JP2013056981A - Ladder-type silsesquioxane, method for producing the same, curing resin composition, and cured material thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a ladder-type silsesquioxane and a composition, having a long pot life before curing, reduced in the amount of low-molecular weight compounds evaporating in curing, and excellent in physical properties after curing and yellowing resistance.SOLUTION: The ladder-type silsesquioxane has in its molecule, a structure represented by formula (1) (wherein Siis a silicon atom constituting a silsesquioxane skeleton of the ladder-type silsesquioxane; X is a single bond or a linking group; Rs and Rs are each independently a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent sulfur atom-containing group; and n is an integer of 1 to 100).

Description

  The present invention relates to a ladder-type silsesquioxane, a method for producing the same, a curable resin composition containing the ladder-type silsesquioxane, and a cured product thereof.

  A material having a heat resistance of 150 ° C. or higher is required as a material for covering a semiconductor element in a semiconductor device having a high heat resistance and a high withstand voltage. In particular, for materials (encapsulating materials) that cover optical materials such as LED elements, in addition to heat resistance, flexibility, transparency, yellowing resistance (for example, yellowing resistance to high temperature and high energy light), etc. It is required to have the physical properties.

  As a resin composition for encapsulating an optical element having excellent transparency, UV resistance, and heat resistance coloring property, a liquid silsesqui-foil having a cage structure containing an aliphatic carbon-carbon unsaturated bond and no H-Si bond. At least one silsesquioxane selected from the group consisting of oxane and liquid silsesquioxane having a cage structure containing an H-Si bond and no aliphatic carbon-carbon unsaturated bond A resin composition for sealing an optical element contained as a resin component is disclosed (see Patent Document 1). However, the cured product of the resin composition containing a cage silsesquioxane is relatively hard and lacks flexibility, and thus has a problem that cracks and cracks are likely to occur.

  And (A) an organic compound such as triallyl isocyanurate containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) at least two SiH groups in one molecule. A curable composition containing a chain-containing and / or cyclic polyorganosiloxane-containing compound and (C) a hydrosilylation catalyst as essential components is disclosed (see Patent Document 2). However, the physical properties such as crack resistance of these materials are still not satisfactory.

JP 2007-31619 A JP 2002-314140 A

  Furthermore, in particular, since the curable composition disclosed in Patent Document 2 contains a low molecular weight linear or cyclic polyorganosiloxane (siloxane compound), the viscosity is likely to increase at room temperature, and pot life (usable) (Time) was short. For this reason, it was difficult to adapt the said curable composition to the various manufacturing processes (specifically, casting process) of an optical semiconductor device. In addition, the curable composition has a problem that the siloxane compound volatilizes when cured, making it difficult to ensure the safety of the worker, and difficult to obtain a cured product having certain physical properties. It was.

Accordingly, an object of the present invention is to provide a curable resin composition having a long pot life and a reduced amount of low molecular weight compounds (particularly, low molecular weight siloxane compounds) that volatilize during curing. An object of the present invention is to provide a ladder-type silsesquioxane capable of forming a cured product excellent in heat resistance, transparency, flexibility and yellowing resistance by curing the composition, and a method for producing the same.
Another object of the present invention is that the pot life is long and the amount of low molecular weight compounds (particularly low molecular weight siloxane compounds) that volatilize during curing is reduced, and further, the heat resistance, transparency and flexibility are improved by curing. Another object of the present invention is to provide a curable resin composition capable of obtaining a cured product excellent in yellowing resistance.
Another object of the present invention is to provide a cured product excellent in heat resistance, transparency, flexibility, and yellowing resistance.

  The inventors of the present invention provide a curable resin composition containing at least a ladder-type silsesquioxane having a specific structure having a long pot life and a low molecular weight compound (particularly a low molecular weight siloxane compound) that volatilizes during curing. The amount was reduced, and furthermore, the cured product obtained by curing the curable resin composition was found to be excellent in heat resistance, transparency, flexibility, and yellowing resistance, and the present invention was completed.

［式（１）中、Ｓｉ^Lはラダー型シルセスキオキサンのシルセスキオキサン骨格を構成するケイ素原子を示す。Ｘは単結合又は二価の連結基を示す。複数個のＲ^aは、それぞれ独立に、水素原子、ハロゲン原子、一価の有機基、一価の酸素原子含有基、一価の窒素原子含有基、又は一価の硫黄原子含有基を示す。複数個のＲ^bは、それぞれ独立に、水素原子、ハロゲン原子、一価の有機基、一価の酸素原子含有基、一価の窒素原子含有基、又は一価の硫黄原子含有基を示す。ｎは１〜１００の整数を示す。］ That is, the present invention provides a ladder-type silsesquioxane characterized by having a structure represented by the following formula (1) in the molecule.

[In Formula (1), Si ^L shows the silicon atom which comprises the silsesquioxane frame | skeleton of ladder type silsesquioxane. X represents a single bond or a divalent linking group. Several R ^<a> shows a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom containing group, a monovalent nitrogen atom containing group, or a monovalent sulfur atom containing group each independently. Several ^Rb shows a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom containing group, a monovalent nitrogen atom containing group, or a monovalent sulfur atom containing group each independently. n shows the integer of 1-100. ]

［式（２）中、複数個のＲ^bは、それぞれ独立に、水素原子、ハロゲン原子、一価の有機基、一価の酸素原子含有基、一価の窒素原子含有基、又は一価の硫黄原子含有基を示す。ｎは１〜１００の整数を示す。］
とを、ヒドロシリル化触媒の存在下で反応させる工程を含むことを特徴とするラダー型シルセスキオキサンの製造方法を提供する。 Moreover, this invention is a manufacturing method of the said ladder type silsesquioxane, Comprising: Ladder type silsesquioxane which has an aliphatic carbon-carbon double bond in a molecule | numerator, It represents with following formula (2). Compound

[In the formula (2), each of the plurality of R ^b is independently a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent group. A sulfur atom-containing group is shown. n shows the integer of 1-100. ]
And a method for producing a ladder-type silsesquioxane, comprising the step of reacting with a hydrosilylation catalyst.

  The present invention also provides a curable resin composition comprising the ladder-type silsesquioxane, a compound having an aliphatic carbon-carbon double bond in the molecule, and a hydrosilylation catalyst. To do.

  Furthermore, the curable resin composition is provided wherein the compound having an aliphatic carbon-carbon double bond in the molecule is a ladder-type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule. .

  Moreover, this invention provides the hardened | cured material obtained by hardening | curing the said curable resin composition.

Since the ladder-type silsesquioxane of the present invention has the above structure, the curable resin composition containing the ladder-type silsesquioxane as an essential component hardly increases in viscosity over time and has a long pot life. Moreover, the said curable resin composition can reduce the quantity of the low molecular compound (especially low molecular weight siloxane compound) volatilized at the time of hardening, and obtains hardened | cured material with high safety | security and a fixed physical property efficiently. be able to. Furthermore, the cured product obtained by curing the curable resin composition is excellent in heat resistance, flexibility, transparency, and yellowing resistance (for example, yellowing resistance to high temperature and high energy light). For this reason, the cured product exhibits heat-resistant yellowing at an unprecedented high temperature (for example, 180 ° C. or more) over a long period of time, and has excellent barrier properties to protect the optical semiconductor element from water vapor and SO _X gas. An optical semiconductor device obtained by sealing an optical semiconductor element (LED element) with the cured product has excellent quality and durability. In particular, the ladder-type silsesquioxane of the present invention is particularly useful as a next-generation light source sealant.

(A) is a chart showing the ¹ H-NMR spectrum of ladder-type phenylmethylvinylsilsesquioxane having a TMS group at the terminal used in Example 1, and (b) was obtained in Example 1. It is a chart which shows the < ¹ > H-NMR spectrum of ladder type silsesquioxane which has SiH content group. It is a graph which shows the viscosity (23 hours after preparing from the start of preparation) at 23 degreeC of the curable resin composition obtained in Example 4. FIG. 6 is a graph showing the light transmittance of the cured product obtained in Example 4.

[Ladder-type silsesquioxane]
The ladder-type silsesquioxane of the present invention has at least a structure (structural unit) represented by the following formula (1) in the molecule (in one molecule). Polysilsesquioxane).

In the above formula (1), Si ^L denotes a silicon atom constituting the silsesquioxane skeleton of the ladder-type silsesquioxane. In the present specification, an atomic group (group) bonded to Si ^L in the structure represented by the above formula (1) may be referred to as “SiH-containing group”. That is, the ladder-type silsesquioxane of the present invention has a structure in which the SiH-containing group is bonded to at least one silicon atom constituting the silsesquioxane skeleton.

