JP2018016616A - Thiol compound and method for producing the same, and curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thiol compound having high heat resistance and excellent handleability and a method for producing the same, and a curable composition containing the thiol compound.SOLUTION: A thiol compound has a 9,9-bisarylfluorene skeleton, is represented by the following formula (1), and is useful for preparing a curable composition using ene/thiol reaction (where ring Zis a polycyclic arene ring such as a naphthalene ring; Rand Rindependently represent a linear or branched chain alkylene group; m is an integer of 0 or 1 or greater; n is an integer of 1 or greater; Rand Rare substituents; p is an integer of 0 or 1 or greater; k is an integer of 0-4).SELECTED DRAWING: None

Description

  The present invention relates to a thiol compound having a 9,9-bisarylfluorene skeleton and useful for improving refractive index and heat resistance, a method for producing the same, a curable composition containing the thiol compound, and a cured product thereof. .

  When a thiol compound having a 9,9-bisarylfluorene skeleton is used as a resin raw material, the heat resistance and refractive index of the resin can be improved. For example, in JP-A-8-59775 (Patent Document 1), a mercaptopropionic acid ester of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene is reacted with an isocyanate compound to provide heat resistance, It is described that a urethane resin excellent in impact resistance and weather resistance is obtained, and that this urethane resin is suitable for a colorless and transparent plastic lens having a high refractive index. JP-A-2006-151959 (Patent Document 2) discloses a mercaptoalkanoic acid ester of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene having a secondary or tertiary mercapto group. A thiol compound and a photosensitive composition containing the thiol compound are described. This document describes that the photosensitive composition has high sensitivity and excellent line width retention of a fine line pattern.

  However, these thiol compounds still have a low refractive index and insufficient heat resistance. Therefore, the use of the thiol compound is limited. Furthermore, the thiol compound is a very viscous compound at room temperature, and the handling property is greatly impaired.

  JP 2010-254732 A (Patent Document 3) describes a curable composition in which at least one of the ethylenically unsaturated compound and the thiol compound is a compound having a 9,9-bisarylfluorene skeleton. In this example, 9,9-bis (4-acryloyloxyethoxyphenyl) fluorene is used as the ethylenically unsaturated compound, and pentaerythritol tetra (3-mercaptobutyrate) is used as the thiol compound. Examples of the thiol compound include 9,9-bis [4- (2-mercaptopropylcarbonyloxyethoxy) phenyl] fluorene and the like, and compounds having a phenyl group as a naphthyl group are also described. An example using is not described.

JP-A-8-59775 (Claims, [0018], Examples) JP 2006-151959 A (Claims, [0010], Examples) JP 2010-254732 A (claim, [0068], Example 1)

  Therefore, the objective of this invention is providing the thiol compound which has high heat resistance, its manufacturing method, a curable composition, and its hardened | cured material.

  Another object of the present invention is to provide a thiol compound that can greatly improve the handleability and the refractive index, and a method for producing the same.

  Still another object of the present invention is to provide a thiol compound which has a polycyclic aryl skeleton and is excellent in transparency and can be colored, and a method for producing the same.

  Another object of the present invention is to provide a heat-resistant resin raw material, a thiol compound useful as a component of a photosensitive resin composition, a method for producing the same, a curable composition utilizing an ene / thiol reaction, and a cured product thereof. There is.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that in a compound having a 9,9-bisarylfluorene skeleton, a thiol compound having a polycyclic aryl group and a mercapto group has a phenyl group and a hydroxyl group. Compared with the hydroxy compound having the above, the heat resistance can be unexpectedly greatly improved, and it is a solid form having a high handleability at room temperature, and the curable composition containing the thiol compound has an extremely high heat resistance ( Or the production of a cured product having a glass transition temperature) to complete the present invention.

  That is, the thiol compound of the present invention has a 9,9-bisarylfluorene skeleton and is represented by the following formula (1). Hereinafter, the compound represented by the formula (1) may be simply referred to as a thiol compound.

Wherein ring Z ₁ is a polycyclic arene ring; R ¹ and R ² are each independently a linear or branched alkylene group; m is an integer of 0 or 1 or more; n is an integer of 1 or more; R ⁴ and R ⁵ are substituents; p is 0 or an integer of 1 or more; k is an integer of 0 to 4.

In the formula (1), the ring Z ₁ is a condensed polycyclic arene ring (for example, a condensed bicyclic or tricyclic arene ring such as a naphthalene ring) or a ring assembly arene ring (for example, a bearene ring such as a biphenyl ring or R ¹ may be a linear or branched C _2-6 alkylene group (for example, a linear or branched C _2-4 alkylene group), and R ² may be a linear chain. Alternatively, it may be a branched C _1-10 alkylene group (for example, a linear or branched C _1-5 alkylene group), m is an integer of 0 to 5 (for example, 0 or 1), and n is It may be an integer of 1 or 2 (for example, 1).

R ⁴ is an alkyl group or an alkoxy group (for example, a C _1-4 alkyl group), p is an integer of 0 to 3 (for example, an integer of 0 to 2), R ⁵ is a cyano group, a halogen atom, or an alkyl group (for example, C _1-4 alkyl group), k may be an integer of 0 to 3 (for example, 0 or 1).

  In the thiol compound, the group -SH may be a primary, secondary or tertiary mercapto group, and may usually be a primary or secondary mercapto group.

  The thiol compound represented by the formula (1) can be produced, for example, by reacting a compound represented by the following formula (2) with a compound represented by the following formula (3).

(Wherein X ¹ represents a halogen atom or a group —OR ³ (R ³ is a hydrogen atom or a C _1-4 alkyl group), and ring Z ₁ , R ¹ , R ² , R ⁴ , R ⁵ , m, n , P and k are the same as above).

  The thiol compound can be used for various purposes by utilizing the activity of the mercapto group. For example, the thiol compound may be used as a raw material (monomer) of a resin, and a curable composition can be obtained by utilizing an ene / thiol reaction. It may be formed. That is, this invention also includes the curable composition containing the said thiol compound and the compound which has an ethylenically unsaturated bond.

In this curable composition, the compound having an ethylenically unsaturated bond is a polyfunctional compound having a plurality of (meth) acryloyl groups [particularly, di (meth) acrylates of bisphenols or their C _2-4 alkylene oxide adducts. And at least one selected from the group consisting of compounds represented by the following formula (4)], in addition to a polyfunctional compound having a plurality of (meth) acryloyl groups, an aryl Oxyalkyl (meth) acrylates may be included.

(Wherein ring Z ₂ is a monocyclic or polycyclic arene ring; X ² is an allyl group or a (meth) acryloyl group; R ¹ , m, n, R ⁴ , R ⁵ , p, k are as defined above. the same).

  The curable composition may further contain a photopolymerization initiator. The present invention also includes a cured product formed from the curable composition.

  In the present specification and claims, acrylic compounds and methacrylic compounds are collectively referred to as “(meth) acrylic” compounds. Therefore, “(meth) acryloyl group” includes both acryloyl group and methacryloyl group, and “(meth) acrylate” includes both acrylate and methacrylate.

  The thiol compound of the present invention has high heat resistance. In addition, the refractive index can be improved and the handling property can be greatly improved since it is in the form of a solid at room temperature. Furthermore, although it has a polycyclic aryl skeleton, coloring can be suppressed and transparency can be improved. Therefore, the thiol compound is useful as a component of a curable composition such as a heat-resistant resin raw material or a photosensitive resin composition.

[Thiol compound]
The thiol compound of the present invention has a mercapto group together with a 9,9-bisarylfluorene skeleton, and is represented by the formula (1).

