WO2020230786A1

WO2020230786A1 - Curable composition and cured product of same

Info

Publication number: WO2020230786A1
Application number: PCT/JP2020/018978
Authority: WO
Inventors: 大澤歩; 芝本明弘; 三宅弘人; 原田美由紀
Original assignee: 学校法人関西大学; 株式会社ダイセル
Priority date: 2019-05-13
Filing date: 2020-05-12
Publication date: 2020-11-19
Also published as: JPWO2020230786A1

Abstract

The purpose of this invention is to provide a curable composition with which it is possible to form a cured product exhibiting outstanding heat resistance and mechanical properties. This invention provides a curable composition comprising: an epoxy compound (A) having a mesogenic group; and a polyorganosilsesquioxane (B) having an epoxy group. The epoxy compound (A) having a mesogenic group preferably contains a compound represented by formula (A). The polyorganosilsesquioxane (B) having an epoxy group is preferably a polyorganosilsesquioxane having a structural unit represented by formula (1). (In formula (A), M represents a mesogenic group. E¹ and E² each independently represent groups having epoxy groups. X¹ and X² each independently represent single bonds or linking groups.) [In formula (1), R¹ represents a group containing an epoxy group.]

Description

Curable composition and its cured product

The present disclosure relates to a curable composition and a cured product thereof. More specifically, the present invention relates to a curable composition having excellent heat resistance, toughness, etc., and which can be suitably used for electric / electronic devices and the like, and a cured product thereof. The present application claims the priority of Japanese Patent Application No. 2019-090991 filed in Japan on May 13, 2019, the contents of which are incorporated herein by reference.

Epoxy resins are used in various industrial applications because they have excellent heat resistance, mechanical properties, electrical properties, adhesive strength, etc. For example, insulating materials, printed wiring boards, encapsulants, laminated boards, etc. Its use as an advanced material in the field of electronic devices such as prepregs and underfills is expanding. In recent years, as electronic devices have been rapidly miniaturized and improved in performance, there is an increasing demand for further improvement of heat resistance and mechanical properties of epoxy resins.

As one of the solutions, an attempt has been made to introduce a rigid mesogen skeleton into an epoxy resin to improve mechanical properties such as heat resistance and toughness (see, for example, Patent Documents 1 and 2). However, the epoxy resin into which the mesogen skeleton disclosed in

Patent Documents

1 and 2 and the like has a clear glass transition point below 150 ° C. and a storage elastic modulus in a region exceeding 200 ° C. in dynamic viscoelasticity measurement, for example. It did not show sufficient heat resistance as an advanced material for electronic devices, such as a sharp drop, a maximum peak value of tan δ, and a drop in area.

Further, in addition to the rigid mesogen skeleton in the epoxy resin, a chain or cyclic siloxane structure is introduced as an inorganic skeleton having excellent thermal properties, and attempts are being made to further improve heat resistance and mechanical properties. (See, for example, Patent Documents 3 and 4).

Japanese Unexamined Patent Publication No. 2014-122337 Japanese Unexamined Patent Publication No. 2016-8218 Japanese Unexamined Patent Publication No. 2008-214599 JP-A-2015-48400

In Patent Documents 3 and 4, a hydrosilylation reaction using a platinum catalyst was carried out in order to introduce a siloxane structure into an epoxy resin having a mesogen group, and the process was complicated and the cost was high. In addition, the heat resistance and mechanical properties of the obtained cured epoxy resin were not satisfactory as advanced materials for electronic devices.

Therefore, it is an object of the present invention to provide a curable composition capable of forming a cured product exhibiting excellent heat resistance and mechanical properties.
Another object of the invention of the present disclosure is to provide a cured product that exhibits excellent heat resistance and mechanical properties.
Furthermore, another object of the invention of the present disclosure is to provide an electronic device provided with a cured product that exhibits excellent heat resistance and mechanical properties.

As a result of diligent studies to solve the above problems, the inventors of the present disclosure have found that a curable composition containing an epoxy compound having a mesogen group and polyorganosylsesquioxane having an epoxy group has heat resistance. It has been found that it is useful as an advanced material for electronic devices because it can form a cured product having excellent mechanical properties (for example, toughness) and high surface hardness. The invention of the present disclosure has been completed based on these findings.

That is, the present disclosure provides a curable composition containing an epoxy compound (A) having a mesogen group and polyorganosylsesquioxane (B) having an epoxy group.

In the curable composition, the content of the polyorganosylsesquioxane (B) having an epoxy group is the total amount of the epoxy compound (A) having a mesogen group and the polyorganosylsesquioxane (B) having an epoxy group. It is preferably 1 to 50% by weight with respect to (100% by weight).

The curable composition may further contain a curing agent (C).
The curing agent (C) may be an amine-based curing agent (C1).

In the curable composition, the content of the amine-based curing agent (C1) is such that the active hydrogen of the amino group contained in the amine-based curing agent (C1) is 0.1 per 1 equivalent of the epoxy group contained in the curable composition. The amount is preferably about 10 equivalents.

In the curable composition, the epoxy compound (A) having a mesogen group is represented by the following formula (A).

(In the formula (A), M represents a mesogen group. E ¹ and E ² each independently represent an epoxy group-containing group. X ¹ and X ² each independently represent a single bond or linking group. Shows.)
It may contain a compound represented by.

In the curable composition, the M may be at least one selected from the group consisting of divalent groups represented by the following formulas (a1) to (a7).

(In the formula (a1), R ^a and R ^b each independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms, and n1 and n2 independently represent 0 to 0 to n2, respectively. If .n1 showing 4 of the integer is 2 or more, plural R ^a, if may be the same or different .n2 is 2 or more, plural R ^b, optionally substituted by one or more identical The wavy line may indicate the binding site with the group represented by -X ^1- E ¹ or -X ^2- E ^2. )

(In the formula (a2), R ^c , R ^d and R ^e independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms. N3, n4 and n5 are n3, n4 and n5, respectively. independently, when the .n3 represents an integer of 0 to 4 is 2 or more, the plurality of R ^c, if may be the same or different .n4 is 2 or more, plural R ^d, the same If may be different even .n5 is 2 or more, plural R ^e, may be the same or different. wavy line is a -X ¹ -E ¹ or -X ² -E ² Indicates the binding site with the represented group.)

(In the formula (a3), R ^f , R ^g and R ^h independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms. N6, n7 and n8 are n6, n7 and n8, respectively. Independently, it indicates an integer of 0 to 4. When n6 is 2 or more, a plurality of R ^fs may be the same or different. When n7 is 2 or more, a plurality of R ^g are the same. It may be different. If n8 is 2 or more, a plurality of R ^h may be the same or different. The wavy line is -X ^1- E ¹ or -X ^2- E ² . Indicates the binding site with the represented group.)

(In the formula (a4), R ⁱ and R ^j each independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms, and n9 and n10 independently represent 0 to 0 to n10, respectively. If .n9 showing 4 of the integer is 2 or more, plural R ^i, if may be the same or different .n10 is 2 or more, plural R ^j, are be the same or different R ^k may be a hydrogen atom, a methyl group, or a cyano group. A wavy line indicates a bond site with a group represented by -X ^1- E ¹ or -X ^2- E ^2. )

(In the formula (a5), R ^l and R ^m independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms, and n11 and n12 independently represent 0 to 0 to n12, respectively. Indicates an integer of 4. If n11 is 2 or more, the plurality of R ^l may be the same or different. If n12 is 2 or more, the plurality of R ^m may be the same or different. The wavy line may indicate the binding site with the group represented by -X ^1- E ¹ or -X ^2- E ^2. )

(In the formula (a6), R ⁿ and R ^o are each independently .N13 and n14 represents a straight-chain or branched alkyl group or a halogen atom having 1 to 6 carbon atoms are each independently 0 to If .n13 showing 4 of the integer is 2 or more, plural R ^n, if may be the same or different .n14 is 2 or more, plural R ^o, not be the same or different Wavy lines may indicate binding sites with groups represented by -X ^1- E ¹ or -X ^2- E ^2. )

(In the formula (a7), R ^p and R ^q independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms, and n15 and n16 independently represent 0 to 0 to n16, respectively. If .n15 showing 4 of the integer is 2 or more, plural R ^p, if may be the same or different .n16 is 2 or more, plural R ^q, optionally substituted by one or more identical Wavy lines may indicate binding sites with groups represented by -X ^1- E ¹ or -X ^2- E ^2. )

In the curable composition, the polyorganosylsesquioxane (B) having an epoxy group may be a polyorganosylsesquioxane having a structural unit represented by the following formula (1).

[In formula (1), R ¹ represents a group containing an epoxy group. ]

In the curable composition, the R ¹ is represented by the following formula (1a).

[In formula (1a), R ^1a represents a linear or branched alkylene group. ]
The group represented by, the following formula (1b)

[In formula (1b), R ^1b represents a linear or branched alkylene group. ]
The group represented by the following formula (1c)

[In formula (1c), R ^1c represents a linear or branched alkylene group. ]
The group represented by or the following formula (1d)

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
It may be a group represented by.

The present disclosure also provides a cured product of a cured product of a curable composition.
Further, the present disclosure provides an electronic device including the cured product.

Since the curable composition of the present disclosure contains an epoxy compound having a mesogen group and polyorganosylsesquioxane having an epoxy group, it is excellent in heat resistance and mechanical properties (for example, toughness) and has high surface hardness. A cured product can be formed. Therefore, the curable composition of the present disclosure is useful as an advanced material in the field of electronic devices such as an insulating material, a printed wiring board, a sealing material, a laminated board, a prepreg, and an underfill.
Further, the curable composition of the present disclosure can be prepared simply by mixing without requiring a chemical reaction such as hydrosilylation in order to introduce a silsesquioxane structure, and thus can be produced easily and at low cost.

It is a chart of FT-IR of the epoxy group-containing polyorganosylsesquioxane obtained in Production Example 2. It is a graph which shows the tan δ caused by the glass transition temperature, and the storage elastic modulus in the dynamic viscoelasticity measurement of Example 1, Comparative Examples 1, 2 and 3. It is a graph which shows the relationship between the flexural modulus and the bending strain in the bending test of Example 1, Comparative Examples 1, 2 and 3.

[Curable composition]
The curable composition of the present disclosure includes an epoxy compound (A) having a mesogen group (hereinafter, may be referred to as “component (A)”) and a polyorganosylsesquioxane (B) having an epoxy group (hereinafter, hereafter , May be referred to as "component (B)"). As will be described later, the curable composition of the present disclosure may further contain other components such as a curing agent (C) (for example, an amine-based curing agent) and a curing accelerator.

[Epoxy compound (A) having a mesogen group]
The component (A), which is an essential component of the curable composition of the present disclosure, is a compound having at least one mesogen group and at least one epoxy group in the molecule. That is, the component (A) is a curable compound having at least an epoxy group in the molecule. Since the component (A) has a rigid mesogen group, it has excellent heat resistance and mechanical properties in the cured product of the curable composition of the present disclosure (hereinafter, may be simply referred to as "the cured product of the present disclosure"). Can be given.

The "mesogen group" possessed by the component (A) is a general term for a rigid molecular structure capable of exhibiting liquid crystallinity. Since the mesogen group has a rigid molecular structure in which molecular motion is suppressed, when the curable composition containing the component (A) is cured, the mesogen structure is oriented to form a tough network structure, resulting in excellent heat resistance. It is thought to exhibit sex and mechanical properties.

The molecular structure of the mesogen group is not particularly limited, and examples thereof include the structures described on pages 14 to 15 of the Journal of the Japanese Society of Adhesion, Vol. 40, No. 1 (2004).

More specifically, the mesogen group includes a group represented by-(-M ¹ -X-) _n- M ^2- . Here, as X, for example, single bond, -CH = N-, -CH = CH-, -CH = C (Me)-, -CH = C (CN)-, -C≡C-, -CH. = N (→ O)-, -CH = CH-CO-, -N = N-, -N = N (→ O)-, -COO-, -CONH-, -CO- and the like. At least one of M ¹ and M ² contains one or more benzene rings, and M ¹ and M ² include, for example, independently of a phenyl group (benzene ring), a biphenyl group, a terphenyl group, and the like. Aromatic groups such as benzyl group, pyrimidine group and pyridine group; saturated or unsaturated cycloalkyl group such as cyclohexyl group and cyclohexenyl group; saturated hetero 6-membered ring group such as piperidine group and tetrahydropyran group can be mentioned. M ¹ and M ² may have a substituent, and examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , Pentyl group, hexyl group and other linear or branched alkyl groups having 1 to 6 carbon atoms, fluorine atoms, chlorine atoms, bromine atoms and other halogen atoms. When M ¹ or M ² has two or more substituents, the substituents may be the same or different. n is an integer of 1 to 3, preferably 1 or 2. When n is 2 or more, the structures represented by a plurality of (-M ¹ -X-) may be the same or different.

More specifically preferred mesogen groups include divalent groups represented by the following formulas (a1) to (a7). The wavy line in the chemical formula of the present specification indicates a binding site with another structure.

In the formula (a1), R ^a and R ^b each independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms. n1 and n2 each independently represent an integer of 0 to 4. When n1 is 2 or more, the plurality of ^Ras may be the same or different. When n2 is 2 or more, a plurality of R ^bs may be the same or different.

In formula (a2), R ^c , R ^d, and R ^e each independently represent a linear or branched-chain alkyl group or halogen atom having 1 to 6 carbon atoms. n3, n4 and n5 each independently represent an integer of 0 to 4. When n3 is 2 or more, a plurality of R ^cs may be the same or different. When n4 is 2 or more, the plurality of R ^ds may be the same or different. When n5 is 2 or more, a plurality of ^Res may be the same or different.

In formula (a3), R ^f , R ^g, and R ^h independently represent a linear or branched-chain alkyl group or halogen atom having 1 to 6 carbon atoms. n6, n7 and n8 each independently represent an integer of 0 to 4. When n6 is 2 or more, a plurality of R ^fs may be the same or different. When n7 is 2 or more, a plurality of R ^g may be the same or different. When n8 is 2 or more, a plurality of R ^h may be the same or different.

In formula (a4), R ⁱ and R ^j each independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms. n9 and n10 each independently represent an integer of 0 to 4. If n9 is 2 or more, plural R ⁱ may be be the same or different. When n10 is 2 or more, a plurality of R ^js may be the same or different. R ^k is a hydrogen atom, a methyl group, or a cyano group.

In the formula (a5), R ^l and R ^m independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms. n11 and n12 each independently represent an integer of 0 to 4. When n11 is 2 or more, a plurality of R ^l may be the same or different. When n12 is 2 or more, the plurality of R ^m may be the same or different.

Wherein (a6), R ⁿ and R ^o each independently represent a straight-chain or branched alkyl group or a halogen atom having 1 to 6 carbon atoms. n13 and n14 each independently represent an integer of 0 to 4. If n13 is 2 or more, plural R ⁿ may be be the same or different. If n14 is 2 or more, plural R ^o may be be the same or different.

