WO2021261133A1 - Photocurable composition, cured product thereof, and method for producing cured product - Google Patents

Abstract

Provided is a photocurable composition comprising a silsesquioxane derivative that is indicated by formula (1) and a hydrosilylation catalyst that contains a transition metal.

Description

A photocurable composition, a cured product thereof, and a method for producing the cured product.

This disclosure belongs to the technical field of heat-resistant materials, the technical field of insulating materials, the technical field of electronic materials, the technical field of automobiles, etc. with respect to the photocurable composition, the cured product thereof, and the method for producing the cured product. More specifically, the present disclosure relates to a photocurable composition comprising an organosilicon compound having a hydrosilylation-reactive carbon-carbon unsaturated group and a hydrosilylation group and a hydrosilylation catalyst. The cured product of the above photocurable composition is useful as a heat-resistant insulating material.

In recent years, there has been an increasing demand for higher heat resistance of various protective films and insulating films used for electronic devices and automobile members due to miniaturization, high integration, high performance, and the like.
From the viewpoints of workability, optical properties, chemical resistance, heat resistance, weather resistance, etc., siloxane compounds such as silicone, which is an organic-inorganic composite material, are used, especially from the viewpoint of high heat resistance and workability. Therefore, an addition-curable silsesquioxane derivative has been attracting attention.

International Publication No. 2005/010077 discloses a thermosetting and highly heat resistant silsesquioxane derivative in which a carbon-carbon unsaturated bond group and a hydrosilyl group are both bonded to a silicon atom having a T structure in the same molecule. There is.

In WO 2009/06668, a thermosetting, highly heat-resistant silsesquioxane derivative having a carbon-carbon unsaturated bond group and a hydrosilyl group in the same molecule and having a T structure, a D structure and an M structure. Is disclosed.

However, since heat treatment is essential for curing the silsesquioxane derivative disclosed in International Publication No. 2005/010077 and International Publication No. 2009/06660 by hydrosilylation cross-linking, the group to which it is applied is applied. The material is limited to those that can withstand the heating temperature, and it takes a long time to cure, which causes a problem in productivity.
According to one embodiment of the present invention, it is possible to provide a photocurable composition containing a silsesquioxane derivative which is excellent in curability and can be applied to various substrates, a cured product thereof, and a method for producing the cured product. can.

The present invention includes the following aspects [1] to [11].
[1]
A photocurable composition containing a silsesquioxane derivative represented by the following formula (1) and a hydrosilylation catalyst containing a transition metal.

[In equation (1),
R ¹ is an organic group having a carbon-carbon unsaturated bond capable of hydrosilylation reaction and having 2 to 12 carbon atoms.
R ² is at least one selected from the group consisting of an alkyl group, an aralkyl group of aryl and 7 to 10 carbon atoms of 6 to 10 carbon atoms in the 1 to 10 carbon atoms,
A plurality of R ³ and R ⁴ are independently capable of hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and a hydrosilylation reaction. It is at least one selected from the group consisting of organic groups having 2 to 12 carbon atoms having a carbon-carbon unsaturated bond.
There exist a plurality of R ³ may be the same or different from each other,
The R ⁴ presence of a plurality may be the same or different from each other,
u, v, w and x are independently 0 or positive numbers, and at least one of them is a positive number.
y and z are independently 0 or positive numbers, respectively.
0 ≦ y / (u + v + w + x) ≦ 2.0,
0 ≦ z / (u + v + w + x) ≦ 2.0,
However, when v = 0, ^{at least one of a plurality of R 3} and R ⁴ is a hydrogen atom, and when w = 0, at least one of ^{a plurality of R 3} and R ^{4 is a hydrosilyl.} It is an organic group having 2 to 12 carbon atoms having a carbon-carbon unsaturated bond capable of undergoing a conversion reaction. ]
[2]
The ratio of the number of hydrogen atoms bonded to silicon atoms to one organic group having a hydrosilylation-reactive carbon-carbon unsaturated bond present in the silsesquioxane derivative is 0.5 to 5.0. The photocurable composition according to [1].
[3]
The photocurable composition according to [1] or [2], wherein the content ratio of the transition metal is 0.1 to 30,000 ppm by weight with respect to 100 parts by weight of the silsesquioxane derivative.
[4]
The photocurable composition according to any one of [1] to [3], wherein the transition metal is a platinum group metal.
[5]
Hydrosilylation catalyst containing the transition metal, beta-diketonate platinum complexes, (.eta. cyclopentadienyl) trialkyl platinum complexes, (η ⁴ -1,5- cyclooctadiene) diaryl platinum complexes and dialkyl azo The photocurable composition according to any one of [1] to [4], which is at least one selected from the group consisting of dicarboxylate platinum complexes.
[6]
The photocurable composition according to any one of [1] to [5], further comprising a heat resistance improver.
[7]
A cured product obtained by curing the photocurable composition according to any one of [1] to [6].
[8]
The cured product according to [7], which has a relative permittivity of 4.0 or less at 1 MHz.
[9]
The cured product according to [7] or [8], wherein the 5% weight loss temperature in the atmosphere in thermogravimetric analysis is 300 ° C. or higher.
[10]
The cured product according to any one of [7] to [9], which is an insulating film.
[11]
A method for producing a cured product, which comprises a step of irradiating the photocurable composition according to any one of [1] to [6] with ultraviolet rays to cure the photocurable composition.

According to one embodiment of the present invention, it is possible to provide a photocurable composition containing a silsesquioxane derivative which is excellent in curability and can be applied to various substrates, a cured product thereof, and a method for producing the cured product. can.

The present disclosure relates to a photocurable composition, a cured product thereof, and a method for producing the cured product.
Hereinafter, the present disclosure will be described in detail.
Unless otherwise specified, "%" means "% by weight", "parts" means "parts by weight", and "ppm" means "ppm by weight". Further, in the present disclosure, the description of "lower limit to upper limit" representing the numerical range means "below the lower limit and below the upper limit", and the description of "upper limit to lower limit" means "below the upper limit and above the lower limit". That is, it represents a numerical range including an upper limit and a lower limit. Further, in the present disclosure, a combination of two or more of the preferred embodiments described below is also a preferred embodiment.
In the present disclosure, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.

Hereinafter, a method for producing a silsesquioxane derivative and a silsesquioxane derivative, a hydrosilylation catalyst, a photocurable composition, a cured product thereof, a method for producing a cured product, and an application thereof will be described.

1. 1. Silsesquioxane derivative The silsesquioxane derivative according to the present disclosure is a silsesquioxane derivative represented by the following formula (1). The silsesquioxane derivative represented by the following formula (1) has an organic group having a carbon-carbon unsaturated bond capable of hydrosilylation reaction and a hydrosilyl group in the same molecule.

Each structural unit that can be possessed by the silsesquioxane derivative according to the present disclosure shall be referred to as the structural units (a) to (f) as follows, and will be described below.

Structural unit (a): (SiO _4/2 ) _u

Structural unit (b): (HSiO _3/2 ) _v

Structural unit (c): (R ¹ SiO _3/2 ) _w

Structural unit (d): (R ² SiO _3/2 ) _x

The structural unit _{^{(e) :( R 3 2 SiO}} 2/2) y

The structural unit _{^{(f) :( R 4 3 SiO}} 1/2) z

The silsesquioxane derivative according to the present disclosure can contain the above-mentioned structural units (a) to (f).
U, v, w and x in the equation (1) are independently 0 or a positive number, at least one of them is a positive number, and y and z are independently 0 or a positive number, respectively. Yes, 0 ≦ y / (u + v + w + x) ≦ 2.0, and 0 ≦ z / (u + v + w + x) ≦ 2.0.
That is, u, v, w, x, y and z in the formula (1) represent the molar ratio of each constituent unit. In the formula (1), u, v, w, x, y and z are relative molar ratios of each structural unit contained in the silsesquioxane derivative according to the present disclosure represented by the formula (1). Represents. That is, the molar ratio is a relative ratio of the total number of each structural unit represented by the formula (1). The molar ratio can be determined from the NMR (nuclear magnetic resonance) analysis value of the silsesquioxane derivative according to the present disclosure. Further, when the reaction rate of each raw material of the present silsesquioxane derivative is clear, or when the yield is 100%, it can be obtained from the charged amount of the raw material.