In the formula (1), examples of the polycyclic arene ring represented by the ring Z ₁ include a condensed polycyclic arene ring (fused polycyclic hydrocarbon ring), a ring assembly arene ring (ring assembly aromatic hydrocarbon ring). ) Etc. are included. Examples of the condensed polycyclic arene ring include a condensed bicyclic arene (for example, a condensed bicyclic C _10-16 arene such as naphthalene) ring, a condensed tricyclic arene (for example, anthracene, phenanthrene, etc.) ring, etc. Examples thereof include fused bi to tetracyclic arene rings. Preferred examples of the condensed polycyclic arene ring include a naphthalene ring and an anthracene ring, and a naphthalene ring is particularly preferable.

Examples of the ring assembly arene ring include biarene rings such as bi-C _6-12 arene rings such as biphenyl ring, binaphthyl ring, and phenylnaphthalene ring (1-phenylnaphthalene ring, 2-phenylnaphthalene ring, etc.), Examples thereof include a tel C _6-12 arene ring such as a terphenylene ring. Preferred ring-assembled arene rings include bi-C _6-10 arene rings, particularly biphenyl rings.

The two rings Z ₁ may be the same or different polycyclic arene rings.

In the formula (1), the alkylene group R ¹ includes a linear or branched alkylene group. Examples of the linear alkylene group include C ₂ such as an ethylene group, a trimethylene group, and a tetramethylene group. _-6 alkylene group (preferably a linear _C2-4 alkylene group, more preferably a linear _C2-3 alkylene group, particularly an ethylene group) can be exemplified, and examples of the branched alkylene group include a propylene group , 1,2-butanediyl group, 1,3-butanediyl group and the like branched chain C _3-6 alkylene group (preferably branched chain C _3-4 alkylene group, particularly propylene group). R ¹ is often a linear or branched C _2-6 alkylene group (eg, a linear or branched C _2-4 alkylene group), particularly an ethylene group or a propylene group. When m is an integer of 2 or more, the type of alkylene group R ¹ may be the same or different. Further, the type of the alkylene group R ¹ may be the same or different in the same or different ring Z ₁ .

The repeating number m of the oxyalkylene group (OR ¹ ) can be selected from a range of about 0 or an integer of 1 or more, particularly an integer of 0 to 20 (for example, an integer of 0 to 15), for example, 0 to 10 (for example, , 1-8), preferably 0-5 (eg, 1-5), more preferably 0-4 (eg, 1-4), especially 0-3 (eg, 1-3). An integer of the order may be used, and an integer of 0 to 2 (for example, 0 or 1) may be generally used.

The alkylene group R ² includes a linear or branched chain such as a methylene group, an ethylidene group, an isopropylidene group, a hexamethylene group, and an octamethylene group in addition to the same linear or branched alkylene group as R ^1. A _C1-10 alkylene group is included. A preferable alkylene group R ² is a linear or branched C _1-5 alkylene group such as a methylene group, an ethylene group, an ethylidene group, a trimethylene group, a propylene group, an isopropylidene group, or a tetramethylene group (for example, a C _{2− 5} alkylene group), usually a linear or branched C _2-4 alkylene group in many cases. Among these, a C _1-4 alkylidene group such as a methylene group, an ethylidene group, an isopropylidene group, and the like is preferable from the viewpoint that coloring is suppressed and transparency can be improved in spite of having a polycyclic aryl skeleton. _{A 1-2} alkylidene group (especially an ethylidene group) is particularly preferred.

  The mercapto group may be a primary, secondary, or tertiary mercapto group, and is usually a primary or secondary mercapto group in many cases. A compound having a primary mercapto group (primary thiol compound) is usually highly reactive and useful for improving adhesiveness. Compounds having secondary and tertiary mercapto groups (secondary and tertiary thiol compounds) are advantageous from the viewpoint of storage stability of the curable composition. In the compound of the present invention, the secondary thiol compound having a secondary mercapto group is not only surprisingly high in reactivity and adhesiveness but also does not impair the storage stability of the curable composition.

In the formula (1), the number of substitutions n of the group [HS—R ² —C (═O) — (OR ¹ ) _m —O—] (sometimes simply referred to as “substituent having a mercapto group”) is Each may independently be an integer of 1 or more (for example, an integer of 1 to 3), preferably 1 or 2, particularly 1. The number of substitutions n may be the same or different in each ring Z ₁ .

Incidentally, a substituent having a mercapto group can be substituted in a suitable position on the ring Z _1, for example, when ring Z ₁ is a naphthalene ring is often a position 5～8- naphthyl group, e.g. , The 1-position or 2-position of the naphthalene ring is substituted with respect to the 9-position of fluorene (substitution is made in the relationship of 1-naphthyl or 2-naphthyl), and the 1,5-position with respect to this substitution position, In many cases, it is substituted by a relationship such as 2,6-position (particularly, when n is 1, the relationship is 2,6-position). Moreover, when n is 2 or more, the substitution position is not particularly limited. In the ring assembly arene ring Z ₁ , the substitution position of the substituent having a mercapto group is not particularly limited. For example, the arylene ring bonded to the 9-position of fluorene and / or the arene ring adjacent to the arene ring May be substituted. For example, it may be of the 3-position or 4-position biphenyl ring Z ₁ is bonded to the 9-position of fluorene, when the 3-position biphenyl ring Z ₁ is attached to the 9-position of fluorene, mercapto The substitution position of the substituent having a group may be any of 2-position, 4-6-position, 2′-6′-position, and usually 4-position, 5-position, 6-position, 3 It may be substituted at the '-position, 4'-position, preferably 4-position, 6-position, 4'-position (particularly the 6-position).

In the formula (1), examples of the substituent R ⁴ include a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, Linear or branched C _1-10 alkyl group such as s-butyl group or t-butyl group, preferably linear or branched C _1-6 alkyl group, more preferably linear or branched chain C _1-4 alkyl group), cycloalkyl group (C _5-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group, etc.), aryl group [phenyl group, alkylphenyl group (methylphenyl (tolyl) group, Dimethylphenyl (xylyl) group, etc.), biphenyl group, C _6-12 aryl group such as naphthyl group], aralkyl group (C such as benzyl group, phenethyl group, etc.) Straight chain or branched C such as _6-10 aryl-C _1-4 alkyl group), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy group). _1-10 alkoxy group), cycloalkoxy group (eg, C _5-10 cycloalkyloxy group such as cyclohexyloxy group), aryloxy group (eg, C _6-10 aryloxy group such as phenoxy group) An aralkyloxy group (for example, a C _6-10 aryl-C _1-4 alkyloxy group such as a benzyloxy group), an alkylthio group (for example, a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, a t-butylthio group) A C _1-10 alkylthio group such as a group, a cycloalkylthio group (for example, cyclohexyl) A C _5-10 cycloalkylthio group such as a ruthio group), an arylthio group (eg a C _6-10 arylthio group such as a thiophenoxy group), an aralkylthio group (eg a C _6-10 aryl-C such as a benzylthio group). _1-4 alkylthio group, etc.), acyl group (eg, C _1-6 acyl group such as acetyl group), carboxyl group, alkoxycarbonyl group (eg, C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group, etc.) , nitro group, cyano group, a dialkylamino group (e.g., di-C _1-4 alkylamino group such as dimethylamino group), dialkyl carbonyl amino group (e.g., di-C _1-4 alkyl, such as di-acetylamino group - carbonylamino Group, etc.).

Of these substituents R ⁴ , typically, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, a carboxyl group, a nitro group, a cyano group, a substituted amino group, etc. Can be mentioned. Preferable substituent R ⁴ includes an alkoxy group, an alkyl group, etc., and particularly a linear or branched C _1-4 alkyl group such as a methyl group. In addition, when the substituent R ⁴ is an aryl group, the substituent R ⁴ may form the ring assembly arene ring together with the ring Z ₁ . The type of the substituent R ⁴ may be the same or different in the same or different ring Z ₁ .

