JP7129055B2 - Curable composition, cured product thereof, and method for producing cured product - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable composition that can be used for photocurable coatings, photoresists, printing plate materials, and the like, its cured product, and a method for producing this cured product.

In recent years, organic-inorganic hybrid materials, which are composites of organic and inorganic materials at the molecular level, have properties derived from organic materials (e.g., lightness, ease of processing, flexibility, etc.) and properties derived from inorganic materials ( It is attracting attention as a material that can achieve both heat resistance, weather resistance, and high elastic modulus.

Japanese Patent Application Laid-Open No. 2016-20472 (Patent Document 1) discloses a photopolymerization method containing a photocationically polymerizable compound (A), a polysilane (B), and a photoacid generator (C) that generates an acid by absorbing visible light. This composition has excellent photosensitivity even when irradiated with visible light in order to suppress the decomposition of polysilane, and can improve the hardness of the cured product. It is described that it can be used for resists, printing plate-making materials, and the like. In the examples of this document, photopolymerization comprising 9,9-bis[3,4-diglycidyloxy-phenyl]fluorene, polymethylphenylsilane or hyperbranched phenylsilane oligomers, and a given photoacid generator. We are preparing a flexible resin composition.

JP 2016-20472 A

Since the cationic photopolymerizable compound (A) disclosed in Patent Document 1 is synthesized by cationic polymerization, adjustment of polymerization conditions such as water control tends to be complicated. Moreover, it is difficult to improve the curing speed at a low temperature, and acid tends to remain in the cured product.

Therefore, an object of the present invention is to provide a curable composition that can obtain a cured product having a high refractive index by radical polymerization even when irradiated with visible light, a cured product thereof, and a method for producing the cured product. .

Another object of the present invention is to provide a curable composition that gives a cured product having a high insolubilization rate and an appropriate Abbe number, a cured product thereof, and a method for producing the cured product.

Still another object of the present invention is to provide a curable composition that does not require heating at a high temperature and that can improve the transparency, heat resistance and water repellency of the cured product, the cured product thereof, and a method for producing the cured product. to do.

The present inventors have made intensive studies to achieve the above object, and found that a radically polymerizable compound having a polysilane and a fluorene skeleton and a thiol compound are polymerized by irradiating visible light in the presence of a radical polymerization initiator. The inventors have also found that a cured product with a high refractive index can be obtained by radical polymerization even when irradiated with visible light, and have completed the present invention.

That is, the curable composition of the present invention contains a polysilane (A), a radical polymerizable compound (B) having a fluorene skeleton, a thiol compound (C) and a radical polymerization initiator (D). The radically polymerizable compound (B) may contain a radically polymerizable compound represented by the following formula (1).

(Wherein, ring Z ¹ is an arene ring, A ¹ is an alkylene group, X is an allyl group or (meth)acryloyl group, R ¹ and R ² are substituents, n is 0 or a number of 1 or more, m is 0 to 4, k is 0 or 1 or more, s is 0 or 1).

In the above formula (1), ring Z ¹ may be a benzene ring, n may be 0, and s may be 1. The thiol compound (C) may contain a polythiol compound having 3 or more thiol groups in the molecule. The thiol compound (C) may contain a dithiol compound having a fluorene skeleton, for example, a dithiol compound represented by the following formula (2).

(Wherein, ring Z ² is an arene ring, A ² and A ³ are alkylene groups, R ³ and R ⁴ are substituents, p is a number of 0 or 1 or more, q is a number of 0 to 4, r is 0 or number greater than or equal to 1).

Said polysilane (A) may be a poly C _1-3 alkyl C _6-10 aryl silane with a number average molecular weight of 100-50,000. The ratio of the radically polymerizable compound (B) may be 100 parts by weight or more with respect to 100 parts by weight of the polysilane (A). The ratio of the thiol compound (C) may be 10 parts by weight or more with respect to a total of 100 parts by weight of the polysilane (A) and the radically polymerizable compound (B).

In the specification and claims of the present application, the number of carbon atoms in a substituent may be indicated by C ₁ , C ₆ , C ₁₀ or the like. That is, for example, an alkyl group having 1 carbon atom is indicated by "C ₁ alkyl", and an aryl group having 6 to 10 carbon atoms is indicated by "C _6-10 aryl".

The present invention also includes a method for producing a cured product, which includes a photocuring step of irradiating the curable composition with visible light to form a photocured product. In the photo-curing step, the curable composition may be irradiated with visible light while being heated at 80 to 150°C. The present invention also includes a cured product obtained by the production method.

In the present invention, when a polysilane, a radically polymerizable compound having a fluorene skeleton, and a thiol compound are polymerized by irradiating visible light in the presence of a radical polymerization initiator, even when visible light is irradiated, the radical polymerization results in refraction. A cured product with a high rate is obtained. In particular, when a polythiol compound having 3 or more thiol groups in the molecule is used, the insolubilization rate of the cured product can be improved. Moreover, the obtained cured product has an appropriate Abbe number. Furthermore, heating at a high temperature is unnecessary, and the transparency, heat resistance and water repellency of the cured product can be improved.

[Curable composition]
The curable composition of the present invention contains a polysilane (A), a radical polymerizable compound (B) having a fluorene skeleton, a thiol compound (C) and a radical polymerization initiator (D). This curable composition can be radically polymerized by irradiation with visible light to form a cured product having a high refractive index. Although the detailed mechanism by which radical polymerization proceeds by irradiation with visible light is unknown, in the presence of the radical polymerization initiator (D), the radically polymerizable compound (B) undergoes an ene/thiol reaction by irradiation with visible light, and It can be presumed that the polymer with the thiol compound (C) reacts with the polysilane (A) split by visible light irradiation to form a network to form a cured product.

(A) Polysilane In the present invention, since the curable composition contains the polysilane (A), the refractive index of the cured product can be increased, and heat resistance and water repellency can also be improved. The polysilane (A) is not particularly limited as long as it is a linear, cyclic, branched, or network compound having Si—Si bonds, and is usually represented by the following formulas (3) and (4). In many cases, it is composed of polysilane having at least one structural unit among the structural units.

(wherein R ⁵ to R ⁷ are the same or different and represent a hydrogen atom, a hydroxyl group, an organic group or a silyl group).

In R ⁵ to R ⁷ of the above formulas (3) and (4), the organic group includes, for example, a hydrocarbon group such as an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, Groups such as alkoxy groups, cycloalkyloxy groups, aryloxy groups, and aralkyloxy groups that form ether bonds with these hydrocarbon groups are included. Typically, the organic groups are hydrocarbon groups such as alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, aralkyl groups and the like. Also, hydrogen atoms, hydroxyl groups, alkoxy groups and silyl groups usually occur when the organic group is at the terminal end of the molecule.

The alkyl group includes, for example, C _1-14 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl and hexyl, preferably C _1-10 alkyl groups, A C _1-6 alkyl group is more preferred.