  X in the above formula (1) represents a single bond or a divalent linking group (a divalent group having one or more atoms). Examples of the divalent linking group include a divalent hydrocarbon group, a carbonyl group, an ether group (ether bond), a thioether group (thioether bond), an ester group (ester bond), a carbonate group (carbonate bond), and an amide. Examples include a group (amide bond) and a group in which a plurality of these groups are linked.

Note that the case where X in the above formula (1) is a single bond means that Si ^L shown in the formula (1) and the left carbon atom of two carbon atoms are directly bonded by a single bond. Means the case.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned, for example. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexene group. And divalent cycloalkylene groups (including cycloalkylidene groups) such as a silylene group, a 1,4-cyclohexylene group, and a cyclohexylidene group.

A plurality of R ^a in the above formula (1) are each independently a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent sulfur. An atom-containing group is shown. That is, a plurality of R ^a may be the same or may be different.

  As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example. Examples of the monovalent organic group include a substituted or unsubstituted hydrocarbon group, alkoxy group, alkenyloxy group, aryloxy group, aralkyloxy group, acyloxy group, alkylthio group, alkenylthio group, arylthio group, aralkylthio group. Group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, cyano group, isocyanate group, carbamoyl group, isothiocyanate group and the like.

Examples of the hydrocarbon group for ^Ra include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. Examples of the alkyl group include C _1-20 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, dodecyl group (preferably C _{1- 10} alkyl group, more preferably C _1-4 alkyl group). Examples of the alkenyl group include a vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, C _2-20 alkenyl groups (preferably C _2-10 alkenyl groups, more preferably C _2-4 alkenyl groups) such as 3-pentenyl group, 4-pentenyl group, 5-hexenyl group and the like can be mentioned. Examples of the alkynyl group include C _2-20 alkynyl groups such as ethynyl group and propynyl group (preferably C _2-10 alkynyl group, more preferably C _2-4 alkynyl group).

Examples of the alicyclic hydrocarbon group include a C _3-12 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a _cyclododecyl group; a C _3-12 cyclo group such as a cyclohexenyl group. An alkenyl group; a C _4-15 bridged cyclic hydrocarbon group such as a bicycloheptanyl group and a bicycloheptenyl group.

As said aromatic hydrocarbon group, _C6-14 aryl groups (especially _C6-10 aryl group), such as a phenyl group and a naphthyl group, etc. are mentioned, for example.

Examples of the group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded include a cyclohexylmethyl group and a methylcyclohexyl group. Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include a C _7-18 aralkyl group (particularly a C _7-10 aralkyl group) such as a benzyl group and a phenethyl group, and a C _6-10 such as a cinnamyl group. Examples thereof include C _1-4 alkyl-substituted aryl groups such as aryl-C _2-6 alkenyl group and tolyl group, and C _2-4 alkenyl-substituted aryl groups such as styryl group.

The hydrocarbon group for R ^a may have a substituent. Carbon number of the substituent in the said hydrocarbon group is 0-20, Preferably it is 0-10. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; hydroxyl group; alkoxy group such as methoxy group and ethoxy group; alkenyloxy group such as allyloxy group; aryloxy group such as phenoxy group; Aralkyloxy groups such as benzyloxy groups; Acyloxy groups such as acetyloxy groups, propionyloxy groups, (meth) acryloyloxy groups and benzoyloxy groups; mercapto groups; alkylthio groups such as methylthio groups and ethylthio groups; alkenyl groups such as allylthio groups Thio group; arylthio group such as phenylthio group; aralkylthio group such as benzylthio group; carboxyl group; alkoxycarbonyl group such as methoxycarbonyl and ethoxycarbonyl group; aryloxycarbonyl group such as phenyloxycarbonyl group; Aralkyloxycarbonyl groups such as cycarbonyl groups; amino groups; mono- or dialkylamino groups such as methylamino groups, dimethylamino groups and diethylamino groups; acylamino groups such as acetylamino groups and benzoylamino groups; epoxy groups such as glycidyloxy groups Containing group; Oxetanyl group-containing group such as ethyl oxetanyloxy group; Acyl group such as acetyl group, propionyl group, benzoyl group; oxo group; two or more of these are bonded via a C _1-6 alkylene group as necessary Group and the like.

Examples of the alkoxy group in R ^a include a C _1-6 alkoxy group (preferably a C _1-4 alkoxy group) such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group. Can be mentioned. Examples of the alkenyloxy group include a C _2-6 alkenyloxy group (preferably a C _2-4 alkenyloxy group) such as an allyloxy group. Examples of the aryloxy group include substituents such as a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, and a C _1-4 alkoxy group on the aromatic ring, such as a phenoxy group, a tolyloxy group, and a naphthyloxy group. And a C _6-14 aryloxy group which may have. Examples of the aralkyloxy group include C _7-18 aralkyloxy groups such as benzyloxy group and phenethyloxy group. Examples of the acyloxy group include C _1-12 acyloxy groups such as acetyloxy group, propionyloxy group, and benzoyloxy group.

Examples of the alkylthio group include C _1-6 alkylthio groups (preferably C _1-4 alkylthio groups) such as a methylthio group and an ethylthio group. Examples of the alkenylthio group include a C _2-6 alkenylthio group (preferably a C _2-4 alkenylthio group) such as an allylthio group. The arylthio group has, for example, a phenylthio group, a tolylthio group, a naphthylthio group, and the like, and an aromatic ring having a substituent such as a C _1-4 alkyl group, a C _2-4 alkenyl group, a halogen atom, a C _1-4 alkoxy group. And a C _6-14 arylthio group which may be used. Examples of the aralkylthio group include C _7-18 aralkylthio groups such as benzylthio group and phenethylthio group. Examples of the alkoxycarbonyl group include C _1-6 alkoxy-carbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. Examples of the aryloxycarbonyl group include C _6-14 aryloxy-carbonyl groups such as a phenoxycarbonyl group, a tolyloxycarbonyl group, and a naphthyloxycarbonyl group. Examples of the aralkyloxycarbonyl group include a C _7-18 aralkyloxy-carbonyl group such as a benzyloxycarbonyl group. Examples of the mono- or dialkylamino group include mono- or di-C _1-6 alkylamino groups such as a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group. Examples of the acylamino group include C _1-11 acylamino groups such as an acetylamino group, a propionylamino group, and a benzoylamino group. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

Examples of the monovalent oxygen-containing group in the above R ^a, for example, a hydroxyl group, hydroperoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, an isocyanate group, a sulfo group, such as a carbamoyl group Is mentioned. Examples of the monovalent nitrogen atom-containing group include an amino group or a substituted amino group (mono or dialkylamino group, acylamino group, etc.), a cyano group, an isocyanate group, an isothiocyanate group, and a carbamoyl group. Examples of the compound having a monovalent sulfur atom include a mercapto group (thiol group), a sulfo group, an alkylthio group, an alkenylthio group, an arylthio group, an aralkylthio group, and an isothiocyanate group. The monovalent organic group, the monovalent oxygen atom-containing group, the monovalent nitrogen atom-containing group, and the monovalent sulfur atom-containing group described above can overlap each other.

上記式（３）中の複数個のＲ^cは、同一でもよいし、それぞれ異なっていてもよい。式（３）中のＲ^cは、水素原子、ハロゲン原子、一価の有機基、一価の酸素原子含有基、一価の窒素原子含有基、又は一価の硫黄原子含有基を示し、これらの基としては、上記Ｒ^aとして例示したものと同様の基が挙げられる。 Further, examples of the R ^a, for example, a group represented by the following formula (3).

A plurality of R ^c in the above formula (3) may be the same or different. R ^c in formula (3) represents a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent sulfur atom-containing group. Examples of the group include the same groups as those exemplified as ^Ra .

In the group represented by the above formula (3), each R ^c is a hydrogen atom, a C _1-10 alkyl group (particularly a C _1-4 alkyl group), a C _2-10 alkenyl group (particularly a C _1-10 group). _2-4 alkyl group), C _3-12 cycloalkyl group, C _3-12 cycloalkenyl group, C _1-4 alkyl group, C _2-4 alkenyl group, halogen atom, C _1-4 alkoxy group on the aromatic ring, etc. A C _6-14 aryl group, a C _7-18 aralkyl group, a C _6-10 aryl-C _2-6 alkenyl group, a hydroxyl group, a C _1-6 alkoxy group, or a halogen atom, which may have a substituent of preferable.

