JP2002363414A - Cage-like silsesquioxane-containing composition - Google Patents

Abstract

[57] [Abstract] [PROBLEMS] To provide excellent molding processability without impairing the excellent electrical, mechanical and chemical properties of resin materials, and to exhibit excellent heat resistance and dimensional stability by crosslinking. To provide a novel cage-like silsesquioxane-containing composition suitable for the production of a molded article. SOLUTION: A cage silsesquioxane (b) containing a plurality of carbon-carbon double bonds in a molecule, a radical initiator (c), and, if necessary, a resin and a crosslinking auxiliary agent are contained. A cage-like silsesquioxane-containing composition. This composition can be used as an insulating material, a heat-resistant material, a structural material, and the like in electronic materials and other wide fields.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cage-like silsesquioxane-containing composition containing a cage-like silsesquioxane containing a plurality of carbon-carbon double bonds in a molecule, and a curing method comprising the composition. The present invention relates to a molded article, a film, and a crosslinked film obtained by crosslinking a film comprising the composition.

[0002]

2. Description of the Related Art In recent years, in the field of electronic equipment for communication, consumer use, industrial use, and the like, there has been a remarkable tendency to reduce the size and density of a base material forming a mounting circuit. In terms of materials to be used, improvement in heat resistance, electrical characteristics, moldability, and the like, and reduction in distortion due to matching of the coefficient of thermal expansion with other components are being demanded. For example, conventionally, a copper-clad laminate made of a phenol resin, an epoxy resin, a polyphenylene ether resin, or the like has been used as a printed wiring board. These have various performances in a well-balanced manner, but when used alone as a material for laminates or sealing materials, there is a difference in the coefficient of thermal expansion from other components, which is reduced to a satisfactory degree. At present it is not possible.

In order to cope with such a situation, attempts have been made to reduce the coefficient of thermal expansion of a resin composition by using an inorganic powder such as silica. However, in order to reduce the coefficient of thermal expansion of the resin composition, it is necessary to add a large amount of the inorganic powder, and when a large amount of the inorganic powder is added, the fluidity of the resin composition decreases, and therefore, the copper-clad laminate However, there is a problem that it becomes difficult to secure the fluidity required for embedding into the through holes.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and makes use of its characteristics not only in the field of electronic materials such as the above-mentioned printed circuit boards, but also in the electric industry, space and aircraft industry, and the like. An object of the present invention is to provide a novel cage-like silsesquioxane-containing composition that can be used for insulating materials, heat-resistant materials, structural materials, and the like in a wide range of fields such as the building industry. A further object of the present invention is to exhibit excellent moldability without impairing the excellent electrical properties, mechanical properties and chemical properties of the resinous material, and to achieve chemical resistance, heat resistance and dimensional stability after crosslinking. It is an object of the present invention to provide a novel cage-like silsesquioxane-containing composition capable of realizing a cured molded article having excellent properties.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a cage-like silsesquioxane containing a plurality of carbon-carbon double bonds in the molecule. Is a cage-like silsesquioxane-containing composition containing a compound and a radical initiator, in the presence of a radical, by cross-linking the cage-like silsesquioxane containing a plurality of carbon-carbon double bonds in the molecule, the above-mentioned It has been found that the object of the present invention is achieved, and the present invention has been completed.

That is, the present invention is as follows. (1) A cage-like silsesquioxane-containing composition comprising a cage-like silsesquioxane containing a plurality of carbon-carbon double bonds in a molecule and a radical initiator. (2) The cage-like silsesquioxane-containing composition according to (1), further comprising a resin. (3) The cage-like silsesquioxane-containing composition according to (1), further comprising an auxiliary crosslinking agent. (4) The cage-like silsesquioxane-containing composition according to (2), further comprising an auxiliary crosslinking agent. (5) The mass ratio of the resin to the cage silsesquioxane containing a plurality of carbon-carbon double bonds in the molecule is 1:99.
-99.9: 0.1, and the cage according to (2) or (4), wherein the radical initiator is contained in an amount of 0.001 to 20% by mass relative to the resin and the inside of the molecule. A silsesquioxane-containing composition.

(6) The crosslinking aid is contained in an amount of 0.1 to 200% by mass based on the total mass of the resin and the cage silsesquioxane containing a plurality of carbon-carbon double bonds in the molecule. The cage-like silsesquioxane-containing composition according to (4), which is characterized in that: (7) The cage silsesquioxane containing a plurality of carbon-carbon double bonds in the molecule is a cage silsesquioxane represented by (1), a cage silsesquioxane represented by (2) A partially-cleaved structure of sesquioxane, and part or all of the hydroxyl groups bonded to the skeleton silicon atom in (2) is a substituent R
Any of (1) to (6), which is at least one kind of cage silsesquioxane selected from the partial cleavage structure of cage silsesquioxane having a structure substituted with The cage-like silsesquioxane-containing composition according to the above. (RSiO _3/2 ) _n (1) (RSiO _3/2 ) _nm (O _1/2 H) _{2 + m} (2) (n is an integer of 6 to 14, m is 0 or 1, R is a hydrogen atom,
A halogen atom, a hydrocarbon having 1 to 20 carbon atoms containing no carbon-carbon double bond, a hydrocarbon having 2 to 20 carbon atoms containing a carbon-carbon double bond, or a partially substituted product thereof; At least one selected from silicon atom-containing groups having 1 to 10 silicon atoms which may contain a heavy bond;
A plurality of Rs in one molecule may be the same or different as long as the resin is a species and has at least two carbon-carbon double bonds.) (8) The resin is a polyphenylene ether-based resin The cage-like silsesquioxane-containing composition according to (2), which is characterized in that:

(9) The cage-like silsesquioxane-containing composition according to (3) or (4), wherein the auxiliary crosslinking agent is triallyl isocyanurate and / or triallyl cyanurate. (10) A cured molded article obtained from the cage-like silsesquioxane-containing composition according to any one of (1) to (9). (11) A film comprising the cage-like silsesquioxane-containing composition according to any one of (1) to (9). (12) A crosslinked film obtained by crosslinking the film according to (11).

Hereinafter, the present invention will be described in detail. The present invention comprises a cage silsesquioxane containing a plurality of carbon-carbon double bonds in a molecule (hereinafter referred to as a cage silsesquioxane containing a double bond) and a radical initiator. Which is a cage-like silsesquioxane-containing composition. This composition may be composed only of the cage-like silsesquioxane containing a double bond and a radical initiator, or may further contain another substance.