Alkoxy groups include, for example, C _1-14 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, pentyloxy and the like.

Alkenyl groups include, for example, C _2-14 alkenyl groups such as vinyl, allyl, butenyl and pentenyl.

Cycloalkyl groups include, for example, C _5-14 cycloalkyl groups such as cyclopentyl, cyclohexyl, methylcyclohexyl and the like. Cycloalkyloxy groups include, for example, C _5-14 cycloalkyloxy groups such as cyclopentyloxy and cyclohexyloxy. Cycloalkenyl groups include, for example, C _5-14 cycloalkenyl groups such as cyclopentenyl and cyclohexenyl.

The aryl group includes, for example, C _6-20 aryl groups such as phenyl, methylphenyl (tolyl), dimethylphenyl (xylyl), naphthyl and the like, preferably C _6-15 aryl groups, more preferably C _{6 -12} aryl groups. Aryloxy groups include, for example, C _6-20 aryloxy groups such as phenoxy and naphthyloxy. Aralkyl groups include, for example, C _6-20 aryl-C _1-4 alkyl groups such as benzyl, phenethyl and phenylpropyl. Aralkyloxy groups include, for example, C _6-20 aryl-C _1-4 alkyloxy groups such as benzyloxy, phenethyloxy and phenylpropyloxy.

Silyl groups include, for example, Si _1-10 silanyl groups such as silyl groups, disilanyl groups and trisilanyl groups. Si _1-10 silanyl groups are preferably Si _1-6 silanyl groups.

In addition, when R ⁵ to R ⁷ are the above organic group (alkyl group, aryl group, etc.) or silyl group, at least one of the hydrogen atoms may be substituted with a substituent (or functional group). good. Such substituents (or functional groups) include, for example, hydroxyl groups, alkyl groups, aryl groups, alkoxy groups, etc. Among these, specific examples of alkyl groups, aryl groups and alkoxy groups are the same as groups.

Among the groups described above, the substituents R ⁵ to R ⁷ are particularly preferably alkyl groups or aryl groups. In particular, alkyl groups are particularly preferably C _1-4 alkyl groups such as methyl groups, and aryl groups are particularly preferably C _6-20 aryl groups such as phenyl groups.

When the polysilane has a straight-chain, branched-chain or network-like acyclic structure, the terminal group (that is, the group substituted at the end of the molecule) is usually a hydrogen atom, a hydroxyl group, a halogen atom (chlorine atoms), alkyl groups, aryl groups, alkoxy groups, silyl groups, and the like. Among these, hydroxyl group, methyl group, and phenyl group are often used. Among them, phenyl group and methyl group are preferable from the viewpoint of improving photocurability, and the terminal group may be a trimethylsilyl group.

Specific polysilanes include, for example, a linear or cyclic polysilane having a structural unit represented by the above formula (3), a polysilane having a structural unit represented by the above formula (4) (branched or network polysilane), and polysilanes (branched or network polysilanes) having a combination of structural units represented by the above formulas (3) and (4). In these polysilanes, the structural units represented by formulas (3) and (4) may be used alone or in combination of two or more. The branched-chain or network-like polysilane may further contain a structural unit represented by the following formula (5).

Representative polysilanes include linear or cyclic polysilanes such as polydialkylsilanes, polyalkylarylsilanes, polydiarylsilanes, dialkylsilane-alkylarylsilane copolymers. Preferred embodiments of polydialkylsilane include, for example, polydimethylsilane, polymethylpropylsilane, polymethylbutylsilane, polymethylpentylsilane, polydibutylsilane, polydihexylsilane, and dimethylsilane-methylhexylsilane copolymer. . Preferred embodiments of polyalkylarylsilanes include, for example, polymethylphenylsilanes and methylphenylsilane-phenylhexylsilane copolymers. A preferred embodiment of polydiarylsilane includes, for example, polydiphenylsilane. Preferred embodiments of the dialkylsilane-alkylarylsilane copolymer include, for example, dimethylsilane-methylphenylsilane copolymer, dimethylsilane-phenylhexylsilane copolymer, and dimethylsilane-methylnaphthylsilane copolymer. These polysilanes can be used alone or in combination of two or more.

A more specific preferred embodiment of the polysilane is a polysilane having a structural unit (3), which does not inhibit radical polymerization and can improve the stability of the cured product, and is a linear or cyclic polysilane. is particularly preferred. For this structural unit (3), R ⁴ is preferably an aryl group, particularly preferably a C _6-20 aryl group. R ⁵ is preferably an aryl group or an alkyl group, particularly preferably a C _6-20 aryl group or a C _1-6 alkyl group. More specifically, such polysilanes include poly-C _1-6 alkyl-C _6-20 arylsilanes (particularly preferably poly-C _1-3 alkyl-C _6-10 arylsilanes), poly-di-C _6-20 aryl Silanes (particularly preferably polydiC _6-10 arylsilanes) may be mentioned. Furthermore, from the viewpoint of compatibility with the radically polymerizable compound (B), chain polyalkylarylsilanes and cyclic diarylsilanes are preferred, and chain polyalkylarylsilanes are particularly preferred.

The polysilane used in the present invention may be a polysilane in which at least one hydroxyl group is directly bonded to a terminal silicon atom of the polysilane, that is, a polysilane having at least one terminal silanol group (hydroxyl group). The content of hydroxyl groups is not limited to this, but is preferably 0.005 to 2.5 on average, more preferably 0.01 to 2.3 on average, and particularly preferably 0 on average per silicon atom. .02 to 2.

The average degree of polymerization of polysilane (A) is, in terms of silicon atoms (that is, as the average number of silicon atoms per molecule), for example, 2 to 200, preferably 5 to 150, more preferably 10 to 130, particularly It is preferably 50-100. The number average molecular weight of the polysilane (A) is preferably 100 to 50,000 as a value measured by the GPC method (converted to polystyrene), and more preferably 500 to 40,000, 1,000 to 30,000, and 5,000 to 20,000 in stages below. and particularly preferably 10,000 to 15,000. If the degree of polymerization and molecular weight are too small, the refractive index of the cured product may be increased, and heat resistance and water repellency may be lowered. be.

Polysilane (A) may be either solid or liquid at room temperature (for example, about 15 to 25° C.). Liquid polysilane may be used because it is easily dispersed uniformly therein.

In the curable composition of the present invention, the content of the polysilane (A) is preferably adjusted, for example, by adjusting the ratio of the content to the radically polymerizable compound (B). Specifically, the preferred range of the content of the radically polymerizable compound (B) with respect to the polysilane (A) will be described later.

(B) Radically polymerizable compound having a fluorene skeleton The radically polymerizable compound (B) having a fluorene skeleton is not particularly limited as long as it has a fluorene skeleton and is radically polymerizable, but 9,9-bisaryl A radically polymerizable compound having a fluorene skeleton is preferred, and a radically polymerizable compound represented by the above formula (1) is particularly preferred.

