および 0. 521であり、本発 明における疎な構造単位となる。 (Where R = atomic radius, Ri = bonding atomic radius, and d = interatomic distance). [0023] In the calculation of the packing coefficient, the atomic radius and interatomic distance used were the values described in the 3rd edition of the Chemistry Handbook Basic Revised by the Chemical Society of Japan. That is, H = 1.2 A, 0 = 1.52A, C = l. 7A, Si = 2.14A are used for the atomic radius, and the interatomic distance is H_C = 1.08 A, C_C = 1.54 lA, Si- C = l. 863A, Si_〇 = l. 609A were used. For example, in the general formula (I), M = key atom, w = 0, x = 2, y = 0, and z = 0, the density of the glass that can be expressed is 2.23g m ³ and its packing coefficient is 0. 747. The density of octakismethylsilsesquioxane having a cubic structure of w = 8, x = 0, y = 0, and z = 0 in the R cation group of general formula (I) is 1.49g m ³ Yes Packing factor is 0.697. In addition, the density of otamethylcyclotetrasiloxane having a general structure (Π) in which R ⁶ and R ⁷ are methyl groups and have a cyclic structure of j = 0, k = 4, and 1 = 0 is 0.956 gm ³ . There is a packing factor of 0.576. Similarly R ³ and R ⁴ , R ⁵ ,

The density of otamethyl trisicoxane having a chain structure of 0.820 gm ³ and a packing coefficient of 0.521. That is, the packing coefficient of a metal oxide having a three-dimensional polyhedral structure in which a key atom is bonded to three or more oxygen atoms is 0.69 or more, which is a dense structural unit in the present invention. The packing coefficients of the compounds having a cyclic structure and a chain structure are 0.576 and 0.521, which are sparse structural units in the present invention.

 [0024] Further, the curable resin of the present invention has a weight ratio (A) / (B) of the structural unit of the dense structural unit (A) to the sparse structural unit (B) of 0.01 to 5.00, preferably Is between 0.5 and 3.00. When (A) / (B) is less than 0.01, the dense structure is too small, and the mechanical properties and heat resistance of a molded product obtained by molding and curing a curable resin are significantly deteriorated. On the other hand, if it is 5.00 or more, there are too few sparse structural parts imparting flexibility to the molded product, and the toughness will be remarkably deteriorated and become brittle.

 [0025] The curable resin of the present invention has an average molecular weight of 800 to 60000. If the average molecular weight is less than 800, it becomes brittle after molding, and on the contrary, if it exceeds 60,000, it may be difficult to cure and process, resulting in inconvenience in handling. The average molecular weight can be measured with a known GPC measurement device.

[0026] A compound represented by RSiX or MX, and a compound represented by R ³ R ⁴ R ⁵ SiX or R ⁶ R ⁷ SiX

3 4 2 Acid catalysts used for hydrolysis and condensation of the compound include hydrochloric acid and sulfuric acid. The These can also be used as a mixture. When the hydrolyzable group is a halogen atom, halogen hydrogen generated during hydrolysis may be used.

 [0027] Basic catalysts used for hydrolysis and condensation include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Examples thereof include ammonium hydroxide salts such as tetraptylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide. Among these, tetramethylammonium hydroxide is preferably used because of its high catalytic activity. Basic catalysts are usually used as aqueous solutions.

 [0028] Although the presence of water is essential for the hydrolysis reaction, it can be supplied from an aqueous solution of the catalyst, or may be added as water separately. The amount of water is not less than the amount sufficient to hydrolyze the hydrolyzable group, preferably 1.0 to 1.5 times the theoretical amount.