A composition comprising only cage-like silsesquioxanes and a radical initiator has a low coefficient of thermal expansion of a crosslinked product when crosslinked, so that a cured molded article having excellent dimensional stability can be obtained from this composition. It is possible to obtain. Therefore, a molded article obtained from the composition of the present invention is suitable for an insulating material, a heat-resistant material, and the like in the field of the electric industry. To the composition of the present invention, a resin or a crosslinking auxiliary agent described later can be added for the purpose of improving properties such as mechanical properties, fluidity at the time of melting, and crosslinking density.

The silsesquioxane containing a double bond used in the present invention will be described below. Silica is represented by the general formula of (SiO ₂ ), while silsesquioxane is a compound represented by (R′SiO _3/2 ).
Silsesquioxane is usually R′SiX ₃ (R ′ is
A polysiloxane synthesized by hydrolysis-polycondensation of a compound having a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group and the like, and X is a halogen, an alkoxy group and the like. The molecular arrangement of silsesquioxane typically has an amorphous structure, a ladder-like structure, a cage-like (completely condensed cage-like) structure or a partially-cleaved structure thereof (a silicon atom is missing from the cage-like structure). And a structure in which a silicon-oxygen bond is partially broken in a structure or a cage structure).

The cage-like silsesquioxane containing a double bond used in the present invention includes, among these silsesquioxane compounds, a cage-like structure, a partially-cleaved structure thereof (a silicon atom is removed from the cage-like structure). A structure in which one atom is missing or a structure in which a silicon-oxygen bond is partially broken in a cage-like structure) and derivatives thereof, which are compounds containing a plurality of carbon-carbon double bonds in the molecule. Specific structures of the double bond-containing cage silsesquioxane include, for example, a cage silsesquioxane represented by formula (1) and a cage silsesquioxane represented by formula (2). A partially cleaved structure, a partially cleaved structure of a cage silsesquioxane having a structure in which some or all of the hydroxyl groups bonded to the skeleton silicon atom in the formula (2) are substituted with a substituent R (hereinafter, referred to as a substituted Partly cleaved body)
And the like, but are not limited thereto. (RSiO _3/2 ) _n (1) (RSiO _3/2 ) _n−m (O _1/2 H) _{2 + m} (2) (n is an integer of 6 to 14, m is 0 or 1, and R is hydrogen atom,
A halogen atom, a hydrocarbon having 1 to 20 carbon atoms containing no carbon-carbon double bond, a hydrocarbon having 2 to 20 carbon atoms containing a carbon-carbon double bond, or a partially substituted product thereof, and carbon-carbon double bond. At least one selected from silicon atom-containing groups having 1 to 10 silicon atoms which may contain a heavy bond;
A plurality of Rs in one molecule may be the same or different as long as they are species and have at least two carbon-carbon double bonds)

The value of n in the cage silsesquioxane represented by the formula (1) is preferably 8, 10 or 12, more preferably 8, or a mixture of 8, 10 and 12. As specific examples, (RSiO _3/2 ) ₆ represented by the formula (3),
(RSiO _3/2 ) ₈ represented by the formula (4), (RSiO _3/2 ) represented by the formula (5)
SiO _3/2 ) ₁₀ , (RSiO _3/2 ) ₁₂ represented by the formula (6),
(RSiO _3/2 ) _{14 and the} like represented by the formula (7).

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

A cage silsesquioxa represented by the formula (2)
Cage formed by partial cleavage of silicon-oxygen bonds
N in the partially cleaved form of silsesquioxane is preferably
Or 8, 10 or 12, more preferably 8, and m is
It is 0 or 1. As a specific example, part of equation (4) is cleaved.
-Trisilanol compound represented by the formula (8) (RSiO
_3/2)₇(O_1/2H)_Three, (9)_3/2)₈
(O_1/2H)_Two, (10), (RSiO_3/2)₈(O
_1/2H)_TwoAnd the like. (8), (9) and (10)
Linked to the silanol group and the same silicon atom in the formula
R may exchange the positions of each other.

Embedded image

Embedded image

Embedded image

In addition, in the present invention, partial cleavage of a cage silsesquioxane having a structure in which some or all of the hydroxyl groups bonded to the skeleton silicon atom in the formula (2) are substituted with the substituent R is used. Structures, i.e., substituted partially cleaved forms, can also be used. In the substituted partial cleavage product, even if a plurality of hydroxyl groups bonded to the skeleton silicon atom are simultaneously substituted with one R to form a crosslinked structure such as a (silicon atom-R-silicon atom) bond. Good.

The substituent R in the double-bonded cage silsesquioxane used in the present invention is a hydrogen atom, a halogen atom, a carbon atom having no carbon-carbon double bond and having 1 to 2 carbon atoms.
0 hydrocarbons or hydrocarbons having 2 to 20 carbon atoms containing a carbon-carbon double bond or partially substituted products thereof, and 1 to 10 silicon atoms which may contain a carbon-carbon double bond
The plurality of Rs in one molecule may be the same or different as long as they are at least one kind selected from silicon-containing groups of formula (I) and contain at least two carbon-carbon double bonds. In the present invention, "carbon-carbon double bond"
Means a conjugated double bond but does not include an aromatic nucleus structure.

The number of hydrogen atoms used as the substituent R is usually 5 or less, preferably 3 or less in one molecule. The halogen atom used as the substituent R may be any halogen atom, but is preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom, in consideration of the handleability of the compound. The number of halogen atoms in one molecule is preferably 3 or less, more preferably 1 or less.

The C 1-20 hydrocarbon group containing no carbon-carbon double bond or the C 2-20 hydrocarbon group containing a carbon-carbon double bond used as the substituent R is For example, an alkyl group, a cycloalkyl group,
Examples thereof include an alkenyl group, a cycloalkenyl group, an alkenyl group containing an aromatic nucleus, a polyene hydrocarbon group, an aryl group, an araalkyl group, and an alkylene group. Examples of the alkyl group include a methyl, ethyl, n-propyl, i-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl group and the like.