In formula (1), examples of the arene ring represented by ring Z ¹ include monocyclic arene rings such as benzene ring, polycyclic arene rings, etc. Polycyclic arene rings include condensed polycyclic Formula arene rings (condensed polycyclic hydrocarbon rings), ring-assembled arene rings (ring-assembled aromatic hydrocarbon rings), and the like are included.

Examples of ring-aggregated arene rings include biarene rings and tellarene rings. Preferred embodiments of the biarene ring include, for example, biC _6-12 arene rings such as biphenyl ring, binaphthyl ring and phenylnaphthalene ring (1-phenylnaphthalene ring, 2-phenylnaphthalene ring, etc.). A preferred embodiment of the tellarene ring includes, for example, a tell C _6-12 arene ring such as a terphenylene ring. A particularly preferred ring-assembled arene ring is a biC _6-10 arene ring, particularly preferably a biphenyl ring.

Examples of condensed polycyclic arene rings include condensed bicyclic arenes, condensed tricyclic arenes, condensed tetracyclic arenes, and the like. Suitable embodiments of fused bicyclic arenes include, for example, fused bicyclic C _10-16 arene rings such as naphthalene. Preferred embodiments of condensed tricyclic arenes include, for example, anthracene and phenanthrene. Preferred embodiments of the fused tetracyclic arene ring include, for example, pyrene. Preferred condensed polycyclic arene rings include naphthalene ring, anthracene ring and the like, and naphthalene ring is particularly preferred.

The two rings Z ¹ may be the same ring or different rings, but are usually the same ring. Among these arene rings, a monocyclic arene ring such as a benzene ring, a biarene ring such as a biphenyl ring, a condensed bicyclic arene ring such as a naphthalene ring, and the like are widely used, and a benzene ring is preferred.

X may be an allyl group or a (meth)acryloyl group, preferably X is a (meth)acryloyl group.

Examples of the alkylene group of the group A ¹ constituting the oxyalkylene group include C _2-6 alkylene groups such as ethylene, propylene, trimethylene, 1,2-butanediyl and tetramethylene. The groups A ¹ on both sides may be the same alkylene group or different alkylene groups. Further, when n is two or more polyoxyalkylene groups, the alkylene groups constituting the polyoxyalkylene groups may be different alkylene groups, or usually the same alkylene group. From the viewpoint of optical properties, the group A ¹ is preferably a C _2-4 alkylene group, more preferably a C _2-3 alkylene group such as ethylene or propylene, and particularly preferably an ethylene group.

The number of repetitions (addition mole number) of the oxyalkylene group A ¹ O (the number of repetitions of each group A 1 O) n (the number of repetitions of each group A ¹ O) may be 0 or 1 or more. ~10, 0-5, 0-3, 0-2, 0 or 1, with 0 being most preferred. Also, when s, which will be described later, is 0, n is most preferably 1. If the number of repetitions is too large, the refractive index of the cured product may decrease.

s, which indicates the presence or absence of a 2-hydroxyoxypropylene group, may be 0 or 1, but is preferably 1. When s=1, a hydroxyl group is present in the molecule, and the hydroxyl group can enhance the adhesion to the substrate when the curable resin composition is cured, which is preferable. In addition, having a hydroxyl group tends to increase the refractive index of the cured product of the curable resin composition, which is preferable.

In the compound of formula (1), it is particularly preferred that the repeating number n of the oxyalkylene group A ¹ O is 0, and s, which indicates the presence or absence of a 2-hydroxyoxypropylene group, is 1.

In the above formula ( ¹ ), the substitution position of the radically polymerizable group containing the group X is not particularly limited. Any position may be used, but the 4th position is preferred. Further, when the ring Z ¹ is a naphthalene ring, it is often the 5- to 8-positions of the naphthyl group. In particular, there are many cases where it is a relationship between the 2nd and 6th positions.

Examples of the substituent R ¹ include hydrocarbon groups such as alkyl groups and aryl groups; cyano groups; and halogen atoms such as fluorine atoms, chlorine atoms and bromine atoms. Preferred examples of alkyl groups include linear or branched C _1-6 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl groups. A preferred embodiment of the aryl group includes, for example, a C _6-10 aryl group such as a phenyl group.

These substituents R ¹ can be used alone or in combination of two or more. Among these, an alkyl group, a cyano group and a halogen atom are preferred, and a C _1-2 alkyl group such as a methyl group and an ethyl group are particularly preferred.

The substitution number m of the substituent R ¹ can each be selected from an integer of 0 to 4, and the preferred range is 0 to 3, 0 to 2, and 0 to 1 in stages below, with 0 being most preferred. In the two benzene rings forming the fluorene skeleton, the number of substitutions m may be the same or different, and the type of R ¹ may be the same or different. Moreover, when m is 2 or more, the types of two or more R ¹ substituted on the same benzene ring may be the same or different. The substitution position of R ¹ is not particularly limited, but is preferably, for example, the 2- to 7-positions of the fluorene ring, more preferably the 2-, 3- and 7-positions.

Examples of the substituent ^R2 include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups; Halogen atoms, nitro groups, cyano groups, dialkylamino groups, dialkylcarbonylamino groups and the like.

Preferred examples of alkyl groups include C _1-6 alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl groups. A preferred embodiment of the cycloalkyl group includes, for example, a C _5-8 cycloalkyl group such as a cyclohexyl group. Preferred embodiments of the aryl group include, for example, C _6-10 aryl groups such as phenyl group, tolyl group and xylyl group. Preferred embodiments of the aralkyl group include, for example, C _6-10 aryl-C _1-4 alkyl groups such as benzyl group and phenethyl group.

A preferred embodiment of the alkoxy group includes, for example, a C _1-6 alkoxy group such as a methoxy group. Preferred embodiments of cycloalkoxy groups include, for example, C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups. A preferred embodiment of the aryloxy group includes, for example, a C _6-10 aryloxy group such as a phenoxy group. Preferred embodiments of the aralkyloxy group include, for example, C _6-10 aryl-C _1-4 alkyl groups such as benzyloxy group. A preferred embodiment of the alkylthio group includes, for example, a C _1-6 alkylthio group such as a methylthio group. A preferred embodiment of the acyl group includes, for example, a C _1-6 acyl group such as an acetyl group. Preferred examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. A preferred embodiment of the dialkylamino group includes, for example, a di-C _1-4 alkylamino group such as a dimethylamino group. A preferred embodiment of the dialkylcarbonylamino group includes, for example, a di-C _1-4 alkyl-carbonylamino group such as a diacetylamino group.

These substituents ^R2 can be used alone or in combination of two or more. Among these, a C _1-6 alkyl group, a C _5-8 cycloalkyl group, and a C _1-4 alkoxy group are preferable, and a C _1-4 alkyl group such as a methyl group is particularly preferable, and has no substituent (described later. The number of substitutions k to be performed is 0) is most preferable.