In the formula (a7), R ^p and R ^q independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms. n15 and n16 each independently represent an integer of 0 to 4. When n15 is 2 or more, a plurality of R ^ps may be the same or different. When n16 is 2 or more, a plurality of R ^qs may be the same or different.

The linear or branched alkyl group having 1 to 6 carbon atoms represented by R ^a to R ^q includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert. -Butyl group, pentyl group, hexyl group and the like can be mentioned, with methyl group and ethyl group being preferable. Examples of the halogen atom represented by R ^a to R ^q include a fluorine atom, a chlorine atom, a bromine atom and the like, and a chlorine atom is preferable.

From the viewpoint of imparting excellent heat resistance and mechanical properties to the cured product of the present disclosure, the mesogen group preferably has a structure represented by the formulas (a1) to (a3), and is represented by the formula (a1) or (a3). The structure represented by the formula (a3) is more preferable, and the structure represented by the formula (a3) is further preferable.

The number of mesogen groups contained in the component (A) is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

The "epoxide group" contained in the component (A) is not particularly limited, and for example, an epoxy group (oxylanyl group), a glycidyl group (2,3-epoxypropyl group), and an alicyclic epoxy group (constituting an alicyclic). (Epoxide group composed of two adjacent carbon atoms and oxygen atoms) and the like. As the alicyclic epoxy group, a group (cyclohexene oxide group) composed of two adjacent carbon atoms and oxygen atoms constituting the cyclohexane ring is preferable.

The number of epoxy groups contained in one molecule of the component (A) is not particularly limited, but two or more are preferable and preferably two or more from the viewpoint of imparting excellent heat resistance and mechanical properties to the cured product of the present disclosure. The number is 2 to 10, more preferably 2 to 5, and even more preferably 2. When the component (A) has two or more epoxy groups in one molecule, the plurality of epoxy groups may be the same or different.

The component (A) is not particularly limited, and examples thereof include a compound represented by the following formula (A).

In the above formula (A), M represents the above-mentioned mesogen group. E ¹ and E ² each independently indicate a group containing an epoxy group. X ¹ and X ² each independently represent a single bond or a linking group (a divalent group having one or more atoms).

Examples of the group containing an epoxy group represented by E ¹ and E ² include known and commonly used groups having an oxylane ring, and the cured product of the present disclosure is not particularly limited, but imparts excellent heat resistance and mechanical properties to the cured product of the present disclosure. From the viewpoint of being capable, the group represented by the following formula (E1) or the group represented by (E2) is preferable, and the group represented by the formula (E1) is more preferable.

In the formula (E1), R ^r represents a linear or branched alkylene group having 1 to 6 carbon atoms. Examples of the linear or branched alkylene group having 1 to 6 carbon atoms include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group and hexamethylene group. Groups, decamethylene groups and the like can be mentioned. Among them, as R ^r , a linear alkylene group having 1 to 4 carbon atoms is preferable, and a methylene group and ethylene are more preferable, from the viewpoint of imparting excellent heat resistance and mechanical properties to the cured product of the present disclosure. It is a group, more preferably a methylene group. R ^s is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

In the formula (E2), R ^t represents a linear or branched alkylene group having 1 to 6 carbon atoms, and a group similar to R ^r is exemplified. Among them, as R ^t , a linear alkylene group having 1 to 4 carbon atoms is preferable, and a methylene group and ethylene are more preferable, from the viewpoint of imparting excellent heat resistance and mechanical properties to the cured product of the present disclosure. It is a group, a trimethylene group, and more preferably a methylene group or an ethylene group. R ^u is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Examples of the linking group represented by X ¹ and X ² include a linear or branched alkylene group having 1 to 6 carbon atoms (a group similar to R ^r is exemplified), an ether bond (-O-), and an amino. group (-NR ^{^X} -; R ^X is a linear or branched alkyl group having 1 to 6 carbon hydrogen atom or a C), sulfenyl group (-S-), sulfinyl group (-SO-), sulfonyl groups ( -SO _2- ), carbonyl group (-CO-), ester bond (-COO-), amide group (-CONR ^Y H-; ^RY is a hydrogen atom or a linear or branched chain with 1 to 6 carbon atoms. Alkyl group), a group in which a plurality of these are linked, and the like. The linking group represented by X ¹ and X ² is an ether bond (-O-) or one or more ether bonds from the viewpoint of imparting excellent heat resistance and mechanical properties to the cured product of the present disclosure. A group in which one or two or more of the alkylene groups are linked is preferable, and an ether bond (—O—) is more preferable.

More specifically, the component (A) is preferably a compound represented by the following formulas (A1) to (A3), and from the viewpoint of imparting excellent heat resistance and mechanical properties to the cured product of the present disclosure. The compound represented by the following formula (A1) or (A3) is more preferable, and the compound represented by the following formula (A3) is further preferable.

The definitions and preferred embodiments of the symbols in the above formulas (A1) to (A3) are the same as above.

In the curable composition of the present disclosure, one type of component (A) may be used alone, or two or more types may be used in combination.

The component (A) can be produced by a known method, and a commercially available product can also be used. Examples of commercially available products of the component (A) include the trade name "YX4000" (biphenyl type epoxy resin; manufactured by Mitsubishi Chemical Corporation).

The content (blending amount) of the component (A) in the curable composition of the present disclosure is not particularly limited, but the solvent is excluded from the viewpoint of imparting excellent heat resistance and mechanical properties to the cured product of the present disclosure. It is preferably 40 to 99% by weight, more preferably 50 to 95% by weight, still more preferably 60 to 90% by weight, based on the curable composition (100% by weight).

[Polyorganosylsesquioxane having an epoxy group (B)]
The component (B), which is an essential component of the curable composition of the present disclosure, has at least one epoxy group in the molecule and is a silsesquioxane structural unit (so-called T) represented by [RSiO _3/2 ]. A compound having a unit). That is, the component (B) is a curable compound (polymerizable compound) having a structure in which polyorganosylsesquioxane having a three-dimensional structure composed of T units has at least one epoxy group. R in the above formula indicates a hydrogen atom or a monovalent organic group, and the same applies to the following. The silsesquioxane constituent unit represented by the above formula is the hydrolyzed of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, the compounds represented by the formulas (a) to (c) described later). It is formed by decomposition and condensation reactions.

When the curable composition of the present disclosure contains the component (B) in addition to the component (A), the heat resistance and mechanical properties (for example, toughness) of the cured product of the present disclosure are improved, and the surface hardness is also increased. improves. This is because the introduction of the three-dimensional structure formed by silsesquioxane contained in the component (B) constrains the motility of the network formed by the mesogen group contained in the component (A), resulting in heat resistance. It is thought that it will improve. Further, it is considered that the introduction of the silsesquioxane structure makes the network density of the mesogen groups sparse, resulting in improvement in mechanical properties (for example, toughness). Further, it is considered that the surface hardness is increased by introducing the silsesquioxane structure which is a hard inorganic skeleton. It should be noted that these mechanisms are merely estimates and should not be construed as limiting the invention of the present disclosure by these mechanisms.

The "epoxide group" contained in the component (B) is not particularly limited, and for example, an epoxy group (oxylanyl group), a glycidyl group (2,3-epoxypropyl group), and an alicyclic epoxy group (constituting an alicyclic). (Epoxide group composed of two adjacent carbon atoms and oxygen atoms) and the like. As the alicyclic epoxy group, a group (cyclohexene oxide group) composed of two adjacent carbon atoms and oxygen atoms constituting the cyclohexane ring is preferable.

Examples of the group containing a glycidyl group include a glycidyloxy C _1-10 alkyl group (for example, a glycidyloxy C _1-4 alkyl group) such as a glycidyloxymethyl group, a 2-glycidyloxyethyl group, and a 3-glycidyloxypropyl group. ) Etc. can be mentioned.

The group containing the alicyclic epoxy group is not particularly limited, but is an epoxy C _5-12 cycloalkyl-linear or branched C _1-10 alkyl group, for example, a 2,3-epoxycyclopentylmethyl group. Epoxycyclopentyl C _1-10 alkyl groups such as 2- (2,3-epoxycyclopentyl) ethyl group, 2- (3,4-epoxycyclopentyl) ethyl group, 3- (2,3-epoxycyclopentyl) propyl group, 4 , 5-Epoxycyclooctylmethyl group, 2- (4,5-epoxycyclooctyl) ethyl group, 3- (4,5-epoxycyclooctyl) propyl group and other epoxycyclooctyl C _1-10 alkyl groups. be able to.

These groups containing an alicyclic epoxy group may have a C _1-6 alkyl group such as a methyl group or an ethyl group as a substituent on the C _5-12 cycloalkane ring. Examples of the group containing an alicyclic epoxy group having a substituent include 4-methyl-3,4-epoxycyclohexylmethyl group, 2- (3-methyl-3,4-epoxycyclohexyl) ethyl group, 2-( C such as 4-methyl-3,4-epoxycyclohexyl) ethyl group, 3- (4-methyl-3,4-epoxycyclohexyl) propyl group, 4- (4-methyl-3,4-epoxycyclohexyl) butyl group _1-4 Alkyl-epoxy C _5-12 Cycloalkyl-Linear or branched C _1-10 Alkyl groups and the like can be mentioned.

The number of epoxy groups contained in one molecule of the component (B) is not particularly limited, but two or more are preferable and preferably two or more from the viewpoint of imparting excellent heat resistance and mechanical properties to the cured product of the present disclosure. The number is 2 to 50, more preferably 2 to 30, and even more preferably 2 to 15. When the component (B) has two or more epoxy groups in one molecule, the plurality of epoxy groups may be the same or different.

The ratio of the monomer unit having an epoxy group to the total amount of the siloxane structural unit in the component (B) [total siloxane structural unit; total amount of M unit, D unit, T unit, and Q unit] is the cured product of the present disclosure. From the viewpoint of providing excellent heat resistance, mechanical properties, and high surface hardness, the content is 50 mol% or more (50 to 100 mol%), preferably 55 to 100 mol%, and more preferably 65 to 100. It is mol%, more preferably 80 to 100 mol%, and even more preferably 90 to 100 mol%.

The component (B) preferably has a structural unit represented by the following formula (1) as a silsesquioxane unit.

[In formula (1), R ¹ represents a group containing an epoxy group. ]

The component (B) is a structural unit represented by the following formula (I) (sometimes referred to as "T3 body") and a structural unit represented by the following formula (II) (referred to as "T2 body"). It may be preferable to have).
Further, the component (B) preferably has a structural unit represented by the formula (4) described later.

The structural unit represented by the above formula (1) is a silsesquioxane structural unit (so-called T unit) generally represented by [RSiO _3/2 ]. The structural unit represented by the above formula (1) is formed by a hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, the compound represented by the formula (a) described later). Will be done.

R ¹ in the formula (1) represents a group containing an epoxy group (monovalent group). Examples of the group containing an epoxy group include known and commonly used groups having an oxylan ring, and the cured product of the present disclosure is not particularly limited, but can impart excellent heat resistance, mechanical properties, and high surface hardness to the cured product of the present disclosure. From the viewpoint, a group represented by the following formula (1a), a group represented by the following formula (1b), a group represented by the following formula (1c), and a group represented by the following formula (1d) are preferable. It is preferably a group represented by the following formula (1a), a group represented by the following formula (1c), and more preferably a group represented by the following formula (1c).

In the above formula (1a), R ^1a represents a linear or branched alkylene group. Examples of the linear or branched alkylene group include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, decamethylene group and the like. Examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms. Among them, R ^1a is a linear alkylene group having 1 to 4 carbon atoms, 3 or 4 carbon atoms, from the viewpoint of imparting excellent heat resistance, mechanical properties, and high surface hardness to the cured product of the present disclosure. The branched alkylene group is preferably an ethylene group, a trimethylene group, a propylene group, and more preferably an ethylene group or a trimethylene group.

In the above formula (1b), R ^1b represents a linear or branched alkylene group, and a group similar to R ^1a is exemplified. Among them, R ^1b is a linear alkylene group having 1 to 4 carbon atoms, 3 or 4 carbon atoms, from the viewpoint of imparting excellent heat resistance, mechanical properties, and high surface hardness to the cured product of the present disclosure. The branched alkylene group is preferably an ethylene group, a trimethylene group, a propylene group, and more preferably an ethylene group or a trimethylene group.

In the above formula (1c), R ^1c represents a linear or branched alkylene group, and a group similar to R ^1a is exemplified. Among them, R ^1c is a linear alkylene group having 1 to 4 carbon atoms, 3 or 4 carbon atoms, from the viewpoint of imparting excellent heat resistance, mechanical properties, and high surface hardness to the cured product of the present disclosure. The branched alkylene group is preferably an ethylene group, a trimethylene group, a propylene group, and more preferably an ethylene group or a trimethylene group.

In the above formula (1d), R ^1d represents a linear or branched alkylene group, and a group similar to R ^1a is exemplified. Among them, R ^1d is a linear alkylene group having 1 to 4 carbon atoms, 3 or 4 carbon atoms, from the viewpoint of imparting excellent heat resistance, mechanical properties, and high surface hardness to the cured product of the present disclosure. The branched alkylene group is preferably an ethylene group, a trimethylene group, a propylene group, and more preferably an ethylene group or a trimethylene group.

R ^{1 in the} formula (1) is a group represented by the above formula (1c) from the viewpoint of imparting excellent heat resistance, mechanical properties, and high surface hardness to the cured product of the present disclosure. A group in which R ^1c is a trimethylene group [among others, a 3- (glycidyloxy) propyl group] is preferable.

The component (B) may have only one type of structural unit represented by the above formula (1), or may have two or more types of structural units represented by the above formula (1). May be good.

The component (B) has a structural unit represented by the following formula (2) in addition to the structural unit represented by the above formula (1) as the silsesquioxane structural unit [RSiO _3/2 ]. You may.

The structural unit represented by the above formula (2) is a silsesquioxane structural unit (T unit) generally represented by [RSiO _3/2 ]. That is, the structural unit represented by the above formula (2) is the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, the compound represented by the formula (b) described later). Is formed by.

R ² in the above formula (2) is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. Indicates an alkenyl group of. Examples of the aryl group include a phenyl group, a tolyl group, a naphthyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like. Examples of the alkyl group include linear or branched alkyl such as methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group and isopentyl group. Group is mentioned. Examples of the alkenyl group include a linear or branched alkenyl group such as a vinyl group, an allyl group, and an isopropenyl group.

Examples of the above-mentioned substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, and substituted alkenyl group include hydrogen atoms or main ribs in each of the above-mentioned aryl group, aralkyl group, cycloalkyl group, alkyl group and alkenyl group. Part or all of the case consists of a group consisting of an ether group, an ester group, a carbonyl group, a siloxane group, a halogen atom (fluorine atom, etc.), an acrylic group, a methacryl group, a mercapto group, an amino group, and a hydroxy group (hydroxyl group). Examples include groups substituted with at least one selected.