Examples of cycloalkyl groups include cyclope
Methyl, cyclohexyl, cyclohexylethyl, cyclo
Roheptyl, cyclooctyl, cyclononyl, methyl
Clopentyl, methylcyclohexyl and the like.
Examples of alkenyl groups include vinyl, allyl, 1-pro
Phenyl, 1-butenyl, 2-butenyl, 3-butenyl,
Pentenyl, hexenyl, heptenyl, octenyl,
Nenyl, decenyl, undecenyl, dodecenyl and the like.
Can be Examples of cycloalkenyl groups include cyclopent
Thenyl, cyclohexenyl, cyclohexenylethyl,
Norbornenyl, norbornenylethyl and the like can be mentioned.
Examples of the aromatic nucleus-containing alkenyl group include cinnamyl (C
₆H_Five-CH = CH-CH_Two-), Styryl (C₆H_Five-C
H = CH-), 4-vinylstyryl (CH_Two= CH-C₆
H _Four—CH ＝ CH—), alkyl-substituted styryl, alcohol
Xyl-substituted styryl groups and the like. Polyene hydrocarbon
Examples of groups include 1,5-hexadienyl, 2,4-pe
Antadienyl, cyclooctadienyl group, etc.
You.

Examples of aralkyl groups include benzyl, phenethyl, 2-methylbenzyl, 4-methylbenzyl,
α-methylbenzyl, 2-vinylphenethyl, 4-vinylphenethyl and the like. Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the aryl group include a phenyl group, a phenylene group, a naphthyl group, a naphthylene group or a group having 1 to 1 carbon atoms.
14, more preferably an aromatic group mono- or plurally substituted with an alkyl group or alkenyl group having 1 to 8 carbon atoms. Examples of the substituted aromatic group include a tolyl group,
4-methylphenyl group, 2,4-dimethylphenyl group,
4-tbutylphenyl group, 4-vinylphenyl group, 2-
Examples thereof include an allylphenyl group, a 4-allylphenyl group, and a vinylnaphthyl group.

The number of carbon atoms of these hydrocarbon groups is usually 20 or less. However, from the viewpoint of ease of synthesis, solubility in a solvent, affinity with a resin, and operability, Preferably no more than 16, more preferably no more than 10, most preferably no more than 6. A partially substituted hydrocarbon having 1 to 20 carbon atoms not containing a carbon-carbon double bond or a portion of a hydrocarbon group having 2 to 20 carbon atoms containing a carbon-carbon double bond, which is used as a substituent R. The substituent is a compound in which the main chain structure or a part of a hydrogen atom of the hydrocarbon group is a hetero atom other than a carbon atom and a hydrogen atom represented by a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or the like, or a hetero atom thereof. This is a structure substituted with an atom-containing group.

The partially substituted product preferably has 16 or less carbon atoms, more preferably 10 or less, and most preferably 6 or less. The ratio of the “sum of the number of carbon atoms and the number of hydrogen atoms of the partial substitution” to the “total number of atoms of the partial substitution” is preferably 50% or more, more preferably 70% or more, and most preferably 85% or more. It is.
For example, the following structures are exemplified as the partial substitution product. _{1) -CH 2 CH 2 CH 2} Cl, -CH 2 CH 2 CH 2 Br,
Halogen atom-containing groups such as -CH ₂ CH ₂ CF _3. 2) a group containing a functional group containing an oxygen atom and / or a sulfur atom such as an ether group, an epoxy group, an ester group, a hydroxyl group, a carboxyl group, a carbonyl group, a sulfonyl group, a thiol group, a thioether group, and a carboxylic anhydride group. , for _{example, -CH 2 CH 2 CH 2 OCH} 3, -CH 2 CH 2 CH 2
_{OCH 2 CH = CH 2, -CH} = CHCH 2 OCH 2 CH =
CH ₂ —CH ₂ CH ₂ CH ₂ OC ₆ H ₅ , —C ₃ H ₆ OC ₆ H ₄ C
_{(CH 3) 2 C 6 H} 4 OCH 2 CH = CH 2, -CH = CHC
_{H 2 OC 6 H 4 OCH 2} CH = CH 2,

[0028]

Embedded image

--CH ₂ CH ₂ CH ₂ OCF ₂ CF ₂ C
_{F 3, -CH 2 CH 2 CH} 2 OCOCH 3, -CH 2 CH 2 C
_{H 2 COOCH 3, -CH 2 CH} 2 CH 2 OCOCH = C
_{H 2, -CH 2 CH 2 CH} 2 OCOC (CH 3) = CH 2, -
OH, —OCH ₃ , —OC ₆ H ₅ , —OC ₆ H ₄ CH ₂ CH =
CH ₂ , —CH ₂ CH ₂ CH ₂ OH, —CH (CH ₃ ) CH _{2
-OH, -CH 2 CH 2 CH 2} CO 2 H, -CH 2 CH 2 CH
_{2 COCH 3, -CH 2 CH 2} CH 2 SO 2 CH 3, -CH 2 C
H ₂ CH ₂ SCH ₃ ,

[0030]

Embedded image

[0031]

Embedded image

And the like. 3) amino group, ammonium salt, amide group, imino group, imide group, nitrile group, a urea group, a urethane group, a nitrogen atom-containing group such as a pyridyl group, e.g., -CH ₂ CH ₂ C
H ₂ N (CH _{3) 2} and salts _{thereof, -CH 2 CH 2 CH 2 NH} 2
And salts _{thereof, -CH 2 CH 2 CH 2 NHCOCH} 3, -CH
_{2 CH 2 CH 2 CN, -ON} (CH 3) 4,

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

--CH ₂ CH ₂ CH ₂ NHCONHC
_{6 H 5, -CH 2 CH 2} CH 2 OCONHC 6 H 5, -CH 2 C
_{H 2 CH 2 N (CH 2} CH = CH 2) 2, -CH 2 CH 2 CH 2
NHCOCH = CH ₂ ,

[0037]

Embedded image

[0038]

Embedded image

And the like. As the silicon atom-containing group having 1 to 10 silicon atoms which may contain a carbon-carbon double bond and used as the substituent R, those having a wide range of structures are employed. For example, a group having the structure of the formula (21) or the formula (22) can be used.

[0040]

Embedded image

[0041]

Embedded image

The number of silicon atoms in the silicon atom-containing group is usually 1 to 10, preferably 1 to 6, more preferably 1 to 3.
Range. When the number of silicon atoms is too large, the handling and purification of the cage-like silsesquioxane partially-cleaved structure tend to be difficult. In the equation (21), n
Is usually an integer of 1 to 10, preferably 1 to
6, more preferably an integer of 1 to 3, R ₅ and R ₆ are a hydrogen atom or an organic group having 1 to 10, preferably 1 to 6 carbon atoms.

Examples of the organic group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group and a cyclohexyl group; an alkoxy group such as a methoxy group and a t-butoxy group; Group, an unsaturated bond-containing group such as an allyl group, a substituted alkyl group such as a fluorinated alkyl such as CF ₃ CH ₂ CH ₂ —, an aryl group such as a phenyl group and a toluyl group, and an aralkyl group such as a benzyl group and a phenethyl group. Is mentioned. Among these, a methyl group, a propyl group, a phenyl group, a vinyl group, and an allyl group are particularly preferred because of good handleability.