 [0029] In the present invention, a curable resin composition may be obtained by blending a hydrosilylation catalyst or a radical initiator with a curable resin, or blending both. A cured product (molded article) can be obtained by thermally curing or photocuring the curable resin composition, followed by hydrosilylation or radical polymerization. Further, in addition to the hydrosilylation catalyst and radical initiator, a compound having a hydrogen atom on the silicon atom or a compound having an unsaturated group in the molecule is further blended to obtain a curable resin composition. Also good. That is, for the purpose of obtaining a molded product by curing a curable resin and improving the physical properties of the resulting molded product, hydrosilylation catalyst, thermal polymerization initiator, thermal polymerization accelerator as additives for promoting the reaction. Then, a photopolymerization initiator, a photoinitiator auxiliary agent, a sharpening agent and the like are blended to obtain a curable resin composition.

[0030] In the curable resin composition, the compound having a hydrogen atom on a silicon atom used together with the curable resin has at least one hydrogen atom on the hydrosilylatable key atom in the molecule. It has oligomers and monomers. Among these, oligomers having a hydrogen atom on a silicon atom include polyhydrosiloxane siloxanes, polydimethylhydroxysiloxanes and copolymers thereof, and siloxanes whose ends are modified with dimethylhydrosiloxy. Is mentioned. In addition, a molecule having a hydrogen atom on the key atom. Examples of the monomers include cyclic siloxanes such as tetramethylcyclotetrasiloxane and pentamethylcyclopenta, dihydrodisiloxanes, trihydromonosilanes, dihydromonosilanes, monohydromonosilanes, dimethylsiloxysiloxanes, and the like. Two or more of these may be mixed.

[0031] Further, in the curable resin composition, the compound having an unsaturated group used together with the curable resin is a reactive oligomer that is a polymer having a structural unit having a repeating power of about ˜20. The reactive monomer is roughly classified into low molecular weight and low viscosity reactive monomers. They are broadly divided into monofunctional unsaturated compounds having one unsaturated group and polyfunctional unsaturated compounds having two or more.

 [0032] Among these, reactive oligomers include polybutylsiloxanes, polydimethylvinylsiloxysiloxanes, and copolymers thereof, siloxanes modified with dimethylvinylsiloxy at the ends, epoxy acrylate, epoxidized oil Examples thereof include acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, butyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, and polystyryl methacrylate. These include monofunctional unsaturated compounds and polyfunctional unsaturated compounds.

 [0033] Examples of the reactive monofunctional monomer include bur-substituted silicon compounds such as triethylbiylsilane and triphenylvinylsilane, cyclic olefins such as cyclohexene, styrene, vinyl acetate, and N-vinyl. Pyrrolidone, butyl acrylate, 2-ethyl hexyl acrylate, n xyl acrylate, n-decyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxetyl acrylate, phenoxychetyl taleate, trifluoro Examples include loetyl methacrylate.

 [0034] Examples of reactive polyfunctional monomers include bur-substituted cation compounds such as tetrabulesilane and dibutyltetramethyldisiloxane, and butyl substitution such as tetramethyltetrabutycyclotetrasiloxane and pentamethylpentabutylcyclopentasiloxane. Circular key compound

, Cyclic polyenes such as norbornagen, dicyclopentadiene, cyclooctagen, bur-substituted cyclic olefins such as burcyclohexene, dibulubenzenes, Turlbenzenes, trimethylolpropane dialyl ether, pentaerythritol triaryl ether, tripropylene glycol ditalylate, 1,6-hexanediol ditalylate, bisphenol A diglycidyl ether ditalylate, tetraethyleneglycol Dimethyl diatalylate, hydroxypentaglycol dipentayl glycol ditalylate, trimethylolpropane tritalylate, pentaerythritol retoralirate, pentaerythritol tetraatalylate, dipentaerythritol hexaatalylate, etc. can do.

 [0035] As the compound having an unsaturated group in the molecule, various reactive oligomers and monomers other than those exemplified above can be used. These reactive oligomer monomers may be used alone or in combination of two or more.

 [0036] The compound having a hydrogen atom on the silicon atom and the compound having an unsaturated group in the molecule used in the present invention may be used alone or in combination of two or more.