The substitution number k of the substituent R ² can be appropriately selected according to the type of the ring Z ¹ , and the preferred range is 0 to 8, 0 to 4, 0 to 2, and 0 to 1 in the following steps. When k is 1, ring Z ¹ may be a benzene, naphthalene or biphenyl ring and R ² may be a methyl group. In particular, when the ring Z ¹ is a benzene ring, the substitution number k of the substituent R ² can be selected from, for example, an integer of 0 to 4, and the preferred range is 0 to 3, 0 to 2, It can be from 0 to 1, with 0 being most preferred. The number of substitutions k in different arene rings may be the same or different. Further, when the substitution number k is 2 or more, the types of the two or more R ² substituted on the same arene ring may be the same or different. The substitution position of R ² is not particularly limited as long as it is substituted at a position other than the bonding position between the arene ring and the ether bond (--O--) or the 9-position of the fluorene ring.

Among the radically polymerizable compounds represented by the formula (1), representative compounds include, for example, 9,9-bis[(meth)acryloyloxy-(poly)ethoxyphenyl]fluorene, 9,9-bis 9,9-bis[(meth)acryloyloxy-(poly)ethoxyaryl]fluorenes such as [(meth)acryloyloxy-(poly)ethoxynaphthyl]fluorene; 9,9-bis[(3-(meth)acryloyl) 9,9-bis[(3-(meth)acryloyloxy) such as oxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[(3-(meth)acryloyloxy-2-hydroxypropoxy)naphthyl]fluorene -2-hydroxypropoxy)aryl]fluorenes; 9,9-bis[(3-(meth)acryloyloxy-2-hydroxypropoxy)(poly)ethoxyphenyl]fluorene, 9,9-bis[(3-(meth) ) 9,9-bis[(3-(meth)acryloyloxy-2-hydroxypropoxy)(poly)ethoxyaryl]fluorenes such as acryloyloxy-2-hydroxypropoxy)(poly)ethoxynaphthyl]fluorene . Among these, 9,9-bis[(3-acryloyloxy-2-hydroxypropoxy)aryl]fluorenes are preferred, and 9,9-bis[(3-acryloyloxy-2-hydroxypropoxy)phenyl]fluorene is particularly preferable.

In the curable composition of the present invention, the proportion of the radically polymerizable compound (B) may be 50 parts by weight or more with respect to 100 parts by weight of the polysilane (A). 100 parts by weight or more, 120 parts by weight or more, 130 parts by weight or more, 140 parts by weight or more. Further, the proportion of the radically polymerizable compound (B) may be 50 to 1000 parts by weight with respect to 100 parts by weight of the polysilane (A). 120 to 300 parts by weight, 130 to 200 parts by weight, 140 to 180 parts by weight, and 150 to 170 parts by weight. If the ratio of the radically polymerizable compound (B) to the polysilane (A) is too small, the insolubilization rate of the cured product may decrease.

(C) Thiol compound The thiol compound (C) may have a thiol group for the ene/thiol reaction with the radically polymerizable compound (B). Polythiol compounds having the above thiol groups are preferred.

The polythiol compound preferably contains a polythiol compound having 3 or more thiol groups in the molecule because it facilitates formation of a network and can improve the insolubilization rate of the cured product.

In the polythiol compound having 3 or more thiol groups in the molecule, the number of thiol groups in the molecule can be selected, for example, from a range of about 3 to 10, and from the viewpoint of excellent balance of various properties, the preferable range is as follows. Stepwise, 3-8, 3-6, 4-5, with 4 being the most preferred.

Such polythiol compounds include, for example, glycerin tri(mercapto C _2-6 carboxylic acid ester) such as glycerin tri(3-mercaptobutyrate); trimethylolpropane such as tri(3-mercaptobutyrate); tri(mercapto C _2-6 carboxylic acid ester); trimethylolethane tri(mercapto C _2-6 carboxylic acid ester) such as trimethylolethane tri(3-mercaptobutyrate); pentaerythritol tri(3-mercaptobutyrate) pentaerythritol tri(mercapto C _2-6 carboxylic acid ester) such as; ditrimethylolpropane tetrakis (mercapto C _2-6 carboxylic acid ester) such as ditrimethylolpropane tetrakis (3-mercaptobutyrate); pentaerythritol tetrakis (mercaptoacetate ), pentaerythritol tetrakis (2-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol Pentaerythritol tetrakis (mercapto C _2-6 carboxylic acid ester) such as tetrakis (4-mercaptobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate); pentaerythritol penta(mercapto C _2-6 carboxylic acid ester); dipentaerythritol hexa(mercapto C _2-6 carboxylic acid ester) such as dipentaerythritol hexa(3-mercaptobutyrate);

These polythiol compounds can be used alone or in combination of two or more. Among these, pentaerythritol tetrakis (mercapto C _2-6 carboxylic acid ester) such as pentaerythritol tetrakis (3-mercaptopropionate) is preferred, and pentaerythritol tetrakis (mercapto C _3-5 carboxylic acid ester) is particularly preferred.

The polythiol compound is preferably a polyol compound having a fluorene skeleton (e.g., a dithiol compound having a fluorene skeleton) when the cured product is used in applications requiring a high refractive index, and is represented by the above formula (2), for example. It may be a dithiol compound.

Examples of the arene ring represented by ring Z ² in the formula (2) include the arene rings exemplified as the arene rings in the formula (1). Among the arene rings, monocyclic arene rings such as a benzene ring, biarene rings such as a biphenyl ring, condensed bicyclic arene rings such as a naphthalene ring, and the like are widely used. Especially preferred.

The alkylene group ^A2 is the same as the alkylene group A1 of the above formula ( ¹ ), including preferred embodiments. p (repeating number of each group A ² O), which is the repeating number (addition mole number) of the oxyalkylene group A ² O, is preferably 0 or 1 or more, and more preferably ranges from 0 to 10, 0-5, 0-3, 0-2, 0 or 1, with 1 being most preferred. Too many repetitions of A ² O may lower the refractive index of the cured product.

Examples of the alkylene group A3 include linear groups such as methylene ^, ethylene, ethylidene, trimethylene, propylene, isopropylidene, tetramethylene group, 1,2-butanediyl, 1,3-butanediyl, hexamethylene group and octamethylene group. or a branched C _1-10 alkylene group. Groups ^A2 on both sides may be the same alkylene group or different alkylene groups. Among these, linear or branched C _1-4 alkylene groups such as methylene, ethylidene, propylene and isopropylidene are preferred, and C _2-3 alkylene groups such as propylene are particularly preferred, from the viewpoint of optical properties. The propylene group may be a 2-methylethanediyl group (a propylene group having a methyl group on the carbon atom to which the thiol group is attached).

The substituent R ³ is the same as those exemplified as the substituent R ¹ in the above formula (1), including its preferred embodiments, and the substitution number q of the substituent R ³ , including its preferred embodiments, is the same as the above It is the same as that exemplified as the number of substitutions m in formula (1).