The number of substitutions p can be appropriately selected according to the type of ring Z _{1 and} the like, and may be, for example, an integer of about 0 to 8, an integer of 0 to 4, preferably 0 to 3 (for example, 0 to 0). It may be an integer of 2), in particular 0 or 1. In particular, when p is 1, the ring Z ₁ may be a naphthalene ring or a biphenyl ring, and the substituent R ⁴ may be a methyl group.

As the substituent R ⁵ , a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a carboxyl group, an alkoxycarbonyl group (for example, a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group), an alkyl group (C _1-6 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group), aryl group (C _6-10 aryl group such as phenyl group) and the like.

Of these substituents R ⁵ , typically, a linear or branched C ₁ such as an alkyl group, a carboxyl group or a C _1-2 alkoxy-carbonyl group, a cyano group, a halogen atom, particularly a methyl group. _{A -4} alkyl group is preferred. The substitution number k is an integer of 0 to 4 (for example, 0 to 3), preferably an integer of 0 to 2 (for example, 0 or 1), particularly 0. The number of substitutions k may be the same or different from each other. When k is 2 or more, the types of the substituents R ⁵ may be the same or different from each other, and are substituted with two benzene rings of the fluorene ring. The type of the substituent R ⁵ may be the same or different. Further, the substitution position of the substituent R ⁵ is not particularly limited, and may be, for example, 2-position to 7-position (2-position, 3-position and / or 7-position, etc.) of the fluorene ring.

In the above formula (1), the compound in which ring Z ₁ is a condensed polycyclic arene ring, m is 0, and n is 1 includes 9,9-bis [(mercaptoalkylcarbonyloxy)] aryl] fluorenes In particular, 9,9-bis [mercapto C _2-6 acyloxy)] fused polycyclic C _10-12 aryl) fluorene and the like are included. As such a compound, for example, (a) 9,9-bis [6- (2-mercaptoacetyloxy) -2-naphthyl] fluorene, 9,9-bis [6- (2-mercaptopropionyloxy)- 2-naphthyl] fluorene, 9,9-bis [6- (3-mercaptopropionyloxy) -2-naphthyl] fluorene, 9,9-bis [6- (2-mercaptobutyryloxy) -2-naphthyl] fluorene 9,9-bis [6- (3-mercaptobutyryloxy) -2-naphthyl] fluorene, 9,9-bis [6- (4-mercaptobutyryloxy) -2-naphthyl] fluorene, 9,9 - bis [6- (2-mercapto-isobutyryl) -2-naphthyl] fluorene such as 9,9-bis [6- (mercapto _{C 2-6} acyloxy) -2- naphth (9) 9,9-bis [5- (mercapto C _2-6 acyloxy)-in which the mercapto C _2-6 acyloxy group is substituted at the 5-position of the 1-naphthyl group in these compounds (a) 1-naphthyl] fluorene and the like can be exemplified.

In the above formula (1), a compound in which ring Z ₁ is a condensed polycyclic arene ring, m is 1 and n is 1, includes 9,9-bis [[(mercaptoalkylcarbonyloxy) alkoxy] aryl]. Fluorenes include, in particular, 9,9-bis [(mercapto C _2-6 acyloxy C _2-4 alkoxy) fused polycyclic C _10-12 aryl] fluorene. Examples of such a compound include (c) 9,9-bis [6- [2- (2-mercaptoacetyloxy) ethoxy] -2-naphthyl) fluorene, 9,9-bis [6- [2- (2-Mercaptopropionyloxy) ethoxy] -2-naphthyl] fluorene, 9,9-bis [6- [2- (3-mercaptopropionyloxy) ethoxy] -2-naphthyl] fluorene, 9,9-bis [6 -[2- (2-mercaptobutyryloxy) ethoxy] -2-naphthyl] fluorene, 9,9-bis [6- [2- (3-mercaptobutyryloxy) ethoxy] -2-naphthyl] fluorene, 9 , 9-bis [6- [2- (4-mercaptobutyryloxy) ethoxy] -2-naphthyl] fluorene, 9,9-bis [6- [2- (2-mercaptoisobutyryloxy) ) Ethoxy] -2-naphthyl] 9,9-bis fluorene [6- [2- (mercapto _{C 2-6} acyloxy) ethoxy] -2-naphthyl] fluorene; (d) These compounds (c) In mercapto _{C 2-6} acyloxy group substituted at the 5-position of the 1-naphthyl group 9,9-bis [5- [2- (mercapto _{C 2-6} acyloxy) ethoxy] -1-naphthyl) fluorene; (e) Examples are compounds in which the ethoxy group of these compounds (c) and (d) is replaced by an alkoxy group such as a propoxy group, such as 9,9-bis [(mercapto C _2-6 acyloxy) C _3-6 alkoxynaphthyl] fluorene. Examples of such a compound (e) include 9,9-bis [6- [2- (2-mercaptopropionyloxy) propoxy] -2-na [Futyl] fluorene, 9,9-bis [6- [3- (2-mercaptopropionyloxy) propoxy] -2-naphthyl] fluorene, 9,9-bis [5- [3- (2-mercaptopropionyloxy) propoxy ] -1-naphthyl] fluorene, 9,9-bis [5- [3- (2-mercaptoisobutyryloxy) propoxy] -1-naphthyl] fluorene, and the like.

In the above formula (1), the compound in which ring Z ₁ is a ring assembly arene ring, m is 0 or 1, and n is 1 is (f) 9,9-bis (C _6-12 aryl- (mercapto) C _2-6 acyloxy) C _6-12 aryl) fluorene, such as 9,9-bis (3-phenyl-4- (2-mercaptopropionyloxy) phenyl) fluorene, 9,9-bis (3-phenyl-4) -(3-mercaptobutyryloxy) phenyl) fluorene, 9,9-bis (4-phenyl-3- (2-mercaptobutyryloxy) phenyl) fluorene, 9,9-bis (4-phenyl-3- ( 3-mercaptobutyryloxy) phenyl) fluorene and the like; (g) 9,9-bis (C _6-12 aryl- (mercapto C _2-6 acyloxy) ethoxy C _6-12 aryl Fluorene, such as 9,9-bis [3-phenyl-4- (2- (2-mercaptopropionyloxy) ethoxy) phenyl] fluorene, 9,9-bis [3-phenyl-4- (2- (3 -Mercaptobutyryloxy) ethoxy) phenyl] fluorene, 9,9-bis [4-phenyl-3- (2- (2-mercaptopropionyloxy) ethoxy) phenyl] fluorene, 9,9-bis [4-phenyl- 3- (2- (3-mercaptobutyryloxy) ethoxy) phenyl] fluorene, 9,9-bis [4-phenyl-3- (2- (2-mercaptoisobutyryloxy) ethoxy) phenyl] fluorene and the like; (H) Compounds in which the ethoxy group of these compounds (g) is replaced with an alkoxy group such as a propoxy group, for example, 9,9-bis [C _{6 -12} aryl- (mercapto C _2-6 acyloxy) C _3-6 alkoxy C _6-12 aryl] fluorene can be exemplified, and examples of such compound (g) include 9,9-bis [3-phenyl- 4- (2- (2-mercaptopropionyloxy) propoxy) phenyl] fluorene, 9,9-bis [3-phenyl-4- (2- (3-mercaptobutyryloxy) propoxy) phenyl] fluorene, 9,9 -Bis [4-phenyl-3- (2- (2-mercaptopropionyloxy) propoxy) phenyl] fluorene, 9,9-bis [4-phenyl-3- (2- (3-mercaptobutyryloxy) propoxy) And phenyl] fluorene.