[0044] (21) R ₇ in the formula is a hydrogen atom or the above-mentioned "carbon - 2 carbon atoms containing a hydrocarbon or carbon-carbon double bond and having from 1 to 20 carbon atoms containing no carbon-carbon double bond 20 hydrocarbon groups or partially substituted products thereof ”. In the formula (21), it is preferable that two or more hydrogen atoms are not simultaneously connected to the same silicon atom. As the compound represented by the formula (21),
For example, trimethylsiloxy, dimethylphenylsiloxy, diphenylmethylsiloxy, dimethylsiloxy, dimethylvinylsiloxy, diphenylvinylsiloxy, phenylmethylvinylsiloxy, methyldivinylsiloxy, trivinylsiloxy, dimethylallylsiloxy, dimethylcyclohexylsiloxy, dimethylcyclohexenyl Siloxy, dimethylnorbornenylethylsiloxy, dimethyl-4-vinylphenethylsiloxy group, X-
(CH ₃ ) ₂ SiO [Si (CH ₃ ) ₂ O] _k- (k is 1 to
9, X is an alkenyl group or a methyl group),

[0045]

Embedded image

[0046]

Embedded image

--OSi (CH ₃ ) ₂ CH ＝ CHC ₆ H ₄ C
H = CH ₂ , —OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ OCH
₂ CH = CH _{2 and the} like. In the equation (22), R
a is a divalent hydrocarbon group having 1 to 10, preferably 2 to 6, and more preferably 2 or 3 carbon atoms. The Ra, for _{example, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -,
_{- (CH 2) m - (} m is 4 to 10) alkylene group such as -
CH = CHCH ₂ -group and the like. (22) R in Formula _5, R _6, R ₇ is, R _5, R respectively (21) where
₆ and R ₇ are the same. R ₈ and R ₉ are the same as R ₅ and R ₆ , respectively. n ′ is 0 or an integer in the range of 1 to 9, preferably 0 or an integer in the range of 1 to 5, more preferably 0, 1 or 2. Note that in equation (22),
It is preferred that two or more hydrogen atoms are not simultaneously connected to the same silicon atom.

The compound of the formula (22) used as R includes, for example, -CH = CH- (CH ₂ ) ₆ -S
_{i (OCH 3) 3, -CH} = CHCH 2 Si (OC
_{H 3) 3, -CH = CHCH} 2 Si (CH 3) 3, -CH 2 C
_{H 2 CH 2 Si (CH 3} ) 2 OSi (CH 3) 3, -CH 2 C
H ₂ Si (CH ₃ ) _{3 and the} like. As the substituent R for substituting a hydroxyl group in the substituted partially-cleaved product used in the present invention, the above-mentioned various substituents R can be used. Among them, fluorine is preferred from the viewpoint of ease of synthesis. An atom or a group represented by the formula (21) is particularly preferred.

The carbon-carbon double bond in the cage-like silsesquioxane containing a double bond used in the present invention includes various carbon-carbon double bonds. For example,
1) a skeleton silicon atom of a cage silsesquioxane or a vinyl group or a substituted vinyl group directly bonded to a silicon atom in a side chain; 2) an allyl group or a substituted allyl group (for example, a group having 1 to 5 carbon atoms; 3) α, β-2 substituted carbon-carbon double bond or carbon-carbon double bond in the ring structure, 4) -Z-CH = CH _2- type carbon-carbon double bond (Z
Is a hetero atom such as an oxygen atom, a sulfur atom and a nitrogen atom),
5) Methacrylate group (—OCOC (CH ₃ ) ＝ CH
₂ ) or an acrylate group (—OCOCH ＝ CH ₂ group),
6) 4-vinylphenyl group (-C ₆ H ₄ -CH = CH
Arom vinyl group represented by ₂ group) (-CH = CH
₂ ) a carbon-carbon double bond directly bonded to 7)-
And a fluorine-substituted carbon-carbon double bond such as a CF = CF ₂ group. However, among these various carbon-carbon double bonds, the carbon-carbon double bond, which has a relatively low radical polymerizability alone, tends to have a greater effect of improving the properties by crosslinking. The “carbon-carbon double bond” in the present invention does not include an aromatic nucleus structure.

The cage silsesquioxane containing a double bond used in the present invention may be used alone or as a mixture of two or more. Further, it may be used in combination with cage silsesquioxane other than the double bond-containing cage silsesquioxane of the present invention, and other silicon-based compounds. In this case, the mixture preferably contains 10% by mass or more of the double bond-containing cage silsesquioxane of the present invention, more preferably 50% by mass.
The content is most preferably 80% by mass or more. Other silsesquioxane compounds that do not form a cage structure have less effect of improving the fluidity during melting, as compared with caged silsesquioxanes containing a double bond.

The method of synthesizing the double bond-containing silsesquioxane used in the present invention will be described below. Skeleton structure of cage silsesquioxane (that is, cage silsesquioxane structure and its partial cleavage structure structure)
Can be synthesized by various methods. For example, various cage silsesquioxanes are described in Brown et al. Am. Che
m. Soc. 1965, 87, 4313, Feher
J. et al. Am. Chem. Soc. 1989, 111,
1741 or Organometallics 1
It is reported that the compound can be synthesized by a method such as 991, 10, 2526. For example, octacyclohexyloctasilsesquioxane (in the formula (4), R is a cyclohexyl group structure) is obtained by reacting cyclohexyltriethoxysilane in water / methyl isobutyl ketone with tetramethylammonium hydroxide as a catalyst. Can be manufactured.

As a method for synthesizing a partially-cleaved cage silsesquioxane, for example, the trisilanol compound and the disilanol compound represented by the formulas (8) to (10) may be completely condensed cage-like. It is reported that silsesquioxane is produced at the same time as the production. Further, it has been reported that synthesis can also be performed by partially cleaving a completely condensed cage silsesquioxane with trifluoromethanesulfonic acid or tetraethylammonium hydroxide (see Feher et al., Chem. Commun., 1998, 1279). I have.