Among them, R ² is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, and further preferably a phenyl group. is there.

The ratio of each of the above-mentioned silsesquioxane structural units (the structural unit represented by the formula (1) and the structural unit represented by the formula (2)) in the component (B) is for forming these structural units. It can be appropriately adjusted depending on the composition of the raw material (hydrolyzable trifunctional silane).

The component (B) is not only the structural unit represented by the above formula (1) and the structural unit represented by the formula (2), but also the structural unit represented by the above formula (1) and the structural unit (2). in in represented by other than structural units silsesquioxane structural units _{_{[RSiO 3/2], [R 3}} SiO 1/2] structural units represented by (so-called M units), [R ₂ SiO _2/2] It may have at least one siloxane structural unit selected from the group consisting of the structural unit represented (so-called D unit) and the structural unit represented by [SiO _4/2 ] (so-called Q unit). .. As the silsesquioxane structural unit other than the structural unit represented by the above formula (1) and the structural unit represented by the formula (2), for example, the structural unit represented by the following formula (3) and the like are used. Can be mentioned.

When the component (B) has a structural unit (T3 body) represented by the above formula (I) and a structural unit (T2 body) represented by the above formula (II), the ratio [T3 body / T2]. The body] is not particularly limited, but can be appropriately selected from a range of, for example, 5 or more (for example, 5 or more, 500 or less). The lower limit of the ratio [T3 / T2] is preferably 20, more preferably 21, more preferably 23, still more preferably 25 (for example, preferably 5, more preferably 6, still more preferably 7). is there. By setting the above ratio [T3 body / T2 body] to 5 or more, the heat resistance, mechanical properties, and surface hardness of the cured product of the present disclosure tend to be improved. On the other hand, the upper limit of the ratio [T3 / T2] is preferably 500, more preferably 100, more preferably 50, still more preferably 40 (for example, preferably less than 20, more preferably 18, more preferably. 16, more preferably 14). By setting the above ratio [T3 / T2] to 500 or less (for example, preferably less than 20, more preferably 18 or less), the compatibility with other components in the curable composition is improved, and the viscosity is also suppressed. It is also easy to handle.

If the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I'). Further, when the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II'). Each of the three oxygen atoms bonded to the silicon atom represented in the structure represented by the following formula (I') is bonded to another silicon atom (silicon atom not represented by the formula (I')). .. On the other hand, the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') become other silicon atoms (silicon atoms not shown in the formula (II')). It is combined. That is, both the T3 body and the T2 body are structural units (T units) formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compounds.

R ^a in the above formula (I) (formula (I ') in the R ^a same) and formula (II) in the R ^b (wherein (II') in the R ^b versa), respectively, an epoxy group A group containing, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom. Shown. Specific examples of R ^a and R ^b include those similar to R ¹ in the above formula (1) and R ² in the above formula (2). In addition, R ^a in the formula (I) and R ^b in the formula (II) are groups (alkoxy group and alkoxy group) bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material of the component (B), respectively. It is derived from a group other than a halogen atom; for example, R ¹ , R ² , hydrogen atom, etc. in the formulas (a) to (c) described later.

R ^c in the formula (II) (Formula (II ') in the R ^c versa) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group. .. The alkyl group in R ^c in the formula (II) is generally an alkoxy group in the hydrolyzable silane compound used as a raw material for the component (B) (for example, an alkoxy group as X ^a to X ^c described later). ) Is derived from the alkyl group forming.

The ratio [T3 body / T2 body] in the component (B) can be determined by, for example, ²⁹ Si-NMR spectrum measurement. ^{29 In the} Si-NMR spectrum, the silicon atom in the structural unit (T3 body) represented by the above formula (I) and the silicon atom in the structural unit (T2 body) represented by the above formula (II) are at different positions. Since a signal (peak) is shown in (chemical shift), the above ratio [T3 / T2] can be obtained by calculating the integration ratio of each of these peaks. Specifically, for example, when the component (B) is represented by the above formula (1) and R ¹ has a structural unit which is a 3- (glycidyloxy) propyl group, it is represented by the above formula (I). The signal of the silicon atom in the structure (T3 body) to be formed appears at -62 to -70 ppm, and the signal of the silicon atom in the structure (T2 body) represented by the above formula (II) appears at -54 to -60 ppm. Therefore, in this case, the above ratio [T3 body / T2 body] can be obtained by calculating the integral ratio of the signal (T3 body) of -62 to -70 ppm and the signal (T2 body) of -54 to -60 ppm. it can. When R ¹ is a group containing an epoxy group other than a 3- (glycidyloxy) propyl group, [T3 body / T2 body] can be obtained in the same manner.

The ²⁹ Si-NMR spectrum of component (B) can be measured by, for example, the following equipment and conditions.
Measuring device: Product name "JNM-ECA500NMR" (manufactured by JEOL Ltd.)
Solvent: Deuterated chloroform Number of integrations: 1800 Measurement temperature: 25 ° C

When the ratio [T3 / T2] of the component (B) is within the above range (for example, 5 or more and 500 or less), a certain amount of T2 is present with respect to the T3 in the component (B). Means that. Examples of such a T2 body include a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), and the like. R ² in R ¹ and the following formula (5) in the following equation (4) is the same as R ² in R ¹ and the formula in the formula (1) (2). R ^c in the following formulas (4) to (6) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, like R ^c in the formula (II).

The polyorganosilsesquioxane in the component (B) may have any of a complete cage type, an incomplete cage type, a ladder type, and a random type silsesquioxane structure, and these silsesquioxane structures may have a structure. You may have two or more in combination.

From the viewpoint of imparting excellent heat resistance, mechanical properties, and high surface hardness to the cured product of the present disclosure, the component (B) has a complete cage type and / or an incomplete cage type silsesquioxane structure. It is preferable to have. Since the component (B) has a three-dimensional structure resulting from a complete cage type and / or an incomplete cage type silsesquioxane structure, the mobility of the network formed by the mesogen group of the component (A) is more constrained. , Heat resistance is more likely to be improved. In addition, the introduction of cage-type and / or incomplete cage-type silsesquioxane structures tends to further reduce the network density of mesogen groups and further improve mechanical properties (eg, toughness).

Component (B) to have a full cage and / or incomplete cage silsesquioxane structure, component (B), respectively intrinsic absorption peak near 1050 cm ^-1 and near 1150 cm ^-1 in the FT-IR spectrum It is confirmed by having one intrinsic absorption peak in the vicinity of 1100 cm ^-1 [Reference: R. H. Laney, M.R. Itoh, A. Sakakibara and T.M. Suzuki, Chem. Rev. 95, 1409 (1995)]. On the other hand, in general, when the FT-IR spectrum has an intrinsic absorption peak near 1050 cm ^-1 and 1150 cm ^-1 , respectively, it is identified as having a ladder type silsesquioxane structure. The FT-IR spectrum of the component (B) can be measured by, for example, the following devices and conditions.
Measuring device: Product name "FT-720" (manufactured by HORIBA, Ltd.)
Measurement method: Transmission method Resolution: 4 cm ^-1
Wavenumber range: 400-4000 cm ^-1
Accumulation number: 16 times

When the component (B) has a structural unit represented by the above formula (4), the total amount of the siloxane structural unit [total siloxane structural unit; total amount of M unit, D unit, T unit, and Q unit] (100 mol%). The ratio (total amount) of the structural unit represented by the above formula (1) and the structural unit represented by the above formula (4) to) is not particularly limited, but is preferably 55 to 100 mol%, more preferably. Is 65 to 100 mol%, more preferably 80 to 99 mol%. By setting the above ratio to 55 mol% or more, the heat resistance, mechanical properties, and surface hardness of the cured product of the present disclosure are remarkably increased. The ratio of each siloxane constituent unit in the component (B) can be calculated by, for example, the composition of the raw material, the NMR spectrum measurement, or the like.

The structural unit represented by the above formula (2) and the total amount of the siloxane structural unit in the component (B) [total siloxane structural unit; total amount of M unit, D unit, T unit, and Q unit] (100 mol%). The ratio (total amount) of the structural units represented by the above formula (5) is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, still more preferably 0 to 40 mol%, and further. More preferably, it is 1 to 15 mol%. By setting the above ratio to 70 mol% or less, the ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) can be relatively increased, and thus the curing of the present disclosure The heat resistance, mechanical properties, and surface hardness of objects tend to be higher.

The structural unit represented by the above formula (1) with respect to the total amount of the siloxane structural unit in the component (B) [total siloxane structural unit; total amount of M unit, D unit, T unit, and Q unit] (100 mol%). The ratio (total amount) of the structural unit represented by the above formula (2), the structural unit represented by the above formula (4), and the structural unit represented by the above formula (5) is not particularly limited, but is 60 to 60. It is preferably 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%. By setting the above ratio to 60 mol% or more, the heat resistance, mechanical properties, and surface hardness of the cured product of the present disclosure tend to be higher.

The standard polystyrene-equivalent number average molecular weight (Mn) of the component (B) by gel permeation chromatography is not particularly limited, but can be appropriately selected from the range of 1000 to 50,000, for example. The lower limit of the number average molecular weight is preferably 1200, more preferably 1500. By setting the number average molecular weight to 1000 or more, the heat resistance, mechanical properties, and surface hardness of the cured product of the present disclosure tend to be further improved. On the other hand, the upper limit of the number average molecular weight is preferably 50,000, more preferably 10000, and even more preferably 8000 (for example, preferably 3000, more preferably 2800, still more preferably 2600). By setting the number average molecular weight to 50,000 or less (for example, 3000 or less), the compatibility with other components in the curable composition is improved, and the heat resistance, mechanical properties, and surface hardness of the cured product of the present disclosure are further improved. Tends to improve.

The molecular weight dispersion (Mw / Mn) of the component (B) in terms of standard polystyrene by gel permeation chromatography is not particularly limited, but can be appropriately selected from the range of 1.0 to 4.0. The lower limit of the molecular weight dispersion is preferably 1.0, more preferably 1.1, and even more preferably 1.2. By setting the molecular weight dispersion to 1.1 or more, the curable composition tends to be liquid and the handleability tends to be improved. On the other hand, the upper limit of the molecular weight dispersion is preferably 4.0, more preferably 3.0, still more preferably 2.5 (for example, preferably 3.0, more preferably 2.0, still more preferably 1. 9). By setting the molecular weight dispersion to 4.0 or less (for example, 3.0 or less), the heat resistance, mechanical properties, and surface hardness of the cured product of the present disclosure tend to be higher.

The number average molecular weight and the degree of molecular weight dispersion of the component (B) can be measured by the following devices and conditions.
Measuring device: Product name "LC-20AD" (manufactured by Shimadzu Corporation)
Columns: Shodex KF-801 x 2, KF-802, and KF-803 (manufactured by Showa Denko KK)
Measurement temperature: 40 ° C
Eluent: THF, sample concentration 0.1-0.2 wt%
Flow rate: 1 mL / min Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation)
Molecular weight: Standard polystyrene conversion

The component (B) can be produced by a known or conventional method for producing a polysiloxane, and is not particularly limited, but is produced, for example, by a method of hydrolyzing and condensing one or more hydrolyzable silane compounds. it can. However, as the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (a compound represented by the following formula (a)) for forming a structural unit represented by the above formula (1) is indispensable. Must be used as a hydrolyzable silane compound.

More specifically, for example, a compound represented by the following formula (a), which is a hydrolyzable silane compound for forming a silsesquioxane structural unit (T unit) in the component (B), if necessary. Further, the component (B) can be produced by a method of hydrolyzing and condensing the compound represented by the following formula (b) and the compound represented by the following formula (c).

The compound represented by the above formula (a) is a compound forming a structural unit represented by the formula (1) in the component (B). R ¹ in the formula (a), like that of R ¹ in the formula (1), a group containing an epoxy group. That is, as R ¹ in the formula (a), the group represented by the above formula (1a), the group represented by the above formula (1b), the group represented by the above formula (1c), and the above formula (1d). ) Is preferred, more preferably the group represented by the above formula (1a), the group represented by the above formula (1c), still more preferably the group represented by the above formula (1c), and even more. It is preferably a group represented by the above formula (1c), wherein R ^1c is a trimethylene group [among others, a 3- (glycidyloxy) propyl group].

X ^a in the above formula (a) represents an alkoxy group or a halogen atom. The alkoxy group in X ^a, for example, a methoxy group, an ethoxy group, a propoxy group, isopropyloxy group, a butoxy group, an alkoxy group having 1 to 4 carbon atoms such as isobutyl group and the like. As the halogen atom of X ^a, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, X ^a is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. Incidentally, the three X ^a may each be the same or may be different.

The compound represented by the above formula (b) is a compound forming a structural unit represented by the formula (2) in the component (B). R ² in formula (b), like the R ² in the formula (2), a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted Indicates an alkyl group of, or a substituted or unsubstituted alkenyl group. That is, as R ² in the formula (b), a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group is preferable, and a substituted or unsubstituted aryl group is more preferable. More preferably, it is a phenyl group.

X ^b in the above formula (b) represents an alkoxy group or a halogen atom. Specific examples of X ^b include those exemplified as X ^a . Among them, as X ^b , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. The three X ^bs may be the same or different.

The compound represented by the above formula (c) is a compound forming a structural unit represented by the formula (3) in the component (B). X ^c in the formula (c) is an alkoxy group or a halogen atom. Specific examples of X ^c include those exemplified as X ^a . Among them, as X ^c , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. The three ^Xc may be the same or different.

As the hydrolyzable silane compound, a hydrolyzable silane compound other than the compounds represented by the above formulas (a) to (c) may be used in combination. For example, hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (a) to (c), hydrolyzable monofunctional silane compounds forming M units, and hydrolyzable bifunctional silanes forming D units. Examples thereof include compounds, hydrolyzable tetrafunctional silane compounds forming Q units, and the like.

The amount and composition of the hydrolyzable silane compound used can be appropriately adjusted according to the structure of the desired component (B). For example, the amount of the compound represented by the above formula (a) is not particularly limited, but is preferably 55 to 100 mol%, more preferably 55 to 100 mol%, based on the total amount (100 mol%) of the hydrolyzable silane compound used. Is 65 to 100 mol%, more preferably 80 to 100 mol%.

The amount of the compound represented by the above formula (b) is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 70 mol%, based on the total amount (100 mol%) of the hydrolyzable silane compound used. Is 0 to 60 mol%, more preferably 0 to 40 mol%, and even more preferably 1 to 15 mol%.

Further, the ratio (ratio of the total amount) of the compound represented by the formula (a) and the compound represented by the formula (b) to the total amount (100 mol%) of the hydrolyzable silane compound used is not particularly limited. It is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%.

Further, when two or more kinds of the hydrolyzable silane compounds are used in combination, the hydrolysis and condensation reactions of these hydrolyzable silane compounds can be carried out simultaneously or sequentially. When the above reactions are carried out sequentially, the order in which the reactions are carried out is not particularly limited.