In the formula (1), examples of the compound in which n is 2 or more include 9,9-bis [(poly) (mercaptoacyloxyalkoxy) arene] fluorenes such as 9,9-bis [[6,8 -Di (2- (2-mercaptopropionyloxy) ethoxy)]-2-naphthyl] fluorene, 9,9-bis [[4,6-di (2- (3-mercaptobutyryloxy) ethoxy)]-2 9,9-bis (di or tri (mercapto) such as -naphthyl] fluorene, 9,9-bis [[5,7-di (2- (3-mercaptobutyryloxy) ethoxy)]-1-naphthyl] fluorene C _2-6 acyloxy C _2-4 alkoxy) C _10-12 aryl) fluorene and the like can be exemplified.

In the formula (1), the compound in which m is 2 or more corresponds to the compound in which m is 0 or 1, and the repeating number m of an oxyalkylene group (particularly an oxyC _2-4 alkylene group) is 2 to 10. Compound etc. are mentioned.

Specific compounds of k = 0, p = 0, n = 1 in the formula (1) are exemplified in Table 1. In Table 1, the substitution position of A indicates the substitution position of “substituent containing mercapto group” A with respect to ring Z ₁ .

Of these, 9,9-bis [6- [2- (2-mercaptoacetyloxy) ethoxy] -2-naphthyl) fluorene, 9,9-bis [6- [2- (2-mercaptopropionyl) ethoxy] -2-naphthyl] 9,9-bis fluorene [6- [2- (mercapto _{C 2-3} acyloxy) ethoxy] -2-naphthyl] fluorene is particularly preferred.

[Method for producing thiol compound]
The thiol compound represented by the formula (1) includes a compound represented by the following formula (2) (hydroxy compound having a 9,9-bisarylfluorene skeleton) and a compound represented by the following formula (3) ( It can be prepared by reaction (esterification reaction) with mercaptoalkanecarboxylic acid or a reactive derivative thereof.

(Wherein X ¹ represents a halogen atom or a group —OR ³ (R ³ is a hydrogen atom or a C _1-4 alkyl group), and ring Z ₁ , R ¹ , R ² , R ⁴ , R ⁵ , m, n , P and k are the same as above).

The hydroxy-containing fluorene compound represented by the formula (2) corresponds to the compound represented by the formula (1). In the formula (1), a mercaptoalkylcarbonyl group (—C (═O) —R ² — A compound in which (SH) is substituted with a hydrogen atom can be exemplified.

A commercially available product may be used as the hydroxy-containing fluorene compound represented by the formula (2), and a conventional method (for example, 9-fluorenones and a group [H- (OR ¹ ) _{m in the} ring Z _1]. A method of reacting a hydroxyl group-containing arene ring compound substituted with —] (for example, aryloxyalkanols such as naphthol and 2-naphthoxyethanol) in the presence of an acid catalyst, hydroxyaryl at the 9-position of fluorenes A fluorene compound substituted with a group [for example, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, etc.] and at least one selected from alkylene oxide, alkylene carbonate and haloalkanol corresponding to the group OR ¹ May be synthesized by a method of reacting

In the compound represented by the formula (3), examples of the halogen atom represented by X ¹ include a chlorine atom, a bromine atom, and an iodine atom. The alkyl group represented by R ³ is a lower alkyl group, for example, a linear or branched chain such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, or a t-butyl group. A _C1-4 alkyl group etc. can be illustrated.

Examples of the compound represented by the formula (3) include mercaptoalkanecarboxylic acid (thioglycolic acid (mercaptoacetic acid), 3-mercaptopropionic acid, 2-mercaptopropionic acid, 4-mercaptobutyric acid, 3-mercaptobutyric acid, 2 Mercaptobutyric acid, 3-mercaptoisobutyric acid, 2-mercaptoisobutyric acid, 5-mercaptovaleric acid, 4-mercaptovaleric acid, 3-mercaptovaleric acid, 3-mercaptoisovaleric acid and other mercapto C _2-10 alkanecarboxylic acids Etc.), and reactive derivatives thereof (for example, acid halides (such as acid chlorides) or lower alkyl esters (such as _C1-2 alkyl esters)). These compounds can be used alone or in combination of two or more.

The compound represented by the formula (3) is usually a mercapto linear or branched C _2-6 alkanecarboxylic acid, preferably a mercapto linear or branched C _3-5 alkanecarboxylic acid (for example, Mercapto C _3-4 alkanecarboxylic acid) is often used. Moreover, although any of a primary thiol compound, a secondary thiol compound, and a tertiary thiol compound can be used, usually a primary thiol compound or a secondary thiol compound is often used.

  In the reaction, the ratio of the compound represented by the formula (3) is 0.5 to 5 mol (for example, 0.7 to 3 mol) with respect to 1 mol of the hydroxyl group of the compound represented by the formula (2). The amount may preferably be about 1 to 2.5 mol. The reaction may be carried out in the absence of a catalyst. For the reaction, if necessary, an esterification catalyst (for example, an acid catalyst such as hydrochloric acid, sulfuric acid, toluenesulfonic acid, strong acidic ion exchange resin, etc.) is used. Also good. The reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include solvents inert to the reaction, such as hydrocarbons (aliphatic hydrocarbons such as hexane, octane and cyclohexane, aromatic hydrocarbons such as toluene), halogenated hydrocarbons (dichloromethane, chloroform, Carbon tetrachloride, dichloroethane, trichloroethylene, etc.), ethers (dialkyl ethers such as diethyl ether and diisopropyl ether, cyclic ethers such as dioxane, tetrahydrofuran), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), amides (dimethyl) Formamide, diethylformamide, dimethylacetamide, diethylacetamide, etc.), nitriles (acetonitrile, benzonitrile, etc.), sulfoxides (dimethylsulfoxide, etc.), cellosolve acetate Over preparative acids, carbitol acetates, carbonates (ethylene carbonate, propylene carbonate, and dimethyl carbonate) and the like. These solvents may be used alone or in combination of two or more. As the solvent, aromatic hydrocarbons are often used.

  The reaction can be carried out at 50 ° C. to the reflux temperature of the solvent. After completion of the reaction, the thiol compound represented by the formula (1) can be prepared by separating and purifying the target compound from the reaction mixture by a conventional method such as concentration, extraction or precipitation in a poor solvent. . This thiol compound is usually solid at room temperature and is often separated from the reaction system in the form of a solid granular material.

[Uses of thiol compounds]
Since the thiol compound of the present invention has an active mercapto group and a 9,9-bisarylfluorene skeleton, it has a high refractive index and extremely high heat resistance. For example, the refractive index (25 ° C., 589 nm) of the thiol compound described in Patent Documents 1 and 2 is about 1.62, whereas the refractive index of the thiol compound of the present invention is as high as about 1.65. Moreover, while the thiol compounds described in Patent Documents 1 and 2 are viscous at room temperature, the thiol compound of the present invention is solid (for example, a granular material) at room temperature (15 to 25 ° C.). Usually, it is colorless and transparent.

  Therefore, the thiol compound of the present invention uses an active mercapto group and is used in various applications, for example, resin raw materials (for example, urethane resins produced by reaction with polyisocyanate, epoxy resins produced by reaction with epichlorohydrin) Such as a resin raw material for optical use), a component of a curable composition utilizing an ene / thiol reaction, and the like.

  The curable composition contains the thiol compound and a multifunctional compound. The polyfunctional compound may be a compound having a polyfunctional ethylenically unsaturated bond (polyfunctional ethylenically unsaturated compound), or a polyfunctional oligomer or resin.