For each of the structural units (c), (d), (e) and (f) in the formula (1), only one type may be used, or two or more types may be used. Further, the sequence order in the formula (1) indicates the composition of the structural unit, and does not mean the sequence order. Therefore, the condensed form of the structural unit in the silsesquioxane derivative according to the present disclosure does not necessarily have to be in the sequence order of the formula (1).

1-1. Structural unit (a): (SiO _4/2 ) _u
The structural unit (a) is a so-called Q unit having four _{O 1/2 (two as oxygen atoms) for one silicon atom.} The Q unit means a unit having four _{O 1/2 for one silicon atom.}
The proportion of the constituent unit (a) in the silsesquioxane derivative according to the present disclosure is not particularly limited, but in consideration of the viscosity of the photocurable composition of the present disclosure and the flexibility of the cured product, all the constituent units. The molar ratio (u / (u + v + w + x + y + z)) to the above is preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.3 or less, and further preferably 0. Here, the fact that the molar ratio is 0 means that the constituent unit is not included, and the same applies hereinafter.

1-2. Structural unit (b): (HSiO _3/2 ) _v
The structural unit (b) is a _{so-called T unit having three O 1/} 2s (1.5 as oxygen atoms) for one silicon atom, and has a hydrogen atom bonded to the silicon atom. The T unit means a unit having three _{O 1/2 for one silicon atom.}
That is, the structural unit (b) includes a hydrosilylation group capable of carrying out a hydrosilylation reaction.
The ratio of the structural unit (b) in the silsesquioxane derivative according to the present disclosure is not particularly limited, but the heat resistance, oxidation resistance, weather resistance and insulation of the photocurable composition and the cured product thereof of the present disclosure are not particularly limited. Considering the properties, the molar ratio (v / (u + v + w + x + y + z)) to all the constituent units is preferably 0 to 0.7, and more preferably considering the heat resistance, oxidation resistance and weather resistance of the insulating film. Is 0 to 0.1.

1-3. Structural unit (c): (R ¹ SiO _3/2 ) _w
The structural unit (c) is a _{T unit having three O 1/} 2s (1.5 as oxygen atoms) for one silicon atom, and has ^{R 1 bonded to the silicon atom.}
R ¹ represents an organic group having 2 to 12 carbon atoms having a carbon-carbon unsaturated bond capable of hydrosilylation reaction. That is, the organic group R ¹ is preferably a functional group having a carbon-carbon double bond or a carbon-carbon triple bond capable of hydrosilylation reaction.
Specific examples of the organic group R ¹ are not particularly limited, but for example, a vinyl group, an orthostyryl group, a metastyryl group, a parastyryl group, an acryloyloxymethyl group, a methacryloyloxymethyl group, and a 2-acryloyloxyethyl group. , 2-methacryloyl oxyemethyl group, 3-acryloyloxypropyl group, 3-methacryloyloxypropyl group, 8-acryloyloxyoctyl group, 8-methacryloyloxyoctyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group , 1-butenyl group, 3-butenyl group, 1-pentenyl group, 4-pentenyl group, 3-methyl-1-butenyl group, 1-phenylethenyl group, 2-phenylethenyl group, ethynyl group, 1-propynyl Examples thereof include a group, a 2-propynyl group, a 1-butynyl group, a 3-butynyl group, a 1-pentynyl group, a 4-pentynyl group, a 3-methyl-1-butynyl group and a phenylbutynyl group.
Hydrosilylation reactivity, and heat resistance of the cured product, from the viewpoint of oxidation resistance and / or weather resistance, the R ^1, preferably a carbon - a hydrocarbon group having a carbon-carbon double bond, more preferably It is a vinyl group and a 2-propenyl group (allyl group) having a small number of carbon atoms, or an aromatic orthostyryl group, a metastyryl group and a parastyryl group, and more preferably a vinyl group.
Silsesquioxane derivative represented by Formula (1) is an organic group R ¹ as a whole may comprise two or more, in which case all of the organic radical R ^1, may be identical to each other, It may be different. For example, vinyl and parastilyl groups may be present if they are different.

The ratio of the constituent unit (c) in the silsesquioxane derivative according to the present disclosure is not particularly limited, but the heat resistance, oxidation resistance, weather resistance and insulation of the photocurable composition and the cured product thereof of the present disclosure are not particularly limited. Considering the sex, the molar ratio (w / (u + v + w + x + y + z)) to all the constituent units is preferably 0 to 0.5, and more preferably 0.1 to 0.3.

1-4. Structural unit (d): (R ² SiO _3/2 ) _x
The structural unit (d) is a _{T unit having three O 1/} 2s (1.5 as oxygen atoms) for one silicon atom, and has ^{R 2 bonded to the silicon atom.}
R ² is at least one selected from the group consisting of an alkyl group, an aralkyl group of aryl and 7 to 10 carbon atoms of 6 to 10 carbon atoms having 1 to 10 carbon atoms. The structural unit (d) has a point that does not contain a hydrogen atom as compared with the above-mentioned structural unit (b) and the structural unit (c), and an organic group having a carbon-carbon unsaturated bond capable of hydrosilylation reaction. It differs in that it does not include it.
The structural unit (d) basically forms 3 siloxane bonds per silicon atom in the photocurable composition and its cured product, but does not form crosslinks due to the hydrosilylation reaction, and Since each silicon atom has an organic group having an appropriate number of carbon atoms, the photocurable composition of the present disclosure and the cured product thereof have heat resistance, oxidation resistance, insulating property, and adhesion to a substrate. Contributes to improvement of sex and / or flexibility. In addition, the amount of hydrogen atoms remaining in the cured product of the photocurable composition of the present disclosure can be reduced.

The alkyl group having 1 to 10 carbon atoms may be either an aliphatic group or an alicyclic group, or may be linear or branched. Although not particularly limited, examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. From the viewpoint of heat resistance, a methyl group, an ethyl group and the like are preferable, and a methyl group is more preferable.

The aryl group having 6 to 10 carbon atoms is not particularly limited, but for example, a phenyl group or a group in which one or more of the hydrogen atoms of the phenyl group is substituted with an alkyl group having 1 to 4 carbon atoms. , And a naphthyl group and the like. From the viewpoint of heat resistance, it is preferably a phenyl group.

The aralkyl group having 7 to 10 carbon atoms is not particularly limited, and examples thereof include a group in which one of the hydrogen atoms of an alkyl group having 1 to 4 carbon atoms is substituted with an aryl group such as a phenyl group. Be done. For example, a benzyl group, a phenethyl group and the like can be mentioned, and from the viewpoint of heat resistance, a benzyl group is preferable.

Silsesquioxane derivative represented by Formula (1) is an organic group R ² as a whole may comprise two or more, in which case all the organic radicals R ² are to be the same to each other, It may be different.

The proportion of the constituent unit (d) in the silsesquioxane derivative according to the present disclosure is not particularly limited, but the molar ratio (x / (u + v + w + x + y + z)) to all the constituent units is the photocurable composition of the present disclosure. And the cured product thereof is preferably 0 to 0.7 in consideration of heat resistance, oxidation resistance, weather resistance and insulation resistance, and more in consideration of heat resistance, oxidation resistance and weather resistance as an insulating film. It is preferably 0.3 to 0.6.

1-5. The structural unit ^{_{(e) :( R 3 2 SiO}} 2/2) y
The structural unit (e) is _{a so-called D unit having two O 1/} 2s (one as an oxygen atom) for one silicon atom. The D unit means a unit having two _{O 1/2 for one silicon atom.}
To R ³ each independently presence of a plurality of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 6 to 10 carbon atoms an aryl group, an aralkyl group having 7 to 10 carbon atoms and hydrosilylatable carbon - it is at least one selected from the group consisting of organic groups having 2 to 12 carbon atoms having a carbon-carbon unsaturated bond, R ³ may be the same or different from each other more than one. Examples of each of these substituents include the same substituents as those exemplified for ^{R 1} of the structural unit (c) and R ^{2 of the structural unit (d) described above.}
Since the structural unit (e) is a D unit, it contributes to lowering the viscosity of the photocurable composition of the present disclosure and improving the flexibility, heat resistance, oxidation resistance and / or insulating property of the cured product. ..
Heat resistance, a raw material for ready availability, and from the viewpoint of imparting flexibility to the cured product, it is preferred that the multiple R ³ groups are each independently a methyl group and a phenyl group.