The hydrolysis and condensation reaction of the hydrolyzable silane compound may be carried out in one step or may be carried out in two or more steps. For example, the component (B) having the above ratio [T3 / T2] of less than 20 and / or the number average molecular weight of less than 2500 (hereinafter, may be referred to as "low molecular weight polyorganosylsesquioxane") is efficiently used. In order to produce it, it is preferable to carry out the hydrolysis and condensation reaction in one step. Further, the component (B) having the above ratio [T3 / T2] of 20 or more and / or the number average molecular weight of 2500 or more (hereinafter, may be referred to as “high molecular weight polyorganosylsesquioxane”) is efficiently used. In order to produce the product, the hydrolysis and condensation reactions are carried out in two or more steps (preferably two steps), that is, one or more times using the low molecular weight polyorganosylsesquioxane as a raw material. It is preferable to carry out hydrolysis and condensation reactions. Hereinafter, the hydrolysis and condensation reaction of the hydrolyzable silane compound is carried out in one step to obtain a low molecular weight polyorganosyl sesquioxane, and the low molecular weight polyorganosyl sesquioxane is further subjected to the hydrolysis and condensation reaction. The embodiment for obtaining a high molecular weight polyorganosylsesquioxane will be described, but the method for producing the component (B) is not limited to this.

When the hydrolysis and condensation reaction of the present disclosure is carried out in two steps, preferably, in the first step of the hydrolysis and condensation reaction, the above ratio [T3 / T2] is 5 or more and less than 20, and the number average molecular weight. A low molecular weight polyorganosylsesquioxane having a value of 1000 or more and less than 2500 is obtained, and in the second stage, the low molecular weight polyorganosylsesquioxane is further subjected to a hydrolysis and condensation reaction to obtain the above ratio [T3]. A high molecular weight polyorganosylsesquioxane having a [body / T2 body] of 20 or more and 500 or less and a number average molecular weight of 2500 or more and 50,000 or less can be obtained.

The first-stage hydrolysis and condensation reaction can be carried out in the presence or absence of a solvent. Above all, it is preferable to carry out in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate and ethyl acetate. , Esters such as isopropyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol and butanol. And so on. Of these, ketones and ethers are preferable as the solvent. It should be noted that one type of solvent may be used alone, or two or more types may be used in combination.

The amount of the solvent used in the first-stage hydrolysis and condensation reaction is not particularly limited, and the desired reaction time is in the range of 0 to 2000 parts by weight with respect to 100 parts by weight of the total amount of the hydrolyzable silane compound. It can be adjusted as appropriate according to the above.

The first stage hydrolysis and condensation reaction is preferably carried out in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkaline catalyst, but an alkaline catalyst is preferable in order to suppress the decomposition of the epoxy group. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitrate, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid and p. -Sulfonic acids such as toluene sulfonic acid; solid acids such as active white clay; Lewis acids such as iron chloride can be mentioned. Examples of the alkali catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; and alkaline earth metals such as magnesium hydroxide, calcium hydroxide and barium hydroxide. Hydroxides; Alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; Alkali earth metal carbonates such as magnesium carbonate; Lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate Alkali metal hydrogen carbonates such as: Lithium acetate, sodium acetate, potassium acetate, cesium acetate and other alkali metal organic acid salts (eg acetates); alkaline earth metal organic acid salts such as magnesium acetate (eg) Acetate); Alkali metal alkoxides such as lithium methoxydo, sodium methoxydo, sodium ethoxide, sodium isopropoxide, potassium ethoxide, potassium t-butoxide; alkali metal phenoxides such as sodium phenoxide; triethylamine, N-methyl Amines such as piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5-ene (tertiary amines, etc.); pyridine , 2,2'-bipyridyl, 1,10-phenanthroline and other nitrogen-containing aromatic heterocyclic compounds and the like. It should be noted that one type of catalyst may be used alone, or two or more types may be used in combination. The catalyst can also be used in a state of being dissolved or dispersed in water, a solvent or the like.

The amount of the catalyst used in the first-stage hydrolysis and condensation reaction is not particularly limited, and is appropriately within the range of 0.002 to 0.200 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound. Can be adjusted.

The amount of water used in the first-stage hydrolysis and condensation reactions is not particularly limited, and is appropriately adjusted within the range of 0.5 to 20 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound. be able to.

The method of adding water in the first-stage hydrolysis and condensation reaction is not particularly limited, and the total amount of water used (total amount used) may be added all at once, or may be added sequentially. Good. When added sequentially, it may be added continuously or intermittently.

As the reaction conditions for the first-stage hydrolysis and condensation reactions, it is possible to select reaction conditions such that the above ratio [T3 / T2] in the low molecular weight polyorganosylsesquioxane is 5 or more and less than 20. is important. The reaction temperature of the first-stage hydrolysis and condensation reaction is not particularly limited, but is preferably 40 to 100 ° C, more preferably 45 to 80 ° C. By controlling the reaction temperature within the above range, the above ratio [T3 / T2] tends to be more efficiently controlled to 5 or more and less than 20. The reaction time of the first-stage hydrolysis and condensation reaction is not particularly limited, but is preferably 0.1 to 10 hours, more preferably 1.5 to 8 hours. Further, the first-stage hydrolysis and condensation reaction can be carried out under normal pressure, or under pressure or reduced pressure. The atmosphere at which the first stage hydrolysis and condensation reaction is carried out is not particularly limited, and may be, for example, under an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as an air atmosphere. However, it is preferable to use an inert gas atmosphere.

Low molecular weight polyorganosylsesquioxane can be obtained by the hydrolysis and condensation reaction of the first stage. After the completion of the first-stage hydrolysis and condensation reaction, it is preferable to neutralize the catalyst in order to suppress decomposition such as ring opening of the epoxy group. In addition, separation means for low molecular weight polyorganosylsesquioxane, for example, washing with water, washing with acid, washing with alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., and separation by combining these. It may be separated and purified by means or the like.

A high molecular weight polyorganosylsesquioxane is produced by subjecting the low molecular weight polyorganosylsesquioxane obtained by the first-stage hydrolysis and condensation reaction to the second-stage hydrolysis and condensation reaction. be able to.
The second-stage hydrolysis and condensation reaction can be carried out in the presence or absence of a solvent. When the second-stage hydrolysis and condensation reaction is carried out in the presence of a solvent, the solvent mentioned in the first-stage hydrolysis and condensation reaction can be used. As the solvent for the hydrolysis and condensation reaction in the second stage, the low molecular weight polyorganosylsesquioxane containing the reaction solvent for the hydrolysis and condensation reaction in the first stage, the extraction solvent, etc. is distilled off as it is or partially. You may use the solvent. It should be noted that one type of solvent may be used alone, or two or more types may be used in combination.

When the solvent is used in the second-stage hydrolysis and condensation reaction, the amount used is not particularly limited and is in the range of 0 to 2000 parts by weight with respect to 100 parts by weight of the low molecular weight polyorganosylsesquioxane. Therefore, it can be appropriately adjusted according to the desired reaction time and the like.

The second stage hydrolysis and condensation reaction is preferably carried out in the presence of a catalyst and water. As the above-mentioned catalyst, the catalyst mentioned in the first-stage hydrolysis and condensation reaction can be used, and in order to suppress the decomposition of the epoxy group, an alkaline catalyst is preferable, and sodium hydroxide is more preferable. Alkali metal hydroxides such as potassium hydroxide and cesium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate. One type of catalyst may be used alone, or two or more types may be used in combination. The catalyst can also be used in a state of being dissolved or dispersed in water, a solvent or the like.

The amount of the catalyst used in the second-stage hydrolysis and condensation reaction is not particularly limited, and is preferably 0.01 to 10000 ppm, more preferably 0, based on the low molecular weight polyorganosylsesquioxane (1000000 ppm). It can be appropriately adjusted within the range of 1 to 1000 ppm.

The amount of water used in the second-stage hydrolysis and condensation reaction is not particularly limited, and is preferably 10 to 100,000 ppm, more preferably 100 to 20,000 ppm, based on the low molecular weight polyorganosylsesquioxane (1,000,000 ppm). It can be adjusted as appropriate within the range of. When the amount of water used is larger than 100,000 ppm, it tends to be difficult to control the ratio [T3 / T2] of high molecular weight polyorganosylsesquioxane and the number average molecular weight within a predetermined range.

The method of adding water in the second-stage hydrolysis and condensation reaction is not particularly limited, and the total amount of water used (total amount used) may be added all at once, or may be added sequentially. Good. When added sequentially, it may be added continuously or intermittently.

The reaction conditions for the second-stage hydrolysis and condensation reactions are such that the ratio [T3 / T2] in the high molecular weight polyorganosylsesquioxane is 20 or more and 500 or less, and the number average molecular weight is 2500 to 50,000. It is preferable to select various reaction conditions. The reaction temperature of the hydrolysis and condensation reactions in the second stage varies depending on the catalyst used and is not particularly limited, but is preferably 5 to 200 ° C, more preferably 30 to 100 ° C. By controlling the reaction temperature within the above range, the ratio [T3 body / T2 body] and the number average molecular weight tend to be controlled more efficiently within the desired range. The reaction time of the hydrolysis and condensation reactions in the second stage is not particularly limited, but is preferably 0.5 to 1000 hours, more preferably 1 to 500 hours.
Further, a desired ratio is obtained by performing timely sampling while performing hydrolysis and condensation reactions within the above reaction temperature range, and performing the reaction while monitoring the above ratio [T3 / T2] and the number average molecular weight. [T3 / T2], high molecular weight polyorganosylsesquioxane having a number average molecular weight can also be obtained.

The second-stage hydrolysis and condensation reaction can be carried out under normal pressure, under pressure or under reduced pressure. The atmosphere for performing the hydrolysis and condensation reactions in the second stage is not particularly limited, and may be, for example, under an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as an air atmosphere. However, it is preferable to use an inert gas atmosphere.

High molecular weight polyorganosylsesquioxane can be obtained by the hydrolysis and condensation reaction in the second stage. After completion of the second-stage hydrolysis and condensation reaction, it is preferable to neutralize the catalyst in order to suppress decomposition such as ring opening of the epoxy group. In addition, separation means for high-molecular-weight polyorganosylsesquioxane, for example, washing with water, washing with acid, washing with alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., and separation by combining these. It may be separated and purified by means or the like.

Since the component (B) has the above-mentioned structure, by curing the curable composition containing the component (A) and the component (B) as essential components, the curing has excellent heat resistance, mechanical properties, and surface hardness. Can form things.

In the curable composition of the present disclosure, one type of component (B) may be used alone, or two or more types may be used in combination.

The content (blending amount) of the component (B) in the curable composition of the present disclosure is not particularly limited, but is preferably 1 to 50% by weight with respect to the total amount (100% by weight) of the curable composition excluding the solvent. %, More preferably 5 to 30% by weight, still more preferably 10 to 20% by weight. By setting the content of the component (B) in this range, the heat resistance, mechanical properties, and surface hardness of the cured product of the present disclosure tend to be improved in a well-balanced manner.

The content (blending amount) of the component (B) in the curable composition of the present disclosure is not particularly limited, but is preferably 1 to 1 to the total amount (100% by weight) of the component (A) and the component (B). It is 50% by weight, more preferably 3 to 40% by weight, still more preferably 5 to 35% by weight. By setting the content of the component (B) in this range, the heat resistance, mechanical properties, and surface hardness of the cured product of the present disclosure tend to be improved in a well-balanced manner.

[Curing agent (C)]
The curable composition of the present disclosure may further contain a curing agent (C). The curing agent (C) is a compound having a function of curing the curable composition of the present disclosure by reacting with a curable compound such as the component (A) and the component (B). As the curing agent (C), a known or conventional curing agent can be used as a curing agent for epoxy resins, and the curing agent is not particularly limited, but for example, an amine-based curing agent (C1) and an acid anhydride-based curing agent (C2) can be used. ), Polyamide-based curing agent (C3), Polymercaptan-based curing agent (C4), Phenol-based curing agent (C5), Polycarboxylic acid-based curing agent (C6) and the like.

As the amine-based curing agent (C1), a known or commonly used amine-based curing agent can be used, and the present invention is not particularly limited, and examples thereof include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, modified polyamines, and secondary amines. Examples thereof include tertiary amines.

Examples of the aliphatic polyamine include polyethylene polyamines (eg, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.), hexamethylenediamine, 1,3-pentanediamine, 2-methylpentamethylenediamine, and the like. Examples thereof include dipropylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine and diethylaminopropylamine. Examples of the alicyclic polyamine include isophoronediamine, 1,3-bisaminomethylcyclohexylamine, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, N-aminoethylpiperazin, and mensendiamine. , 4,4'-Methylenebiscyclohexyl, 4,4'-methylenebis (2-methylcyclohexylamine), bis (aminomethyl) norbornan, laromin C-260 and the like. Examples of the aromatic polyamine include m-phenylenediamine, p-phenylenediamine, diaminodiphenylsulfone (for example, 4,4'-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, etc.), m-xylenediamine. , Diaminodiphenylmethanes (eg, 4,4'-methylenedianiline (4,4'-diaminodiphenylmethane), 4,4'-methylenebis (2-methylaniline), 4,4'-methylenebis (2-ethylaniline) , 4,4'-methylenebis (2-isopropylaniline), 4,4'-methylenebis (2-chloroaniline), 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-methylenebis (2) , 6-Diethylaniline), 4,4'-methylenebis (2-isopropyl-6-methylaniline), 4,4'-methylenebis (2-ethyl-6-methylaniline), 4,4'-methylenebis (2- Bromo-6-ethylaniline), 4,4'-methylenebis (N-methylaniline), 4,4'-methylenebis (N-ethylaniline), 4,4'-methylenebis (N-sec-butylaniline), etc.) , 4,4'-cyclohexylenedianiline, 4,4'-(9-fluorenilidene) dianiline, 4,4'-(9-fluorenilidene) bis (N-methylaniline), 4,4'-diaminobenzanilide, 4,4'-oxydianiline, 2,4-bis (4-aminophenylmethyl) aniline, 4-methyl-m-phenylenediamine, 2-methyl-m-phenylenediamine, N, N'-di-sec- Butyl-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, diethyltoluenediamine [2,4-diethyl-6-methyl-m-phenylenediamine and 4, 6-Diethyl-2-methyl-m-phenylenediamine mixture, etc.], Bis (methylthio) toluenediamine [6-methyl-2,4-bis (methylthio) -m-phenylenediamine and 2-methyl-4,6- Bis (methylthio) -m-phenylenediamine mixture, etc.], 4,6-dimethyl-m-phenylenediamine, trimethylenebis (4-aminobenzoate), 1,3-bis (4-aminophenoxy) benzene, 1, 3-Bis (3-aminophenoxy) benzene, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene, 1,3-bis ( m-aminophenyl) benzene and the like can be mentioned.