[Polyfunctional ethylenically unsaturated compound]
As the polyfunctional ethylenically unsaturated compound, compounds having an allyl group such as diallyl phthalate and triallyl isocyanurate can be used, but polyfunctional (meth) acrylates having a plurality of (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 -C _2-10 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; bridging ring (meth) such as tricyclodecane dimethanol di (meth) acrylate Acrylates], poly (meth) acrylates having 3 or more (meth) acryloyl groups [e.g., trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Alkane polyol poly (meth) acrylates such as pentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; tri (meth) acrylates of C _2-4 alkylene oxide adducts of alkane polyols such as trimethylolpropane And tri (meth) acrylates having a triazine ring such as tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate].

The polyfunctional ethylenically unsaturated compound may be a compound having a bisaryl skeleton. Examples of such compounds include bisphenols (bisphenols such as bisphenol A, F, and S) or di (meth) acrylates of C _2-4 alkylene oxide adducts thereof [for example, 2,2-bis (4 -(Meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, etc.] A 9,9-bisarylfluorene compound [for example, a compound represented by the following formula (4)] and the like.

(Wherein ring Z ₂ is a monocyclic or polycyclic arene ring; X ² is an allyl group or a (meth) acryloyl group; R ¹ , m, n, R ⁴ , R ⁵ , p, k are as defined above. the same).

Examples of the monocyclic arene ring of the ring Z _2, such as a benzene ring can be exemplified. Preferred ring Z ₂ is a benzene ring in addition to the preferred polycyclic arene ring Z ₁ . X ² may be an allyl group or a (meth) acryloyl group, and preferred X ² is a (meth) acryloyl group. Preferred R ¹ , n, R ⁴ , R ⁵ , p and k are the same as described above. The repeating number m of the oxyalkylene group (OR ¹ ) can be adjusted according to the application, and in an application where heat resistance is required, m may be 2 or less, preferably 0 or 1, more preferably 1. In applications where flexibility is required, m may be 3 or more, for example, 3 to 15, preferably 4 to 10, more preferably 4 to 8 (particularly 4 to 5). May be.

  As a typical polyfunctional ethylenically unsaturated compound having a 9,9-bisarylfluorene skeleton in which m is 1 or more, the following compounds can be exemplified.

(A) 9,9-bis ((meth) acryloyloxyalkoxyphenyl) fluorenes such as 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [ 9,9-bis ((meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene such as 4- (2- (meth) acryloyloxypropoxy) phenyl] fluorene; 9,9-bis (alkyl- (meth) acryloyloxy Alkoxyphenyl) fluorene, for example, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) ) -3-Methylphenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxy) 9,9-bis (mono or diC _1-4 alkyl- (meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene such as (ciethoxy) -3,5-dimethylphenyl] fluorene (in the above formula (4), A compound in which ring Z ₂ is a benzene ring and m = 1 and n = 1).

(B) 9,9-bis ((meth) acryloyloxyalkoxynaphthyl) fluorenes such as 9,9-bis [6- (2- (meth) acryloyloxyethoxy) -2-naphthyl] fluorene, 9,9 - bis [6- (2- (meth) acryloyloxy propoxy) -2-naphthyl] 9,9-bis fluorene ((meth) acryloyloxy _{C 2-4} alkoxy naphthyl) fluorene (the formula (4) , Ring Z ₂ is a naphthalene ring, and m = 1 and n = 1.

(C) 9,9-bis (aryl- (meth) acryloyloxyalkoxyphenyl) fluorenes such as 9,9-bis [4- (2- (meth) acryloyloxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis (mono- or di-C _6-10 aryl- (meth) acryloyloxy C ₂₋ such as 9,9-bis [4- (2- (meth) acryloyloxypropoxy) -3-phenylphenyl] fluorene ₄ alkoxyphenyl) fluorene and the like (in the formula (4), a compound in which the ring Z ₂ is a biphenyl ring, m = 1, n = 1).

(D) 9,9-bis ((meth) acryloyloxy (poly) alkoxyaryl) fluorenes such as 9,9-bis ((meth) acryloyloxydialkoxyphenyl) fluorene {eg 9,9-bis { phenyl of these compounds; 4- [2- (2- (meth) acryloyloxy) ethoxy] phenyl} fluorene such as 9,9-bis ((meth) acryloyloxy-di _{C 2-4} alkoxyphenyl) fluorene} etc. A compound in which the group is substituted with a naphthyl group or biphenyl group (a compound in which m is 2 to 10 in the formula (4)).

Of these, bisphenols or di (meth) acrylates of C _2-4 alkylene oxide adducts thereof, and compounds represented by the above formula (4) are preferable. When di (meth) acrylates of bisphenols or their C _2-4 alkylene oxide adducts are used, transparency can be improved while maintaining the refractive index. In the compound represented by the formula (4), the repeating number m of the oxyalkylene group (OR ¹ ) can be adjusted according to the use, and in the use requiring heat resistance, X ² is a (meth) acryloyl group. A compound in which Z ₂ is a benzene ring, n is 1 and m is 0 or 1 (particularly 1), and X ² is a (meth) acryloyl group in applications where flexibility is required. And a compound in which Z ₂ is a benzene ring, n is 1 and m is 3 to 8 (particularly 4 to 5) is preferable.

[Polyfunctional oligomer or resin]
Polyfunctional compounds include polyfunctional oligomers such as polyester (meth) acrylates formed by reaction of polycarboxylic acids, polyols with (meth) acrylic acid and / or hydroxyalkyl (meth) acrylates; Epoxy compound having a group (bisphenol type epoxy resin such as bisphenol A, F, S, novolac type epoxy resin, epoxy resin having a 9,9-bisarylfluorene skeleton in which X ² is a glycidyl group in the above formula (4)) Epoxy (meth) acrylates obtained by ring-opening addition of (meth) acrylic acid to an epoxy resin, etc .; produced by reaction of polyisocyanate and polyol, and reacted with an oligomer having a terminal isocyanate group with hydroxyalkyl (meth) acrylate Made polyureta (Meth) acrylates and the like are also included.

  Examples of typical epoxy resins having a 9,9-bisarylfluorene skeleton include the following compounds.

(E) 9,9-bis (glycidyloxyphenyl) fluorenes such as 9,9-bis (4-glycidyloxyphenyl) fluorene; 9,9-bis (alkyl-glycidyloxyphenyl) fluorene such as 9,9 9,9-bis (mono or di-C _1-4 ) such as 9-bis (4-glycidyloxy-3-methylphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-dimethylphenyl) fluorene Alkyl-glycidyloxyphenyl) fluorene; 9,9-bis (polyglycidyloxyphenyl) fluorene, such as 9,9-bis (3,5-diglycidyloxyphenyl) fluorene, 9,9-bis (3,4) Diglycidyloxyphenyl) fluorene, 9,9-bis (2,4-diglycidyloxyphenyl) fluorene 9,9-bis (di- or triglycidyloxyphenyl) fluorene, etc. (in formula (4), ring Z ₂ is a benzene ring, X ² is a glycidyl group, m = 0, n = 1-3. Compound).

(F) 9,9-bis (glycidyloxynaphthyl) fluorenes such as 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene, 9,9-bis (5-glycidyloxy-1-naphthyl) Fluorene and the like (in the formula (4), a compound in which ring Z ₂ is a naphthalene ring, X ² is a glycidyl group, and m = 0 and n = 1).

(G) 9,9-bis (mono- or di-C ₆ ) such as 9,9-bis (aryl-glycidyloxyphenyl) fluorenes such as 9,9-bis (4-glycidyloxy-3-phenylphenyl) fluorene _-10 aryl-glycidyloxyphenyl) fluorene and the like (in the above formula (4), a compound in which ring Z ₂ is a biphenyl ring, X ² is a glycidyl group, m = 0, n = 1).