Among the above, each R ^a is preferably ^a hydrogen atom or a substituted or unsubstituted hydrocarbon group, more preferably a hydrogen atom.

A plurality of R ^b in the above formula (1) are each independently a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent sulfur. An atom-containing group is shown. That is, the plurality of R ^b may be the same or different. Examples of the halogen atom, monovalent organic group, monovalent oxygen atom-containing group, monovalent nitrogen atom-containing group, and monovalent sulfur atom-containing group include the same groups as those exemplified as ^Ra. . In addition, when n in Formula (1) is an integer greater than or equal to 2, ^Rb in each parenthesis to which n is attached may be the same or different.

Among the above, R ^b is preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group, more preferably a substituted or unsubstituted hydrocarbon group, still more preferably a methyl group or a phenyl group.

  N in the above formula (1) represents an integer of 1 to 100 (preferably 1 to 30, more preferably 1 to 10, and further preferably 1 to 5). When n is too large, there is a tendency that the barrier property of the cured product is lowered, and thus, for example, it may not be suitable as a sealant for an optical semiconductor.

  In the ladder-type silsesquioxane of the present invention, the number of structural units represented by the above formula (1) in the molecule (in one molecule) (that is, the number of the SiH-containing groups) is not particularly limited. One or more (for example, 2 to 50) is preferable, and 2 to 30 is more preferable. By having the SiH-containing group within the above range, the heat resistance of the cured product of the curable resin composition tends to be improved.

Silsesquioxane is a kind of polysiloxane. Polysiloxane refers to a compound having a main chain (skeleton) composed of siloxane bonds (Si—O—Si), and the basic structural units thereof are represented by the following formulas (M), (D), (T), ( Q) (hereinafter referred to as M unit, D unit, T unit, and Q unit, respectively).

  In the above formula, R represents an atom or atomic group bonded to a silicon atom. The M unit is a unit composed of a monovalent group in which a silicon atom is bonded to one oxygen atom, and the D unit is a unit composed of a divalent group in which a silicon atom is bonded to two oxygen atoms. The T unit is a unit composed of a trivalent group in which a silicon atom is bonded to three oxygen atoms, and the Q unit is a unit composed of a tetravalent group in which a silicon atom is bonded to four oxygen atoms.

Silsesquioxane is a polysiloxane having the T unit as a basic structural unit, and its empirical formula (basic structural formula) is represented by RSiO _3/2 . As the structure of the Si—O—Si skeleton of silsesquioxane, a random structure, a ladder structure, a cage structure, and the like are known. The ladder-type silsesquioxane of the present invention has a silsesquioxane skeleton having a Si—O—Si skeleton having a ladder structure as the silsesquioxane skeleton (sometimes referred to as “ladder-type silsesquioxane skeleton”). Is a compound containing at least The ladder-type silsesquioxane of the present invention may contain a silsesquioxane skeleton other than the ladder-type silsesquioxane skeleton as a silsesquioxane skeleton, for example, both a ladder structure and a random structure. It may have a silsesquioxane skeleton.

なお、上記式（Ｌ）中に示されたケイ素原子（Ｓｉ）が、上記式（１）中のＳｉ^L（シルセスキオキサン骨格を構成するケイ素原子）にあたる。 The ladder-type silsesquioxane of the present invention can be represented by, for example, the following formula (L).

The silicon atom (Si) shown in the formula (L) corresponds to Si ^L (silicon atom constituting the silsesquioxane skeleton) in the formula (1).

In said formula (L), p is an integer greater than or equal to 1 (for example, 1-5000), Preferably it is 1-2000, More preferably, it is 1-1000. Examples of R in the formula (L) include the same groups as those exemplified as ^Ra . However, at least one (preferably two or more) of R in the formula (L) is a SiH-containing group represented by the above formula (1). The position at which the SiH-containing group is bonded is not particularly limited, and may be bonded to the silicon atom constituting the M unit in the ladder-type silsesquioxane or bonded to the silicon atom constituting the T unit. It may be.

  The ladder-type silsesquioxane of the present invention is not particularly limited. In the formula (L), in R, a substituted or unsubstituted hydrocarbon group is 50 mol% or more (more preferably 80 mol% or more, particularly preferably). Is preferably 90 mol% or more). Particularly, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (particularly an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group), an aryl group having 6 to 10 carbon atoms (particularly a phenyl group). It is preferable that the aralkyl group having 7 to 10 carbon atoms (particularly benzyl group) occupies 50 mol% or more (more preferably 80 mol% or more, particularly preferably 90 mol% or more).

The content of the hydrosilyl group (SiH group) in the ladder-type silsesquioxane of the present invention is not particularly limited, but is preferably 0.01 to 0.5 mmol / g, more preferably 0.08 to 0.28 mmol / g. Further, the content by weight of the hydrosilyl group (SiH group) in the ladder-type silsesquioxane of the present invention is not particularly limited, but is 0.0 (in terms of H) in terms of H (hydride) in the SiH group. The content is preferably from 01 to 0.50% by weight, more preferably from 0.08 to 0.28% by weight. If the content of the hydrosilyl group is too small (for example, less than 0.01 mmol / g and less than 0.01% by weight in terms of H), curing of the curable resin composition may not proceed. On the other hand, when there is too much content of a hydrosilyl group (for example, when it exceeds 0.50 mmol / g, when it exceeds 0.50 weight% in conversion of H), the hardness of hardened | cured material may become hard and it may become easy to crack. In addition, content of the hydrosilyl group in the ladder type silsesquioxane of this invention can be measured by < ¹ > H-NMR etc., for example.

  The content of the SiH-containing group with respect to the total amount of hydrosilyl groups (100 mol%) in the ladder-type silsesquioxane of the present invention is not particularly limited, but is preferably 50 to 100 mol% from the viewpoint of the degree of curing. More preferably, it is 80-100 mol%.

  The molecular weight of the ladder-type silsesquioxane of the present invention is not particularly limited, but is preferably from 100 to 800,000, more preferably from 200 to 100,000, still more preferably from 300 to 30,000, particularly preferably from 1000 to 20000. If the molecular weight is less than 100, the heat resistance of the cured product may decrease. On the other hand, when the molecular weight exceeds 800,000, it is no longer liquid and compatibility with other compounds may be reduced. The ladder-type silsesquioxane of the present invention may be a mixture having various molecular weights in the above range. The molecular weight can be calculated, for example, as a molecular weight in terms of polystyrene by gel permeation chromatography.

  The weight-average molecular weight of the ladder-type silsesquioxane of the present invention is not particularly limited, but is preferably 100 to 800,000, more preferably 200 to 100,000, still more preferably 300 to 30,000, and particularly preferably 1000 to 8,000. is there. In addition, the said weight average molecular weight is computable based on the molecular weight (polystyrene conversion) measured by the gel permeation chromatography, for example.

  The ladder-type silsesquioxane of the present invention is not particularly limited, but is preferably liquid at normal temperature (about 25 ° C.). More specifically, the ladder-type silsesquioxane of the present invention has a viscosity at 23 ° C. of preferably 100 to 100,000 mPa · s, more preferably 500 to 10,000 mPa · s, and still more preferably 1000 to 8000 mPa · s. . If the viscosity is less than 100 mPa · s, the heat resistance of the cured product may decrease. On the other hand, when the viscosity exceeds 100,000 mPa · s, it may be difficult to prepare and handle the curable resin composition. The viscosity at 23 ° C. is, for example, using a rheometer (trade name “Physica UDS-200”, manufactured by Anton Paar) and a cone plate (cone diameter: 16 mm, taper angle = 0 °), temperature: 23 ° C. The number of rotations can be measured under the condition of 20 rpm.

［式（２）中、Ｒ^b、ｎは、前記に同じ。］
とを、ヒドロシリル化触媒の存在下で反応させる工程（「反応工程」と称する場合がある）を少なくとも含む方法が好ましい。 The method for producing the ladder-type silsesquioxane of the present invention is not particularly limited. However, from the viewpoint of productivity and availability of raw materials, a ladder-type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule (“ And may be referred to as “vinyl-type ladder silsesquioxane”) and a compound represented by the following formula (2):

[In formula (2), R ^b and n are the same as above. ]
Is preferably included in the presence of a hydrosilylation catalyst (sometimes referred to as “reaction step”).