The ratio of the constituent unit (e) in the silsesquioxane derivative according to the present disclosure is not particularly limited, but in consideration of lowering the viscosity of the photocurable composition of the present disclosure and the weather resistance and flexibility of the cured product. Then, the molar ratio (y / (u + v + w + x)) to all Q units and T units is preferably 0 ≦ y / (u + v + w + x) ≦ 2.0, more preferably 0.1 to 1.0. More preferably, it is 0.1 to 0.5. However, when v = 0, at least one of the plurality of to R ⁴ in plurality of R ³ s and below the structural unit (f) is a hydrogen atom, when w = 0, R ³ there are a plurality of and at least one of R ⁴ is hydrosilylatable carbon - is an organic group having 2 to 12 carbon atoms having a carbon-carbon unsaturated bond.

1-6. The structural unit ^{_{(f) :( R 4 3 SiO}} 1/2) z
The structural unit (f) is a so-called M unit having one _{O 1/2 (0.5 as an oxygen atom) for one silicon atom.} The M unit means a unit having one _{O 1/2 for one silicon atom.}
To R ⁴ each independently presence of a plurality of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 6 to 10 carbon atoms an aryl group, an aralkyl group having 7 to 10 carbon atoms and hydrosilylatable carbon - it is at least one selected from the group consisting of organic groups having 2 to 12 carbon atoms having a carbon-carbon unsaturated bond, R ⁴ may be the same or different from each other more than one. Examples of each of these substituents include the same substituents as those exemplified for ^{R 1} of the structural unit (c) and R ^{2 of the structural unit (d) described above.}
Since the structural unit (f) is an M unit, it contributes to lowering the viscosity of the photocurable composition of the present disclosure and improving the flexibility and / or insulating property of the cured product.

M units in the silsesquioxane derivative according to the present disclosure, since the siloxane bond attached to a silicon atom is one, therefore flexibility is high, hydrogen atom or a hydrosilylation R ⁴ a plurality exists independently In the case of an organic group having a reactive carbon-carbon unsaturated bond, the hydrosilylation reactivity is generally higher and the curing reaction proceeds better than in the case where those groups are bonded to T units and D units. .. Further, R ⁴ in which there are a plurality each independently a hydrogen atom or a hydrosilylatable carbon - when an organic group having 2 to 12 carbon atoms having a carbon unsaturated bond, M units in the cured product of the siloxane since binding and via two bonding hydrosilylation crosslinking and thus incorporated into the backbone of the cured product, than when R ⁴ does not have such a group, the heat resistance and weather resistance of the cured product Is improved.
Of the three R ⁴ in this order structural unit (f), at least one is a hydrogen atom or a hydrosilylatable carbon - is preferably an organic group having 2 to 12 carbon atoms having a carbon-carbon unsaturated bond .. As the organic group having a carbon-carbon unsaturated bond capable of hydrosilylation reaction and having 2 to 12 carbon atoms, a vinyl group is preferable from the viewpoint of heat resistance and availability of a raw material.

Further, the flexibility of the cured product, from the viewpoint of improvement in heat resistance and weather resistance, of the three R ⁴ in the structural unit (f), at least one alkyl group having 1 to 10 carbon atoms, carbon atoms It is preferably at least one selected from the group consisting of an aryl group of 6 to 10 and an aralkyl group having 7 to 10 carbon atoms. From the viewpoint of heat resistance, easy availability of raw materials, and imparting flexibility to the cured product, methyl groups and phenyl groups are preferable.

The ratio of the constituent unit (f) in the silsesquioxane derivative according to the present disclosure is not particularly limited, but in consideration of lowering the viscosity of the photocurable composition of the present disclosure and the weather resistance and flexibility of the cured product. Then, the molar ratio (z / (u + v + w + x)) to all Q units and T units is preferably 0 ≦ z / (u + v + w + x) ≦ 2.0, more preferably 0.1 to 1.0, and further. It is preferably 0.1 to 0.5.
^{However, when v = 0, at least one of R 3} and R ⁴ in the above-mentioned structural unit (e) is a hydrogen atom, and when w = 0, at least one of ^{R 3} and R ^{4 is.} It is an organic group having 2 to 12 carbon atoms having a carbon-carbon unsaturated bond capable of hydrosilylation reaction.

1-7. Other structural units (g)
Silsesquioxane derivative according to the present disclosure may further comprise a structural unit containing no Si and ^(R _{5 O 1/2)} ^{(hereinafter,} referred to as structural unit (g)).
Wherein, R ⁵ is a hydrogen atom and / or an alkyl group having 1 to 6 carbon atoms may be any of aliphatic groups and alicyclic groups, also may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like.

This structural unit is an alkoxy group which is a hydrolyzable group contained in a raw material monomer described later, or an alkoxy group generated by substituting an alcohol contained in a reaction solvent with a hydrolyzable group of the raw material monomer. , It is a hydroxyl group that remains in the molecule without hydrolysis / polycondensation, or is a hydroxyl group that remains in the molecule without hydrolysis / polycondensation.

1-8. Hydrosilylatable carbon present in the silsesquioxane derivative according to functional groups present disclosure hydrosilylation - against one organic group having a carbon-carbon unsaturated bond, the ratio of the number of hydrogen atoms bonded to the silicon atom, Although not particularly limited, from the viewpoint of heat resistance, oxidation resistance and weather resistance of the cured product, it is preferably 0.5 to 5.0, more preferably 0.8 to 3.0, and even more preferably. It is 0.9 to 1.5.

1-9. Molecular weight and the like The weight average molecular weight (hereinafter referred to as “Mw”) of the silsesquioxane derivative according to the present disclosure is not particularly limited, but is preferably in the range of 300 to 30,000. The silsesquioxane derivative itself is a liquid, has a low viscosity suitable for handling, is easily dissolved in an organic solvent, is easy to handle the viscosity of the solution, and is excellent in storage stability. Mw is more preferably 500 to 15,000, still more preferably 700 to 10,000, and particularly preferably 1,000 to 5,000.
In addition, Mw in this disclosure means the value which converted the molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard substance. As the measurement condition of Mw, for example, the measurement condition in [Example] described later can be used.

The state of the silsesquioxane derivative according to the present disclosure is not particularly limited, and examples thereof include liquids, solids, and semi-solids. It is preferably a liquid, and its viscosity is not particularly limited, and the viscosity at 25 ° C. is preferably 1,000,000 mPa · s or less, more preferably 100,000 mPa · s or less, and further preferably 80. It is 000 mPa · s or less, and particularly preferably 50,000 mPa · s or less. The lower limit of the viscosity is not particularly limited, but is, for example, 1 mPa · s.
In the present disclosure, the viscosity means a value measured at 25 ° C. using an E-type viscometer (cone plate-type viscometer, for example, TVE22H-type viscometer manufactured by Toki Sangyo Co., Ltd.).

2. 2. Method for Producing Sylsesquioxane Derivative The silsesquioxane derivative according to the present disclosure can be produced by a known method. The method for producing the silsesquioxane derivative is described in International Publication No. 2005/01007, International Publication No. 2009/066608, International Publication No. 2013/099909, Japanese Patent Application Laid-Open No. 2011-052170 and Japanese Patent Application Laid-Open No. 2013-1476559. It is disclosed in detail as a method for producing polysiloxane in Japanese Patent Publication No.

The silsesquioxane derivative according to the present disclosure can be produced, for example, by the following method.
That is, the method for producing a silsesquioxane derivative according to the present disclosure is a condensation step in which a hydrolysis / polycondensation reaction of a raw material monomer giving a structural unit in the above formula (1) is carried out by condensation in an appropriate reaction solvent. Can be provided. In this condensation step, for example, a silicon compound having four siloxane bond-forming groups (hereinafter referred to as “Q monomer”) forming the structural unit (a) (Q unit) and the structural units (b) to ( d) A silicon compound having three siloxane bond-forming groups (hereinafter referred to as “T monomer”) that forms (T unit) and a siloxane bond-forming group that forms structural units (e) (D unit). A silicon compound (hereinafter referred to as "M monomer") that forms a structural unit (f) (M unit) having two silicon compounds (hereinafter referred to as "D monomer") and one siloxane bond-forming group. And can be used.

In the method for producing a silsesquioxane derivative according to the present disclosure, a raw material monomer is hydrolyzed and polycondensed in the presence of a reaction solvent, and then the reaction solvent, by-products, residual monomers, water and the like in the reaction solution are used. It is preferable to provide a distilling step for distilling off.