The substituent R ⁴ , including its preferred embodiments, is the same as those exemplified as the substituent R ² in the formula (1), and the substitution number r of the substituent R ⁴ , including its preferred embodiments, is the same as the above This is the same as that exemplified as the number of substitutions k in formula (1).

Examples of the compound represented by the formula (2) include 9H-fluorene-9-ylidenebis(4,1-phenyleneoxy-2,1-ethanediyl) 2-mercaptoacetate (or 9,9-bis[4- (2-mercaptoacetoxyethoxy)phenyl]fluorene), 9H-fluorene-9-ylidenebis(4,1-phenyleneoxy-2,1-ethanediyl) 3-mercaptopropionate (BPEFMP), 9H-fluorene-9-ylidenebis (4,1-phenyleneoxy-2,1-ethanediyl) 2-mercaptopropionate, 9H-fluorene-9-ylidenebis(4,1-phenyleneoxy-2,1-ethanediyl) 3-mercaptobutyrate (BPEFMB) 9H-fluorene-9-ylidenebis(aryleneoxy-C _2-4 alkanediyl) mercapto such as 9H-fluorene-9-ylidenebis(6,2-naphthyleneoxy-2,1-ethanediyl) 3-mercaptobutyrate (BNEFMB) and C _2-6 acylate. Of these, 9H-fluorene-9-ylidenebis(4,1-phenylene-2,1-ethanediyl)mercapto C _3-5 acylates such as BPEFMB are preferred.

These thiol compounds can be appropriately selected and used depending on the intended use. compound) may be used alone or in combination, but from the viewpoint of improving the insolubilization rate of the cured product and having an excellent balance between optical properties and mechanical properties, 3 or more thiols in the molecule It preferably contains a polythiol compound having a group. The polythiol compound having 3 or more thiol groups in the molecule may be 50% by weight or more with respect to the entire thiol compound, and the preferred range is 60 to 100% by weight, 80 to 100% by weight, in stages below. , 90 to 100% by weight, with 100% by weight being most preferred.

In the curable composition of the present invention, the proportion of the thiol compound (C) may be 1 part by weight or more with respect to a total of 100 parts by weight of the polysilane (A) and the radically polymerizable compound (B), preferably 5 parts by weight or more, 10 parts by weight or more, 11 parts by weight or more, 12 parts by weight or more, and 12.5 parts by weight or more. Further, the ratio of the thiol compound (C) may be 1 to 100 parts by weight with respect to a total of 100 parts by weight of the polysilane (A) and the radically polymerizable compound (B). Typically, 5-80 parts by weight, 10-50 parts by weight, 11-40 parts by weight, 12-30 parts by weight, 12.5-20 parts by weight, 13-15 parts by weight. If the ratio of the thiol compound (C) to the total amount of the polysilane (A) and the radically polymerizable compound (B) is too small, the refractive index of the cured product may decrease.

(D) Radical polymerization initiator As the radical polymerization initiator (D), a conventional photoradical polymerization initiator such as a ketone compound (acetophenone compound, benzophenone compound, benzoin compound, benzyl compound, anthraquinone compound , thioxanthone-based compounds, morpholine-based compounds, etc.), phosphine-based compounds, sulfide-based compounds (dibutyl sulfide, diphenyl disulfide, dibenzyl sulfide, decylphenyl sulfide, tetramethylthiuram monosulfide, etc.). Among these radical photopolymerization initiators, phosphine compounds are preferred.

Phosphine compounds include, for example, phenyl-bis(2,4,6-trimethylbenzoyl)-phosphine oxide (BAPO), diphenyl-2,4,6-trimethylbenzoyl-phosphine oxide (MAPO), phenyl-2,4 ,6-trimethylbenzoyl-ethoxy-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-methyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-ethyl-phosphine oxide, bis(2,4 ,6-trimethylbenzoyl)-n-butyl-phosphine oxide. These phosphine compounds can be used alone or in combination of two or more.

Among these phosphine compounds, acylphosphine oxide polymerization initiators are preferred, and _{bisacylphosphine} oxide polymerization initiators are more preferred from the viewpoint of improving polymerizability. Alkylbenzoyl)-phosphine oxides are particularly preferred.

In the curable composition of the present invention, the preferred range of content of the radical polymerization initiator (D) can be defined, for example, as a ratio relative to 100 parts by weight of the radically polymerizable compound (B). The content ratio of the radical polymerization initiator (D) to 100 parts by weight of the radically polymerizable compound (B) is preferably, for example, 0.01 to 10 parts by weight, and then stepwise, 0.05 to 5 parts by weight, 0.1 to 3 parts by weight, 0.3 to 2 parts by weight, particularly preferably 0.5 to 1.5 parts by weight.

(E) Other radically polymerizable compound As the other radically polymerizable compound (E), a conventional radically polymerizable compound having no fluorene skeleton and having a radically polymerizable ethylenically unsaturated bond can be used. However, polyfunctional ethylenically unsaturated compounds are preferred from the viewpoint of polymerizability.

As polyfunctional ethylenically unsaturated compounds, compounds having allyl groups such as diallyl phthalate and triallyl isocyanurate can also be used, but polyfunctional (meth)acrylates having multiple (meth)acryloyl groups may be used. many. Polyfunctional (meth)acrylates include di(meth)acrylates [e.g., ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4 - _C2-10 alkanediol di(meth)acrylates such as butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate; diethylene glycol di(meth)acrylate; Polyalkylene glycol di(meth)acrylates such as , triethylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate; Bridged cyclic (meth)acrylates such as tricyclodecanedimethanol di(meth)acrylate etc.], poly(meth)acrylates having 3 or more (meth)acryloyl groups [e.g., trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipenta alkane polyol poly(meth)acrylates such as erythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate; tri(meth)acrylates of C _2-4 alkylene oxide adducts of alkane polyols such as trimethylolpropane; Tri(meth)acrylates having a triazine ring such as tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate] can be exemplified.

The polyfunctional ethylenically unsaturated compound may be a compound having a bisaryl skeleton. Such compounds include, for example, bisphenols (bisphenols such as bisphenol A, F, and S) or their C _2-4 alkylene oxide adduct di(meth)acrylates [for example, 2,2-bis(4 -(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, etc.] etc.

Among these, poly(meth)acrylates having 3 or more (meth)acryloyl groups such as dipentaerythritol hexa(meth)acrylate are commonly used.

The ratio of the other radically polymerizable compound (E) may be 100 parts by weight or less with respect to 100 parts by weight of the radically polymerizable compound (B). More preferably, it is 50 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, and more preferably 1 part by weight or less. It is most preferable not to contain other radically polymerizable compounds (E). On the other hand, if the ratio of the other radically polymerizable compound (E) is too high, the refractive index of the cured product may be lowered.