  The vinyl-type ladder silsesquioxane is not particularly limited as long as it is a ladder-type silsesquioxane having an aliphatic carbon-carbon double bond at the terminal or side chain. For example, in the above formula (L) In the ladder-type silsesquioxane represented, a compound in which at least one of R (preferably two or more) is a group having an aliphatic carbon-carbon double bond is exemplified. The vinyl-type ladder silsesquioxane may contain a silsesquioxane skeleton other than the ladder-type silsesquioxane skeleton, for example, a silsesquioxane skeleton containing both a ladder structure and a random structure. You may have.

Examples of the group having an aliphatic carbon-carbon double bond include a vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, C _2-20 alkenyl groups (preferably C _2-10 alkenyl groups, more preferably C _2-4 alkenyl groups) such as 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group and 5-hexenyl group Group); C _3-12 cycloalkenyl group such as cyclohexenyl group; C _4-15 bridged cyclic unsaturated hydrocarbon group such as bicycloheptenyl group; C _2-4 alkenyl-substituted aryl group such as styryl group; cinnamyl Group and the like. In the group having an aliphatic carbon-carbon double bond, in the group represented by the above formula (3), at least one of three R ^c is the above C _2-20 alkenyl group, C _3-12. And a group such as a C _4-15 bridged cyclic unsaturated hydrocarbon group, a C _2-4 alkenyl substituted aryl group, a cinnamyl group, and the like.

［式（４）中、Ｓｉ^L、Ｘ、Ｒ^aは、前記に同じ。］ Specifically, examples of the vinyl-type ladder silsesquioxane include ladder-type silsesquioxane having at least a structure (structural unit) represented by the following formula (4).

[In the formula (4), Si ^L , X, and R ^a are the same as described above. ]

  The number of aliphatic carbon-carbon double bonds in the molecule (in one molecule) in the vinyl-type ladder silsesquioxane is not particularly limited, but is preferably 2 or more (for example, 2 to 50), more Preferably it is 2-30. By having an aliphatic carbon-carbon double bond within the above-mentioned range, it may be easy to control the amount of SiH group of the ladder-type silsesquioxane of the present invention within an appropriate range.

  The molecular weight of the vinyl ladder silsesquioxane is not particularly limited, but is preferably from 100 to 800,000, more preferably from 200 to 100,000, still more preferably from 300 to 10,000, and particularly preferably from 500 to 6000. When the molecular weight of the vinyl-type ladder silsesquioxane is within this range, it is liquid at room temperature, and its viscosity is relatively low, so that handling may be easy. The vinyl-type ladder silsesquioxane may be a mixture having various molecular weights in the above range.

  The content of the aliphatic carbon-carbon double bond in the vinyl type ladder silsesquioxane is not particularly limited, but is preferably 0.7 to 5.5 mmol / g, more preferably 1.1 to 4.4 mmol. / G. Moreover, the ratio (weight basis) of the aliphatic carbon-carbon double bond contained in the vinyl-type ladder silsesquioxane is not particularly limited, but is, for example, 2.0 to 15.0% by weight in terms of vinyl group. Preferably, it is 3.0 to 12.0% by weight.

  The vinyl ladder silsesquioxane can be produced by a known method. The vinyl type ladder silsesquioxane includes, for example, [1] hydrolysis / condensation reaction (sol-gel reaction) of hydrolyzable silane having an aliphatic carbon-carbon double bond, [2] ladder having a hydrolyzable group. It can be obtained by reaction of a type silsesquioxane with a silane compound having an aliphatic carbon-carbon double bond.

［式（５ａ）中、Ｒ¹は脂肪族炭素−炭素二重結合を有する基を示し、３つのＹは、同一又は異なって、加水分解性基又はヒドロキシル基を示す。］
で表される加水分解性シラン化合物の１種若しくは２種以上を、又は、上記式（５ａ）で表される加水分解性シラン化合物の１種若しくは２種以上と下記式（６ａ）若しくは（６ａ’）

［式（６ａ）及び（６ａ’）中、Ｒ²は前記Ｒに同じ。複数個のＲ²は同一でもよいし、それぞれ異なっていてもよい。Ｙは前記に同じ。］
で表されるシラン化合物の１種若しくは２種以上とを、加水分解・縮合反応（ゾルゲル反応）に付す方法が挙げられる。 [1] As a method for producing a vinyl-type ladder silsesquioxane by hydrolysis / condensation reaction (sol-gel reaction) of a hydrolyzable silane having an aliphatic carbon-carbon double bond, for example, the following formula (5a)

[In formula (5a), R ¹ represents a group having an aliphatic carbon-carbon double bond, and three Ys are the same or different and each represent a hydrolyzable group or a hydroxyl group. ]
Or one or more hydrolyzable silane compounds represented by the above formula (5a) and the following formula (6a) or (6a): ')

[In the formulas (6a) and (6a ′), R ² is the same as R. A plurality of R ² may be the same or different. Y is the same as above. ]
The method of attaching | subjecting 1 type, or 2 or more types of the silane compound represented by these to a hydrolysis and condensation reaction (sol-gel reaction) is mentioned.

［式（５ｂ）中、Ｒ³は前記Ｒに同じ。３つのＹは、同一又は異なって、加水分解性基又はヒドロキシル基を示す。］
で表される加水分解性シラン化合物の１種若しくは２種以上と、下記式（６ｂ）若しくは（６ｂ’）

［式（６ｂ）及び（６ｂ’）中、Ｒ⁴は、前記Ｒに同じ。複数個のＲ⁴は同一でもよいし、それぞれ異なっていてもよい。但し、式（６ｂ）、（６ｂ’）のそれぞれにおいて、Ｒ⁴のうち少なくとも１つは脂肪族炭素−炭素二重結合を有する基である。］
で表されるシラン化合物の１種若しくは２種以上とを、加水分解・縮合反応（ゾルゲル反応）に付すことにより得ることができる。 The vinyl ladder silsesquioxane is, for example, the following formula (5b)

[In formula (5b), R ³ is the same as R. Three Y's are the same or different and each represents a hydrolyzable group or a hydroxyl group. ]
And one or more hydrolyzable silane compounds represented by the following formula (6b) or (6b ′)

[In the formulas (6b) and (6b ′), R ⁴ is the same as the above R. A plurality of R ⁴ may be the same or different. However, in each of the formulas (6b) and (6b ′), at least one of R ⁴ is a group having an aliphatic carbon-carbon double bond. ]
It can obtain by attaching | subjecting 1 type, or 2 or more types of the silane compound represented by these to a hydrolysis and condensation reaction (sol-gel reaction).

  The vinyl ladder silsesquioxane is represented by, for example, one or more hydrolyzable silane compounds represented by the above formula (5a) and the above formula (6b) or (6b ′). It can also be obtained by subjecting one or more silane compounds to a hydrolysis / condensation reaction (sol-gel reaction).

  The hydrolyzable silane compounds represented by the formulas (5a) and (5b) are used for forming the T unit of the vinyl ladder silsesquioxane, and are represented by the formulas (6a), (6a ′), (6b). The silane compound represented by (6b ′) functions as an end-capping agent and is used for forming the M unit of the vinyl ladder silsesquioxane.

The hydrolyzable group in Y may be a group that can form a siloxane bond by hydrolysis and silanol condensation, such as halogen atoms such as chlorine atom, bromine atom, iodine atom; methoxy group, ethoxy group, propoxy group C _1-10 alkoxy groups such as C _1-10 acyloxy groups such as acetyloxy group, propionyloxy group and benzoyloxy group. Among these, a chlorine atom and a C _1-4 alkoxy group are preferable.

  The hydrolysis / condensation reaction described above is carried out, for example, by silanol condensation of the silane compound in water or a mixed solvent of water and an organic solvent in the presence of a silanol condensation catalyst, and during and after the reaction, It can be carried out by distilling off organisms (such as alcohol). The reaction temperature is -78 to 150 ° C, preferably -20 to 100 ° C. The usage-amount of water is 1 mol or more (for example, 1-20 mol, Preferably it is 1-10 mol) with respect to 1 mol of total of a silane compound.

  Examples of the organic solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; chloroform, dichloromethane, 1, 2 Halogenated hydrocarbons such as dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate; Amides such as N-dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benzonitrile; Methanol, ethanol, isopropyl alcohol and butano Alcohols such as Le; and mixed solvents thereof. The usage-amount of an organic solvent is 0.5-30 volume parts with respect to a total of 1 volume part of a silane compound, for example.