2-1. Raw Material Monomer The siloxane bond-forming group contained in the raw material Q monomer, T monomer, D monomer and M monomer is a hydroxyl group and / or a hydrolyzable group. Among these, examples of the hydrolyzable group include a halogeno group, an alkoxy group and a syroxy group. In the condensation step, the hydrolyzable group is preferably an alkoxy group, and more preferably an alkoxy group having 1 to 3 carbon atoms, because the hydrolyzable group is good and no acid is produced as a by-product. Further, in the M monomer, a siloxy group is preferable as the hydrolyzable group because of the availability of raw materials, and a disiloxane composed of two structural units (f) can be used.

In the condensation step, the siloxane bond-forming group of the Q monomer, T monomer and D monomer corresponding to each structural unit is preferably an alkoxy group, and the siloxane bond-forming group contained in the M monomer is an alkoxy group or a syroxy group. Is preferable. Further, the monomer corresponding to each structural unit may be used alone or in combination of two or more.

Examples of the Q monomer giving the structural unit (a) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
Examples of the T monomer giving the structural unit (b) include trimethoxysilane, triethoxysilane, tripropoxysilane, and trichlorosilane.
Examples of the T monomer giving the structural unit (c) include trimethoxyvinylsilane, triethoxyvinylsilane, trichlorovinylsilane, allyltrimethoxysilane, (p-styryl) trimethoxysilane, (p-styryl) triethoxysilane, and (3-methacryloyl). Oxypropyl) trimethoxysilane, (3-methacryloyloxypropyl) triethoxysilane, (3-acryloyloxypropyl) trimethoxysilane, (3-acryloyloxypropyl) triethoxysilane, (8-methacryloyloxyoctyl) trimethoxysilane And (8-acryloyloxyoctyl) trimethoxysilane and the like.
Examples of the T monomer giving the structural unit (d) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, and propyltriethoxy. Examples thereof include silane, butyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane.
Examples of the D monomer giving the structural unit (e) include dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, dipropoxydimethylsilane, dipropoxydiethylsilane, dimethoxymethylphenylsilane, and diethoxymethylphenylsilane. , Dimethoxydiphenylsilane, Diethoxydiphenylsilane, Dimethoxybenzylmethylsilane, Diethoxybenzylmethylsilane, Dichlorodimethylsilane, Dimethoxymethylsilane, Dimethoxyphenylsilane, Dimethoxymethylvinylsilane, Diethoxymethylsilane, Diethoxyphenylsilane and Diethoxymethyl Examples include vinylsilane.
As the M monomer giving the structural unit (f), hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, 1,1,3,3-tetramethyldi, which give two structural units (f) by hydrolysis, are used. In addition to siloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, methoxydimethylsilane, ethoxydimethylsilane, methoxydimethylvinylsilane, ethoxydimethylvinylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, methoxydimethylphenyl Examples thereof include silane, ethoxydimethylphenylsilane, chlorodimethylsilane, chlorodimethylvinylsilane, chlorotrimethylsilane, dimethylsilanol, dimethylvinylsilanol, trimethylsilanol, triethylsilanol, tripropylsilanol and tributylsilanol.
Examples of the compound that reacts with the raw material monomer to give a structural unit (g) include water and alcohols such as methanol, ethanol, 1-propanol, 2-propanol and 2-butanol.

The charging ratio of the Q monomer, T monomer, D monomer and M monomer which are the raw material monomers may be appropriately set according to the values of u to z of the target formula (1) in the present silsesquioxane derivative.

2-2. In the reaction solvent condensation step, alcohol can be used as the reaction solvent. The alcohol according to the present disclosure is an alcohol in a narrow sense represented by the general formula R-OH, and is a compound having no functional group other than an alcoholic hydroxyl group.
The alcohol is not particularly limited, but specific examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, and 2-methyl-2-butanol. , 3-Methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 2-methyl-3-pentanol, 3- Examples thereof include methyl-3-pentanol, 2-ethyl-2-butanol, 2,3-dimethyl-2-butanol, cyclohexanol and the like. Among these, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 3-methyl-2-pentanol And secondary alcohols such as cyclohexanol are preferably used.
In the condensation step, these alcohols can be used alone or in combination of two or more. A more preferred alcohol is a compound capable of dissolving water at the concentration required in the condensation step. An alcohol having such properties is a compound having a water solubility of 10 g or more in 100 g of alcohol at 20 ° C.

The alcohol used in the condensation step is 0.5% by mass or more based on the total amount of all reaction solvents, including the additional charge during the hydrolysis / polycondensation reaction. It is possible to suppress the gelation of the derivative. The amount used is preferably 1% by mass or more and 60% by mass or less, and more preferably 3% by mass or more and 40% by mass or less.

The reaction solvent used in the condensation step may be only alcohol, or may be a mixed solvent with at least one kind of auxiliary solvent. The auxiliary solvent may be either a polar solvent or a non-polar solvent, or may be a combination of both. Preferred polar solvents are secondary or tertiary alcohols having 3 or 7 to 10 carbon atoms and diols having 2 to 20 carbon atoms.

The non-polar solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, ethers, amides, ketones, esters, and cellosolves. Among these, aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons are preferable. The non-polar solvent is not particularly limited, but for example, n-hexane, isohexane, cyclohexane, heptane, toluene, xylene, methylene chloride and the like are preferable because they azeotrope with water, and these compounds are used in combination. After the condensation step, water can be efficiently distilled off from the reaction mixture containing the silsesquioxane derivative when the reaction solvent is removed by distillation. As the non-polar solvent, xylene, which is an aromatic hydrocarbon, is particularly preferable because it has a relatively high boiling point.

2-3. The water to be subjected to the hydrolysis reaction and the hydrolysis / polycondensation reaction in the catalytic condensation step proceed in the presence of water.
The amount of water used to hydrolyze the hydrolyzable group contained in the raw material monomer is preferably 0.5 to 5 times mol, more preferably 1 to 1 to the amount of substance (molar) of the hydrolyzable group. It is twice the mole.
Further, the hydrolysis / polycondensation reaction of the raw material monomer may be carried out without a catalyst or may be carried out using a catalyst. When a catalyst is used, an acid catalyst exemplified by an inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid; and an organic acid such as formic acid, acetic acid, oxalic acid and paratoluenesulfonic acid is preferably used.
The amount of the acid catalyst used is preferably an amount corresponding to 0.01 to 20 mol%, and corresponds to 0.1 to 10 mol%, based on the total amount (mol) of silicon atoms contained in the raw material monomer. It is more preferable that the amount is to be used.

2-4. The end of the hydrolysis / polycondensation reaction in the other additive condensation steps can be appropriately detected by the methods described in various publications and the like. In the condensation step of the production of the silsesquioxane derivative according to the present disclosure, an auxiliary agent can be added to the reaction system.
Examples thereof include a defoaming agent that suppresses foaming of the reaction solution, a scale control agent that prevents scale from adhering to the reaction tank and the stirring shaft, a polymerization inhibitor, a hydrosilylation reaction inhibitor, and the like. The amount of these auxiliaries used is arbitrary, but is preferably about 1 to 100% by weight based on the concentration of the silsesquioxane derivative according to the present disclosure in the reaction mixture.

2-5. Distillation of reaction solvent, etc. After the condensation step in the production of the silsesquioxane derivative according to the present disclosure, the reaction solvent and by-products, residual monomers, water, catalyst and the like contained in the reaction solution obtained by the condensation step are distilled off. By providing the distillation step, the stability of the produced silsesquioxane derivative according to the present disclosure can be improved. Distillation can be carried out under normal pressure or reduced pressure, at room temperature or under heating, and can also be carried out under cooling.