The other radically polymerizable compound (E) can improve the insolubilization rate of the cured product, so that in the above formula (1), which is a radically polymerizable compound (B) having a high refractive index, ring Z ¹ is a naphthalene ring. preferably in combination with a toxic compound. When both compounds are combined, the ratio of the other radically polymerizable compound (E) is selected from the range of about 1 to 100 parts by weight with respect to 100 parts by weight of the radically polymerizable compound (B) in which ring Z ¹ is a naphthalene ring. A preferable range is 3 to 80 parts by weight, 5 to 60 parts by weight, 10 to 50 parts by weight, 20 to 40 parts by weight, and most preferably 25 to 35 parts by weight.

(F) Other Additives The curable composition of the present invention may further contain other additives. Other additives include conventional additives such as photosensitizers used together with radical polymerization initiators [eg, dialkylaminobenzoic acid or its esters, tertiary amines such as acridine; 3-(2- benzothiazolyl)-7-(diethylamino)coumarin; quinolines such as 2-(2-(4-dimethylaminophenyl)ethenyl)quinoline; quinones such as benzoquinone and anthraquinone; pyrenes such as 1-nitropyrene; aromatic hydrocarbons, etc.] Colorants (dyes and pigments), thickeners, stabilizers (anti-aging agents, antioxidants, anti-ozonants, etc.), defoaming agents, leveling agents, dispersants, flame retardants, Examples include antistatic agents, fillers, lubricants, and the like. These additives can be used alone or in combination of two or more. The ratio of these other additives can be appropriately selected according to the type of additive. , 0.1 to 50 parts by weight, 0.3 to 30 parts by weight, and 0.5 to 20 parts by weight.

The curable composition of the present invention may contain a solvent from the viewpoint of improving handling properties and coating properties. Examples of solvents include hydrocarbons (hexane, cyclohexane, toluene, etc.), alcohols (ethanol, propanol, etc.), ethers [diethyl ether, tetrahydrofuran (THF), etc.], ketones [ethyl methyl ketone (2-butanone ), cyclohexanone, etc.], esters (ethyl acetate, butyl acetate, etc.), diols (ethylene glycol, propylene glycol, polyoxyethylene glycol, etc.), cellosolves [methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether (dimethoxyethane), propylene glycol monomethyl ether, etc.], carbitols [carbitol, diethylene glycol dimethyl ether (diglyme), diethylene glycol methyl ethyl ether, etc.], cellosolve acetates (propylene glycol methyl acetate, etc.), and the like.

These solvents can be used alone or in combination of two or more. Among these solvents, ethers, ketones, cellosolves, carbitols, cellosolve acetates and the like are preferred.

The solvent may be used in an appropriate amount so as to obtain a coating liquid viscosity suitable for coating. The photopolymerizable resin composition can be selected from the range of 1 to 60% by weight in these solvents. , 25 to 35% by weight.

The curable composition comprises a polysilane (A), a radically polymerizable compound (B), a thiol compound (C) and a radical polymerization initiator (D), and optionally other additives, and optionally a solvent. and uniformly mixed by dissolving, dispersing and mixing.

[Cured product and its manufacturing method]
In the present invention, the cured product may be produced by a production method including a photocuring step of irradiating the curable composition with visible light to form a photocured product. Examples of the cured product include, but are not limited to, a three-dimensional cured product, a one-dimensional or two-dimensional cured product such as a cured film or a cured pattern, and a point- or dot-shaped cured product.

In the photo-curing step, the photo-cured product (photo-cured film, photo-cured pattern, etc.) is formed by applying the curable composition onto a substrate, forming a coating film, and then irradiating (exposure) with visible light. may be formed. In addition, it is preferable to irradiate the curable composition with visible light while heating, because a high degree of three-dimensional cross-linking occurs to promote network formation and improve the cross-linking strength and insolubilization rate of the cured product.

The curable compositions may be used, for example, to produce coatings (thin films) on substrates. When the curable composition is applied to a substrate to produce a coating film, the curable composition may be dissolved or dispersed in the solvent and then applied to the substrate.

Examples of coating methods include flow coating, spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roll coating, gravure coating, dipping, and slitting. be done.

The thickness of the coating film can usually be selected from the range of about 0.01 μm to 10 mm depending on the use of the cured product. In the case of photoresist, the thickness of the coating film is usually about 0.05 to 10 μm, and may be, for example, about 0.1 to 5 μm. In the case of printed wiring boards, the thickness of the coating film is usually about 10 μm to 5 mm, and may be, for example, about 100 μm to 1 mm. In the case of an optical thin film, the thickness of the coating film is usually about 0.1 to 100 μm, and may be, for example, about 0.3 to 50 μm.

If the curable composition contains a solvent, it may be dried to remove the solvent. Drying may be natural drying, but drying by heating is preferable from the viewpoint of productivity. The heating temperature for drying is, for example, 40-80°C, preferably 50-70°C.

The wavelength of the visible light can be selected from the range of 380 to 780 nm, and the preferred range is 380 to 600 nm, 385 to 500 nm, 390 to 450 nm, and 400 to 410 nm in stages below. Most preferred is the h-line (405 nm) that can be emitted.

The irradiation light amount (exposure amount) of visible light can be selected from a range in which the resin composition can be cured according to the thickness of the coating film, and is, for example, 10 mJ/cm ² or more (for example, 100 to 10,000 mJ/cm ² ). A preferable range is 1000 to 9000 mJ/cm ² , 3000 to 8500 mJ/cm ² , 4000 to 8000 mJ/cm ² and 5000 to 7000 mJ/cm ² in stages. If the amount of exposure is too small, the photocurability may deteriorate.

Examples of visible light sources include high-pressure mercury lamps, deuterium lamps, halogen lamps, metal halide lamps, xenon lamps, and laser beams (such as LED lasers).

The irradiation time of visible light can be appropriately selected according to the amount of irradiation light and the heating temperature. typically 0.1-10 minutes, 0.3-8 minutes, 0.5-5 minutes, 1-4 minutes, 1.2-3 minutes, and 1.5-2.5 minutes Most preferred.

When heating with visible light irradiation, the heating temperature can be selected, for example, from the range of about 80 to 150 ° C., and the preferred range is 90 to 130 ° C., 100 to 120 ° C., and 105 to 115 ° C. in stages. be. In the present invention, although it is irradiated with visible light, heating at a high temperature is unnecessary, and a strong cured product can be formed by heating at a low temperature (for example, 120 ° C. or less), and deformation and deterioration of the cured product. can also be suppressed.

The curable composition may be used for forming patterns and images (such as for producing printed wiring boards). When producing a printed wiring board, the curable composition may be applied onto a substrate to form a coating film, and the formed coating film may be irradiated with light (pattern exposure). Pattern exposure may be performed by scanning with laser light, or by light irradiation through a photomask. A pattern or image may be formed by developing (or dissolving) and removing non-irradiated areas (unexposed areas) generated by pattern exposure. Examples of the developer include water, alkaline aqueous solution, hydrophilic solvent (e.g., alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and cyclohexanone, ethers such as dioxane and tetrahydrofuran, cellosolves, and cellosolve acetates. etc.) and mixtures thereof.