Examples of the modified polyamine include modified amines with carboxylic acids (polyaminoamides and aminoamides), modified amines with epoxy compounds (amine-epoxyadducts), modified amines with Michael reaction (Michael-added polyamines), modified amines with Mannig reaction, and ureas. Alternatively, modified amines by reaction with thiourea, modified amines by reaction with ketones (ketimine, Schiff base), modified amines by reaction with epichlorohydrin, modified amines by reaction with benzyl chloride, modified amines by reaction with phosphorus compounds, Modified amines by reaction with benzoquinone, trialkylsilylated amines, modified amines by reaction between amino groups and isocyanate compounds, modified amines by reaction between amine compounds with hydroxyl groups and isocyanate compounds, modified amines by reaction with carbonates, etc. Can be mentioned.

In addition, polyoxypropylene diamine (for example, Jeffamine D230, etc.), polyoxypropylene triamine (for example, Jeffamine T403, etc.), polycyclohexylpolyamine mixture, N-aminoethylpiperazine, etc. may be used.

Examples of the secondary amine or tertiary amine include imidazoles [for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole. , 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecyl Imidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6- [2-methylimidazolyl- ( 1)]-Ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]-ethyl-s-triazine, etc.], piperidine, morpholine, N-methylpiperazin, Diciandiamide, organic acid dihydrazide, N, N'-dimethylurea derivative, linear diamine such as tetramethylethylenediamine, linear tertiary amine such as dimethylethylamine, triethanolamine, N, N-dimethylethanolamine, N, Ethanolamines such as N-diethylethanolamine, N, N-dibutylethanolamine, alkyl tertiary monoamines such as triethylamine, aliphatic tertiary amines such as benzyldimethylamine and 2- (dimethylaminomethyl) phenols, 2, An aliphatic tertiary amine having an aromatic ring having at least one phenolic hydroxyl group such as 4,6-tris (dimethylaminomethyl) phenol (DMP-30), N, N'-dimethylpiperazine, 1,4-diazazicyclo. [2.2.2] Heterocyclic tertiary amines such as octane, triethylenediamine (TEDA), pyridine, picolin, 1.8-diazabicyclo [5.4.0] -7-undecene (DBU) and the like can be mentioned. Be done.

As the acid anhydride-based curing agent (C2), a known or commonly used acid anhydride-based curing agent can be used, and is not particularly limited, and for example, methyltetrahydrophthalic anhydride (4-methyltetrahydrophthalic anhydride, 3-Methyltetrahydrophthalic anhydride, etc.), Methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), Dodecenyl succinic anhydride, Methylendomethylenetetrahydrophthalic anhydride, Phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexendicarboxylic acid anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, nagicic anhydride, methylnadic anhydride Phthalic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanoic anhydride, methylcyclohexenetetracarboxylic anhydride, Examples thereof include vinyl ether-phthalic anhydride copolymer and alkylstyrene phthalic anhydride copolymer.

Examples of the polyamide-based curing agent (C3) include a polyamide resin having either or both of a primary amino group and a secondary amino group in the molecule.

Examples of the polymercaptan-based curing agent (C4) include liquid polymercaptan and polysulfide resin.

As the phenolic curing agent (C5), a known or commonly used phenolic curing agent can be used, and is not particularly limited. For example, novolak type phenol resin, novolac type cresol resin, paraxylylene-modified phenol resin, paraxylylene / metaxylylene. Examples thereof include aralkyl resins such as modified phenol resins, terpen-modified phenol resins, dicyclopentadiene-modified phenol resins, and triphenol propane.

Examples of the polycarboxylic acid-based curing agent (C6) include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and carboxyl group-containing polyester.

As the curing agent (C), an amine-based curing agent (C1) is preferable from the viewpoint of imparting excellent heat resistance, mechanical properties, and high surface hardness to the cured product of the present disclosure. Among them, as the amine-based curing agent (C1), aromatic polyamines and aliphatic polyamines are preferable from the viewpoint of imparting excellent heat resistance and mechanical properties to the cured product of the present disclosure.

As the amine-based curing agent (C1), a compound represented by the following formula (C1a) and a compound represented by the following formula (C1b) are more preferable, and a compound represented by the following formula (C1a) is further preferable.

In the formula (C1a), R ^v and R ^w each independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms. m1 and m2 each independently represent an integer of 0 to 4. When m1 is 2 or more, a plurality of R ^vs may be the same or different. When m2 is 2 or more, a plurality of R ^ws may be the same or different. Z represents a single bond or a linking group (a divalent group having one or more atoms).

In the formula (C1b), m3 independently represents an integer of 0 to 6, preferably an integer of 2 to 5, and more preferably 3 or 4.

The linear or branched alkyl group having 1 to 6 carbon atoms represented by R ^v and R ^w includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert. -Butyl group, pentyl group, hexyl group and the like can be mentioned, with methyl group and ethyl group being preferable. Examples of the halogen atom represented by R ^v and R ^w include a fluorine atom, a chlorine atom, a bromine atom and the like, and a chlorine atom is preferable.

Examples of the linking group represented by Z include groups similar to the linking groups represented by X ¹ and X ² described above. The linking group represented by Z includes a linear or branched alkylene group having 1 to 6 carbon atoms and an ether bond (-) from the viewpoint of imparting excellent heat resistance and mechanical properties to the cured product of the present disclosure. O-), sulphenyl group (-S-), sulfinyl group (-SO-), sulfonyl group (-SO _2- ) and the like are preferable, and methylene group (-CH _2- ), ether bond (-O-), A sulfonyl group (-SO _2- ) is more preferred, and a methylene group is more preferred.

As a preferable specific of the amine-based curing agent (C1), diaminodiphenylmethanes and polyethylene polyamines are more preferable, and the amine-based curing agent (C1) is composed of triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4,4'-methylenedianiline and the like. At least one selected from the group is more preferred.

In the curable composition of the present disclosure, one type of curing agent (C) may be used alone, or two or more types may be used in combination. Further, as the curing agent (C), commercially available reagents can also be used.

The content (blending amount) of the curing agent (C) in the curable composition of the present disclosure is not particularly limited, but is 1 with respect to 100 parts by weight of the total amount of the curable compound contained in the curable composition excluding the solvent. It is preferably up to 50 parts by weight, more preferably 5 to 30 parts by weight. By setting the content of the curing agent (C) in the above range, it can be sufficiently cured, and the heat resistance and mechanical properties of the cured product of the present disclosure tend to be further improved.

When an amine-based curing agent (C1) is used as the curing agent (C), the content (blending amount) of the amine-based curing agent (C1) is not particularly limited, but is included in the curable composition of the present disclosure. It is preferable to use the active hydrogen of the amino group of the amine-based curing agent (C1) at a ratio of 0.1 to 10 equivalents per 1 equivalent of the epoxy group in all the compounds having an epoxy group, preferably 0.3 to 10 equivalents. It is more preferable to use it in a ratio of 5 equivalents. By setting the content of the curing agent (C) in the above range, it can be sufficiently cured, and the heat resistance and mechanical properties of the cured product of the present disclosure tend to be further improved.

[Curing accelerator (D)]
When the curable composition of the present disclosure contains a curing agent (C), it may further contain a curing accelerator (D). The curing accelerator (D) is a compound having a function of accelerating the reaction rate of a curing compound (for example, a compound having an epoxy group) when it reacts with the curing agent (C). As the curing accelerator (D), a known or commonly used curing accelerator can be used, and is not particularly limited, but for example, a tertiary amine [for example, lauryldimethylamine, N, N-dimethylcyclohexylamine, N. , N-dimethylbenzylamine, N, N-dimethylaniline, (N, N-dimethylaminomethyl) phenol, 2,4,6-tris (N, N-dimethylaminomethyl) phenol, 1,8-diazabicyclo [5 .4.0] Undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] Nonen-5 (DBN), etc.]; Tertiary amine salt [For example, carboxylate of the above tertiary amine , Ssulfonates, Inorganic Acidates, etc.]; imidazoles [eg 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl -4-Methylimidazole, 1-benzyl-2-methylimidazole, etc.]; Organic phosphorus compounds [eg, triphenylphosphine, triphenyl phosphite, etc.]; Tertiary ammonium salts [eg, tetraethylammonium bromide, tetrabutyl Ammonium bromide, etc.], quaternary phosphonium salts [eg, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, tetrabutylphosphonium myristate, tetrabutylphosphonium palmitate, tetrabutylphosphonium cation and bicyclo [2. 2.1] Heptane-2,3-dicarboxylic acid and / or methylbicyclo [2.2.1] Heptane-2,3-dicarboxylic acid salt with anion, tetrabutylphosphonium cation and 1,2,4,5 -Salts of cyclohexanetetracarboxylic acids with anions, etc.], quaternary arsonium salts, tertiary sulfonium salts, tertiary selenonium salts, secondary iodonium salts, onium salts such as diazonium salts; strong acid esters [eg, sulfuric acid] Esters, sulfonic acid esters, phosphoric acid esters, phosphinic acid esters, phosphonic acid esters, etc.]; Complexes of Lewis acid and base [for example, boron trifluoride / aniline complex, boron trifluoride / p-chloroaniline complex, tri. Boron fluoride / monoethylamine complex, boron trifluoride / isopropylamine complex, boron trifluoride / benzylamine complex, boron trifluoride / dimethylamine complex, boron trifluoride / diethylamine complex, boron trifluoride / dibutylamine Complex, Sanfu Boron trifluoride / piperidine complex, boron trifluoride / dibenzylamine complex, boron trichloride / dimethyloctylamine complex, etc.]; Organic metal salts [tin octylate, zinc octylate, dibutyltin dilaurate, aluminum acetylacetone complex, etc.], etc. And so on.

In the curable composition of the present disclosure, one type of curing accelerator (D) may be used alone, or two or more types may be used in combination. The curing accelerators (D) include the product names "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U-CAT 18X", and "U-CAT 12XD" ( (Manufactured by Sun Appro Co., Ltd.); Product names "TPP-K" and "TPP-MK" (manufactured by Hokuko Kagaku Kogyo Co., Ltd.); Commercial products such as can also be used.

The content (blending amount) of the curing accelerator (D) in the curable composition of the present disclosure is not particularly limited, but is 0.01 with respect to 100 parts by weight of the total amount of the curable compound contained in the curable composition. It is preferably from 5 parts by weight, more preferably 0.03 to 3 parts by weight, and even more preferably 0.03 to 2 parts by weight. By setting the content of the curing accelerator (D) to 0.01 parts by weight or more, a more efficient curing promoting effect tends to be obtained. On the other hand, when the content of the curing accelerator (D) is 5 parts by weight or less, coloring is suppressed and a cured product having an excellent hue tends to be obtained.

The curable composition of the present disclosure may further contain a curing catalyst (for example, instead of the curing agent (C)). The curing catalyst is a compound capable of initiating or accelerating the polymerization reaction of a curable compound such as the component (A) and the component (B). The curing catalyst is not particularly limited, and examples thereof include polymerization initiators such as a photocationic polymerization initiator (photoacid generator) and a thermocationic polymerization initiator (thermoacid generator).

As the photocationic polymerization initiator, a known or commonly used photocationic polymerization initiator can be used. For example, a sulfonium salt (a salt of a sulfonium ion and an anion) and an iodonium salt (a salt of an iodonium ion and an anion) can be used. , Selenium salt (salt of selenium ion and anion), ammonium salt (salt of ammonium ion and anion), phosphonium salt (salt of phosphonium ion and anion), salt of transition metal complex ion and anion, etc. .. These can be used alone or in combination of two or more.

Examples of the sulfonium salt include [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, triphenylsulfonium salt, and tri-p-tolylsulfonium salt. Tri-o-tolyl sulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenyl sulfonium salt, 2-naphthyldiphenyl sulfonium salt, tris (4-fluorophenyl) sulfonium salt, tri-1-naphthyl sulfonium salt, Triaryl such as tri-2-naphthyl sulfonium salt, tris (4-hydroxyphenyl) sulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt, 4- (p-tolylthio) phenyldi- (p-phenyl) sulfonium salt, etc. Sulfonium salt; Diarylsulfonium salt such as diphenylphenacil sulfonium salt, diphenyl4-nitrophenacil sulfonium salt, diphenylbenzylsulfonium salt, diphenylmethylsulfonium salt; phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, 4- Monoaryl sulfonium salts such as methoxyphenyl methyl benzyl sulfonium salt; trialkyl sulfonium salts such as dimethyl phenacyl sulfonium salt, phenacyl tetrahydrothiophenyl salt, dimethyl benzyl sulfonium salt and the like can be mentioned.

As the diphenyl [4- (phenylthio) phenyl] sulfonium salt, for example, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate and the like can be used. ..

Examples of the iodonium salt include the trade name "UV9380C" (manufactured by Momentive Performance Materials Japan GK, bis (4-dodecylphenyl) iodonium = hexafluoroantimonate 45% alkylglycidyl ether solution), and the trade name " RHODORSIL PHOTOINITIATOR 2074 "(manufactured by Rhodia Japan Co., Ltd., tetrakis (pentafluorophenyl) borate = [(1-methylethyl) phenyl] (methylphenyl) iodonium), trade name" WPI-124 "(Wako Pure Chemical Industries, Ltd. Co., Ltd.), diphenyl iodonium salt, di-p-tolyl iodonium salt, bis (4-dodecylphenyl) iodonium salt, bis (4-methoxyphenyl) iodonium salt and the like.

Examples of the selenium salt include triaryl selenium salts such as triphenyl selenium salt, tri-p-tolyl selenium salt, tri-o-tolyl selenium salt, tris (4-methoxyphenyl) selenium salt, and 1-naphthyldiphenyl selenium salt. Salts; Diarylselenium salts such as diphenylphenacyl selenium salt, diphenylbenzyl selenium salt, diphenylmethyl selenium salt; Monoaryl selenium salts such as phenyl methyl benzyl selenium salt; Trialkyl selenium salts such as dimethyl phenacyl selenium salt and the like. ..

Examples of the ammonium salt include tetra, such as tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, and trimethyl-n-butylammonium salt. Alkylammonium salt; Pyrrolidium salt such as N, N-dimethylpyrrolidium salt, N-ethyl-N-methylpyrrolidium salt; N, N'-dimethylimidazolinium salt, N, N'-diethylimidazolinium salt, etc. Imidazolinium salt; tetrahydropyrimidium salt such as N, N'-dimethyltetrahydropyrimidium salt, N, N'-diethyltetrahydropyrimidium salt; N, N-dimethylmorpholinium salt, N, N -Morholinium salts such as diethylmorpholinium salt; piperidinium salts such as N, N-dimethylpiperidinium salt, N, N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt and N-ethylpyridinium salt. Imidazolium salts such as N, N'-dimethylimidazolium salt; quinolium salts such as N-methylquinolium salt; isoquinolium salts such as N-methylisoquinolium salt; thiazonium salts such as benzylbenzothiazonium salt; Examples thereof include acridium salts such as benzylacrydium salts.

Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt and tetrakis (2-methoxyphenyl) phosphonium salt; triarylphosphonium salt such as triphenylbenzylphosphonium salt; triethyl. Examples thereof include tetraalkylphosphonium salts such as benzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt and triethylphenacylphosphonium salt.

Examples of the salt of the transition metal complex ion include salts of chromium complex cations such as (η5-cyclopentadienyl) (η6-toluene) Cr ⁺ and (η5-cyclopentadienyl) (η6-xylene) Cr ^+. Examples thereof include salts of iron complex cations such as (η5-cyclopentadienyl) (η6-toluene) Fe ⁺ and (η5-cyclopentadienyl) (η6-xylene) Fe ⁺ .

The anion constituting the salt described above, for _{^{_{^{example, SbF 6 -, PF 6 -}}}} , BF 4 -, (CF 3 CF 2) 3 PF 3 -, (CF 3 CF 2 CF 2) 3 PF 3 -, (C _{_{_{^{6 F 5) 4 B -,}}}} (C 6 F 5) 4 Ga -, a sulfonate anion (trifluoromethanesulfonic acid anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, benzenesulfonic acid anion, p- toluenesulfonate anion, _{_{etc.), (CF 3 SO 2)}} 3 C -, (CF 3 SO 2) 2 N -, perhalogenated acid ion, a halogenated sulfonic acid ion, carbonate ion, aluminate Examples thereof include an ion, a hexafluorobismasic acid ion, a carboxylic acid ion, an arylborate ion, a thiocyanate ion, and a nitrate ion.

Examples of the thermal cationic polymerization initiator include aryl sulfonium salts, aryl iodonium salts, allen-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes and the like.

Examples of the aryl sulfonium salt include hexafluoroantimonate salt and the like. In the curable composition of the present disclosure, for example, trade names "SP-66" and "SP-77" (all manufactured by ADEKA Corporation); trade names "Sun Aid SI-60L" and "Sun Aid SI-80L". , "Sun Aid SI-100L", "Sun Aid SI-150L" (all manufactured by Sanshin Chemical Industry Co., Ltd.) and other commercially available products can be used. Examples of the aluminum chelate include ethyl acetoacetate aluminum diisopropyrate and aluminum tris (ethyl acetoacetate). Examples of the boron trifluoride amine complex include a boron trifluoride monoethylamine complex, a boron trifluoride imidazole complex, and a boron trifluoride piperidine complex.

In the curable composition of the present disclosure, one type of curing catalyst may be used alone, or two or more types may be used in combination.

The content (blending amount) of the curing catalyst in the curable composition of the present disclosure is not particularly limited, but is 0.01 to 3.0 with respect to 100 parts by weight of the total of the component (A) and the component (B). It is preferably parts by weight, more preferably 0.05 to 3.0 parts by weight, and even more preferably 0.1 to 1.0 parts by weight (for example, 0.3 to 1.0 parts by weight). By setting the content of the curing catalyst to 0.01 parts by weight or more, the curing reaction can proceed efficiently and sufficiently, and the heat resistance and mechanical properties of the cured product of the present disclosure tend to be further improved. .. On the other hand, when the content of the curing catalyst is 3.0 parts by weight or less, the storage stability of the curable composition tends to be further improved, and the coloring of the cured product tends to be suppressed.

The curable composition of the present disclosure further comprises curable compounds other than the component (A) and the component (B) (sometimes referred to as "other curable compounds") as long as the effects of the present disclosure are not impaired. It may be included. As the other curable compound, a known or commonly used curable compound can be used, and is not particularly limited, but for example, an epoxy compound other than the component (A) and the component (B) (“other epoxy compound”). (Sometimes referred to as), oxetane compounds, vinyl ether compounds and the like. In the curable composition of the present disclosure, one type of other curable compound may be used alone, or two or more types may be used in combination.

As the other epoxy compound, a known or commonly used compound having one or more epoxy groups (oxylan rings) in the molecule can be used, and the present invention is not particularly limited, but for example, an alicyclic epoxy compound (alicyclic ring type). (Epoxy resin), aromatic epoxy compound (aromatic epoxy resin), aliphatic epoxy compound (aliphatic epoxy resin) and the like can be mentioned.

Examples of the alicyclic epoxy compound include known and commonly used compounds having one or more alicyclics and one or more epoxy groups in the molecule, and are not particularly limited, but for example, (1) in the molecule. A compound having an epoxy group (referred to as "alicyclic epoxy group") composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic; (2) The epoxy group is directly bonded to the alicyclic by a single bond. Compounds; (3) Compounds having an alicyclic and a glycidyl ether group in the molecule (glycidyl ether type epoxy compound) and the like can be mentioned.

Examples of the compound (1) having an alicyclic epoxy group in the molecule include a compound represented by the following formula (i).

In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like. Examples thereof include a group in which a plurality of groups are linked.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group and the like. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group and 1,3-. Examples thereof include a divalent cycloalkylene group (including a cycloalkylidene group) such as a cyclohexylene group, a 1,4-cyclohexylene group and a cyclohexylidene group.

Examples of the alkenylene group in the alkenylene group in which a part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as "epoxidized alkenylene group") include a vinylene group, a propenylene group, and a 1-butenylene group. , 2-Butenylene group, butazienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like, such as a linear or branched alkenylene group having 2 to 8 carbon atoms. As the epoxidized alkenylene group, an alkenylene group in which the entire carbon-carbon double bond is epoxidized is preferable, and more preferably, an alkenylene group having 2 to 4 carbon atoms in which the entire carbon-carbon double bond is epoxidized. Is.

Typical examples of the alicyclic epoxy compound represented by the above formula (i) are 3,4,3', 4'-diepoxybicyclohexane, and the following formulas (i-1) to (i-10). Examples thereof include compounds represented by. In addition, l and m in the following formulas (i-5) and (i-7) represent integers of 1 to 30, respectively. R'in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear or branched chain having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group and an isopropylene group. The shape of the alkylene group is preferable. N1 to n6 in the following formulas (i-9) and (i-10) represent integers of 1 to 30, respectively. Examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis (3,4-epoxycyclohexyl) propane and 1,2-bis (3,4-epoxycyclohexyl). ) Ethane, 2,3-bis (3,4-epoxycyclohexyl) oxylane, bis (3,4-epoxycyclohexylmethyl) ether and the like.

Examples of the compound in which the epoxy group is directly bonded to the alicyclic (2) by a single bond include a compound represented by the following formula (ii).

In the formula (ii), R "is a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of the p-valent alcohol, and p and n each represent a natural number. Examples of the valent alcohol [R "(OH) _p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (alcohols having 1 to 15 carbon atoms) and the like. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each group in () (inside the outer parentheses) may be the same or different. Specific examples of the compound represented by the above formula (ii) include 1,2-epoxy-4- (2-oxylanyl) cyclohexane adducts of 2,2-bis (hydroxymethyl) -1-butanol [for example. , Product name "EHPE3150" (manufactured by Daicel Corporation), etc.] and the like.

Examples of the compound having an alicyclic and glycidyl ether group in the above-mentioned (3) molecule include glycidyl ether of an alicyclic alcohol (for example, an alicyclic polyhydric alcohol). More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy)). Cyclohexyl] A compound obtained by hydrogenating a bisphenol A type epoxy compound such as propane (hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2,5-dimethylpropoxy) 3-Epoxypropoxy) Cyclohexyl] A compound obtained by hydrogenating a bisphenol F-type epoxy compound such as methane (hydrogenated bisphenol F-type epoxy compound); a hydrogenated biphenol-type epoxy compound; a hydrogenated phenol novolac-type epoxy compound; Novolak type epoxy compound; bisphenol A hydride cresol novolak type epoxy compound; hydride naphthalene type epoxy compound; hydride epoxy compound of epoxy compound obtained from trisphenol methane; hydride epoxy compound of the following aromatic epoxy compound, etc. Be done.

Examples of the aromatic epoxy compound include epibis-type glycidyl ether-type epoxy resins obtained by a condensation reaction between bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and epihalohydrin; High molecular weight epibis-type glycidyl ether-type epoxy resin obtained by further addition-reacting a bis-type glycidyl ether-type epoxy resin with the above bisphenols; phenols [for example, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] and aldehydes [for example, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.] and polyhydric alcohols obtained by condensing reaction with epihalohydrin. Alkyl type glycidyl ether type epoxy resin; Two phenol skeletons are bonded to the 9-position of the fluorene ring, and glycidyl is attached to the oxygen atom obtained by removing the hydrogen atom from the hydroxy group of these phenol skeletons, either directly or via an alkyleneoxy group. Examples thereof include an epoxy compound to which a group is bonded.

Examples of the aliphatic epoxy compound include glycidyl ethers of alcohols having no q-valent cyclic structure (q is a natural number); monovalent or polyvalent carboxylic acids [eg, acetic acid, propionic acid, butyric acid, stearic acid, etc. Glycidyl ester of adipic acid, sebacic acid, maleic acid, itaconic acid, etc.; epoxidized fats and oils with double bonds such as epoxidized flaxseed oil, epoxidized soybean oil, epoxidized castor oil; polyolefin (poly) such as epoxidized polybutadiene Examples thereof include epoxidized compounds (including alkadiene). Examples of the alcohol having no q-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol and 1-butanol; ethylene glycol, 1,2-propanediol, 1 , 3-Propanediol, 1,4-Butanediol, Neopentyl glycol, 1,6-hexanediol, Diethylene glycol, Triethylene glycol, Tetraethylene glycol, Dipropylene glycol, Polyethylene glycol, Polypropylene glycol and other dihydric alcohols; Examples thereof include trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. Further, the q-valent alcohol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol or the like.

Examples of the oxetane compound include known and commonly used compounds having one or more oxetane rings in the molecule, and are not particularly limited, but for example, 3,3-bis (vinyloxymethyl) oxetane and 3-ethyl-3-. (Hydroxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3- Ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-ethyl (3-ethyl) Oxetane)] methyl} ether, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bicyclohexyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] cyclohexane, 1 , 4-Bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3-{[(3-ethyloxetane-3-yl) methoxy] methyl)} oxetane, xylylene bisoxetane , 3-Ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxane, phenol novolac oxetane and the like.

As the vinyl ether compound, a known or commonly used compound having one or more vinyl ether groups in the molecule can be used, and is not particularly limited, but for example, 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxy. Propyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutylvinyl ether, 2-hydroxyisobutylvinyl ether, 1-methyl-3 -Hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexylvinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether, 1,8- Octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,2-cyclohexane Dimethanol monovinyl ether, 1,2-cyclohexanedimethanol divinyl ether, p-xylene glycol monovinyl ether, p-xylene glycol divinyl ether, m-xylene glycol monovinyl ether, m-xylene glycol divinyl ether, o-xylene glycol monovinyl ether, o-xylene glycol divinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, pentaethylene glycol monovinyl ether, Pentaethylene glycol divinyl ether, oligoethylene glycol monovinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, dipropylene glycol monovinyl ether, dipropylene Recall divinyl ether, tripropylene glycol monovinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol monovinyl ether, tetrapropylene glycol divinyl ether, pentapropylene glycol monovinyl ether, pentapropylene glycol divinyl ether, oligopropylene glycol monovinyl ether, oligopropylene glycol di Vinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, isosorbide divinyl ether, oxanorbornene divinyl ether, phenyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, hydroquinone divinyl ether, 1,4-butanediol Divinyl Ether, Cyclohexanedimethanol Divinyl Ether, Trimethylol Propane Divinyl Ether, Trimethylol Propane Trivinyl Ether, Bisphenol A Divinyl Ether, Bisphenol F Divinyl Ether, Hydroxyoxanorbornane Methanol Divinyl Ether, 1,4-Cyclohexanediol Divinyl Ether, Pentaerythritol Tri Examples thereof include vinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether and the like.

Examples of the vinyl ether compound having one or more hydroxyl groups in the molecule include 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, and 4-hydroxy. Butyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutylvinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxy Methylpropyl vinyl ether, 4-hydroxycyclohexylvinyl ether, 1,6-hexanediol monovinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1, 2-Cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether , Oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, pentapropylene glycol monovinyl ether, oligopropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, pentaerythritol trivinyl ether, dipentaerythritol penta Examples include vinyl ether.

The content (blending amount) of the other curable compound in the curable composition of the present disclosure is not particularly limited, but is the total amount (100% by weight; curing) of the component (A), the component (B) and the other curable compound. 50% by weight or less (for example, 0 to 50% by weight), more preferably 30% by weight or less (for example, 0 to 30% by weight), still more preferably 10% by weight or less, based on the total amount of the sex compound. is there. By setting the content of the other curable compound to 50% by weight or less (preferably 10% by weight or less), the heat resistance, mechanical properties, and surface hardness of the cured product of the present disclosure tend to be further improved. On the other hand, by setting the content of other curable compounds to 10% by weight or more, desired performance (for example, quick curability and viscosity adjustment for the curable composition) can be obtained with respect to the curable composition and the cured product. It may be possible to grant.

The curable compositions of the present disclosure further include precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, as any other components. , Carbon black, silicon carbide, silicon nitride, boron nitride and other inorganic fillers, and these fillers treated with organic silicon compounds such as organohalosilane, organoalkoxysilane and organosilazane; silicone resin, epoxy resin , Fluororesin and other organic resin fine powders; fillers such as conductive metal powders such as silver and copper, curing aids, solvents (organic solvents, etc.), stabilizers (antioxidants, ultraviolet absorbers, light resistance stabilizers) , Heat stabilizers, heavy metal defoamers, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardants, reinforcing materials (other fillers, etc.), nuclei Agents, coupling agents (silane coupling agents, etc.), lubricants, waxes, plasticizers, mold release agents, impact resistance improvers, hue improvers, clearing agents, rheology adjusters (fluidity improvers, etc.), processability Improvement agents, colorants (dye, pigment, etc.), antistatic agents, dispersants, surface conditioners (defoamers, leveling agents, armpit inhibitors, etc.), surface modifiers (slip agents, etc.), matting agents, It may contain conventional additives such as defoaming agents, defoaming agents, antibacterial agents, preservatives, viscosity modifiers, thickeners, photosensitizers, foaming agents and the like. These additives may be used alone or in combination of two or more.

The curable composition of the present disclosure is not particularly limited, but can be prepared by stirring and mixing each of the above components at room temperature or, if necessary, while heating. The curable composition of the present disclosure can be used as a one-component composition in which each component is mixed in advance and used as it is, or for example, two or more components stored separately. Can also be used as a multi-component (for example, two-component) composition which is used by mixing in a predetermined ratio before use.