[0037] As described above, the curable resin composition of the present invention includes a hydrosilylation catalyst, a radical initiator, a compound containing a hydrogen atom on a silicon atom, or a compound having an unsaturated group. It is obtained by blending. The molded product of the present invention is obtained by molding and curing this curable resin composition. That is, a cured product can be obtained by hydrosilylation curing and radical polymerization of the curable resin composition.

 [0038] When the hydrosilylation catalyst is blended, the addition amount is preferably in the range of 1 to 1000 ppm, more preferably 20 to 500 ppm as metal atoms with respect to the weight of the curable resin. In addition, when a photopolymerization initiator or a thermal polymerization initiator is blended as a radical initiator, the amount added is preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the curable resin. It is more preferable to use the range of the amount part. If the amount of the additive is less than 0.1 parts by weight, the curing is insufficient and the strength and rigidity of the obtained sealing material are lowered. On the other hand, if it exceeds 5 parts by weight, problems such as coloring of the sealing material may occur. In addition, the hydrosilylation catalyst and the radical initiator may be used alone or in combination of two or more.

[0039] Hydrosilylation catalysts include platinous chloride, chloroplatinic acid, chloroplatinic acid and alcohol, aldehydes, ketone complexes, chloroplatinic acid and olefins complexes, platinum and bursiro. Platinum group metal catalysts such as complexes with xanthine, dicarbonyl diplatinum platinum and palladium catalysts, rhodium catalysts, and the like can be mentioned. Among these, chloroplatinic acid, a complex of chloroplatinic acid and olefins, and a complex of platinum and vinylsiloxane are preferable from the viewpoint of catalytic activity. These may be used alone or in combination of two or more.

 [0040] Examples of the photopolymerization initiator used when the curable resin composition is a photocurable resin composition include compounds such as acetophenone-based, benzoin-based, benzophenone-based, thixanthone-based, and acylphosphine oxide-based compounds. It can be preferably used. Specifically, trichloroacetophenone, methoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 -(4-Methylthiophene) -2-morpholinopropan-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thixanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenyl Examples thereof include dalioxylate, camphorquinone, benzyl, anthraquinone, Michler's ketone and the like. Further, a photoinitiator auxiliary agent or a sharpening agent that exhibits an effect in combination with a photopolymerization initiator can be used in combination.

 [0041] Examples of the thermal polymerization initiator used for the above purpose include ketone peroxides, peroxide ketals, hide port peroxides, dialkyl peroxides, disyl peroxides, peroxide dicarbonates, peroxides. Various organic peroxides such as xyesters can be preferably used. Specifically, cyclohexanone peroxide, 1,1 bis (t-hexaperoxy) cyclohexanone, cumene hydride peroxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, t -Petylvaoxy- A force that can exemplify 2-ethyl hexanoate, etc. S, not limited to this. These thermal polymerization initiators may be used alone or in combination of two or more.

 [0042] To the curable resin composition, it is possible to add various additives within a range not departing from the object of the present invention. Various additives include organic / inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, UV absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, Crosslinking agents, dispersion aids, resin components and the like can be exemplified.

[0043] A molded product comprising the curable resin of the present invention comprises a hydrosilylation catalyst and a radical polymerization initiator. It can be produced by curing a curable resin composition containing the above, misalignment, or both by heating or light irradiation. When a copolymer (molded product) is produced by heating, the molding temperature can be selected from a wide range from room temperature to around 200 ° C., depending on the selection of the thermal polymerization initiator and accelerator. In this case, a silicone resin molded body having a desired shape can be obtained by polymerization and hardening in a mold or on a steel belt. More specifically, all general molding methods such as injection molding, extrusion molding, compression molding, transfer molding, calendar molding, and casting (casting) molding can be applied.