3. 3. Hydrosilylation Catalyst The photocurable compositions of the present disclosure include a hydrosilylation catalyst containing a transition metal. As a result, the silsesquioxane derivative can be photocured.
The transition metal contained in the hydrosilylation catalyst is not particularly limited, and is, for example, a simple substance of a group 8 to 10 metal such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or a metal complex. , Metal salts, metal oxides and the like.
The hydrosilylation catalyst preferably contains one or more platinum group metals composed of ruthenium, rhodium, palladium, osmium, iridium and platinum, and is a catalyst containing platinum from the viewpoint of reactivity and availability. Is more preferable, and more preferably a platinum complex.
The platinum complex, beta-diketonate platinum complexes, (.eta. cyclopentadienyl) trialkyl platinum complexes, (η ⁴ -1,5- cyclooctadiene) diaryl platinum complexes and a dialkyl azodicarboxylate platinum complex It is preferably at least one selected from the group consisting of classes. The platinum complexes are particularly preferably β-diketonato platinum complexes represented by the following formula (2), (η-cyclopentadienyl) trialkyl platinum complexes represented by the following formula (3), and the following formula. comprising represented by (eta ^{4-1,5-cyclooctadiene)} diaryl platinum complexes with (4), and dialkyl azodicarboxylate represented by the following formula (5) as a ligand, the dialkyl azodicarboxylate Lat platinum complexes.

[In the formula (2), R ⁶ and R ⁷ are each independently selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group, and may be the same or different from each other, and are R ⁸ and R. ⁹ , R ¹⁰ and R ¹¹ are each independently selected from the group consisting of an alkyl group, an aryl group and an alkoxy group, and may be the same or different from each other. ]

(In formula (3), Cp is a cyclopentadienyl group η-bonded to a platinum atom and may or may not be substituted with a substituent, and R ¹² , R ¹³ and R ¹⁴ are independent of each other. It represents an aliphatic group having 1 to 18 carbon atoms bonded to a platinum atom by σ-, and may be the same or different from each other.]

[In formula (4), R ¹⁵ is a linear, branched or cyclic alkadiene group π-bonded to a platinum atom, and may or may not have a substituent, respectively, and R ¹⁷ and R ¹⁸ are independent of each other. It is an aryl group σ-bonded to a platinum atom and may or may not have a substituent, and may be the same or different from each other. R ¹⁶ and R ¹⁹ are independently hydrogen atoms, alkyl groups, alkoxy groups and It is at least one selected from the group consisting of halogen atoms, and may be the same or different from each other, may be substituted at any position of the aryl group, and may be substituted with a plurality of substituents, respectively. ]

[In the formula (5), each of the plurality of R ^20s independently represents a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different from each other. ]
In the formula (5), only the ligand is described, and the description of the platinum atom is omitted.

Specific examples of the β-diketonato platinum complexes represented by the formula (2) include bis (acetylacetonato) platinum (II).
Specific examples of the (η-cyclopentadienyl) trialkyl platinum complexes represented by the above formula (3) include trimethyl (methylcyclopentadienyl) platinum (IV) and (cyclopentadienyl) trimethyl platinum. (IV) and the like.
Represented by the formula (4) Specific examples of (eta ^{4-1,5-cyclooctadiene)} diaryl platinum complexes, (eta ^{4-1,5-cyclooctadiene)} bis (4-methoxyphenyl) Platinum (II) and the like can be mentioned.
Specific examples of the platinum complexes containing the dialkylazodicarboxylate represented by the formula (5) as a ligand include diethylazodicarboxylate platinum (II).
Among these compounds, bis (acetylacetonato) platinum (II) and trimethyl (methylcyclopentadienyl) platinum (IV) are more preferable.

The content ratio of the transition metal is not particularly limited, but is preferably 0.1 to 30,000 ppm by weight, preferably 1.0 to 100 parts by weight, based on 100 parts by weight of the total amount of the silsesquioxane derivatives according to the present disclosure. It is more preferably ~ 10,000 ppm by weight, and even more preferably 10 to 2,000 ppm by weight.

4. Photocurable Composition The photocurable composition of the present disclosure (hereinafter, also referred to as “the composition of the present disclosure”) contains a silsesquioxane derivative and a hydrosilylation catalyst according to the present disclosure.
The composition of the present disclosure has excellent fluidity and, as will be described later, excellent heat resistance and insulating properties of the cured product, and thus is a good insulating material for insulating elements that require heat resistance. In addition, the composition of the present disclosure can be used as an adhesive composition or a binder composition because it can exhibit good curability and adhesiveness by itself.
The composition of the present disclosure contains the silsesquioxane derivative and a hydrosilylation catalyst, but may contain various components (hereinafter, referred to as "other components"), if necessary.
As other components, a heat resistance improver, a hydrosilylation reaction inhibitor, a solvent and the like are preferable.
Hereinafter, other components will be described.

4-1. Heat resistance improver The composition of the present disclosure may contain a heat resistance improver.
The heat resistance improving agent is not particularly limited, and known ones can be used. For example, iron 2-ethylhexanoate such as iron (III) tris (2-ethylhexanoic acid) and tris (2-ethylhexanoic acid) can be used. ) Cerium 2-ethylhexanoate such as cerium (III), and zirconium 2-ethylhexanate such as tetra (2-ethylhexanoic acid) zirconium (IV) and bis (2-ethylhexanoic acid) zirconium oxide (IV). Examples thereof include organic carboxylic acid metal salts such as, and metal oxides such as iron oxide, cerium oxide and zirconium oxide.
The proportion of the heat resistance improving agent used is not particularly limited, but is, for example, 0 to 10,000 wt ppm, preferably 1 to 1, with respect to 100 parts by weight of the total amount of the silsesquioxane derivative according to the present disclosure. It is 000 ppm by weight, more preferably 5 to 500 ppm by weight, and even more preferably 10 to 300 ppm by weight.
By adding a heat resistance improving agent, the temperature for reducing the heat weight is improved or suppressed, the relative dielectric constant is suppressed from being lowered, the insulating property is suppressed from being lowered, and the generation of cracks is suppressed during use and storage under heating and at room temperature. , And color suppression and the like can be performed.

4-2. Hydrosilylation Reaction Inhibitor The composition of the present disclosure can include a hydrosilylation reaction inhibitor.
By doing so, the storage stability of the composition of the present disclosure can be improved. The hydrosilylation reaction inhibitor is not particularly limited, and examples thereof include compounds that can coordinate with the hydrosilylation catalytic metal, such as vinylsiloxanes such as methylvinyltetrasiloxane and 2-methyl-3-butin-2-ol. Examples thereof include acetylene alcohols such as acetylene alcohols, siloxane-modified acetylene alcohols, hyperoxides, and known hydrosilylation reaction inhibitors containing a nitrogen atom, a sulfur atom or a phosphorus atom. Among these, the group having a carbon-carbon triple bond disclosed in Japanese Patent Application Laid-Open No. 2010-143973 is a group having a carbon-carbon triple bond, which has an appropriate reaction suppressing effect, low volatility, and suppresses odor and coloring. A siloxane compound having a structure bonded to a silicon atom is preferable.
The ratio of the hydrosilylation reaction inhibitor to be used is not particularly limited, but is, for example, 0 to 5.0% by weight, preferably 0 to 2% based on 100 parts by weight of the total amount of the silsesquioxane derivatives according to the present disclosure. It is 0.0% by weight, more preferably 0 to 1.0% by weight.

4-3. Solvent The composition of the present disclosure can be applied as it is to the surface of a substrate as long as it is a liquid substance, but it can also be diluted with a solvent and used if necessary. When a solvent is used, a solvent that dissolves the silsesquioxane derivative according to the present disclosure is preferable, and for example, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a chlorinated hydrocarbon solvent, an alcohol solvent, an ether solvent, etc. Various organic solvents such as amide solvent, ketone solvent, ester solvent and cellosolve solvent can be mentioned.
When a solvent is used, it is preferable to volatilize the solvent contained in the applied film prior to curing the composition of the present disclosure. The solvent may be volatilized in the atmosphere or in an atmosphere of an inert gas such as nitrogen. It may be heated because of the volatilization of the solvent, but the heating temperature in that case is preferably less than 100 ° C.

4-4. Other Ingredients Other Ingredients The compositions of the present disclosure may also contain components other than the above-mentioned components as other components, if necessary.
Specifically, surfactants, antistatic agents (for example, conductive polymers), leveling agents, photosensitizers, ultraviolet absorbers, antioxidants, stabilizers, lubricants, etc. It can contain any other auxiliary agents such as pigments, dyes, plastics, suspending agents, nanoparticles, nanofibers, nanosheets and fillers. Further, it can also contain a silane-based reactive diluent such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes and disiloxanes.
Further, other photocurable compounds such as radical curable compounds and cationic curable compounds can be contained, and a photopolymerization initiator for that purpose can also be contained.

5. Cured product The cured product of the present disclosure is a cured product obtained by curing the above-mentioned composition of the present disclosure.