The curable composition of the present disclosure is not particularly limited, but is preferably a liquid at room temperature (about 25 ° C.). More specifically, the curable composition of the present disclosure has a viscosity at 25 ° C. of a solution diluted in a solvent of 20% [for example, a curable composition (solution) in which the proportion of methyl isobutyl ketone is 20% by weight]. , 300 to 20000 mPa · s, more preferably 500 to 10000 mPa · s, still more preferably 1000 to 8000 mPa · s. By setting the viscosity to 300 mPa · s or more, the heat resistance of the cured product tends to be further improved. On the other hand, when the viscosity is 20000 mPa · s or less, the curable composition is easily prepared and handled, and bubbles tend to be less likely to remain in the cured product. The viscosity of the curable composition of the present disclosure is determined by using a viscometer (trade name "MCR301", manufactured by Anton Pearl Co., Ltd.), a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature: Measured under the condition of 25 ° C.

[Cured product]
By advancing the polymerization reaction of the curable compound (component (A), component (B), etc.) in the curable composition of the present disclosure, the curable composition can be cured, and the cured product of the present disclosure can be obtained. Obtainable. The curing method can be appropriately selected from well-known methods, and is not particularly limited, and examples thereof include a method of irradiating with active energy rays and / or heating. As the active energy ray, for example, any of infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used. Of these, ultraviolet rays are preferable because they are easy to handle.

The conditions for curing the curable composition of the present disclosure by irradiation with active energy rays (irradiation conditions for active energy rays, etc.) depend on the type and energy of the active energy rays to be irradiated, the shape and size of the cured product, and the like. It can be adjusted as appropriate, and is not particularly limited, but when irradiating with ultraviolet rays, it is preferably about 1 to 1000 mJ / cm ² for example. For irradiation of the active energy ray, for example, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser or the like can be used. After the irradiation with the active energy rays, further heat treatment (annealing, aging) can be performed to further proceed the curing reaction.

On the other hand, the conditions for curing the curable composition of the present disclosure by heating are not particularly limited, but are preferably, for example, 30 to 250 ° C, more preferably 50 to 200 ° C. The curing time can be set as appropriate.

As described above, the curable composition of the present disclosure can be cured to form a cured product having excellent heat resistance and mechanical properties (for example, toughness) and high surface hardness. Therefore, the curable compositions of the present disclosure are useful in various industrial applications such as electronic devices, adhesives, paints, etc., and electronic such as insulating materials, printed wiring boards, encapsulants, laminates, prepregs, underfills, etc. It can be suitably used as an advanced material in the field of equipment.

The cured product of the present disclosure has excellent heat resistance, and the glass transition point is high or the glass transition point is not clearly observed. The glass transition point specified by the peak of tan δ when the dynamic viscoelasticity of the cured product of the present disclosure is measured is preferably 150 ° C. or higher, more preferably 160 ° C. or higher, more preferably 170 ° C. or higher, more preferably. Is 180 ° C. or higher, more preferably 190 ° C. or higher, even more preferably 200 ° C. or higher, and even more preferably no clear peak of tan δ is observed, that is, the glass transition point is not clearly observed. The dynamic viscoelasticity measurement of the cured product of the present disclosure can be carried out by the method described in Examples described later.

The cured product of the present disclosure has excellent mechanical properties. The storage elastic modulus at 250 ° C. when the dynamic viscoelasticity of the cured product of the present disclosure is measured is preferably 100 MPa or more, more preferably 150 MPa or more. The dynamic viscoelasticity measurement of the cured product of the present disclosure can be carried out by the method described in Examples described later.

In addition, the cured product of the present disclosure has excellent mechanical properties (for example, toughness). When the bending test of the cured product of the present disclosure is carried out, the bending strain is preferably 9.0% or more, more preferably 9.1% or more, more preferably 9.2% MPa or more, and more preferably 9.3. % Or more, more preferably 9.4% or more, still more preferably 9.5% or more. The bending test of the cured product of the present disclosure can be carried out by the method described in Examples described later.

The pencil hardness of the cured product of the present disclosure is not particularly limited, but is preferably 2H or more, more preferably 3H or more, still more preferably 4H or more. The pencil hardness can be evaluated according to the method described in ISO15184.

The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples.

The molecular weight of the product was measured under the following conditions.
Measuring device: Product name "LC-20AD" (manufactured by Shimadzu Corporation)
Columns: Shodex KF-801 x 2, KF-802, and KF-803 (manufactured by Showa Denko KK)
Measurement temperature: 40 ° C
Eluent: THF, sample concentration 0.1-0.2 wt%
Flow rate: 1 mL / min Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation)
Molecular weight: Standard polystyrene conversion

In addition, FT-IR was measured under the following conditions.
Measuring device: Fourier transform infrared spectrophotometer IR Infinity-1, manufactured by Shimadzu Corporation Measuring range: 4000 to 650 cm ^-1
Number of integrations: 16 times Resolution: 4 cm ^-1
Measurement method: NaCl plate, permeation method

Production Example 1: Production of 1- (4-glycidyloxy-3-methylphenyl) -4- (4-glycidyloxyphenyl) -cyclohexene In a 500 mL separable flask, 4,4'-dihydroxy-3-methyl-1 , 4-diphenyl cyclohexene ^{15.00g (5.36 × 10 -2 mol)} , 12 times for one phenolic hydroxyl group equivalents of epichlorohydrin 119.64g (1.29mol), DMSO90mL was added at room temperature as a solvent It was completely dissolved. Next, 0.90 × ^10-2 g (3.24 × 10 ^-5 mol) of tetrabutylammonium chloride was added as a catalyst, and the mixture was heated and stirred in an oil bath at 60 ° C. for 1 hour. Then, a 50 wt% sodium hydroxide aqueous solution prepared using 5.15 g (1.29 × 10 ^-1 mol) of sodium hydroxide equivalent to 1.2 times the amount of one phenolic hydroxyl group was added dropwise over 30 minutes. Then, the mixture was further heated and stirred at 60 ° C. for 1.5 hours. After stirring, the inorganic salt was removed by filtration, and methanol (750 mL), which is a poor solvent, was added to the filtrate to precipitate a white solid. Then, it cooled in a refrigerator (8 ° C.) for 13 hours. After cooling, the precipitate was removed by suction filtration and washed 5 times with methanol (20 mL). The resulting solid was dried 60 ° C. · 2.5 hours under reduced pressure a constant temperature bath, a white solid ^{15.69g (3.99 × 10 -2 mol,} 75% yield).
¹ H-NMR (CDCl ₃ ) δ: 1.9 (q, 2H, CH ₂ ), 2.1 (d, 2H, CH ₂ ), 2.3 (s, 3H, CH ₃ ), 2.5 ( t, 2H, CH ₂ ), 2.8 (m, 1H, CH), 2.9 (d, 4H, CH ₂ , epoxy), 3.4 (m, 2H, CH, epoxy), 3.9 ( d, 2H, CH ₂ , epoxy), 4.1 (d, 2H, CH ₂ , epoxy), 6.1 (s, 1H, CH), 6.7 (d, 2H, CH, aromatic), 6. 9 (d, 2H, CH, aromatic), 7.1 (d, 2H, CH, aromatic), 7.2 (d, 2H, CH, aromatic), 7.3 (d, 2H, CH, aromatic)
The samples used for the above synthesis are shown below.
4,4'-Dihydroxy-3-methyl-1,4-diphenylcyclohexene (Mw280, mp 202 ° C., purity 97.9%, manufactured by Honshu Chemical Industry Co., Ltd.)
-Epichlorohydrin (Mw = 93, bp 118 ° C, purity 99%, manufactured by Wako Pure Chemical Industries, Ltd.)
-DMSO (bp 189 ° C., purity 98%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
-Tetrabutylammonium chloride (mp 83-86 ° C, purity 98%, Tokyo Chemical Industry Co., Ltd.)
-Sodium hydroxide (Mw = 40, purity 97%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
-Methanol (bp 65 ° C, purity 99%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

Production Example 2: Production of epoxy group-containing polyorganosylsesquioxane 3-glycidyloxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 94.5 parts by weight (0.4 mol parts), 378.0 parts by weight of acetone 105.1 parts by weight (5.8 mol parts) of ion-exchanged water was placed in a 1 L flask under a nitrogen stream and heated to 50 ° C. with stirring. 11.1 parts by weight (0.4 mmol part) of a 5.0% by weight aqueous potassium carbonate solution was added dropwise over 5 minutes. After stirring at 50 ° C. for 5 hours, the reaction solution was cooled to room temperature. After diluting with 100 parts by weight of methyl isobutyl ketone (MIBK), it was washed 7 times with ion-exchanged water, and it was confirmed that the pH of the aqueous layer was 7 or less. After separating the organic layer, the solvent was distilled off under reduced pressure to obtain 76.2 parts by weight of an epoxy group-containing polyorganosylsesquioxane containing 18.8% MIBK as a colorless and transparent liquid. The number average molecular weight was 1719 and the weight average molecular weight was 2058. When the FT-IR spectrum of the epoxy group-containing polyorganosylsesquioxane obtained in Production Example 1 was measured by the above method, it had no inherent absorption peaks near 1050 cm ^-1 and 1150 cm ^-1 , respectively, and was 1100 cm. It was confirmed that it had one intrinsic absorption peak near ^-1 . The FT-IR spectrum is shown in FIG.

Example 1
Biphenyl type epoxy resin (trade name "YX4000", 4,4'-bis (3-glycidyloxy) -3,3', 5,5'-tetramethylbiphenyl, manufactured by Mitsubishi Chemical Corporation) 1.00 g (epoxy) Group: 5.64 mmol) was placed in an aluminum cup (3.0 × 3.0 × 2.0 cm ³ ), and the epoxy group-containing polyorganosylsesquioxane obtained in Production Example 2 was added to the net amount excluding MIBK. 0.262 g (epoxy group: 1.57 mmol) was added, and the mixture was dissolved on a hot plate at 120 ° C. for 10 minutes. Then, MIBK was removed by heating at 120 ° C. for 30 minutes in a decompression constant temperature bath. Then, 0.357 g (active hydrogen of amino group: 7.20 mmol) of 4,4'-diaminodiphenylmethane was melted on a hot plate at 130 ° C. and then added, and the mixture was stirred on a hot plate at 120 ° C. for 1 minute. Then, it was cured at 190 ° C. for 3 hours. The rate of temperature rise was 5 ° C./min, and stirring was performed using an aluminum cup in an air atmosphere.

Examples 2 to 3, Comparative Examples 1 to 7
A cured product was prepared in the same manner as in Example 1 except that the composition was changed to the composition shown in Tables 1 and 2.

<Evaluation>
The following evaluation tests were carried out on the cured products obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

-Dynamic viscoelasticity measuring device: Non-resonant forced vibration type viscoelasticity measuring device (manufactured by Rphysel-E4000 UBM Co., Ltd.)
Measuring jig: Tensile measurement temperature range: 25 ° C to 300 ° C
Measurement mode: Temperature-dependent waveform: Sine wave heating rate: 2.0 ° C / min
Frequency: 10Hz
Displacement vibration: 5 μm
Specimen size: length 30 mm x width 4.0 mm x thickness 0.40 mm

・ Bending test measuring device: Instron type tensile test (AGS-J, manufactured by Shimadzu Corporation)
Standard: ISO178
Sample size: Thickness 1.0 mm x Width 4.0 mm x Length 30.0 mm
Distance between fulcrums: 17.8 mm
Test speed: 2 mm / min

Bending stress σ (MPa) = 3FL / 2bh ²
Bending strain ε = 6sh / L ²
Flexural modulus Ef (MPa) = (σ _2- σ ₁ ) / (ε _2- ε ₁ )
F: Force (N)
L: Distance between fulcrums (mm)
b: Mean width (mm) of test piece
h: Average thickness of test piece (mm)
s: Deflection (mm)

-Pencil hardness test standard: ISO 15184
Pencil: HB-6H (manufactured by Hi-uni MITSU-BISHI)
Test speed: 0.5-1.0 mm / s
Angle: 45 degrees Sample size: Thickness 1.5 mm x Width 1.5 mm x Length 30.0 mm

The graph showing the tan δ caused by the glass transition temperature in the dynamic viscoelasticity measurement of Example 1, Comparative Examples 1, 2 and 3 and the storage elastic modulus is shown in FIG. 2, showing the relationship between the flexural modulus and the flexural modulus in the bending test. The graph is shown in FIG.

Compared with Comparative Examples 1 and 2 containing a bisphenol A epoxy compound having no mesogen group, and Comparative Example 3 containing a component (A) having a mesogen group but not containing a component (B), the components ( In Example 1 in which A) and the component (B) were blended, the decrease in storage elastic modulus was suppressed in the region of 200 ° C. to 250 ° C., and the maximum value of the peak of tan δ and the decrease in area were observed (FIG. 2, Table). 1). A similar tendency was observed in Example 2 and Comparative Example 4 (see Table 1). Further, in Example 3 and Comparative Examples 5 to 6, a similar tendency was observed at around 150 ° C. (see Table 2).
It is considered that this is because the heat resistance was improved due to the decrease in the motility of the network chain of the mesogen group due to the addition of the rigid silsesquioxane.

Compared with Comparative Examples 1 and 2 containing a bisphenol A epoxy compound having no mesogen group, and Comparative Example 3 containing a component (A) having a mesogen group but not containing a component (B), the components ( In Example 1 in which A) and the component (B) were blended, higher bending strain was exhibited (see Tables 1 and 3). A similar tendency was observed in Example 2 and Comparative Example 4 (see Table 1).
This is because the introduced silsesquioxane side chain partially loosens the peripheral network structure, forming nanopores in the system, and the pores act as stress concentration points in the peripheral part. It is considered that the toughness was improved by inducing the plastic deformation of the network chain. Since this effect occurs more prominently in the component (A) having a mesogen group, it is considered that a large distortion is obtained.

Compared with Comparative Examples 1 and 2 containing a bisphenol A epoxy compound having no mesogen group, and Comparative Example 3 containing a component (A) having a mesogen group but not containing a component (B). In Example 1 in which (A) and the component (B) were blended, higher surface hardness was exhibited (see Table 1). A similar tendency was observed in Example 2 and Comparative Example 4 (see Table 1).
It is considered that this is because the hardness was improved by introducing the silsesquioxane structure which is hard as an inorganic skeleton.

The components shown in Tables 1 and 2 are as follows.
[Component (A)]
-JER 828 EL: Product name "JER 828 EL", bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, compound represented by the following formula (n = 0.1)

-YX4000: Product name "YX4000", biphenyl type epoxy resin, Mitsubishi Chemical Corporation, compound represented by the following formula

-Production Example 1: The compound obtained in Production Example 1, the compound represented by the following formula.

[Component (B)]
Production Example 2: Epoxy group-containing polyorganosylsesquioxane obtained in Production Example 2.

[Component (C)]
-DDM: 4,4'-diaminodiphenylmethane, manufactured by Tokyo Chemical Industry Co., Ltd., compound represented by the following formula

-TEPA: Tetraethylenepentamine, manufactured by Tokyo Chemical Industry Co., Ltd., a compound represented by the following formula

Each aspect disclosed herein can be combined with any other feature disclosed herein.
Each configuration and a combination thereof in each embodiment is an example, and the configurations can be added, omitted, replaced, and other changes as appropriate without departing from the gist of the present disclosure. The present disclosure is not limited by embodiment, but only by the scope of the claims.