  As the silanol condensation catalyst, for example, an acid catalyst or a base catalyst can be used. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid. Sulfonic acids such as activated clay; solid acids such as activated clay; Lewis acids such as iron chloride. Examples of the base catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals such as barium hydroxide and magnesium hydroxide; alkali metal carbonates such as sodium carbonate; barium carbonate Alkaline earth metal carbonates such as magnesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; alkaline earth metal alkoxides such as barium methoxide; sodium phenoxide and the like Alkali metal phenoxides; quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide; tetramethylammonium hydroxide; Quaternary phosphonium hydroxides such as tetraalkylphosphonium hydroxides such as ruphosphonium hydroxide; triethylamine, N-methylpiperidine, 4-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene ( DBU) and other amines such as tertiary amines; and nitrogen-containing aromatic heterocyclic compounds such as pyridine. Moreover, fluorine compounds, such as tetrabutylammonium fluoride, potassium fluoride, sodium fluoride, can also be used as a silanol condensation catalyst.

  The reaction product can be separated and purified by separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a combination of these.

［式（７）中、Ｒ⁵は前記Ｒに同じ。３つのＲ⁵は同一でもよいし、それぞれ異なっていてもよい。但し、Ｒ⁵のうち少なくとも１つは脂肪族炭素−炭素二重結合を有する基である。Ｙは前記に同じ。］
の１種又は２種以上とを反応させる方法などが挙げられる。 Moreover, as a manufacturing method of the vinyl type ladder silsesquioxane by reaction with the above-mentioned [2] ladder type silsesquioxane which has a hydrolyzable group, and the silane compound which has an aliphatic carbon-carbon double bond, A ladder-type silsesquioxane having one or more hydrolyzable groups or hydroxyl groups, and a silane compound represented by the following formula (7)

[In the formula (7), R ⁵ is the same as R. The three R ⁵ may be the same or different from each other. However, at least one of R ⁵ is a group having an aliphatic carbon-carbon double bond. Y is the same as above. ]
The method of making these 1 type, or 2 or more types react is mentioned.

The hydrolyzable group in ladder-type silsesquioxane having one or more hydrolyzable groups or hydroxyl groups, the hydrolyzable group in Y of the silane compound represented by the above formula (7), the aliphatic carbon in R ^5- Examples of the group having a carbon double bond include the same groups as the hydrolyzable group and the group having an aliphatic carbon-carbon double bond. As the hydrolyzable group in the ladder-type silsesquioxane having one or more hydrolyzable groups or hydroxyl groups, a C _1-4 alkoxy group such as a methoxy group or an ethoxy group is particularly preferable.

In the silane compound represented by the above formula (7), the remaining R ⁵ excluding the group having an aliphatic carbon-carbon double bond is the same or different, and is substituted or unsubstituted, having 1 to 10 carbon atoms. An alkyl group (particularly an alkyl group having 1 to 4 carbon atoms such as methyl and ethyl groups), an aryl group having 6 to 10 carbon atoms (particularly a phenyl group), or an aralkyl group having 7 to 10 carbon atoms (particularly a benzyl group). ) Is preferred.

  More specifically, examples of the silane compound represented by the above formula (7) include monohalogenated vinyl silane, monohalogenated allyl silane, monohalogenated 3-butenyl silane, monoalkoxy vinyl silane, monoalkoxy allyl silane, monoalkoxy 3-butenyl silane, and the like. Is mentioned.

  Representative examples of the monohalogenated vinylsilane include chlorodimethylvinylsilane, chloroethylmethylvinylsilane, chloromethylphenylvinylsilane, chlorodiethylvinylsilane, chloroethylphenylvinylsilane, chlorodiphenylvinylsilane, and the like.

  Representative examples of the monohalogenated allylsilane include allylchlorodimethylsilane, allylchloroethylmethylsilane, allylchloromethylphenylsilane, allylchlorodiethylsilane, allylchloroethylphenylsilane, allylchlorodiphenylsilane, and the like.

  Representative examples of the monohalogenated 3-butenylsilane include 3-butenylchlorodimethylsilane, 3-butenylchloroethylmethylsilane, 3-butenylchloromethylphenylsilane, 3-butenylchlorodiethylsilane, 3-butenylchlorosilane, Examples thereof include tenenyl chloroethyl phenyl silane and 3-butenyl chloro diphenyl silane.

  Representative examples of the monoalkoxy vinyl silane include methoxy dimethyl vinyl silane, ethyl methoxy methyl vinyl silane, methoxy methyl phenyl vinyl silane, diethyl methoxy vinyl silane, ethyl methoxy phenyl vinyl silane, methoxy diphenyl vinyl silane, ethoxy dimethyl vinyl silane, ethoxy ethyl methyl vinyl silane, ethoxy methyl phenyl vinyl silane. , Ethoxydiethylvinylsilane, ethoxyethylphenylvinylsilane, and the like.

  Representative examples of the above monoalkoxyallylsilane include allylmethoxydimethylsilane, allylethylmethoxymethylsilane, allylmethoxymethylphenylsilane, allyldiethylmethoxysilane, allylethylmethoxyphenylsilane, allylmethoxydiphenylsilane, allylethoxydimethylsilane, allylethoxy. Examples include ethylmethylsilane, allylethoxymethylphenylsilane, allylethoxydiethylsilane, and allylethoxyethylphenylsilane.

  Representative examples of the monoalkoxy 3-butenylsilane include 3-butenylmethoxydimethylsilane, 3-butenylethylmethoxymethylsilane, 3-butenylmethoxymethylphenylsilane, 3-butenyldiethylmethoxysilane, and 3-butenyl. Ethylmethoxyphenylsilane, 3-butenylmethoxydiphenylsilane, 3-butenylethoxydimethylsilane, 3-butenylethoxyethylmethylsilane, 3-butenylethoxymethylphenylsilane, 3-butenylethoxydiethylsilane, 3-butenyl Examples include tenenyl ethoxyethyl phenyl silane and 3-butenyl ethoxy diphenyl silane.

  The reaction between the ladder-type silsesquioxane having one or more hydrolyzable groups or hydroxyl groups and the silane compound represented by the formula (7) is usually performed in a solvent. Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; chloroform, dichloromethane, 1,2-dichloroethane. Halogenated hydrocarbons such as: diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane, etc .; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate; N, N— Amides such as dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benzonitrile; Methanol, ethanol, isopropyl alcohol, butanol, etc. Such as alcohol and the like. These solvents are used alone or in admixture of two or more.

  Although the usage-amount of the silane compound represented by Formula (7) is not specifically limited, The reactive group (hydrolyzable group, hydroxyl group in ladder type silsesquioxane which has one or more hydrolyzable groups or hydroxyl groups. ) Is preferably 1 to 20 mol, more preferably 2 to 10 mol, and still more preferably 5 to 9 mol.

  The reaction between the ladder-type silsesquioxane having one or more hydrolyzable groups or hydroxyl groups and the silane compound represented by the formula (7) is performed in the presence of a silanol condensation catalyst. As the silanol condensation catalyst, those exemplified above can be used. Among these, a base catalyst is preferably used as the silanol condensation catalyst.

  Although the usage-amount of the said silanol condensation catalyst is not specifically limited, It is 1 mol in total of the reactive group (hydrolyzable group, hydroxyl group) in the ladder type silsesquioxane which has one or more hydrolyzable groups or hydroxyl groups. On the other hand, for example, 0.1 to 10 mol is preferable, and 0.1 to 1.0 mol is more preferable. The amount of silanol condensation catalyst used may be a catalytic amount.

  The above reaction may be performed in the presence of a polymerization inhibitor. Although reaction temperature can be suitably selected according to the reaction component, the kind of catalyst, etc., 0-200 degreeC is preferable normally, More preferably, it is 20-100 degreeC, More preferably, it is 30-60 degreeC. The reaction may be carried out at normal pressure or under reduced pressure or increased pressure. The atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  In the above method, a reactive group (hydrolyzable group such as an alkoxy group, hydroxyl group) in a ladder-type silsesquioxane having one or more hydrolyzable groups or hydroxyl groups and a silane compound represented by the formula (7) Ladder-type silsesquines in which the reactive group (hydrolyzable group such as alkoxy group, hydroxyl group) is hydrolyzed / condensed (or condensed) and has an aliphatic carbon-carbon double bond in the corresponding molecule Oxane is formed.

  After completion of the reaction, the reaction product is separated by separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a combination of these. It can be purified.

Used for the manufacture of ladder-type silsesquioxane of the present invention, the R ^b in the compound represented by the formula (2), the same as R ^b in the formula (1) are exemplified. Moreover, n in the said Formula (2) shows the integer of 1-100 similarly to n of the said Formula (1).