5-1. Physical characteristics of the cured product The cured product of the present disclosure has excellent heat resistance. The index of heat resistance is not particularly limited, and examples thereof include thermal weight reduction temperature, relative permittivity, insulating property, coloring, adhesiveness, adhesiveness, light transmittance, and crack generation.

5-1-1. Thermogravimetric reduction temperature The cured product of the present disclosure has excellent heat resistance and a high thermogravimetric reduction temperature. The thermal weight reduction temperature can be determined by thermogravimetric differential thermal analysis (hereinafter referred to as TG / DTA). The measurement atmosphere is not particularly limited, and the measurement can be performed in the atmosphere or in an atmosphere of an inert gas such as nitrogen. The measurement atmosphere is appropriately selected in consideration of the environment in which the cured product of the present disclosure is used, but it is preferable to measure in the atmosphere. The rate of temperature rise at the time of measurement is not particularly limited and may be, for example, 5, 10 or 20 ° C./min. Considering that the measurement can be performed in a short time, 20 ° C./min is preferable. The index of the weight loss temperature is not particularly limited, and may be, for example, the temperature at the time when a certain percentage of the original weight is reduced, such as the weight loss start temperature and the 1, 5 or 10% weight loss temperature. It can also be expressed as a weight loss rate at a certain temperature, for example, a weight loss rate at 400 ° C.

The 5% weight loss temperature of the cured product of the present disclosure measured at 20 ° C./min is, for example, 300 ° C. or higher, preferably 370 ° C. or higher, more preferably 400 ° C. or higher, and particularly preferably. It is 500 ° C. or higher.

5-1-2. Relative Permittivity The cured product of the present disclosure has a low relative permittivity and is excellent in insulation in a wide frequency band. The relative permittivity of the cured product of the present disclosure is not particularly limited, but is, for example, 4.0 or less, preferably 3.6 or less, and more preferably 3.5 or less. The frequency band in which the relative permittivity is used is not particularly limited, and is, for example, 1 kHz to 100 GHz, preferably 1 kHz to 1 GHz, and more preferably 1 kHz to 10 MHz. For example, the cured product of the present disclosure has a relative permittivity of 4.0 or less at 1 MHz.
When the value of the relative permittivity is compared between the cured products, the measurement frequency is not particularly limited, but for example, the relative permittivity at 1 kHz, 10 kHz, 100 kHz, 1 MHz, 10 MHz, 1 GHz, etc. is measured and the cured product is used. Insulation properties can be compared. Further, the insulating property can be evaluated by showing that the relative permittivity is equal to or less than a certain value over a certain frequency band. The frequency band is not particularly limited, but for example, the relative permittivity in 1 kHz to 10 MHz can be shown.
The relative permittivity in the present disclosure means a value measured at room temperature (23 ° C. ± 2 ° C.).

As described above, the cured product of the present disclosure has a low relative permittivity and is excellent in insulating properties in a wide frequency band. Therefore, the cured product of the present disclosure can be an insulating film.
The cured product (insulating film) of the present disclosure is obtained by curing the composition of the present disclosure, and the curing means is not particularly limited, but for example, it may be cured by irradiating with ultraviolet rays. The details of the curing means will be described in "Method for producing a cured product" described later.

6. Method for Producing Cured Product The method for producing a cured product (insulating film) of the present disclosure includes a step of irradiating the composition of the present disclosure with ultraviolet rays to cure it. The obtained cured product (insulating film) may be the cured product (insulating film) of the present disclosure described above.
When the composition of the present disclosure is cured, for example, the composition of the present disclosure is applied to an appropriate substrate and then irradiated with light such as ultraviolet rays to promote the hydrosilylation reaction and cure.
The composition of the present disclosure may or may not contain a solvent, and when it contains a solvent, it is preferable to remove the solvent and then subject it to photocuring or the like as described above.

6-1. Coating Method When the composition of the present disclosure is coated on a substrate and used, the coating method is not particularly limited, and for example, a casting method, a spin coating method, a bar coating method, a dip coating method, a spray coating method, and a roll coating method are used. Ordinary coating methods such as a method, a flow coating method and a gravure coating method can be used.
The thickness of the composition of the present disclosure is not particularly limited, and is appropriately set according to the intended purpose.
The base material to which the composition of the present disclosure can be applied is not particularly limited and can be applied to various materials, and examples thereof include wood, metal, inorganic materials, plastics, paper, fibers and fabrics.
Examples of the metal include copper, silver, iron, aluminum, silicon, silicon steel and stainless steel. Examples of the inorganic material include metal oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, zinc oxide, indium tin oxide and gallium oxide, metal nitrides such as aluminum nitride, gallium nitride and silicon nitride, silicon carbide and nitrided materials. Examples thereof include ceramics such as boron, mortar, concrete and glass. Specific examples of plastics include acrylic resins such as polymethylmethacrylate, polyester resins such as polyethylene terephthalate, polyvinyl chloride resins, polycarbonate resins, epoxy resins, polyamide resins such as nylon and aramid, polyimide resins, polyamideimide resins, and 4 hooks. Examples thereof include a fluororesin such as an ethylene resin, a polyolefin resin such as a crosslinked polyethylene resin, a composite resin such as polychloroprene, polyphenylene sulfide, polysulphon, polyether sulfone, polyether ether ketone, polyurethane resin and glass epoxy resin. Examples of the fiber include natural fiber, regenerated fiber, semi-synthetic fiber, metal fiber, glass fiber, carbon fiber, ceramic fiber, known chemical fiber and the like. The cloth may be a woven cloth or a non-woven fabric, and can be produced by using, for example, the above-mentioned fibers.
These materials may be used alone, or may be used in combination of two or more, mixed, or combined.
The shape of the base material is not particularly limited, and examples thereof include plates, sheets, films, rods, spheres, fibers, powders, and structures having complicated shapes.

6-2. Curing method An active energy ray can be irradiated to cure the composition of the present disclosure, and examples of the active energy ray include electron beam, ultraviolet light, visible light, X-ray, and the like, which are preferable. Is light, and ultraviolet light is more preferred because inexpensive equipment can be used.
Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED.
The irradiation energy should be appropriately set according to the type of active energy ray and the composition of the compound. For example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region (315 nm to 400 nm) is 0. .1 to 30 J / cm ² is preferable, 0.5 to 20 J / cm ² is more preferable, and 1.0 to 15 J / cm ² is further preferable.

Further, heat curing can be appropriately combined before and / or after photo-curing.
For example, the composition of the present disclosure is impregnated into a substrate having a shaded portion when irradiated with light, and then the composition of the present disclosure of the portion exposed to the light is first cured by irradiating with light. Then, it is also possible to perform two-step curing in which heat is applied to cure the composition of the present disclosure in a portion not exposed to light. Such a base material is not particularly limited, and examples thereof include a base material having a complicated shape such as a cloth-like shape, a fibrous shape, a powder-like shape, a porous shape, and an uneven shape, and two or more of these shapes are mentioned. May be a combined shape.

7. Applications The cured product of the composition of the present disclosure is excellent in heat resistance, oxidation resistance, weather resistance, hardness, transparency, and flexibility, and the material having the cured film of the composition of the present disclosure has this property. It can be used for various purposes by making the best use of.
For example, it can be used in various industrial product fields such as electrical and electronic fields. In particular, specific examples of preferable applications include lighting devices such as LED lighting and organic EL lighting, electronic circuit boards such as semiconductor modules, printed wiring boards and flexible wiring boards, and electric rotating devices such as small motors and in-vehicle motors. Examples thereof include power supply devices such as transformers, power storage devices such as lithium batteries, and power generation devices such as solar panels.
For example, a composite material having a cured product of the composition of the present disclosure and the above-mentioned base material is useful as a heat-resistant insulating member. As the base material, the base material described in the above-mentioned "6. Method for producing a cured product" can be used.

Next, the present disclosure will be specifically described based on Examples and Comparative Examples, but the present disclosure is not limited to the following Examples.
The Mw (weight average molecular weight) is the GPC columns "TSK gel G4000HX" and "TSK gel G2000HX" linked at 40 ° C. in a toluene solvent by a gel permeation chromatography method (hereinafter referred to as "GPC"). (Model name, manufactured by Toso Co., Ltd.) was used for separation, and the molecular weight was calculated using standard polystyrene from the retention time.
The molar ratio of each constituent unit of the obtained silsesquioxane derivative is calculated by dissolving the sample in deuterated chloroform, ^{performing 1} H-NMR analysis, and further ^{performing 29} Si-NMR analysis as necessary. did. The alkoxysilane monomer reacted quantitatively and was introduced into the silsesquioxane derivative, but the M unit derived from the disiloxane monomer was not quantitatively introduced depending on the composition of the silsesquioxane derivative.