In particular, when visible light is irradiated while heating, heating can cause high degree of cross-linking in the irradiated area (exposed area) of the coating film. can be formed. Therefore, the curable composition of the present invention may be used in applications requiring precise patterns, such as the manufacture of printed wiring boards for electronic devices.

When forming an optical thin film, a plurality of layers of the curable composition may be formed on the substrate. Moreover, after forming other functional layers on the substrate, a layer of the curable composition may be formed on the functional layers. The curable composition of the present invention has excellent visible light transmittance, has a high refractive index, and has excellent optical properties. may be used for the optical thin film of

The material of the substrate is selected according to the application. For example, in the case of printed wiring boards and optical thin films, semiconductors (silicon, gallium arsenide, gallium nitride, silicon carbide, etc.), metals (aluminum, copper, etc.), ceramics, etc. (zirconium oxide, titanium oxide, PZT, etc.), transparent inorganic materials (glass, quartz, magnesium fluoride, calcium fluoride, etc.), transparent resins (polymethyl methacrylate, polymethyl acrylate, polystyrene, etc.).

The obtained cured product has excellent cross-linking strength, and the insolubilization rate with tetrahydrofuran (THF) may be 5% or more, and a preferable range is 10% or more (for example, 10 to 99% ), 20% or more (eg 20-98%), 40% or more (eg 40-95%), 50% or more (eg 50-90%), 60% or more (eg 60-85%), 70% Above (eg, 70-80%) is most preferred. In this specification and claims, the insolubilization rate can be calculated from the film thickness ratio before and after immersion in THF for 10 minutes.

The refractive index of the obtained cured product is a high refractive index, and may be 1.6 or more at 25° C. and 589 nm. 1.605-1.64, 1.61-1.63. Also, at 25° C. and 656 nm, it may be 1.59 or more. It may be about 0.6 to 1.62.

The Abbe number of the obtained cured product can be selected from the range of about 10 to 50, and the preferred ranges are 12 to 45, 15 to 40, 18 to 30, and 20 to 25 in stages.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples. The materials used in the following examples and comparative examples are as follows, and the properties and evaluation of the cured products obtained in the examples and comparative examples were measured as follows.

[material]
(Radical polymerizable compound)
A-DPH: dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. PEMB: pentaerythritol tetrakis (3-mercaptobutyrate) represented by the following formula, manufactured by Showa Denko K.K.

BPFGA: 9,9-bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]fluorene represented by the following formula, synthesized according to Example 1 of JP-A-2001-354735

BNEFA: 9,9-bis[6-(2-acryloyloxyethoxy)-2-naphthyl]fluorene represented by the following formula, synthesized according to Example 1 of JP-A-2009-173648

(thiol compound)
BPEFMB: 9H-fluorene-9-ylidenebis(4,1-phenyleneoxy-2,1-ethanediyl) 3-mercaptobutyrate (or 9,9-bis[4-(2-(3- Mercaptobutyroyloxy)ethoxy)phenyl]fluorene), synthesized according to Synthesis Example 1 of JP-A-2006-151959

BPEFMP: 9H-fluorene-9-ylidenebis(4,1-phenyleneoxy-2,1-ethanediyl) 3-mercaptopropionate (or 9,9-bis[4-(2-(2 -Mercaptopropionyloxy)ethoxy)phenyl]fluorene), synthesized according to Synthesis Example 1 of JP-A-2006-151959.

BNEFMB: 9H-fluorene-9-ylidenebis(6,2-naphthyleneoxy-2,1-ethanediyl) 3-mercaptobutyrate (or 9,9-bis[6-(2-(3-mercaptobutyroyloxy)ethoxy) -2-naphthyl]fluorene), synthesized according to Synthesis Example 1 of JP-A-2006-151959.

(polysilane)
PMPS: Polymethylphenylsilane, "PMPS" manufactured by Osaka Gas Chemicals Co., Ltd., number average molecular weight Mn=11,000.

(Radical polymerization initiator)
MAPO: Phenyl-bis(2,4,6-trimethylbenzoyl)-phosphine oxide, manufactured by Aldrich BAPO: Diphenyl-2,4,6-trimethylbenzoyl-phosphine oxide, manufactured by Aldrich.

[Thickness]
The thicknesses of the cured products obtained in Examples and Comparative Examples were measured using a non-contact film thickness measuring device ("Nsnospec/AFT M-3000" manufactured by Nanometrics Japan Co., Ltd.).

[Insolubilization rate]
After measuring the thickness of the cured products obtained in Examples and Comparative Examples, the cured products were immersed in THF (tetrahydrofuran) for 10 minutes, then taken out of THF and measured for thickness after immersion. The ratio was calculated as the insolubilization rate.

[Optical properties (refractive index and Abbe number)]
Using a multi-wavelength Abbe refractometer (manufactured by Atago Co., Ltd. "DR-M4"), at a temperature of 25 ° C., the refractive indices nF, nD and nC at the F line, D line and C line (wavelengths of 486 nm and 589 nm respectively) , using an interference filter at 656 nm).

Example 1
67 parts by weight of PMPS, 109 parts by weight of BPFGA, 25 parts by weight of PEMB, 500 parts by weight of cyclohexanone (solvent), and 1 part by weight of BAPO as a photopolymerization initiator are mixed in a sample tube and stirred to mix uniformly. let me This mixed solution was spin-coated on a silicon substrate at 2000 rpm for 20 seconds, and then prebaked on a hot plate at 60° C. for 2 minutes to remove the solvent to obtain a thin film with a thickness of about 1 μm. This thin film was cured at 110° C. for 126 sec while irradiating a predetermined amount of visible light of 405 nm using an LED laser (“BP300” manufactured by Pall Semiconductor Co., Ltd., 47.6 mW/cm ² ) (irradiation light amount: 6000 mJ/ ^cm2 ). When the refractive index of the obtained cured film was measured with an Abbe refractometer, the refractive index at 589 nm was 1.6128. Moreover, the insolubilization rate of the cured film was 74%.

Example 2
A cured film was produced in the same manner as in Example 1 except that PMPS was 100 parts by weight, BPFGA was 82 parts by weight, and PEMB was 13 parts by weight. , the insolubilization rate was 28%.

Example 3
A thin film was produced in the same manner as in Example 1 except that PMPS was 67 parts by weight, BPFGA was 88 parts by weight, and ^BPEFMB was 49 parts by weight. C. for 252 sec to prepare a cured film. When the optical properties and insolubilization rate of the cured film were measured, the refractive index was 1.6141 and the insolubilization rate was 24%.