Specifically, examples of the compound represented by the above formula (2) include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane Linear polydimethylsiloxane having 1 to 10 (preferably 2 to 5) (Si-O) units having SiH groups, linear polydialkylsiloxane having SiH groups at both ends (preferably linear) Polydi-C _1-10 alkylsiloxane).

  Although the usage-amount of the compound represented by said Formula (2) is not specifically limited, said (2) with respect to 1 mol of the total amount of the aliphatic carbon-carbon double bond which the said vinyl type ladder silsesquioxane has. It is preferable to make it the usage-amount that the hydrosilyl group (Si-H) which the compound represented by becomes 3 mol or more (for example, 3-500 mol), More preferably, it is 5-300 mol, More preferably The amount is 8 to 100 mol, particularly preferably 8 to 20 mol. When the amount of the hydrosilyl group is less than 3 mol, the vinyl-type ladder silsesquioxane and the compound represented by the formula (2) may be cured and gelled. On the other hand, when the amount used exceeds 500 moles, it may be disadvantageous in terms of cost.

  Examples of the hydrosilylation catalyst include known hydrosilylation reaction catalysts such as platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Specifically, platinum fine powder, platinum black, platinum-supported silica fine powder, platinum Supported activated carbon, chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, platinum olefin complexes, platinum carbonyl complexes such as platinum-carbonylvinylmethyl complexes, platinum-divinyltetramethyldisiloxane complexes and platinum- Platinum-based catalysts such as platinum vinylmethylsiloxane complexes such as cyclovinylmethylsiloxane complexes, platinum-phosphine complexes, platinum-phosphite complexes, etc., and palladium-based catalysts containing palladium atoms or rhodium atoms instead of platinum atoms in the platinum-based catalysts A catalyst or a rhodium-type catalyst is mentioned. The said hydrosilylation catalyst may be used individually by 1 type, and may use 2 or more types together. Among these, a platinum vinylmethylsiloxane complex, a platinum-carbonylvinylmethyl complex, and a complex of chloroplatinic acid, an alcohol, and an aldehyde are preferable because the reaction rate is good.

Although the usage-amount of the said hydrosilylation catalyst is not specifically limited, It is 1 * 10 ^{< -8} > ^-1 * 10 ^<-2 > with respect to 1 mol of total amounts of the aliphatic carbon-carbon double bond of the said vinyl type ladder silsesquioxane. Mol is preferable, and more preferably 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻³ mol. If the amount used is less than 1 × 10 ⁻⁸ mol, the reaction may not proceed sufficiently. On the other hand, if the amount used exceeds 1 × 10 ⁻² mol, the cured product may be colored.

  In the method for producing a ladder-type silsesquioxane of the present invention, it is necessary when the vinyl-type ladder silsesquioxane and the compound represented by the above formula (2) are reacted in the presence of a hydrosilylation catalyst. Depending on the case, other additives may be added to the reaction system. Moreover, you may implement the said reaction in a solvent (for example, the organic solvent illustrated above etc.) as needed. The atmosphere for carrying out the reaction is not particularly limited as long as it does not inhibit the reaction, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  Although the reaction temperature in the said reaction process is not specifically limited, 0-200 degreeC is preferable, More preferably, it is 20-150 degreeC, More preferably, it is 30-100 degreeC. When the reaction temperature is less than 0 ° C., the progress of the reaction is slow, and the productivity may be lowered. On the other hand, when the reaction temperature exceeds 200 ° C., decomposition of the reactants and side reactions may occur together, resulting in a decrease in yield. The reaction temperature may be controlled to be constant during the reaction, or may be changed sequentially or continuously.

  Moreover, the reaction time in the said reaction process is although it does not specifically limit, 10-1400 minutes are preferable, More preferably, it is 60-720 minutes. If the reaction time is less than 10 minutes, the reaction cannot sufficiently proceed, and the yield may be reduced. On the other hand, if the reaction time exceeds 1400 minutes, decomposition of the reactants and side reactions may occur simultaneously, resulting in a decrease in yield or a deep coloration.

  The pressure in the reaction step (reaction pressure) is not particularly limited, and the reaction can be carried out under normal pressure, increased pressure, reduced pressure, or the like.

  The method for producing a ladder-type silsesquioxane of the present invention may include other steps other than the reaction step. As said other process, the process of preparing a raw material, the process of refine | purifying and isolating a reaction product, etc. are mentioned, for example. In purification and isolation of the reaction product, for example, water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and other separation means, or a combination of these A known or conventional method such as a separation means can be used.

［式（８）中、Ｘ、Ｙ、Ｒ^a、Ｒ^b、ｎは、前記に同じ。］ The method for producing the ladder-type silsesquioxane of the present invention is not limited to the above-described method. For example, the ladder-type silsesquioxane of the present invention is a hydrolyzable silane having a SiH-containing group (for example, the following formula ( The compound represented by 8) can be used as an essential monomer component and hydrolyzed / condensed (sol-gel reaction).

[In the formula (8), X, Y, R ^a , R ^b and n are the same as above. ]

[Curable resin composition]
The curable resin composition of the present invention is a resin composition comprising the ladder-type silsesquioxane of the present invention, a compound having an aliphatic carbon-carbon double bond in the molecule, and a hydrosilylation catalyst as essential components. is there.

(Ladder type silsesquioxane of the present invention)
The content of the ladder-type silsesquioxane of the present invention in the curable resin composition of the present invention is not particularly limited, but is 10% by weight or more (for example, with respect to the curable resin composition (100% by weight)) 10 to 90% by weight) is preferable, more preferably 20 to 80% by weight, and still more preferably 30 to 70% by weight. When the content is less than 10% by weight, the curing reaction does not proceed sufficiently, and the heat resistance of the cured product may decrease. In addition, the ladder type silsesquioxane of this invention can be used individually by 1 type or in combination of 2 or more types.

(Compound having an aliphatic carbon-carbon double bond in the molecule)
In the curable resin composition of the present invention, the compound having an aliphatic carbon-carbon double bond in the molecule is not particularly limited as long as it is a compound having at least an aliphatic carbon-carbon double bond in the molecule. Any known or conventional compounds can be used. Especially, the compound which has 2 or more (for example, 2-20) of aliphatic carbon-carbon double bonds in a molecule | numerator is preferable. In addition, the compound which has an aliphatic carbon-carbon double bond in the said molecule | numerator may remove | exclude the ladder type silsesquioxane of this invention. Moreover, the compound which has an aliphatic carbon-carbon double bond in the said molecule | numerator can be used individually by 1 type or in combination of 2 or more types.

  Specifically, the compound having an aliphatic carbon-carbon double bond in the molecule is preferably a polysiloxane having an aliphatic carbon-carbon double bond in the molecule (organopolysiloxane). Ladder type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule is preferred. Examples of the ladder-type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule include the above-described vinyl-type ladder silsesquioxane, specifically, a ladder represented by the above formula (L). Examples of the type silsesquioxane include compounds in which at least one (preferably two or more) of Rs are groups having an aliphatic carbon-carbon double bond. By setting the curable resin composition of the present invention to such a configuration, particularly, the heat resistance, transparency, flexibility, and yellowing resistance of the cured product can be further improved.

  The content (blending amount) of the compound having an aliphatic carbon-carbon double bond in the curable resin composition of the present invention is not particularly limited, but is relative to the curable resin composition (100% by weight). 8 to 88% by weight or more, more preferably 18 to 78% by weight. If the content is less than 8% by weight, the curing reaction may not proceed. On the other hand, if the content exceeds 88% by weight, the curing reaction may not proceed.

  Specifically, the curable resin composition of the present invention is not particularly limited, but the aliphatic carbon-carbon double bond is 0.2 to 4 mol per 1 mol of the hydrosilyl group present in the resin composition. It is preferable that it is a composition (formulation composition) which becomes like this, More preferably, it is 0.5-1.5 mol, More preferably, it is 0.8-1.2 mol. By controlling the ratio of the hydrosilyl group and the aliphatic carbon-carbon double bond within the above range, the heat resistance, transparency, flexibility, and yellowing resistance of the cured product tend to be further improved.

(Hydrosilylation catalyst)
As the hydrosilylation catalyst in the curable resin composition of the present invention, for example, those exemplified in the method for producing a ladder-type silsesquioxane of the present invention can be used. A hydrosilylation catalyst can be used individually by 1 type or in combination of 2 or more types.