The cage-like silsesquioxane containing a double bond is prepared, for example, by using R′SiX ₃ (X is a halogen atom or an alkoxy group) comprising a substituent R ′ containing a carbon-carbon double bond as a raw material. Can be synthesized by the same synthesis method as the above cage-like silsesquioxane and its partially cleaved structure. As an example, Zh. Obsch. Khi
m. (1979), 49 (7) and 1522-5 show C
H = octavinyloctasilsesquioxane from CHSiCl ₃ (in the formula (4), R is a structure of a vinyl group)
And decavinyl decasilsesquioxane (in the formula (5), R is a structure of a vinyl group).

In addition, cage-like silsesquioki containing double bonds
Suns are derived from various cage silsesquioxanes.
You can also. For example, various cage silsesquioxa
Metathesis reaction, hydrosilyl
Using a hydrogenation or dehydrohalogenation condensation reaction
But also limited to these methods
is not. a) {Si} -CH = CH_Two + CH₂= CH-R_x→
 {Si} -CH = CH-R_x (Metathesis reaction) ({Si} is a cage-like silsesquioxane skeleton or a cage-like silsesquioxane
Forms a partially cleavable skeleton of rusesquioxane
Silicon atom, R_xIs a hydrocarbon group having 1 to 18 carbon atoms or
B) {Si} —OSi (CH_Three)_TwoCH = CH_Two + C
H_Two= CH-R_x → {Si} -OSi (CH_Three)_TwoCH = C
HR_x (Metathesis reaction) (R_xIs the same as in a). )

As a method for synthesizing a cage silsesquioxane containing various carbon-carbon double bonds utilizing a metathesis reaction, for example, a method described in US Pat. No. 5,942,638 can be mentioned. c) {Si} -OSi (CH 3) 2 H + CH 2 = CH
-R _y -CH = CH ₂ → {Si} -OSi (CH ₃ ) ₂ C
_{H 2 CH 2 -R y -CH =} CH 2 ( hydrosilylation reaction) (R _y is a divalent hydrocarbon group or a substitution product thereof of 1 to 16 carbon atoms) d) {Si} -OY + Cl-Si (CH ₃ ) _2- (C
H ₂ ) _p -CH = CH ₂ → {Si} -OSi (CH ₃ ) _2-
(CH ₂ ) _p —CH ＝ CH ₂ (hydrohalogen condensation reaction) (p is an integer of 0 to 10, Y is a hydrogen atom or a quaternary ammonium group) d) -Si (CH ₃ ) utilizing the reaction ) examples of ₂ -CH = CH ₂ group-containing cage-type silsesquioxane synthesis reaction,
For example, Journal of organometa
llic Chemistry, 441 (1992) 3
73-3800.

The structural analysis of the cage-like silsesquioxanes containing a double bond of the present invention was carried out by X-ray structural analysis (Alsiv Kemi 16, 209 (196) of Larsson et al.).
0)), infrared absorption spectrum, NMR spectrum (for example, Vogt et al., Inorga. Chem. 2, 189).
(1963)) and mass spectrometry. Examples of the method for purifying the double bond-containing silsesquioxane containing a double bond of the present invention include sublimation purification, recrystallization, purification using an ion exchange resin, and the like, and these methods remove various impurities. be able to.

Next, the radical initiator used in the present invention will be described. Examples of the radical initiator used in the present invention include: 1) a radical initiator that generates a radical upon heating (for example, benzoyl peroxide, t-butyl peroxide, alkyl peroxide, azobisisobutyronitrile, etc.); ) Radical initiators that generate radicals by light irradiation in the visible light and ultraviolet wavelength regions (for example, acetophenone, substituted acetophenone, benzoin group-containing compound, substituted benzoin group-containing compound, benzophenone, substituted benzophenone, thioxanthone, etc.).

In the composition of the present invention containing a cage-like silsesquioxane containing a double bond and a radical initiator, the ratio of the radical initiator is as follows. 1) When the composition of the present invention comprises only double bond-containing cage silsesquioxane and a radical initiator, the ratio of the radical initiator is based on the mass of the double bond-containing cage silsesquioxane. , 0.001 to 20% by mass, more preferably 0.005 to 15% by mass, and most preferably 0.01 to 10% by mass. 2) When a resin is contained in the former two, the ratio of the radical initiator is 0.001 to 20% by mass relative to the total mass of the double bond-containing cage silsesquioxane and the resin. Preferably, it is more preferably 0.005 to 15% by mass, and most preferably 0.01 to 10% by mass. By using 0.001 to 20% by mass of the radical initiator as described above, the radical generation efficiency is further improved, and the crosslinking reaction of the double bond-containing cage silsesquioxane is sufficiently performed, and Since the generation speed is easily controlled, the quality and safety of the molded body can be further improved.

When the above composition is crosslinked by heating, the crosslinking temperature is usually from 80 to 300 ° C., preferably from 150 to 2 ° C., depending on the presence or absence of the crosslinking agent and its type.
It is selected in the range of 50 ° C. Crosslinking time is 1 minute to 10 hours,
Preferably, it is 1 minute to 5 hours. It is effective to add a resin to the cage-like silsesquioxane-containing composition of the present invention in order to improve properties such as mechanical properties of a cured molded product obtained from the cage-like silsesquioxane-containing composition. is there.

The resins used in the cage-like silsesquioxane-containing composition of the present invention include a wide variety of resins such as various thermoplastic resins, solvent-soluble resins, and thermosetting resins, depending on the use. Can be Examples of the thermoplastic resin include polyvinyl acetate, polyolefin resins represented by polypropylene and polyethylene, styrene resins, acrylic resins such as polymethyl methacrylate, addition polymers such as various vinyl monomer copolymers, nylon-6 and Polyamide resins such as nylon-6, 6; polycarbonate resins; polyester resins such as polyethylene terephthalate and polytrimethylene terephthalate; polyether resins such as polyacetal and polypropylene glycol; aromatic polyether resins such as polyphenylene ether; polysulfone and polyether sulfone Polysulfone resin,
Examples thereof include a silicon atom-containing polymer such as a thermoplastic polyimide resin, a polyarylate resin, and a silicone polymer, and a fluorine atom-containing polymer such as a fluorine-based olefin polymer.

Examples of the solvent-soluble resin include, among the above-mentioned thermoplastic resins, polymers having good solubility in various solvents, and polyacrylonitrile which is difficult to heat-melt but is soluble in the solvent. . Examples of the thermosetting resin include a phenol resin, an epoxy resin, a cyanate ester resin, a polyimide resin, an unsaturated polyester resin, a silicone resin, a cyanate ester resin, a bismaleimide triazine resin, and the like. The resins may be used alone or in combination of two or more, and may be used as a copolymer.