Example 4
A thin film was produced in the same manner as in Example 1 except that PMPS was 67 parts by weight, ^BPFGA was 84 parts by weight, and BNEFMB was 49 parts by weight. was cured for 252 sec to produce a cured film. When the optical properties and insolubilization rate of the cured film were measured, the refractive index was 1.6122 and the insolubilization rate was 6%.

Comparative example 1
A cured film was produced in the same manner as in Example 1 except that PMPS was 67 parts by weight, BPFGA was 78 parts by weight, and PEMB was 55 parts by weight. , the insolubilization rate was 77%.

Example 5
A thin film was produced in the same manner as in Example 1 except that PMPS was 67 parts by weight, A-DPH was 23 parts by weight, BNEFA was 78 parts by weight, and PEMB was 33 parts by weight. cm ² and cured at 110° C. for 378 sec to produce a cured film. When the optical properties and insolubilization rate of the cured film were measured, the refractive index was 1.6147 and the insolubilization rate was 44%.

Comparative example 2
A thin film was produced in the same manner as in Example 1 except that PMPS was not used, 132 parts by weight of BPFGA, 68 parts by weight of BPEFMP, and 1 part by weight of TPO were used instead of BAPO. ) "BP300", 300 mW), a xenon lamp ("MAX301", 300 W, manufactured by Asahi Spectrosco Co., Ltd.) was used, and the light intensity was 2.7 mW/cm ² through an interference filter for 405 nm, and the light irradiation amount was 3,000 mJ. /cm ² and cured at 120°C for 1107 sec to produce a cured film. When the optical properties and insolubilization rate of the cured film were measured, the refractive index was 1.6050 and the insolubilization rate was 61%.

Comparative example 3
A thin film was produced in the same manner as in Example 1 except that PMPS was not used, 132 parts by weight of BPFGA, 68 parts by weight of BPEFMP, and 1 part by weight of TPO were used instead of BAPO. A xenon lamp (“MAX301”, 300 W, manufactured by Asahi Spectrosco Co., Ltd.) was used instead of the “BP300”, 300 mW manufactured by the company, and the light intensity was 1.3 mW/cm ² through an interference filter for 365 nm, and the light irradiation amount was 1,000 mJ/. cm ² and cured at 120° C. for 763 sec to produce a cured film. When the optical properties and insolubilization rate of the cured film were measured, the refractive index was 1.6050 and the insolubilization rate was 68%.

Comparative example 4
A thin film was produced in the same manner as in Example 1 except that PMPS was not used, 134 parts by weight of BPFGA, 66 parts by weight of BPEFMB, and 1 part by weight of TPO were used instead of BAPO. /cm ² and cured at 120°C for 1107 sec to produce a cured film. When the optical properties and insolubilization rate of the cured film were measured, the refractive index was 1.5953 and the insolubilization rate was 6%.

Comparative example 5
A thin film was produced in the same manner as in Example 1 except that PMPS was not used, 134 parts by weight of BPFGA, 66 parts by weight of BPEFMB, and 1 part by weight of TPO were used instead of BAPO. ) "BP300", 300 mW), a xenon lamp ("MAX301", 300 W, manufactured by Asahi Spectrosco Co., Ltd.) was used, and the light intensity was 1.3 mW/cm ² through an interference filter for 365 nm, and the light irradiation amount was 2,000 mJ. /cm ² and cured at 120°C for 1527 sec to produce a cured film. When the optical properties and insolubilization rate of the cured film were measured, the refractive index was 1.5953 and the insolubilization rate was 15%.

Comparative example 6
A cured film was produced in the same manner as in Example 1 except that no PMPS was used, 163 parts by weight of BPFGA and 37 parts by weight of PEMB were used, and the optical properties and insolubilization rate were measured. , the insolubilization rate was 84%.

Comparative example 7
A thin film was prepared in the same manner as in Example 1 except that PMPS was not used and 77 parts by weight of A-DHP and 123 parts by weight of BPEFMB were used, and then cured at 110° C. for 126 seconds to prepare a cured film. When the optical properties and insolubilization rate of the cured film were measured, the refractive index was 1.5690 and the insolubilization rate was 86%.

Table 1 shows the evaluation results of the cured products obtained in Examples and Comparative Examples.

From the results in Table 1, the cured products obtained in Examples have a better balance between the insolubilization rate and the optical properties than the cured products obtained in Comparative Examples. The cured product obtained in Example 1) is excellent in balance.

The curable composition of the present invention and its cured product can be used as coating materials, wire coating materials, sealing materials and insulating materials for electronic devices, printed wiring boards, protective films, photoresists, printing plate materials, inks, adhesives, and adhesives. , optical thin films (high refractive index layers of antireflection films such as liquid crystal displays, reflectors, etc.).

Claims (12)

Polysilane (A) ;
a radical polymerizable compound (B) having a fluorene skeleton represented by the following formula (1) ;
a thiol compound (C) having two or more thiol groups in the molecule ;
A curable composition comprising a radical polymerization initiator (D).

(Wherein, ring Z ¹ is an arene ring, A ¹ is an alkylene group, X is an allyl group or (meth)acryloyl group, R ¹ and R ² are substituents, n is 0 or a number of 1 or more, m is 0 to number of 4, k is 0 or 1 or more, s is 0 or 1) 2. The curable composition according to claim 1 , wherein in formula (1), ring Z ¹ is a benzene ring, n is 0, and s is 1. In formula (1), ring Z ¹ is a naphthalene ring, n is 1, and s is 0. The curable composition according to any one of claims 1 to 3, wherein the thiol compound (C) contains a polythiol compound having 3 or more thiol groups in the molecule. The curable composition according to any one of claims 1 to 4, wherein the thiol compound (C) contains a dithiol compound having a fluorene skeleton. 6. The curable composition according to claim 5, wherein the dithiol compound having a fluorene skeleton is a dithiol compound represented by the following formula (2).

(Wherein, ring Z ² is an arene ring, A ² and A ³ are alkylene groups, R ³ and R ⁴ are substituents, p is a number of 0 or 1 or more, q is a number of 0 to 4, r is 0 or 1 or more) The curable composition according to any one of claims 1 to 6, wherein the polysilane (A) is a polyC _1-3 alkyl C _6-10 arylsilane having a number average molecular weight of 100 to 50,000. The curable composition according to any one of claims 1 to 7, wherein the ratio of the radically polymerizable compound (B) is 100 parts by weight or more per 100 parts by weight of the polysilane (A). The curable composition according to any one of claims 1 to 8, wherein the ratio of the thiol compound (C) is 10 parts by weight or more with respect to the total 100 parts by weight of the polysilane (A) and the radically polymerizable compound (B). . A method for producing a cured product, which comprises a photocuring step of irradiating the curable composition according to any one of claims 1 to 9 with visible light to form a photocured product. 11. The production method according to claim 10, wherein in the photocuring step, the curable composition is irradiated with visible light while being heated at 80 to 150°C. A cured product obtained by curing the curable composition according to any one of claims 1 to 9 with visible light .