[0044] When a copolymer (molded product) is produced by light irradiation, a molded product can be obtained by irradiating ultraviolet rays having a wavelength of 100 to 400 nm or visible light having a wavelength of 400 to 700 nm. The wavelength of light to be used is not particularly limited, but in particular, near ultraviolet rays having a wavelength of 200 to 400 nm are preferably used. Lamps used as ultraviolet light sources include low-pressure mercury lamps (output: 0.4 to 4 W / m), high-pressure mercury lamps (40 to 160 W / m), ultra-high pressure mercury lamps (173 to 435 W / m), metal halide lamps. (80 to 160 Wm), pulse xenon lamp (80 to 120 Wm), electrodeless discharge lamp (80 to 120 cm), and the like. Each of these ultraviolet lamps is characterized by its spectral distribution and is selected according to the type of photoinitiator used.

 [0045] As a method of obtaining a silicone resin copolymer (molded body) by light irradiation, for example, it is injected into a mold having an arbitrary cavity shape and made of a transparent material such as quartz glass, and the above-mentioned A method of producing a molded body having a desired shape by irradiating ultraviolet rays with an ultraviolet lamp to carry out polymerization and curing, and removing from the mold, or when not using a mold, for example, on a moving steel belt Examples thereof include a method for producing a sheet-shaped molded article by applying the curable resin composition of the present invention using a doctor blade or a roll-shaped coater and polymerizing and curing with the above ultraviolet lamp. Furthermore, in the present invention, a method of obtaining a molded body by heating and light irradiation may be used in combination.

 The invention's effect

[0046] According to the curable resin of the present invention, molding capable of achieving both strength, transparency, heat resistance, and dimensional stability like inorganic glass, high toughness like plastic, and workability. The ability to obtain a body can be achieved, for example, lenses, optical discs, optical fibers and flat panel displays. It can be used for a variety of applications such as optical applications such as circuit boards and window materials for various transport machinery and houses. In addition, the obtained molded body is a transparent member having a light weight and high impact strength, and has a wide range of use as a glass substitute material and has high industrial utility value.

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0047] Examples of the present invention will be described below.

 Example 1

 [0048] Into a 2 L 4-neck flask equipped with a stirrer and a dropping funnel, 300 mL of isopropyl alcohol and 600 mL of toluene, 22.37 g of a 20 w% tetramethylammonium hydroxide aqueous solution (4.55 g / tetramethylammonium hydroxide) 0. 05 mol, water 17 · 82 g / 0.99 mol) were charged. The dropping funnel was charged with a mixed solution of 44.4 g / 0.330 mol of vinylol trimethoxysilane and 50 mL of isopropyl alcohol, and the mixture was added dropwise at room temperature over 3 hours while stirring the reaction vessel. After completion of dropping, the mixture was stirred for 3 hours without heating. After stirring for 3 hours, the stirring was stopped and the reaction solution was aged at room temperature for 18 hours. The reaction solution was neutralized by adding 1 L of 0.1 M aqueous citrate solution, and further washed with water until neutral, and then anhydrous magnesium sulfate was dehydrated. Anhydrous magnesium sulfate was filtered off and concentrated under reduced pressure. The concentrate was dissolved in 200 mL of dehydrated tetrahydrofuran and charged into a 1 L 4-neck flask equipped with a stirrer and a dropping funnel. Add dimethyl chlorosilane (3.2 g / 0.025 mol), trimethylchlorosilane (2.7 g / 0.025 mol), and tetrahydrofuran (30 mL) to a deuterated pyridine (lOOmL) and a dropping funnel while stirring the reaction vessel under a nitrogen stream. The solution was added dropwise at room temperature over 3 hours. After completion of the dropwise addition, the mixture was stirred for 3 hours without heating. After stirring for 3 hours, 300 mL of toluene was added, and the reaction solution was washed with water until neutral, and anhydrous magnesium sulfate was added for dehydration. The anhydrous magnesium sulfate was filtered off and concentrated under reduced pressure to obtain 2 7. lg of a curable resin [general formula (1)] as a colorless and transparent liquid.

[0049] In m-NMR of this curable resin, a sharp signal of the vinyl group was observed. It was confirmed that the hydrolysis condensate from vinyltrimethoxysilane had a cage structure. Thus, the dense structural unit (A), which is a three-dimensional polyhedral structure composed of metal oxides, ie, key oxides, is composed of eight key atoms and twelve oxygen atoms (Si 〇) can be assumed to be a cubic structure, and the derived Kp is 0.73. there were. In addition, the portion other than (A) of the curable resin is a residue of (HC = CH—SiO 2).