(H) 9,9-bis (glycidyloxyalkoxyphenyl) fluorene, such as 9,9-bis [4- (2-glycidyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-glycidyloxy) propoxy) phenyl] fluorene such as 9,9-bis (glycidyloxy _{C 2-4} alkoxyphenyl) fluorene; 9,9-bis (alkyl - glycidyl oxy alkoxyphenyl) fluorene, e.g., 9,9-bis [4- ( 2-glycidyloxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-glycidyloxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-glycidyloxy) 9,9-bis (mono or di-C) such as ethoxy) -3,5-dimethylphenyl] fluorene _1-4 alkyl-glycidyloxy C _2-4 alkoxyphenyl) fluorene and the like (in the formula (4), ring Z ₂ is a benzene ring, X ² is a glycidyl group, m = 1, n = 1 to 3) .

(I) 9,9-bis (glycidyloxyalkoxynaphthyl) fluorenes such as 9,9-bis [6- (2-glycidyloxyethoxy) -2-naphthyl] fluorene, 9,9-bis [6- ( 9,9-bis (glycidyloxy C _2-4 alkoxynaphthyl) fluorene such as 2-glycidyloxypropoxy) -2-naphthyl] fluorene (in the above formula (4), ring Z ₂ is a naphthalene ring, X ² is glycidyl) Group, m = 1, n = 1).

(J) 9,9-bis (aryl-glycidyloxyalkoxyphenyl) fluorene, such as 9,9-bis [4- (2-glycidyloxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4 9,9-bis (mono- or di-C _6-10 aryl-glycidyloxy C _2-4 alkoxyphenyl) fluorene such as-(2-glycidyloxypropoxy) -3-phenylphenyl] fluorene (in the above formula (4) , Ring Z ₂ is a biphenyl ring, X ² is a glycidyl group, and m = 1 and n = 1).

(K) 9,9-bis (glycidyloxydialkoxyphenyl) fluorene {9,9-bis (for example, 9,9-bis {4- [2- (2-glycidyloxyethoxy) ethoxy] phenyl} fluorene) in glycidyloxy di _{C 2-4} alkoxyphenyl) fluorene} etc. 9,9-bis (glycidyloxy polyalkoxy phenyl) fluorenes (formula (4), ^{X 2} is a glycidyl group, m = 2~10, n = 1).

  Further, the polyfunctional compound (particularly polyfunctional oligomer) may be an alkali-soluble resin (or alkali-soluble oligomer) having a carboxyl group in order to form a predetermined pattern by alkali development using lithography technology. . Such an alkali-soluble resin may be, for example, a carboxyl group-containing polyester resin, a carboxyl group-containing urethane resin, a carboxyl group-containing epoxy resin, or the like.

The carboxyl group-containing polyester-based resin includes a diol component (such as a linear or branched C _2-10 alkanediol such as ethylene glycol, propylene glycol, and neopentyl glycol, cyclohexanediol, and an alkylene oxide adduct of bisphenols). Dicarboxylic acid components (alkane dicarboxylic acids such as adipic acid, alkene dicarboxylic acids such as phthalic anhydride, cycloalkane dicarboxylic acids such as cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc. ) And polyhydric carboxylic acid having 3 or more carboxyl groups or acid anhydride thereof (trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, etc.) ) And a (meth) acrylic monomer having a functional group capable of reacting with a reactive group of the produced polyester resin (or oligomer). For example, by a method in which (meth) acrylic acid is reacted with the hydroxyl group of the produced polyester resin (or oligomer), a method in which hydroxyalkyl (meth) acrylate and / or glycidyl (meth) acrylate is reacted with a carboxyl group A polyfunctional ethylenically unsaturated compound as a polyfunctional oligomer having a plurality of (meth) acryloyl groups in one molecule may be prepared.

The carboxyl group-containing urethane-based resin includes a hydroxyalkyl (meth) acrylate component (such as hydroxy C _2-10 alkyl (meth) acrylate such as hydroxyethyl (meth) acrylate) and a diol component (such as polytetramethylene ether glycol). Ether diol, polyester diol, polycarbonate diol, etc.) and a polyisocyanate component in the reaction, dihydroxycarboxylic acid (such as dimethylolpropionic acid) and / or polyvalent carboxylic acid having three or more carboxyl groups as a diol component Or it can prepare by using the polyester diol which introduce | transduced the carboxyl group using the acid anhydride. Examples of the polyisocyanate component include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, methylene bis (cyclohexyl isocyanate) and cyclohexane dimethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, 1 , 5-naphthalene diisocyanate and other aromatic diisocyanates, and modified products thereof (allophanate, burette, triisocyanurate modified products, etc.). As the diol component, the linear or branched C _2-10 alkanediol exemplified in the section of the polyester resin may be used in combination.

The weight average molecular weight of the carboxyl group-containing polyester resin and the urethane resin is, for example, 0.1 × 10 ⁴ to 10 × 10 ⁴ , preferably 0.3 × 10 ^{4 to} 5 × 10 ⁴ (for example, 0.5 in terms of polystyrene). It may be about × 10 ⁴ to 1 × 10 ⁴ ).

  Carboxyl group-containing epoxy resins include hydroxyl group-containing products (epoxy (meth) acrylates) produced by ring-opening addition reaction between epoxy resins such as bisphenol type epoxy resins and (meth) acrylic acid, and acid anhydrides (anhydrous maleic anhydride). Acid, succinic anhydride, phthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, etc.). Such a carboxyl group-containing epoxy resin has a plurality of (meth) acryloyl groups in one molecule, and forms a polyfunctional ethylenically unsaturated compound as a polyfunctional oligomer.

The weight average molecular weight of the carboxyl group-containing epoxy resin (carboxyl group-containing epoxy (meth) acrylate) is, for example, 0.3 × 10 ⁴ to 2 × 10 ⁴ , preferably 0.5 × 10 ⁴ to 1 × 10 in terms of polystyrene. ^It may be about ⁴ .

  Among such alkali-soluble resins, a carboxyl group-containing polyfunctional oligomer (polyester resin, urethane resin, epoxy resin) having a plurality of (meth) acryloyl groups in one molecule, particularly a carboxyl group-containing epoxy resin is used. There are many.

  The acid value of the alkali-soluble resin may be about 15 to 200 KOH mg / g (for example, 30 to 150 KOH mg / g, preferably 50 to 120 KOH mg / g).

  These polyfunctional oligomers or resins can be used alone or in combination of two or more.

[Monofunctional unsaturated compound]
If necessary, the curable composition may further contain a monofunctional unsaturated compound (monofunctional ethylenically unsaturated compound) having one ethylenically unsaturated bond in the molecule. When a monofunctional unsaturated compound is blended, the viscosity of the curable composition can be reduced and the handleability can be improved.

Monofunctional unsaturated compounds include styrene monomers, N-vinyl pyrrolidone, vinyl ethers, compounds having a (meth) acryloyl group [(meth) acrylic acid; methyl (meth) acrylate, butyl (meth) acrylate, t _-C1-24 alkyl (meth) acrylates such as butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate; trifluoroethyl (meta ) acrylates, fluoroalkyl C _1-10 alkyl (meth) acrylates such as hexafluoroisopropyl (meth) acrylate; cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate; dicyclopentadienyl (meth) acrylate Bridged (meth) acrylates such as bornyl (meth) acrylate and isobornyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl ( Hydroxy C _2-10 alkyl (meth) acrylates such as meth) acrylate and hydroxybutyl (meth) acrylate; aryloxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate; alkoxy such as methoxyethyl (meth) acrylate Alkyl (meth) acrylates; glycidyl (meth) acrylate, dialkylamino (meth) acrylate, (meth) acrylamide, tetrahydrofurfuryl (meth) acrylate, etc.], Unsaturated polyvalent carboxylic acids such as in acid, fumaric acid, itaconic acid or their anhydrides, carboxyl group-containing compounds such as half esters thereof, phosphate group-containing compounds such as (meth) acryloyloxyethyl acid phosphate, etc. Can be illustrated. A monofunctional unsaturated compound can be used individually or in combination of 2 or more types.