For applications in the field of electronic materials, among the various resins described above, thermoplastic resins and thermosetting resins having excellent properties such as heat resistance and electrical properties are preferable, and furthermore, the flame retardancy and dielectric properties of the resins themselves are preferable. In consideration of the above, a polyphenylene ether-based resin is particularly preferable. Examples of the polyphenylene ether-based resin include poly (2,6-dimethyl-1,4-phenylene ether) and poly (2,6-dimethyl-1,4) obtained by homopolymerization of 2,6-dimethylphenol.
-Phenylene ether) styrene graft copolymer,
Copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymer of 2,6-dimethylphenol and 2-methyl-6-phenylphenol, 2,
A polyfunctional polyphenylene ether resin obtained by polymerization in the presence of 6-dimethylphenol and a polyfunctional phenol compound, for example, as disclosed in JP-A-63-301222 and JP-A-1-297428.
Nitrogen-containing polyphenylene ether resin obtained by polymerizing 2,6-dimethylphenol in the presence of substituted aniline or aliphatic secondary amine is exemplified.

The polyphenylene ether-based resin also includes modified polyphenylene ether-based resins. Examples of such modified products include a) polyphenylene ether resins containing an unsaturated group (JP-A-64-69628, JP-A-1-113425, JP-A-1-113426, etc.), and b) polyphenylene ether. Reaction products of the resin with unsaturated carboxylic acids and / or acid anhydrides are included. By using a modified product of a) or b) above, for example, a maleic anhydride-modified polyphenylene ether or the like as the polyphenylene ether-based resin, a cage-like silsesquioki containing a plurality of carbon-carbon double bonds in the molecule can be obtained. Compatibility with suns can be improved.

The polyphenylene ether-based resin used in the present invention can have a wide range of molecular weights.
One having a viscosity number ηsp / C measured in a chloroform solution of 0.5 g / dl at 0.5 ° C. in the range of 0.1 to 1.0. The mass ratio of the resin to the double bond-containing cage silsesquioxane is preferably from 1:99 to 99.9: 0.1, more preferably from 10:90 to 99: 1, and most preferably. 20:80 to 95: 5. 0.1 to 99% by mass of the double-bonded cage silsesquioxane
By this, the fluidity and the dimensional stability of the cured molded article during molding of the composition of the resin and the double bond-containing cage-like silsesquioxane are further improved, and the mechanical properties of the cured molded article are improved. The reinforcing effect by the resin having physical properties such as strength is further improved. Triallyl isocyanurate or triallyl cyanurate used as an auxiliary crosslinking agent of the present invention,
It is a trifunctional monomer represented by the formula (27) or (28).

[0065]

Embedded image

In practicing the present invention, triallyl isocyanurate and triallyl cyanurate can be used not only singly, but also can be used by mixing them at an arbitrary ratio. In the present invention,
Triallyl isocyanurate and triallyl cyanurate exhibit their effects as auxiliary crosslinking agents, and improve the crosslinking density of the cured product during crosslinking and molding. Further, in the present invention, triallyl isocyanurate and triallyl cyanurate are compatible with a double bond-containing cage-like silsesquioxane or a resin depending on the kind of the resin to form a uniform composition. Also functions as an agent.

When the cross-linking auxiliary agent is composed of only the double bond-containing cage silsesquioxane and the radical initiator, the content of the crosslinking auxiliary is 0.1 to 200 with respect to the double bond-containing cage silsesquioxane. % By mass, more preferably 1 to
It is 100% by weight, most preferably 10 to 80% by weight. When the resin is contained, the crosslinking auxiliary is preferably 0.1 to 200% by mass, more preferably 1 to 200% by mass based on the total mass of the double bond-containing cage silsesquioxane and the resin. It is 100% by weight, most preferably 10 to 80% by weight. By using the crosslinking aid in the above range, the crosslinking reaction proceeds more properly, and the impact resistance of the obtained molded article is improved.

As a method for mixing the components used in the composition of the present invention, a solution mixing method in which all the components to be used are uniformly dissolved or dispersed in a solvent and mixing, or a kneading method using an extruder or the like is used. Can be adopted. The solvent used for the solution mixing is selected in consideration of the solubility and operability of each component. As the solvent used for producing the cage-like silsesquioxane-containing composition of the present invention, for example, halogen-based solvents such as dichloromethane, chloroform, trichloroethylene, benzene, toluene, aromatic solvents such as xylene, acetone, methyl ethyl ketone And ketone solvents such as methyl isobutyl ketone, and solvents such as dimethylformamide and dimethyl sulfoxide. These may be used alone or in combination of two or more.

The cage-like silsesquioxane-containing composition of the present invention may be preliminarily formed into a desired shape according to its use. However, any molding method can be used. For example, a casting method in which the composition of the present invention is dissolved in the above-described solvent and molded into a desired shape, and a thermoforming method in which the composition of the present invention is molded into a desired shape under heating or under pressure if necessary. Method is used. The above-described casting method and heat molding method may be performed alone or in combination.

As an example of the “film” of the present invention, for example, a thickness of 0.5 μm to 5 μm
mm uncrosslinked film. Examples of the “crosslinked film obtained by crosslinking a film” of the present invention include, for example, a crosslinked film obtained by heating and crosslinking the above-mentioned uncrosslinked film. The crosslinkable composition of the present invention,
In addition to the above-mentioned components, fillers and additives can be blended and used in amounts not to impair the original properties, for the purpose of imparting desired performance according to the use. The filler may be fibrous or powdery, and examples thereof include silicates such as carbon black, alumina, barium titanate, talc, mica, glass beads, glass hollow spheres, and calcium silicate. Examples of the additives include an antioxidant, a heat stabilizer, an antistatic agent, a plasticizer, a pigment, a dye, a colorant, and rubber.

[0071] In order to increase the effect of the flame retardant, chlorine, bromine, phosphorus-based, and flame retardants such as metal hydroxides or organic metal _{compounds, Sb 2 O 3, Sb 2} O 5, NaSbO 3 · 1 / 4
A flame retardant auxiliary such as H ₂ O can be used in combination. The composition of the obtained cage-like silsesquioxane-containing composition can be analyzed by a method such as infrared absorption spectroscopy, high-resolution solid-state nuclear magnetic resonance spectroscopy, and pyrolysis gas chromatography.