[Synthesis of silsesquioxane derivative]
<Synthesis example 1>
Trimethoxyvinylsilane (7.4 g, 50 mmol), methyltriethoxysilane (26.7 g, 150 mmol), dimethoxydimethylsilane (3.) in a 200 mL four-necked round-bottom flask equipped with a thermometer, dropping funnel and stirring blade. 0 g, 25 mmol), 1,1,3,3-tetramethyldisiloxane (3.4 g, 25 mmol), xylene (15 g) and 2-propanol (15 g) were weighed and stirred well in a water bath at about 20 ° C. Here, a solution prepared by separately mixing 1 mol / L hydrochloric acid aqueous solution (0.45 g, 4.4 mmol), pure water (11.4 g) and 2-propanol (4.5 g) was added from a dropping funnel. The solution was added dropwise in about 1 hour, and stirring was continued overnight at room temperature. The solvent and the like were removed from the obtained solution at 60 ° C. under reduced pressure to obtain 119 g of a silsesquioxane derivative as a colorless and transparent liquid.

<Synthesis example 2>
Syl except that allyltrimethoxysilane (50 mmol), phenyltrimethoxysilane (150 mmol), dimethoxydiphenylsilane (25 mmol) and 1,1,3,3-tetramethyldisiloxane (25 mmol) were used as raw material silane monomers. By performing the same operation as that of the sesquioxane derivative 1, the silanesquioxane derivative 2 was obtained as a colorless and transparent liquid.

<Synthesis example 3>
Sylsesquioki, except that triethoxysilane (150 mmol), trimethoxyvinylsilane (50 mmol), dimethoxydimethylsilane (25 mmol) and 1,1,3,3-tetramethyldisiloxane (50 mmol) were used as raw material silane monomers. By performing the same operation as the sun derivative 1, silsesquioxane derivative 3 was obtained as a colorless and transparent liquid.

<Synthesis example 4>
The same operation as for silsesquioxane derivative 1 except that triethoxysilane (150 mmol), trimethoxyvinylsilane (50 mmol) and 1,1,3,3-tetramethyldisiloxane (50 mmol) were used as the raw material silane monomer. To obtain silsesquioxane derivative 4 as a colorless and transparent liquid.

<Synthesis Example 5>
Other than using triethoxysilane (150 mmol), trimethoxyvinylsilane (25 mmol), (p-styryl) trimethoxysilane (25 mmol) and 1,1,3,3-tetramethyldisiloxane (50 mmol) as raw material silane monomers. Obtained the silanesquioxane derivative 5 as a colorless and transparent liquid by performing the same operation as that of the sylsesquioxane derivative 1.

<Synthesis example 6>
Sylsesquioxane except that triethoxysilane (200 mmol), dimethoxymethylsilane (75 mmol) and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (50 mmol) were used as raw material silane monomers. By performing the same operation as that of the derivative 1, the silsesquioxane derivative 6 was obtained as a colorless and transparent liquid.

<Synthesis example 7>
A colorless and transparent liquid by performing the same operation as the silsesquioxane derivative 1 except that triethoxysilane (100 mmol), trimethoxyvinylsilane (100 mmol) and dimethoxymethylsilane (100 mmol) were used as the raw material silane monomer. As a result, a silsesquioxane derivative 7 was obtained.

<Synthesis Example 8>
By performing the same operation as the silsesquioxane derivative 1 except that triethoxysilane (150 mmol) and trimethoxyvinylsilane (120 mmol) were used as the raw material silane monomer, the silsesquioxane derivative 8 was used as a colorless and transparent liquid. Got

<Synthesis example 9>
Silsesquioki, except that triethoxysilane (150 mmol), trimethoxyvinylsilane (50 mmol), phenyldimethoxysilane (25 mmol) and 1,1,3,3-tetramethyldisiloxane (50 mmol) were used as raw material silane monomers. By performing the same operation as the sun derivative 1, silsesquioxane derivative 9 was obtained as a colorless and transparent liquid.

<Synthesis Example 10>
As raw material silane monomers, tetramethoxysilane (100 mmol), dimethoxydimethylsilane (100 mmol), 1,1,3,3-tetramethyldisiloxane (12.5 mmol) and 1,3-divinyl-1,1,3,3 -By carrying out the same operation as that of the silsesquioxane derivative 1 except that tetramethyldisiloxane (12.5 mmol) was used, the silsesquioxane derivative 10 was obtained as a colorless and transparent liquid.

<Synthesis Example 11>
As the raw material silane monomer, tetramethoxysilane (90 mmol), triethoxysilane (36 mmol), trimethoxyvinylsilane (30 mmol), dimethoxydimethylsilane (36 mmol), 1,1,3,3-tetramethyldisiloxane (7.5 mmol) And 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (22.5 mmol) was used, but the same operation as that of silsesquioxane derivative 1 was carried out to obtain a colorless semi-solid. A silsesquioxane derivative 11 was obtained.

The compositions of Synthesis Examples 1 to 11, Mw, and the molar ratio of each introduced constituent unit are summarized in Tables 1 and 2.

<Reference example 1>
[Synthesis of 3-acryloyloxypropylsilsesquioxane]
By performing the same operation as the silsesquioxane derivative 1 except that (3-acryloyloxypropyl) trimethoxysilane was used as the raw material silane monomer and only 2-propanol was used as the reaction solvent, a colorless and transparent liquid was used. As a result, 3-acryloyloxypropylsilsesquioxane was obtained. Mw was 2370.
<Reference example 2>
AC-SQ SI-20 (composite derivative of 3-acryloyloxypropylsilsesquioxane and silicone) manufactured by Toagosei Co., Ltd. was used as it was.

<Example 1>
(1) Preparation of Photocurable Composition Weighing 10 g of the silsesquioxane derivative obtained in Synthesis Example 1 and 10 mg of _{bis (acetylacetonato) platinum (II) (hereinafter referred to as Pt (acac) 2).} Then, it was dissolved by stirring with a rotation / revolution mixer.
(2) Confirmation of Photohydrosilylation Curability The photocurable composition of (1) described above was applied to a copper plate with a bar coater to form a film having a thickness of about 100 μm. Then, ultraviolet irradiation was performed under the following conditions, and it was confirmed that the surface tack was eliminated. Furthermore, the film formed from the copper plate was peeled off, and FT-IR (Fourier transform infrared spectroscopy) analysis (Spectrum 100 manufactured by PerkinElmer) confirmed that the hydrosilylation group and vinyl group were reduced and the hydrosilylation reaction proceeded. did.
[Ultraviolet irradiation conditions]
Lamp: 80W / cm High pressure mercury lamp Lamp height: 10cm
Conveyor speed: 4.5m / min
Integrated light intensity per pass: 990 mJ / cm ²
Atmosphere: Atmospheric Pass Count: 10 times

<Example 2>
[Preparation of photocurable composition and confirmation of photocurability]
Using the silsesquioxane derivative 2 obtained in Synthesis Example 2, a photocurable composition was prepared in the same manner as in Example 1 (1). It was subjected to the same photocuring as in Example 1 (2), and it was confirmed that the photohydrosilylation reaction proceeded to give a cured product.

<Examples 3 to 11>
[Preparation of photocurable composition and confirmation of photocurability]
Using the silsesquioxane derivatives 3 to 11 obtained in Synthesis Examples 3 to 11, each photocurable composition was prepared in the same manner as in Example 1 (1). They were subjected to the same photocuring as in Example 1 (2) except that they were subjected to the following ultraviolet irradiation conditions, and it was confirmed that the photohydrosilylation reaction proceeded in each case to give a cured product.
[Ultraviolet irradiation conditions]
Lamp: 80W / cm High pressure mercury lamp Lamp height: 10cm
Conveyor speed: 10m / min
Integrated light intensity per pass: 210 mJ / cm ²
Atmosphere: Atmospheric Pass Count: 30 times

<Example 12>
Heat resistance evaluation of cured product Using the silsesquioxane derivative 1 obtained in Synthesis Example 1, the photocurable composition prepared in Example 1 (1) was used as the substrate of Example 1 (2). Was replaced with a PET film, and a photohydrosilylated cured product was prepared in the same manner as in Example 1 (2). The obtained cured product was peeled off from the PET film and subjected to thermal weight differential thermal analysis (hereinafter referred to as TG / DTA) (TG / DTA6300 manufactured by Seiko Instruments, Inc., in the air, heating rate 20 ° C./min). As a result of determining the 5% weight loss temperature (hereinafter _{referred to as T d5} ), it was 396 ° C.