  The content of the hydrosilylation catalyst in the curable resin composition of the present invention is not particularly limited. For example, platinum, palladium, or rhodium in the hydrosilylation catalyst is in the range of 0.01 to 1,000 ppm by weight. The amount is preferably in the range of 0.1 to 500 ppm. When the content of the hydrosilylation catalyst is in such a range, the crosslinking rate is not remarkably slow, and there is less possibility of causing problems such as coloring in the crosslinked product.

  The curable resin composition of the present invention may contain a compound having an SiH group other than the ladder-type silsesquioxane of the present invention (sometimes referred to as “SiH compound”). Examples of the SiH compound include 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopenta Cyclic siloxanes having SiH groups such as siloxane and cyclotrisiloxane; methyl (trisdimethylsiloxy) silane, tetrakis (dimethylsiloxy) silane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3 5,5-hexamethyltrisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,1,1,3,5,5,7,7,7-nonamethyltetrasiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane Emissions, such as straight-chain or branched-chain siloxanes having SiH groups, such as 1,1,1,3,5,5,7,7,9,9,9- down decamethylpentasiloxane. Especially, as said SiH compound, what has two or more SiH groups in a molecule | numerator is preferable. In addition, a SiH compound can be used individually by 1 type or in combination of 2 or more types. Although content of the said SiH compound is not specifically limited, 5 weight% or less (for example, 0-5 weight%) is preferable with respect to 100 weight% of curable resin compositions, More preferably, 1.5 weight% or less It is.

  In addition, the curable resin composition of the present invention may contain a hydrosilylation reaction inhibitor in order to adjust the speed of the hydrosilylation reaction. Examples of the hydrosilylation reaction inhibitor include alkyne alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and phenylbutynol; 3-methyl-3-pentene Ene-in compounds such as -1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1, Examples include 3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, thiazole, benzothiazole, and benzotriazole. The content of the hydrosilylation reaction inhibitor varies depending on the crosslinking conditions of the curable resin composition, but practically, the content in the curable resin composition is preferably in the range of 0.00001 to 5% by weight. .

(solvent)
The curable resin composition of the present invention may contain a solvent. Examples of the solvent include conventionally known solvents such as toluene, hexane, isopropanol, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate, and the like. A solvent can be used individually by 1 type or in combination of 2 or more types.

(Additive)
Further, the curable resin composition of the present invention includes, as other optional components, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, carbonic acid. Inorganic fillers such as calcium, carbon black, silicon carbide, silicon nitride, boron nitride and the like, inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilane, organoalkoxysilane, organosilazane; silicone resin, epoxy Resin, organic resin fine powder such as fluororesin; filler such as conductive metal powder such as silver and copper, solvent, stabilizer (antioxidant, ultraviolet absorber, light stabilizer, heat stabilizer, etc.), Flame retardants (phosphorous flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents, Pulling agents, silane coupling agents, lubricants, waxes, plasticizers, mold release agents, impact modifiers, hue improvers, fluidity improvers, colorants (dyes, pigments, etc.), dispersants, antifoaming agents, defoamers Conventional additives such as foaming agents, antibacterial agents, preservatives, viscosity modifiers, and thickeners may be included. These additives can be used alone or in combination of two or more.

  The curable resin composition of the present invention is not particularly limited, but can be obtained by stirring and mixing each of the above components at room temperature. In addition, the curable resin composition of the present invention may be used as a one-component composition in which each component is mixed in advance, for example, two or more components stored separately. May be used as a multi-liquid composition (for example, a two-liquid composition) used by mixing them at a predetermined ratio before use.

  Although the curable resin composition of this invention is not specifically limited, It is preferable that it is a liquid at normal temperature (about 25 degreeC). More specifically, the viscosity at 23 ° C. of the curable resin composition of the present invention is preferably 300 to 20000 mPa · s, more preferably 500 to 10000 mPa · s, and still more preferably 1000 to 8000 mPa · s. If the viscosity is less than 300 mPa · s, the heat resistance of the cured product may decrease. On the other hand, when the viscosity exceeds 20000 mPa · s, it is difficult to prepare and handle the curable resin composition, and bubbles may remain in the cured product. The viscosity at 23 ° C. can be measured, for example, by the same method as that for the ladder type silsesquioxane described above.

  Since the ladder-type silsesquioxane of the present invention, which is an essential component of the curable resin composition of the present invention, has a relatively flexible structural unit represented by the formula (1) in the molecule, the curable resin composition described above It is possible to impart flexibility to a cured product obtained by curing the product. In general, in order to obtain a cured product having excellent flexibility, as a constituent component of the curable resin composition, a polyfunctional low molecular compound having a flexible structural unit in the molecule (particularly, a low molecular weight siloxane compound, for example, , A method using a compound represented by the above formula (2), etc. is employed. However, in such a technique, the low molecular weight compound is easily volatilized when the curable resin composition is cured, and there has been a problem in terms of obtaining a cured product having safety and certain physical properties. On the other hand, since the ladder-type silsesquioxane of the present invention has a structural unit for imparting flexibility to the cured product, the low molecular weight compound described above is used in the curable resin composition of the present invention. Can be eliminated, and the amount of low molecular weight compounds (particularly low molecular weight siloxane compounds) that volatilize during curing can be eliminated.

[Cured product]
A cured product can be obtained by curing the curable resin composition of the present invention by a hydrosilylation reaction. The conditions for curing (hydrosilylation) are not particularly limited, and conventionally known conditions can be employed. For example, from the viewpoint of reaction rate, the temperature (curing temperature) is room temperature to 180 ° C. (preferably 60 ° C. to 150 ° C.). C.), and the time (curing time) is preferably 5 to 720 minutes. The cured product of the present invention is excellent in physical properties such as heat resistance, transparency, flexibility, and yellowing resistance. Further, in obtaining the cured product of the present invention, when the curable resin composition of the present invention is cured, the amount of the low-molecular compound that volatilizes (particularly, the low-molecular weight siloxane compound) is small, so that the safety is high. A cured product having certain physical properties can be obtained efficiently.

[Sealant]
The sealant of the present invention is a sealant containing the curable resin composition of the present invention as an essential component. The encapsulant of the present invention is reduced in the amount of low molecular weight compounds (particularly low molecular weight siloxane compounds) that volatilize when cured to form a cured material, and has high safety and certain physical properties. This is advantageous in that the sealing material having it can be obtained efficiently. Moreover, the sealing material obtained by hardening the sealing agent of this invention is excellent in physical properties, such as heat resistance, transparency, a softness | flexibility, and yellowing resistance. For this reason, the sealing agent of this invention can be preferably used especially as sealing agents, such as an optical semiconductor element in an optical semiconductor device.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The reaction product was identified by ¹ H-NMR. ¹ H-NMR analysis was performed by JEOL ECA500 (500 MHz). In addition, the weight average molecular weight of the reaction product was measured using Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskel GMH _HR- M × 2 (manufactured by Tosoh Corporation), guard column. : Tskel guard column H _HR L (manufactured by Tosoh Corporation), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 ° C.

Example 1
[Synthesis of ladder-type silsesquioxane (prepolymer) having SiH-containing group]
In a 50 ml four-necked flask, ladder-type phenylmethylvinylsilsesquioxane having a trimethylsilyl group (TMS group) at the end (weight average molecular weight Mw2900, phenyl group / methyl group / vinyl group (side chain molar ratio) = 17/68 / 15) 10 g, 1,1,3,3-tetramethyldisiloxane (Tokyo Chemical Industry Co., Ltd.) 20 g, 1.7% platinum-cyclovinylsiloxane complex vinylcyclosiloxane solution (Wako Pure Chemical Industries, Ltd.) 20 μl) was prepared. Subsequently, the reaction was completed by heating at 70 ° C. for 8 hours. Then, after concentrating with an evaporator, it reduced in pressure for 30 minutes using the vacuum pump, and 11.8g of ladder-type silsesquioxane which has SiH containing group was obtained. The ladder-type silsesquioxane having the SiH-containing group has a weight average molecular weight (Mw) of 3800, and the SiH group content (average content) per molecule is 0 in terms of the weight of H (hydride) in the SiH group. .11% by weight.
⁽¹ H-NMR spectrum of ladder-type silsesquioxane having SiH-containing group)
¹ H-NMR (JEOL ECA500 (500 MHz, CDCl ₃ )) δ: 0.1 ppm (br), 0.5 ppm (br), 4.7 ppm (s), 6.8-7.8 ppm (br)
1 shows a ¹ H-NMR spectrum (FIG. 1A) of a ladder-type phenylmethylvinylsilsesquioxane having a TMS group at the terminal as a raw material, and a ladder-type silyl having a SiH-containing group as a product. The ¹ H-NMR spectrum of sesquioxane (FIG. 1B) is shown.