As described above, the cage-like silsesquioxane-containing composition of the present invention is excellent in molding workability due to excellent fluidity at the time of melting, and the cured molded article is excellent in dimensional stability. The cage-like silsesquioxane-containing composition containing a resin has significantly improved fluidity compared to the base resin, improving moldability and dimensional stability due to the low coefficient of thermal expansion of the crosslinked product. It is possible to obtain a cured molded article having excellent properties. These can be used as insulating materials, heat-resistant materials, structural materials and the like in the fields of the electric industry, the space / aircraft industry, the building industry, and the like.

Further, the cage-like silsesquioxane-containing composition containing the auxiliary crosslinking agent has a further reduced coefficient of thermal expansion, and is suitable for obtaining a cured molded article having more excellent dimensional stability. It is suitable for use as an insulating material, a heat-resistant material, and the like in the field of the electric industry. In particular, a composition using polyphenylene ether resin as a resin exhibits excellent chemical resistance, dielectric properties, heat resistance, and flame retardancy in addition to the above-mentioned properties. It can be used for materials and structural materials. A polyphenylene ether-based crosslinkable resin composition, a crosslinkable film and a crosslinked film made of this composition are used for a single-sided printed wiring board, a double-sided printed wiring board, a multilayer printed wiring board, a flexible printed wiring board, and particularly, a plating step and a sputtering step. It is suitable for a multi-layer build-up wiring board or the like in which a wiring circuit is formed by using.

[0074]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described specifically with reference to examples and comparative examples, but the present invention is not limited to these. Molding of a cage-like silsesquioxane-containing composition,
The method for evaluating the physical properties of the crosslinked product is as follows. (1) Thermal expansion characteristics, glass transition temperature The cross-linked molded article was cut into short pieces of 7 mm long × 7 mm wide × 3 mm thick, and the coefficient of thermal expansion in the thickness direction and the glass transition temperature were measured at a heating rate of 20 ° C./min. Measured by a thermomechanical analyzer. Divided number). (2) Physical properties of film (2) -1 Resin fluidity The film was heated at a heating rate of 7 using a viscoelasticity measuring device (Rheometer RMS (trademark), manufactured by Rheometrics).
The temperature is raised at a rate of ° C / min, and the melt viscosity in a temperature range of 100 ° C to 300 ° C is measured. During the measurement, the crosslinking reaction proceeds simultaneously with the melting due to the presence of silsesoxane and the radical initiator, so that the melt viscosity is improved. Here, the minimum viscosity at the time when the measurement temperature is increased is used as an index of the resin fluidity.

(3) Evaluation of physical properties of cross-linked film (3) -1 Dielectric constant, dielectric loss tangent Using a LF impedance analyzer HP-4192 (trademark) (manufactured by Yokogawa-Hewlett-Packard Co., Ltd.), a frequency of 1 MHz was measured. Then, the dielectric constant and the dielectric loss tangent of the crosslinked film made of the cage-like silsesquioxane-containing composition are measured. (3) -2 Solder heat resistance The ferrite chloride solution ((ferric chloride content: 37 to 39% by mass) Tsurumi Soda Co., Ltd.) was applied to the copper foil-coated laminate prepared in Examples 3 to 6. After removing the copper foil by immersing the laminate for 10 minutes, the laminate was cut into 25 mm squares, floated in a 260 ° C. solder bath for 120 seconds, and visually observed for changes in appearance. (3) -3 Thermal expansion characteristics and glass transition temperature A crosslinked film from which copper foil was removed in the same manner as described above was used.
A 3 mm-wide strip is cut out, and the coefficient of thermal expansion and glass transition temperature in the length direction are measured at a heating rate of 20 ° C./min by a thermomechanical analyzer.

The coefficient of thermal expansion is a value obtained by dividing the rate of increase of the sample thickness when the temperature of the sample is increased from 30 ° C. to 200 ° C. by 170 ° C. (200 ° C.-30 ° C.), which is the change in temperature. The compounds used in the examples are as follows. Polyphenylene ether resin Resin A: poly (2,6-dimethyl-1,4-phenylene ether ηsp / C = 0.56 (30 ° C., 0.5 g / dl, chloroform solution) Resin B: 100 parts by mass of resin A, anhydrous maleic 1.5 parts by mass of an acid and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (Perhexa 2 manufactured by NOF Corporation)
5B (trademark)) was dry-blended at room temperature, the cylinder temperature was 300 ° C, and the screw speed was 23.
Extruded with a twin-screw extruder at 0 rpm, polymer A
To obtain a modified polyphenylene ether-based resin in which maleic anhydride is added to a methyl group or terminal hydroxyl group. This polymer is referred to as resin B.

Polycarbonate resin Polycarbonate (S3000 (trademark), manufactured by Mitsubishi Engineering-Plastics Corporation) Basket-shaped silsesquioxane Basket-shaped silsesquioxane (a): In the formula (4), R
Is —CH ＝ CH _{2, and in} the formula (5), R is —C
In the case of H = CH2 and the formula (6), R is -CH =
Mixture of CH ₂ (Hybrid Plastic)
s company) cage silsesquioxane (b): In the formula (4), R
Is -OSi (CH ₃ ) ₂ CH = CH ₂ (TAL M
materials) (c): In the formula (4), R
Is —OSi (CH ₃ ) ₂ CH ₂ CH ₂ -3-Cyclohe
xenyl (manufactured by TAL Materials) caged silsesquioxane (d): In the formula (4), R
Is -OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ -Methac
rylate (manufactured by TAL Materials) Radical initiator 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (manufactured by NOF Corporation) Triallyl isocyanurate Tyke (trademark) (Japan) Rubber (polystyrene containing butadiene) HIPS (registered trademark) 8117 (manufactured by Asahi Kasei Corporation) Flame retardant melamine polyphosphate Particle size <1 μm (manufactured by DSM)

[0078]

Examples 1 and 2 A polycarbonate resin or a polyphenylene ether resin (resin A), cage silsesoxane and a radical initiator were dissolved in a toluene solution at 80 ° C. in the composition shown in Table 1. Thereafter, toluene was removed by an evaporator, and the mixture was dried in a vacuum dryer at 80 ° C. for 1 hour to obtain a cage-like silsesquioxane-containing composition. Thereafter, the cage-like silsesquioxane-containing composition was weighed 20 mm long × 20 mm wide.
260 ° C, surface pressure 30kg in a mold of 3mm x 3mm
/ Cm ² , vacuum press molding for 1 hour to obtain a cross-linked molded body. Table 1 shows the results of measuring the thermal expansion characteristics and the glass transition temperature (Tg).

[0079]

Comparative Examples 1 and 2 A molded article was produced in the same manner as in Example 1 except that only the resin was used, and the performance was evaluated. Table 1 shows the results. The obtained molded body had a higher coefficient of thermal expansion than those of Examples 1 and 2.