<Examples 13 to 16>
[Evaluation of heat resistance of cured product]
Using the silsesquioxane derivatives 3, 4, 7 and 10 obtained in Synthesis Examples 3, 4, 7 and 10, the photocurable compositions prepared in Examples 3, 4, 7 and 10 were used. The TG / DTA of the cured product was measured in the same manner as in Example 12, and each T _d5 was determined.

Table 3 summarizes _{T d5} obtained in Examples 12 to 16.

<Example 17>
Relative permittivity measurement of cured product Using the silsesquioxane derivative 1 obtained in Synthesis Example 1, the photocurable composition prepared in Example 1 (1) was prepared using a silicone rubber sheet having a thickness of 1 mm. A hole having a size of 40 mm × 40 mm was cut out and poured into a mold, sandwiched between a PET film and white plate glass, and a photohydrosilylated cured product was prepared under the same ultraviolet irradiation conditions as in Example 1 (2).
The obtained cured product was subjected to a relative permittivity measurement (impedance analyzer 4294A manufactured by Agilent Technologies), and the relative permittivity was measured at room temperature (23 ° C.). As a result, the relative permittivity at 1 MHz was 3.38. rice field. Table 4 shows the relative permittivity at 1 MHz and the relative permittivity at other frequency bands.

<Example 18>
Relative permittivity measurement of cured product Using the silsesquioxane 4 obtained in Synthesis Example 4, the photocurable composition prepared in Example 4 was used, and the relative permittivity was measured in the same manner as in Example 17. As a result, the relative permittivity at 1 MHz was 3.28. Table 4 shows the relative permittivity at 1 MHz and the relative permittivity at other frequency bands.

<Comparative Example 1>
Add 0.3 g of 2-Hydroxy-2-methylpropiophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) to 10 g of 3-acryloyloxypropylsilsesquioxane obtained in Reference Example 1 and stir to dissolve to prepare a photocurable composition. did. This was applied on a PET film with a bar coater to form a film having a thickness of about 10 μm. Then, ultraviolet irradiation was performed under the following conditions to prepare a cured product.
[Ultraviolet irradiation conditions]
Lamp: 80W / cm High pressure mercury lamp Lamp height: 10cm
Conveyor speed: 10 m / min Cumulative light intensity per pass of irradiation: 210 mJ / cm ²
Atmosphere: Number of passes in the atmosphere: 30 times T _d5 (in the atmosphere) determined in the same manner as in Example 12 was 360 ° C.
Further, the relative permittivity at 1 MHz obtained in the same manner as in Example 17 was 4.24. Table 4 shows the relative permittivity at 1 MHz and the relative permittivity at other frequency bands.

<Comparative Example 2>
A cured product was prepared in the same manner as in Comparative Example 1 except that AC-SQ SI-20 of Reference Example 2 was used, and the relative permittivity was measured with _{T d5 (in the atmosphere) of the cured product.} T _d5 (in the atmosphere) was 340 ° C. and the relative permittivity at 1 MHz was 4.31. Table 4 shows the relative permittivity at 1 MHz and the relative permittivity at other frequency bands.

The photohydrosilylation-curable composition of the present disclosure has good photocurability, has a wider range of applicable base materials than known thermohydrosilylation-curable compositions, and can be applied to various applications. It becomes.
_{Further, the T d5} of the photohydrosilylated cured product of the present disclosure is compared with the cured product (Comparative Examples 1 and 2) of the photoradical curable composition, which is a typical example of the conventional photocurable silsesquioxane derivative. Very high and has excellent heat resistance.
Further, the relative permittivity of the photohydrosilylated cured product of the present disclosure is much lower than that of the cured product of the photoradical curable composition (Comparative Examples 1 and 2), and the insulating property is excellent at any measured frequency. ing. Further, in the measured wide frequency band of 1 kHz to 10 MHz, the relative permittivity of the photohydrosilylated cured product of the present disclosure is 3.5 or less, and the photohydrosilylated cured product of the present disclosure has high heat resistance and excellent insulation. Has sex.

The photocurable composition of the present disclosure is a liquid composition that is useful for forming a heat-resistant film and is easy to apply and fill in any shape. It can be cured at room temperature, and has water resistance and chemical resistance. Since it is possible to form a film having various properties such as stability, electrical insulation, and mechanical strength such as scratch resistance, it is possible to form a film, etc., in the fields of electronics, optical functional materials, mobility, aerospace, and building materials. It can be used as a film or layer for articles or parts in a wide range of fields including fields. It can be used for forming passivation films, resist films, interlayer insulating films, various protective films and the like in semiconductors and the like. The photocurable composition and the cured product thereof disclosed in the present disclosure are useful in various fields in which both high heat resistance and insulating properties are required in the future.

The disclosure of Japanese Patent Application No. 2020-106880 filed June 22, 2020 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated by reference herein.

Claims (11)

1. A photocurable composition containing a silsesquioxane derivative represented by the following formula (1) and a hydrosilylation catalyst containing a transition metal.
   

   

   
   [In equation (1),
   R ¹ is an organic group having a carbon-carbon unsaturated bond capable of hydrosilylation reaction and having 2 to 12 carbon atoms.
   R ² is at least one selected from the group consisting of an alkyl group, an aralkyl group of aryl and 7 to 10 carbon atoms of 6 to 10 carbon atoms in the 1 to 10 carbon atoms,
   A plurality of R ³ and R ⁴ are independently capable of hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and a hydrosilylation reaction. It is at least one selected from the group consisting of organic groups having 2 to 12 carbon atoms having a carbon-carbon unsaturated bond.
   There exist a plurality of R ³ may be the same or different from each other,
   The R ⁴ presence of a plurality may be the same or different from each other,
   u, v, w and x are independently 0 or positive numbers, and at least one of them is a positive number.
   y and z are independently 0 or positive numbers, respectively.
   0 ≦ y / (u + v + w + x) ≦ 2.0,
   0 ≦ z / (u + v + w + x) ≦ 2.0,
   However, when v = 0, ^{at least one of a plurality of R 3} and R ⁴ is a hydrogen atom, and when w = 0, at least one of ^{a plurality of R 3} and R ^{4 is a hydrosilyl.} It is an organic group having 2 to 12 carbon atoms having a carbon-carbon unsaturated bond capable of undergoing a conversion reaction. ]
2. The ratio of the number of hydrogen atoms bonded to silicon atoms to one organic group having a hydrosilylation-reactive carbon-carbon unsaturated bond present in the silsesquioxane derivative is 0.5 to 5.0. The photocurable composition according to claim 1.
3. The photocurable composition according to claim 1 or 2, wherein the content ratio of the transition metal is 0.1 to 30,000 ppm by weight with respect to 100 parts by weight of the silsesquioxane derivative.
4. The photocurable composition according to any one of claims 1 to 3, wherein the transition metal is a platinum group metal.
5. Hydrosilylation catalyst containing the transition metal, beta-diketonate platinum complexes, (.eta. cyclopentadienyl) trialkyl platinum complexes, (η ⁴ -1,5- cyclooctadiene) diaryl platinum complexes and dialkyl azo The photocurable composition according to any one of claims 1 to 4, which is at least one selected from the group consisting of dicarboxylate platinum complexes.
6. The photocurable composition according to any one of claims 1 to 5, further comprising a heat resistance improver.
7. A cured product obtained by curing the photocurable composition according to any one of claims 1 to 6.
8. The cured product according to claim 7, wherein the relative permittivity at 1 MHz is 4.0 or less.
9. The cured product according to claim 7 or 8, wherein the 5% weight loss temperature in the atmosphere in thermogravimetric analysis is 300 ° C. or higher.
10. The cured product according to any one of claims 7 to 9, which is an insulating film.
11. A method for producing a cured product, which comprises a step of irradiating the photocurable composition according to any one of claims 1 to 6 with ultraviolet rays to cure the photocurable composition.