  The ladder-type phenylmethylvinylsilsesquioxane having a TMS group at the end used as a raw material is composed of triethoxyphenylsilane, triethoxymethylsilane, and triethoxyvinylsilane (molar ratio: 17/68/15). It was prepared by hydrolysis and condensation by the method.

Example 2
[Synthesis of ladder-type silsesquioxane (prepolymer) having SiH-containing group]
In a 50 ml four-necked flask, 5 g of ladder-type phenylmethylvinylsilsesquioxane having a TMS group at its end (weight average molecular weight Mw 2900, phenyl group / methyl group / vinyl group (side chain molar ratio) = 17/68/15) 10 g of 1,1,3,3,5,5-hexamethyltrisiloxane (manufactured by Gelest) and 20 μl of a 1.7% platinum-cyclovinylsiloxane complex vinylcyclosiloxane solution (manufactured by Wako Pure Chemical Industries, Ltd.) And charged. Subsequently, the reaction was completed by heating at 70 ° C. for 6 hours. Subsequently, after concentrating with an evaporator, the pressure was reduced for 30 minutes using a vacuum pump to obtain 5.7 g of ladder-type silsesquioxane having a SiH-containing group. The ladder-type silsesquioxane having the SiH group has a weight average molecular weight (Mw) of 6400, and the SiH group content (average content) per molecule is 0. 0 in terms of the weight of H (hydride) in the SiH group. It was 11% by weight.
⁽¹ H-NMR spectrum of ladder-type silsesquioxane having SiH-containing group)
¹ H-NMR (JEOL ECA500 (500 MHz, CDCl ₃ )) δ: 0.1 ppm (br), 0.5 ppm (br), 4.7 ppm (s), 6.8-7.8 ppm (br)

  The ladder-type phenylmethylvinylsilsesquioxane having a TMS group at the end used as a raw material is composed of triethoxyphenylsilane, triethoxymethylsilane, and triethoxyvinylsilane (molar ratio: 17/68/15). It was prepared by hydrolysis and condensation by the method.

Example 3
[Synthesis of ladder-type silsesquioxane having SiH-containing group]
In a 50 ml four-necked flask, ladder type phenylmethylvinylsilsesquioxane having a TMS group at the end (weight average molecular weight Mw 2400, phenyl group / methyl group / vinyl group (side chain molar ratio) = 42.5 / 42.5 / 15) 10 g, 1,1,3,3-tetramethyldisiloxane (Tokyo Chemical Industry Co., Ltd.) 20 g, 1.7% platinum-cyclovinylsiloxane complex vinylcyclosiloxane solution (Wako Pure Chemical Industries, Ltd.) 20 μl) was prepared. Subsequently, the reaction was completed by heating at 70 ° C. for 6 hours. Then, after concentrating with an evaporator, it pressure-reduced for 30 minutes using the vacuum pump, and obtained 11.2g of ladder type silsesquioxanes which have SiH containing group. The ladder-type silsesquioxane having the SiH group has a weight average molecular weight (Mw) of 5400, and the SiH group content (average content) per molecule is 0. 0 in terms of the weight of H (hydride) in the SiH group. It was 12% by weight.
⁽¹ H-NMR spectrum of ladder-type silsesquioxane having SiH-containing group)
¹ H-NMR (JEOL ECA500 (500 MHz, CDCl ₃ )) δ: 0.1 ppm (br), 0.5 ppm (br), 4.7 ppm (s), 6.8-7.8 ppm (br)

  The ladder-type phenylmethylvinylsilsesquioxane having a TMS group at the end used as a raw material is composed of triethoxyphenylsilane, triethoxymethylsilane, and triethoxyvinylsilane (molar ratio: 42.5 / 42.5 / 15) Prepared by hydrolysis and condensation by conventional methods.

Example 4
[Production of curable resin composition and cured product thereof]
1.0 g of ladder-type silsesquioxane having a SiH-containing group synthesized in Example 1 and ladder-type phenylmethylvinylsilsesquioxane having a TMS group at the terminal (weight average molecular weight Mw 2900, phenyl group / methyl group / vinyl) 1 g of the group (side chain molar ratio) = 17/68/15) was weighed between 6 ml screws and stirred at room temperature for 2 hours. The compatibility between the two was good, and a transparent and uniform mixed solution was obtained. Obtained. To the obtained mixed solution, 0.8 μl of a platinum vinylmethylsiloxane complex (manufactured by Aldrich, platinum 2.0% by weight) was charged and stirred again to obtain a curable resin composition (heat-resistant curable composition).
When the obtained curable resin composition was applied to a glass plate and heated in an oven at 90 ° C. for 1 hour and 150 ° C. for 5 hours, a colorless and transparent cured product was obtained.

Comparative Example 1
[Production of curable resin composition]
1,1,3,3-tetramethyldisiloxane 0.11 g (manufactured by Tokyo Chemical Industry Co., Ltd.) and ladder-type phenylmethylvinylsilsesquioxane having a TMS group at the terminal (weight average molecular weight Mw 2900, phenyl group / 1 g of methyl group / vinyl group (side chain molar ratio) = 17/68/15) was weighed between 6 ml screws and stirred at room temperature for 30 minutes. The compatibility of both was good, transparent and uniform A liquid mixture was obtained. To the obtained mixed solution, 0.8 μl of platinum vinylmethylsiloxane complex (manufactured by Aldrich, 2.0 wt% platinum) was charged and stirred again.

(Evaluation)
[Evaluation of curable resin composition]
Viscosity immediately after preparation of the curable resin composition obtained in Example 4, viscosity after 2 hours after preparation, viscosity after 4 hours, viscosity after 6 hours, viscosity after 8 hours, and after 24 hours Using a rheometer (trade name “Physica UDS-200”, manufactured by Anton Paar) and a cone plate (cone diameter: 16 mm, taper angle = 0 °), temperature: 23 ° C., rotation speed: 20 rpm Measured under conditions. The curable resin composition was stored in an environment of 23 ° C. and 50% RH throughout from the viscosity measurement immediately after preparation to the viscosity measurement 24 hours after preparation.
The measurement results of the viscosity are shown in FIG. As shown in FIG. 2, the curable resin composition of the present invention had a small viscosity increase with time and a long pot life.
On the other hand, the curable resin composition obtained in Comparative Example 1 was charged with a platinum vinylmethylsiloxane complex and gelled about 10 minutes after stirring, so the viscosity could not be measured and the pot life was very high. It was short.

[Evaluation of physical properties of cured product]
About the hardened | cured material obtained in Example 4, the physical property as described in Table 1 was evaluated by the test method shown in Table 1. The evaluation results are shown in Table 1.
Moreover, in FIG. 3, the measurement result of the light transmittance with respect to the light of wavelength 300-800 nm of the said hardened | cured material is shown.

[Heat resistance and yellowing resistance test of cured products]
When the cured product obtained in Example 4 was heated in an oven at 180 ° C. for 1000 hours, no discoloration (yellowing) was observed.

Claims (5)

A ladder-type silsesquioxane having a structure represented by the following formula (1) in the molecule.

[In Formula (1), Si ^L shows the silicon atom which comprises the silsesquioxane frame | skeleton of ladder type silsesquioxane. X represents a single bond or a divalent linking group. Several R ^<a> shows a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom containing group, a monovalent nitrogen atom containing group, or a monovalent sulfur atom containing group each independently. Several ^Rb shows a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom containing group, a monovalent nitrogen atom containing group, or a monovalent sulfur atom containing group each independently. n shows the integer of 1-100. ] A method for producing a ladder-type silsesquioxane according to claim 1,
A ladder-type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule, and a compound represented by the following formula (2)

[In the formula (2), each of the plurality of R ^b is independently a hydrogen atom, a halogen atom, a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent group. A sulfur atom-containing group is shown. n shows the integer of 1-100. ]
And a method for producing a ladder-type silsesquioxane, comprising the step of:   A curable resin composition comprising the ladder-type silsesquioxane according to claim 1, a compound having an aliphatic carbon-carbon double bond in a molecule, and a hydrosilylation catalyst.   The curable resin composition according to claim 3, wherein the compound having an aliphatic carbon-carbon double bond in the molecule is a ladder-type silsesquioxane having an aliphatic carbon-carbon double bond in the molecule.   A cured product obtained by curing the curable resin composition according to claim 3 or 4.

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