[0080]

Comparative Examples 3 and 4 A molded body was produced in the same manner as in Example 1 with the same composition as in Examples 1 and 2 except that no radical initiator was added, and the performance was evaluated. Show. This molded article had a higher coefficient of thermal expansion than Examples 1 and 2.

[0081]

Comparative Examples 5 and 6 Except that silica was added in place of the cage-shaped silsesoxane, the same composition as in Examples 1 and 2 was carried out in the same manner as in Example 1 to produce a molded article. Table 1 shows the results of the evaluation. This molded product was obtained in Example 1.
And the thermal expansion coefficient was larger than that of 2.

[0082]

Examples 3 to 6 Polyphenylene ether resin (resin B), cage silsesoxanes (a) to (d), radical initiator and / or triallyl isocyanurate and rubber as auxiliary material at 80 DEG C. Was dissolved in a toluene solution of Using this solution, a cage-like silsesquioxane-containing composition film having a thickness of 45 μm was produced by cast molding.

The two films were stacked in a vacuum press and molded and cross-linked at 180 ° C. and a surface pressure of 30 kg / cm ² for 1 hour to obtain a cross-linked film having a thickness of 90 μm. Similarly, in order to measure these electric properties and solder heat resistance, several cross-linkable resin films are stacked so that the thickness after cross-linking becomes 100 μm, and a copper foil having a thickness of 12 μm is formed on both surfaces thereof. Put and press molding machine
It was crosslinked to produce a crosslinked film. The fluidity of the film thus obtained and various physical properties of the crosslinked film were measured. This film showed good results, as evident from Table 2.

[0084]

Comparative Example 7 A crosslinked film was produced in the same manner as in Examples 3 to 5, except that silica was added in place of the cage silsesoxane, and in the same manner. Table 2 shows the results of evaluating the performance of the obtained film. This film had lower fluidity and lower coefficient of thermal expansion than those of the examples.

[0085]

[Table 1]

[0086]

[Table 2]

[0087]

EFFECT OF THE INVENTION The crosslinkable composition of the present invention is excellent in molding processability due to excellent fluidity at the time of melting, and is excellent in dimensional stability of molded articles, and is suitable for electric industry, space / aircraft industry, building industry, etc. In the field of, it can be used as an insulating material, a heat-resistant material, a structural material and the like. In particular, the composition to which polyphenylene ether resin is added as a resin, in addition to the above-described properties, shows excellent chemical resistance, dielectric properties, heat resistance, flame retardancy, and in the field of the electric industry, dielectric materials, insulating materials, heat-resistant materials, It can be used for structural materials and the like. The polyphenylene ether-based resin composition is particularly suitable for a single-sided printed wiring board, a double-sided printed wiring board, a multilayer printed wiring board, a flexible printed wiring board, a multilayered build-up wiring board, and the like.

Continued on the front page F-term (reference) 4F071 AA02 AA14 AA15 AA20 AA22 AA26 AA28 AA33 AA34 AA40 AA41 AA42 AA43 AA46 AA48 AA49 AA51 AA60 AA64 AA67 AA69 AD07 AE22 AF54 AF61 AF62 AB12 BBXBBC BB BBBC BF02X BG03X BG06X BG09X CB00X CC04X CD00X CE00X CF03X CF06X CF07X CF16X CF21X CG00X CH02X CH06X CL00X CL01X CL03X CM04X CN03X CP03X CP13W CP14W EC046 EE036 EK006 EK0300 ER006GN01 197006 GM00

Claims (12)

[Claims] 1. A cage-like silsesquioxane-containing composition comprising: a cage-like silsesquioxane containing a plurality of carbon-carbon double bonds in a molecule; and a radical initiator. 2. The cage-shaped silsesquioxane-containing composition according to claim 1, further comprising a resin. 3. The cage-like silsesquioxane-containing composition according to claim 1, further comprising an auxiliary crosslinking agent. 4. The cage-shaped silsesquioxane-containing composition according to claim 2, further comprising an auxiliary crosslinking agent. 5. The mass ratio of the resin to the cage silsesquioxane containing a plurality of carbon-carbon double bonds in the molecule is 1:99 to 99.9: 0.1, and the resin and the molecule With respect to the total mass of the cage silsesquioxanes containing a plurality of carbon-carbon double bonds in the
The cage-like silsesquioxane-containing composition according to claim 2 or 4, wherein the composition is contained in an amount of from 01 to 20% by mass. 6. A crosslinking assistant is contained in an amount of 0.1 to 200% by mass based on the total mass of the resin and the cage silsesquioxane containing a plurality of carbon-carbon double bonds in the molecule. The cage-like silsesquioxane-containing composition according to claim 4, wherein 7. A cage silsesquioxane having a plurality of carbon-carbon double bonds in a molecule thereof, wherein the cage silsesquioxane is represented by the formula (1) and the cage silsesquioxane is represented by the formula (2) And a cage-like silsesquioxane having a structure in which some or all of the hydroxyl groups bonded to the skeleton silicon atom in the formula (2) are substituted with a substituent R. The cage-like silsesquioxane-containing composition according to any one of claims 1 to 6, which is at least one kind of cage-like silsesquioxane selected from a partially cleaved structure. (RSiO _3/2 ) _n (1) (RSiO _3/2 ) _nm (O _1/2 H) _{2 + m} (2) (n is an integer of 6 to 14, m is 0 or 1, R is a hydrogen atom,
A halogen atom, a hydrocarbon having 1 to 20 carbon atoms not containing a carbon-carbon double bond, a hydrocarbon having 2 to 20 carbon atoms containing a carbon-carbon double bond, or a partially substituted product thereof, and a carbon-carbon double bond. At least one selected from silicon atom-containing groups having 1 to 10 silicon atoms which may contain a heavy bond;
A plurality of Rs in one molecule may be the same or different as long as they are species and have at least two carbon-carbon double bonds) 8. The cage-like silsesquioxane-containing composition according to claim 2, wherein the resin is a polyphenylene ether-based resin. 9. The cage-like silsesquioxane-containing composition according to claim 3, wherein the auxiliary crosslinking agent is triallyl isocyanurate and / or triallyl cyanurate. 10. A cured molded article obtained from the cage-like silsesquioxane-containing composition according to any one of claims 1 to 9. 11. A film comprising the cage-like silsesquioxane-containing composition according to any one of claims 1 to 9. 12. A crosslinked film obtained by crosslinking the film according to claim 11.