Among these monofunctional unsaturated compounds, aryloxyalkyl (meth) acrylates are preferable from the viewpoint that handling properties can be improved without impairing optical properties and heat resistance, and phenoxy C ₁ such as phenoxyethyl (meth) acrylate. _-4 alkyl (meth) acrylates are particularly preferred.

  The curable composition of the present invention is a compound having an ethylenically unsaturated bond (an ethylene containing a polyfunctional ethylenically unsaturated compound and a monofunctional ethylenically unsaturated compound) among the polyfunctional compound and the monounsaturated compound. In particular, at least a polyfunctional ethylenically unsaturated compound.

  The weight ratio of the polyfunctional compound (particularly the polyfunctional ethylenically unsaturated compound) and the monofunctional unsaturated compound is the former / the latter = 30/70 to 100/0 (for example, 40/60 to 95/5), Preferably, it is about 50/50 to 100/0 (for example, 60/40 to 90/10), and may be about 70/30 to 100/0 (for example, 75/25 to 80/20). The molar ratio of the polyfunctional compound (particularly the polyfunctional ethylenically unsaturated compound) to the monofunctional ethylenically unsaturated compound is the former / the latter = 90/10 to 10/90, preferably 70/30 to 30/70. More preferably, it may be about 60/40 to 40/60.

  The ratio of thiol compound (especially polythiol compound having a plurality of mercapto groups) to ethylenically unsaturated compound (especially a polyfunctional ethylenically unsaturated compound having a plurality of ethylenically unsaturated bonds) It can be selected from the range of about 0.1 to 1.5 (for example, 0.15 to 1.3) of the number of moles of mercapto group with respect to mole, and is usually 0.25 to 1.25 (for example, 0.3 to 1.2), preferably 0.4 to 1.1 (for example, 0.4 to 1), more preferably about 0.45 to 1 (for example, 0.5 to 0.9). Moreover, the ratio of the thiol compound to the ethylenically unsaturated compound is the ethylenically unsaturated bond (in particular, when combining the monofunctional ethylenically unsaturated compound and the polyfunctional ethylenically unsaturated compound, the total ethylenically unsaturated bond) The number of moles of a mercapto group may be 0.5 to 1.5, preferably 0.8 to 1.2, and more preferably about 0.9 to 1.1 with respect to 1 mole.

[Polymerization initiator and sensitizer]
The curable composition may contain a polymerization initiator, for example, a thermal polymerization initiator (thermal radical generator), a photopolymerization initiator (photo radical generator). A preferred polymerization initiator is a photopolymerization initiator.

  Examples of thermal polymerization initiators include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [lauroyl peroxide, benzoyl peroxide, etc.], peracid esters [t-butyl. Percarboxylic acid alkyl esters such as peroxybenzoate], organic peroxides such as ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds [2,2′-azobis (2,4-dimethylvalero] Nitrile), 2,2′-azobis (isobutyronitrile)], azoamide compounds, azoamidine compounds, azoalkane compounds, azo compounds having an oxime skeleton, and the like. You may use a thermal-polymerization initiator individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator include benzoins (benzoin alkyl ethers such as benzoin, benzoin methyl ether, and benzoin isopropyl ether); acetophenones (acetophenone, p-dimethylacetophenone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-phenyl-2-hydroxy-acetophenone, 1,1 -Dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc .; propiophenones (p-dimethylaminopropiophenone, 2-hydroxy-2-methyl-propiophenone, 2,2-dimethoxy-1,2-di) Butenylylphenones [1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1 -Phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, etc.]; aminoacetophenones [2-methyl-2-morpholino (4-thiomethyl) Phenyl) propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butan-1-one, 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-fur Nylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan-1-one, 1- (4 -Butylphenyl) -2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1- (4-methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl -1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) -butan-1-one, etc.]; benzophenones (benzophenone, N, N 'N, N' such as -bis (dimethylamino) benzophenone (Michler's ketone), 3,3-dimethyl-4-methoxybenzophenone, benzyl -Dialkylaminobenzophenone etc.); ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal etc.); thioxanthenes (thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene etc.); anthraquinones (2-ethylanthraquinone) 1-chloroanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc.); (thio) xanthones (thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2 , 4-diisopropylthioxanthone); acridines (1,3-bis- (9-acridinyl) propane, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pen Triazines (2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4- Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine); sulfides (such as benzyldiphenyl sulfide); acylphosphine oxides (2,4,6-trimethylbenzoyldiphenylphosphine) Examples thereof include oxides); titanocene photopolymerization initiators; oxime esters. These photopolymerization initiators can be used alone or in combination of two or more.

  Photopolymerization initiators are commercially available products, for example, trade names “Irgacure” “Darocur” (manufactured by BASF Japan), trade names “OMNIRAD” (manufactured by IGM), and trade names “Syracure” (Union Carbide). Etc.).

  The ratio of the polymerization initiator is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the ethylenically unsaturated compound (polyfunctional ethylenically unsaturated compound and monofunctional ethylenically unsaturated compound) and the thiol compound. For example, it may be about 0.5 to 8 parts by weight (for example, 1 to 8 parts by weight), preferably about 1 to 7 parts by weight (for example, 2 to 5 parts by weight).

  The photopolymerization initiator may be combined with a photosensitizer. Examples of the photosensitizer include conventional components such as tertiary amines [for example, trialkylamine, trialkanolamine (such as triethanolamine), ethyl N, N-dimethylaminobenzoate, N, N-dimethyl. Dialkylaminobenzoic acid alkyl esters such as amyl aminobenzoic acid, bis (dialkylamino) benzophenones such as 4,4′-bis (dimethylamino) benzophenone (Michler's ketone), 4,4′-diethylaminobenzophenone, etc.], triphenylphosphine, etc. Phosphines, toluidines such as N, N-dimethyltoluidine, anthracene such as 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. Can be mentioned. The photosensitizers may be used alone or in combination of two or more.

  The amount of the photosensitizer used is, for example, 0.1 to 150 parts by weight (for example, 1 to 100 parts by weight), preferably 5 to 75 parts by weight (for example, with respect to 100 parts by weight of the photopolymerization initiator). 10 to 50 parts by weight).

[resin]
The curable composition may contain a resin, for example, a water-insoluble resin (acrylic resin, etc.), a water-soluble resin (polyvinyl alcohol, cellulose ethers, etc.), etc., if necessary. In order to form a pattern by alkali development, an alkali-soluble resin may be included. The alkali-soluble resin may be, for example, a carboxyl group-containing acrylic resin, a carboxyl group-containing polyester resin, a carboxyl group-containing urethane resin, a carboxyl group-containing epoxy resin, or the like.

The carboxyl group-containing acrylic resin can be composed of a copolymer of the above-mentioned unsaturated polyvalent carboxylic acid or its acid anhydride such as (meth) acrylic acid and maleic anhydride, and a copolymerizable monomer, Examples of the copolymerizable monomer include the monofunctional unsaturated compounds exemplified above [for example, C _1-24 alkyl (meth) acrylates such as methyl (meth) acrylate; cycloalkyl (meth) acrylates; Cyclic (meth) acrylates; hydroxy C _2-10 alkyl (meth) acrylates; phenoxyalkyl (meth) acrylates; glycidyl (meth) acrylate, (meth) acrylamide, etc.], vinyl aromatic compounds (for example, styrene, α-methylstyrene, vinyltoluene, etc.), fatty acid vinyl esters (vinyl acetate, vinyl propionate) Nil, vinyl pivalate, etc.). A copolymerizable monomer can be used individually or in combination of 2 or more types.