 2 3/2 8

 It is a sparse structural part (B) which is a vinyl group (Me SiO 2) and (Me SiO 2), and from these

 3 1/2 2

 The required weight ratio [(A) / (B)] was 1.302, and the number average molecular weight Mn by GPC was 5200. Also, the sparse structural unit (B) is derived from a bur group, (Me 2 SiO 3), and (Me 2 SiO).

 3 1/2 2 and did not take a three-dimensional polyhedron structure, and Kp was less than 0.69. When calculating Κρ of dense structural unit (Α), (SiO) is part of (A) and exists as a part of general formula (I) resin.

 3/2 8

 Because it exists, it cannot be taken out, and Kp cannot be obtained directly. Therefore, calculation was performed using (HSiO 2) as an approximate compound with the least effect on Kp.

 3/2 8

 Example 2

 [0050] 100 parts by weight of the curable resin obtained in Example 1 and 2 parts by weight of dicumyl peroxide (Nippon Yushi Co., Ltd. Park Mill D) were mixed until uniform to obtain a curable resin composition. . Pour this into a mold made of glass plates to a thickness of lmm, 100 ° C for 1 hour, 120 ° C for 1 hour, 140 ° C for 1 hour, 160 ° C for 1 hour, and 180 ° C And cured for 2 hours to obtain a cured product.

 Example 3

 [0051] 58 parts by weight of the curable resin obtained in Example 1, 42 parts by weight of terminal trimethylsilyl-modified polymethylhydroxide siloxane (HMS _992 manufactured by AMAX Co., Ltd.), and a platinum-butylsiloxane complex (SIP6830.3 manufactured by AMAX Co., Ltd.) 0.5 parts by weight were mixed until uniform to obtain a curable resin composition. Pour this into a mold made of glass plates to a thickness of lmm, 100 ° C for 1 hour, 120 ° C for 1 hour, 140 ° C for 1 hour, 160 ° C for 1 hour, and 180 ° C Heated for 2 hours to obtain a cured product.

 Example 4

[0052] 58 parts by weight of the curable resin obtained in Example 1, 21 parts by weight of terminal trimethylsilyl-modified polymethylhydroxide siloxane (HMS _992 manufactured by AMAX Co., Ltd.), dicumyl peroxide (Park Mill D manufactured by NOF Corporation) 2 parts by weight and platinum-bulusiloxane complex (SIP6830.3, manufactured by AMAX Co., Ltd.) 0.5 parts by weight were mixed until uniform to obtain a curable resin composition. Pour this into a mold made of glass plates to a thickness of 1 mm, 100 ° C for 1 hour, 120 ° C for 1 hour, 140 ° C for 1 hour, 160 ° C for 1 hour, and 180 ° C 2 hours heating To obtain a cured product.

 [0053] [Comparative Example 1]

 100 parts by weight of dipentaerythritol hexaatalylate and 2 parts by weight of dicumyl peroxide (Nippon Yushi Co., Ltd. Park Mill D) were mixed until uniform to obtain a curable resin composition. Pour this into a mold made of glass plates to a thickness of lmm, 1 hour at 100 ° C, 1 hour at 120 ° C, 1 hour at 140 ° C, 1 hour at 160 ° C, and 180 ° C Heated for 2 hours to obtain a cured product.

 [0054] The transmittance of each cured product obtained above was measured using a spectrophotometer. Measurement wavelength 800

Table 1 shows the transmittance results at 600 nm, 400 nm, and 400 nm.