The variations of the present disclosure described above are added below.
[1] A curable composition containing an epoxy compound (A) having a mesogen group and polyorganosylsesquioxane (B) having an epoxy group.
[2] The curable composition according to the above [1], wherein the mesogen group is a group represented by the following formula.
-(-M ¹ -X-) _n -M ^2-
(In the above formula, X is a single bond, -CH = N-, -CH = CH-, -CH = C (Me)-, -CH = C (CN)-, -C≡C-, -CH = N (→ O)-, -CH = CH-CO-, -N = N-, -N = N (→ O)-, -COO-, -CONH-, or -CO-. M ¹ and M. ² are independently aromatic groups (eg, phenyl group (benzene ring), biphenyl group, terphenyl group, benzyl group, pyrimidine group, pyridine group, etc.); saturated or unsaturated cycloalkyl group (eg, cyclohexyl). A group, a cyclohexenyl group, etc.); or a saturated hetero6-membered ring group (eg, a piperidine group, a tetrahydropyran group, etc.); at least one of M ¹ and M ² contains one or more benzene rings. n is an integer of 1 to 3.)
[3] The curability according to the above [1] or [2], wherein the mesogen group is at least one selected from the group consisting of divalent groups represented by the above formulas (a1) to (a7). Composition.
[4] The mesogen group is represented by at least one selected from the group consisting of divalent groups represented by the above formulas (a1) to (a3) (preferably represented by the above formula (a1) or (a3). The curable composition according to the above [3], which is a divalent group, more preferably a divalent group represented by the above formula (a3).
[5] The epoxy compound (A) having a mesogen group has 1 to 3 (preferably 1 or 2, more preferably 1) mesogen groups in one molecule. 4] The curable composition according to any one of.
[6] The epoxy group of the epoxy compound (A) having a mesogen group is an epoxy group (oxylanyl group), a glycidyl group, or an alicyclic epoxy group (preferably a cyclohexene oxide group). 5] The curable composition according to any one of.
[7] The number of epoxy groups contained in one molecule of the epoxy compound (A) having a mesogen group is 2 or more (preferably 2 to 10, more preferably 2 to 5, still more preferably 2). The curable composition according to any one of the above [1] to [6].
[8] The epoxy compound (A) having a mesogen group is represented by the following formula (A).

(In the formula (A), M represents a mesogen group. E ¹ and E ² each independently represent an epoxy group-containing group. X ¹ and X ² each independently represent a single bond or linking group. Shows.)
The curable composition according to any one of the above [1] to [7], which comprises the compound represented by.
[9] The groups E ¹ and E ² are independently represented by the above formula (E1) or the above formula (E2) (preferably the group represented by the above formula (E1)). ), The curable composition according to the above [8].
[10] The linking groups represented by X ¹ and X ² are independently linked with an ether bond (-O-) or one or two or more ether bonds and one or two or more alkylene groups. The curable composition according to the above [8] or [9], which is (preferably an ether bond (—O—)).
[11] The M is any one of the above [8] to [10], which is at least one selected from the group consisting of divalent groups represented by the above formulas (a1) to (a7). The curable composition according to description.
[12] The epoxy compound (A) having a mesogen group is at least one selected from the group consisting of the compounds represented by the above formulas (A1) to (A3) (preferably by the above formula (A1) or (A3). The curable composition according to any one of the above [1] to [11], which is a compound represented by the above, more preferably a compound represented by the above formula (A3)).
[13] The content (blending amount) of the epoxy compound (A) having a mesogen group is 40 to 99% by weight (preferably 50 to 95% by weight) with respect to the curable composition (100% by weight) excluding the solvent. , More preferably 60 to 90% by weight), the curable composition according to any one of the above [1] to [12].

[14] The number of epoxy groups contained in one molecule of polyorganosylsesquioxane (B) having an epoxy group is 2 or more (preferably 2 to 50, more preferably 2 to 30, and even more preferably. The curable composition according to any one of the above [1] to [13], which is 2 to 15).
[15] The ratio of the monomer unit having an epoxy group to the total amount of the siloxane constituent units in the polyorganosylsesquioxane (B) having an epoxy group is 50 mol% or more (preferably 55 to 100 mol%). , More preferably 65 to 100 mol%, further preferably 80 to 100 mol%, even more preferably 90 to 100 mol%), to any one of the above [1] to [14]. The curable composition according to description.
[16] Any of the above [1] to [15], wherein the polyorganosylsesquioxane (B) having an epoxy group is a polyorganosylsesquioxane having a structural unit represented by the following formula (1). The curable composition according to one.

[In formula (1), R ¹ represents a group containing an epoxy group. ]
[17] The R ¹ is represented by the group represented by the above formula (1a), the group represented by the above formula (1b), the group represented by the above formula (1c), or the above formula (1d). (Preferably a group represented by the above formula (1a), a group represented by the above formula (1b), a group represented by the above formula (1c), or a group represented by the above formula (1d). , More preferably a group represented by the above formula (1a), or a group represented by the above formula (1c), more preferably a group represented by the above formula (1c)). Curable composition.
[18] The polyorganosilsesquioxane (B) having an epoxy group has a complete cage type and / or an incomplete cage type silsesquioxane structure in any one of the above [1] to [17]. The curable composition according to description.
[19] The number average molecular weight (Mn) of the polyorganosylsesquioxane (B) having an epoxy group is 1000 to 50,000 (the lower limit is preferably 1200, more preferably 1500, and the upper limit is preferably 1500. The curable composition according to any one of the above [1] to [18], which is 10000, more preferably 8000, even more preferably 3000, even more preferably 2800, and even more preferably 2600).
[20] The molecular weight dispersion (Mw / Mn) of the polyorganosylsesquioxane (B) having an epoxy group is 1.0 to 4.0 (the lower limit is preferably 1.0, more preferably 1. 1, more preferably 1.2, and the upper limit is preferably 4.0, more preferably 3.0, even more preferably 2.5, even more preferably 2.0, even more preferably 1.9. ), The curable composition according to any one of the above [1] to [19].
[21] The content (blending amount) of the polyorganosylsesquioxane (B) having an epoxy group is 1 to 50% by weight (preferably) based on the total amount (100% by weight) of the curable composition excluding the solvent. The curable composition according to any one of the above [1] to [20], wherein is 5 to 30% by weight, more preferably 10 to 20% by weight).
[22] The content of the polyorganosylsesquioxane (B) having an epoxy group is the total amount (100% by weight) of the epoxy compound (A) having a mesogen group and the polyorganosylsesquioxane (B) having an epoxy group. The curable composition according to any one of the above [1] to [21], which is 1 to 50% by weight (preferably 3 to 40% by weight, more preferably 5 to 35% by weight). ..

[23] The curable composition according to any one of the above [1] to [22], further comprising a curing agent (C).
[24] The curing agent (C) is an amine-based curing agent (C1), an acid anhydride-based curing agent (C2), a polyamide-based curing agent (C3), a polymercaptan-based curing agent (C4), and a phenol-based curing agent (C). The curable composition according to the above [23], which is at least one selected from the group consisting of C5) and a polycarboxylic acid-based curing agent (C6).
[25] The curable composition according to the above [24], wherein the curing agent (C) is an amine-based curing agent (C1).
[26] The amine-based curing agent (C1) is a compound represented by the above formula (C1a) or a compound represented by the above formula (C1b) (preferably a compound represented by the above formula (C1a)). , The curable composition according to the above [24] or [25].
[27] The content (blending amount) of the curing agent (C) is 1 to 50 parts by weight (preferably 5 to 30 parts by weight) with respect to 100 parts by weight of the total amount of the curing compound contained in the curable composition excluding the solvent. The curable composition according to any one of the above [23] to [26], which is (part by weight).
[28] The content of the amine-based curing agent (C1) is 0.1 to 10 equivalents of the active hydrogen of the amino group contained in the amine-based curing agent (C1) per 1 equivalent of the epoxy group contained in the curable composition (C1). The curable composition according to any one of the above [25] to [27], which is preferably an amount (preferably 0.3 to 5 equivalents).
[29] The curable composition according to any one of the above [23] to [28], which further comprises a curing accelerator (D).
[30] The content (blending amount) of the curing accelerator (D) is 0.01 to 5 parts by weight (preferably 0.03) with respect to 100 parts by weight of the total amount of the curable compound contained in the curable composition. The curable composition according to the above [29], which is ~ 3 parts by weight, more preferably 0.03 to 2 parts by weight).
[31] The curable composition according to any one of the above [1] to [22], further comprising a curing catalyst.
[32] The content (blending amount) of the curing catalyst is 0.01 to 100 parts by weight in total of the epoxy compound (A) having a mesogen group and the polyorganosylsesquioxane (B) having an epoxy group. 3.0 parts by weight (preferably 0.05 to 3.0 parts by weight, more preferably 0.1 to 1.0 parts by weight, still more preferably 0.3 to 1.0 weight), the above [31]. The curable composition according to.

[33] The cured product of the curable composition according to any one of the above [1] to [32].
[34] The glass transition point specified by the peak of tan δ when dynamic viscoelasticity measurement is performed is 150 ° C. or higher (preferably 160 ° C. or higher, more preferably 170 ° C. or higher, still more preferably 180 ° C. or higher, further. The cured product according to the above [33], more preferably 190 ° C. or higher, even more preferably 200 ° C. or higher, and even more preferably no clear peak of tan δ is observed).
[35] The bending strain when the bending test is performed is 9.0% or more (preferably 9.1% or more, more preferably 9.2% MPa or more, still more preferably 9.3% or more, still more. The cured product according to the above [33] or [34], which is preferably 9.4% or more, and even more preferably 9.5% or more).
[36] An electronic device comprising the cured product according to any one of the above [33] to [35].

The curable compositions of the present disclosure are useful in a variety of industrial applications such as electronic devices, adhesives, paints and the like, especially electronic materials such as insulating materials, printed wiring boards, encapsulants, laminates, prepregs and underfills. It can be suitably used as an advanced material in the field of equipment.

Claims

A curable composition containing an epoxy compound (A) having a mesogen group and polyorganosylsesquioxane (B) having an epoxy group.
The content of the polyorganosylsesquioxane (B) having an epoxy group is based on the total amount (100% by weight) of the epoxy compound (A) having a mesogen group and the polyorganosylsesquioxane (B) having an epoxy group. The curable composition according to claim 1, which is 1 to 50% by weight.
The curable composition according to claim 1 or 2, further comprising a curing agent (C).
The curable composition according to claim 3, wherein the curing agent (C) is an amine-based curing agent (C1).
The content of the amine-based curing agent (C1) is such that the active hydrogen of the amino group contained in the amine-based curing agent (C1) is 0.1 to 10 equivalents per 1 equivalent of the epoxy group contained in the curable composition. The curable composition according to claim 4.
The epoxy compound (A) having a mesogen group has the following formula (A).

(In the formula (A), M represents a mesogen group. E 1 and E 2 each independently represent an epoxy group-containing group. X 1 and X 2 each independently represent a single bond or linking group. Shows.)
The curable composition according to any one of claims 1 to 5, which comprises the compound represented by.
The curable composition according to claim 6, wherein M is at least one selected from the group consisting of divalent groups represented by the following formulas (a1) to (a7).

(In the formula (a1), R a and R b each independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms, and n1 and n2 independently represent 0 to 0 to n2, respectively. If .n1 showing 4 of the integer is 2 or more, plural R a, if may be the same or different .n2 is 2 or more, plural R b, optionally substituted by one or more identical The wavy line may indicate the binding site with the group represented by -X 1- E 1 or -X 2- E 2. )

(In the formula (a2), R c , R d and R e independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms. N3, n4 and n5 are n3, n4 and n5, respectively. independently, when the .n3 represents an integer of 0 to 4 is 2 or more, the plurality of R c, if may be the same or different .n4 is 2 or more, plural R d, the same If may be different even .n5 is 2 or more, plural R e, may be the same or different. wavy line is a -X 1 -E 1 or -X 2 -E 2 Indicates the binding site with the represented group.)

(In the formula (a3), R f , R g and R h independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms. N6, n7 and n8 are n6, n7 and n8, respectively. Independently, it indicates an integer of 0 to 4. When n6 is 2 or more, a plurality of R fs may be the same or different. When n7 is 2 or more, a plurality of R g are the same. It may be different. If n8 is 2 or more, a plurality of R h may be the same or different. The wavy line is -X 1- E 1 or -X 2- E 2 . Indicates the binding site with the represented group.)

(In the formula (a4), R i and R j each independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms, and n9 and n10 independently represent 0 to 0 to n10, respectively. If .n9 showing 4 of the integer is 2 or more, plural R i, if may be the same or different .n10 is 2 or more, plural R j, are be the same or different R k may be a hydrogen atom, a methyl group, or a cyano group. A wavy line indicates a bond site with a group represented by -X 1- E 1 or -X 2- E 2. )

(In the formula (a5), R l and R m independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms, and n11 and n12 independently represent 0 to 0 to n12, respectively. Indicates an integer of 4. If n11 is 2 or more, the plurality of R l may be the same or different. If n12 is 2 or more, the plurality of R m may be the same or different. The wavy line may indicate the binding site with the group represented by -X 1- E 1 or -X 2- E 2. )

(In the formula (a6), R n and R o are each independently .N13 and n14 represents a straight-chain or branched alkyl group or a halogen atom having 1 to 6 carbon atoms are each independently 0 to If .n13 showing 4 of the integer is 2 or more, plural R n, if may be the same or different .n14 is 2 or more, plural R o, not be the same or different Wavy lines may indicate binding sites with groups represented by -X 1- E 1 or -X 2- E 2. )

(In the formula (a7), R p and R q independently represent a linear or branched alkyl group or halogen atom having 1 to 6 carbon atoms, and n15 and n16 independently represent 0 to 0 to n16, respectively. If .n15 showing 4 of the integer is 2 or more, plural R p, if may be the same or different .n16 is 2 or more, plural R q, optionally substituted by one or more identical Wavy lines may indicate binding sites with groups represented by -X 1- E 1 or -X 2- E 2. )
The method according to any one of claims 1 to 7, wherein the polyorganosylsesquioxane (B) having an epoxy group is a polyorganosylsesquioxane having a structural unit represented by the following formula (1). Curable composition.

[In formula (1), R 1 represents a group containing an epoxy group. ]
The R 1 is the following formula (1a).

[In formula (1a), R 1a represents a linear or branched alkylene group. ]
The group represented by, the following formula (1b)

[In formula (1b), R 1b represents a linear or branched alkylene group. ]
The group represented by the following formula (1c)

[In formula (1c), R 1c represents a linear or branched alkylene group. ]
The group represented by or the following formula (1d)

[In formula (1d), R 1d represents a linear or branched alkylene group. ]
The curable composition according to claim 8, which is a group represented by.
A cured product of the curable composition according to any one of claims 1 to 9.
An electronic device including the cured product according to claim 10.