[0055] [Table 1] Examples Comparative examples

 2 3 4 1

 800nm transmittance 90% 90% 90% 76%

 600nm transmittance 89% 89% 89% 74%

 400nm transmittance 86% 85% 86% 65%

Claims

The scope of the claims  [1] A curable resin having a molecular structure composed of a dense structural unit (A) and a sparse structural unit (B) represented by the following general formula (1), the dense structural unit (A) Is a structural unit composed of a metal oxide having a packing coefficient Kp of 0.68 to 0.8 calculated from the following equation (2) calculated from the free volume fraction. ) Is a structural unit having the packing coefficient Kp of less than 0.68 and comprising an organic substance and an organometallic oxide, and the weight ratio of the structural unit (A) / (B) is from 0 · 01 to A curable resin having an organometallic structure which is 5.00 and has at least one unsaturated bond and an average molecular weight of 800 to 60000.  -{(A)-(B)}-(1)  m n  (However, m and n are integers of 1 or more.)  Kp = An-Vwp / Mw (2) (However, An = Avogadro number, Vw = Van der Waals volume, p = Density, Mw = Molecular weight, Vw = ∑ Va, Va = 4 π / R ³ -∑ 1/3 π hi ² (3Ra- hi) ^{, hi = Ra- (Ra 2 +} di 2 - Ri 2) / shows 2di, Ra = atomic radius, Ri = bond atomic radius, and di = interatomic distances. ] [2] The dense structural unit (A) consists of a metal oxide part having a three-dimensional polyhedral structure skeleton excluding the organic part of the following general formula (I), and the sparse structural unit (B) is The curable resin according to claim 1, comprising a chain unit composed of an organometallic oxide represented by the general formula (II) and an organic substance site represented by the general formula (I).  (RSiO) (MO) (RXSiO) (XMO) (I)  3/2 w 2 x y 3/2 z (R ³ R ⁴ R ⁵ SiO) (R ⁶ R ⁷ SiO) {R ⁶ R ⁷ XSiO} (II)  1/2 j k 1/2 1 [However, R is indicated by (aH ^ -OCO-CR ^ CH, (b) -R ¹ -CR ² = CH or (c) _CH = CH 2 2 2 is an unsaturated group, an alkyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a hydrogen atom, an alkoxyl group, or an alkylsiloxy group, and a plurality of R in the formula (I) are different from each other. However, at least one includes any of the above (a), (b), or (c), R ¹ represents an alkylene group, an alkylidene group, or a phenylene group, and R ² represents hydrogen or alkyl. Indicates a kill group. R ^{3 to} R ⁷ are (aH ^ -OCO-CR ^ CH, (b) -R ¹ -CR ² = CH or (c) _  twenty two An unsaturated group represented by CH = CH, an alkyl group, a cycloalkyl group, a cycloalkenyl group, A phenyl group, a hydrogen atom, an alkoxyl group, or an alkylsiloxy group. Further, M is a metal atom of silicon, germanium, titanium, or zirconium, X is a halogen atom, or an alkoxyl group, _w is an integer of 4 or more, and X, y, and z are w + x + y + It is an integer that satisfies z≥8. j, k, and 1 each represent an integer of 0 or more. ] [3] General formula (I) is RSiX, MX or a mixture thereof (where R, M and X are those in general formula (I)  3 4  3. The curable resin according to claim 2, wherein the curable resin is a hydrolysis condensate. [4] General formula (Π), R ³ R ⁴ R ⁵ SiX, R ⁶ R ⁷ SiX or a mixture thereof (provided that R ^{3 to} R ⁷ and X are one  2  Same as general formula (般). ), And at least a part of the organic moiety of the general formula (I) or X is bonded to the hydrolytic condensate to form the structural moiety (B) of the general formula (1). 2. The curable resin according to 2. [5] A curable resin composition comprising the curable resin according to any one of claims 1 to 4 and a hydrosilylation catalyst, a radical initiator, or both. 6. The curable resin composition according to claim 5, further comprising a hydrosilylatable compound having a hydrogen atom on at least one silicon atom, a compound having an unsaturated group in the molecule, or a combination thereof. object.  [7] A molded product obtained by molding and curing the curable resin composition according to claim 5 or 6.