  The carboxyl group-containing polyester resin has a functional group capable of reacting with a reactive group of the produced polyester resin (or oligomer) in the preparation of the carboxyl group-containing polyester resin as the polyfunctional ethylenically unsaturated compound. Without reacting the (meth) acrylic monomer, it can be prepared by using a polyvalent carboxylic acid having three or more carboxyl groups or an acid anhydride thereof in the esterification reaction of a diol component and a dicarboxylic acid component.

  The carboxyl group-containing urethane resin is a reaction between the diol component and the polyisocyanate component without using a hydroxyalkyl (meth) acrylate component in the preparation of the carboxyl group-containing urethane resin as the polyfunctional ethylenically unsaturated compound. Can be prepared by using, as the diol component, dihydroxycarboxylic acid and / or polyester diol introduced with a carboxyl group.

The weight average molecular weights of the carboxyl group-containing acrylic resin, polyester resin, and urethane resin are, for example, 0.1 × 10 ⁴ to 10 × 10 ⁴ , preferably 0.3 × 10 ^{4 to} 5 × 10 ⁴ (for example, in terms of polystyrene). , About 0.5 × 10 ⁴ to 1 × 10 ⁴ ).

  The acid value of such an alkali-soluble resin may be, for example, about 20 to 200 KOH mg / g (for example, 30 to 150 KOH mg / g, preferably 50 to 120 KOH mg / g).

  The amount of the resin used is, for example, 1 to 250 parts by weight (for example, based on 100 parts by weight of the total amount of the ethylenically unsaturated compound (polyfunctional ethylenically unsaturated compound and monofunctional ethylenically unsaturated compound) and the thiol compound) 5 to 220 parts by weight), usually 10 to 200 parts by weight (for example, 25 to 100 parts by weight).

[solvent]
The curable composition may further contain a solvent. Examples of the solvent include alcohols (alkyl alcohols such as ethanol, propanol, and isopropanol), hydrocarbons (aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, toluene, xylene, and the like. Aromatic hydrocarbons), halogenated hydrocarbons (methylene chloride, chloroform, etc.), ethers (chain ethers such as diethyl ether, cyclic ethers such as dioxane, tetrahydrofuran, etc.), esters (ethyl acetate, Butyl acetate, ethyl lactate, etc.), ketones (acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), carbitols (methyl carbitol, ethyl carbonate) Bitol, butyl carbitol, etc.), propylene glycol monoalkyl ethers (propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-butyl ether, etc.), glycol ether esters (ethylene glycol monomethyl ether acetate (methyl cellosolve acetate)) , Ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, butyl carbitol acetate, etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), sulfoxides (Dimethyl sulfoxide, etc.), nitriles (acetonitrile, benzonitrile, etc.) Solvents. The solvent can be used alone or as a mixed solvent.

  If necessary, the composition of the present invention can be prepared by adding various additives such as a thermal polymerization inhibitor (hydroquinone, hydroquinone monoethyl ether, etc.), an antifoaming agent, a coating property improving agent, a thickener, a lubricant, Stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), plasticizers, surfactants, dissolution accelerators, colorants, fillers, antistatic agents, silane coupling agents, leveling agents, dispersants, dispersions An auxiliary agent or the like may be included. An additive can be used individually or in combination of 2 or more types.

  The solid content (or non-volatile content) concentration of the curable composition containing the solvent is, for example, about 0.5 to 50% by weight, preferably about 2 to 40% by weight (for example, 5 to 30% by weight). Good.

  The curable composition of this invention can be prepared by a conventional method, for example, mixing each component and filtering with a filter if needed.

  The curable composition of the present invention is easily cured by an ene / thiol reaction by applying active energy (thermal energy and / or light energy). Therefore, the curable composition of the present invention is useful for forming a cured product using as an active energy. For example, a cured film can be formed by applying a curable composition to a base material or a substrate, drying it if necessary, and then exposing it to heating or actinic rays. Moreover, the cured | curing material (for example, three-dimensional-shaped cured | curing material) of a predetermined | prescribed form can also be formed by repeating the application | coating or adhesion process of a curable composition, and an exposure hardening process.

  Base material or substrate can be selected according to the application, porous materials such as wood, metals such as aluminum, copper and silicon, ceramics such as glass and quartz, plastics such as polymethyl methacrylate and polycarbonate, copper-clad laminates, etc. It may be. The application method is not particularly limited, and may be, for example, a spin coating method, a spray coating method, a screen printing method, a casting method, a bar coating method, a curtain coating method, a roll coating method, a gravure coating method, a dipping method, or the like.

  In the curable composition, after application, if necessary, the solvent can be removed by drying (for example, drying at about 40 to 150 ° C.) to form a photosensitive layer. The thickness of the photosensitive layer varies depending on the application, but may be about 0.01 to 10 μm, preferably about 0.05 to 8 μm (particularly 0.1 to 5 μm).

  When the coating film is cured by heating, the heating temperature may be, for example, 60 to 200 ° C. (for example, 80 to 180 ° C.), preferably about 100 to 150 ° C.

In the curing of the coating film by exposure, a latent image may be formed by whole-surface exposure or pattern exposure that selectively exposes using a photomask or the like. For the exposure, actinic rays such as radiation (gamma rays, X-rays, electron beams, etc.), ultraviolet rays, visible rays and the like can be used, and usually ultraviolet rays are often used. In ultraviolet exposure, the amount of irradiation light (irradiation energy) varies depending on the thickness of the coating film, but is, for example, 50 to 10000 mJ / cm ² (for example, 75 to 2000 mJ / cm ² ), preferably 100 to 1000 mJ / cm ² (for example, It may be about 100 to 500 mJ / cm ² ). The curable composition of the present invention has little polymerization inhibition due to oxygen. Therefore, even if the curable composition of this invention exposes in air, a coating film hardens | cures efficiently and forms the cured film (or hardened | cured material) which has a three-dimensional structure.

  If necessary, after exposure, for example, heat treatment (after-cure or post-bake) may be performed at a temperature of about 60 to 200 ° C., preferably about 100 to 150 ° C.

  By developing the generated latent image pattern, a visualized coating pattern (particularly a thin film pattern) can be formed. Developers include water, alkaline aqueous solutions (eg, tetramethylammonium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc.), hydrophilic or water-soluble solvents (eg, alcohols such as ethanol and isopropanol, acetone, etc.) Ketones, the cyclic ethers, cellosolves, cellosolve acetates, etc.), and mixtures thereof. The development can be performed using immersion, washing, spraying or spray development.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The abbreviations and details of the raw materials used are shown below. In the following examples and comparative examples, various characteristics were measured as follows.

[material]
BNEF: 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, Osaka Gas Chemical Co., Ltd. BPEF: 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, BNEFA manufactured by Osaka Gas Chemical Co., Ltd .: 9,9-bis [6- (2-acryloyloxyethoxy) -2-naphthyl] fluorene, BPEFA manufactured by Osaka Gas Chemical Co., Ltd .: 9,9-bis [4- (2 -Acrylyloxyethoxy) phenyl] fluorene, manufactured by Osaka Gas Chemical Co., Ltd. BPEF-9EOA: 9 moles in average with respect to 1 mole of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene Diacrylate of adduct added with ethylene oxide FA-324A: 4 moles on average per mole of bisphenol A Diacrylate adducts of ethylene oxide Le are added, Hitachi Chemical Co., Ltd. PO-A: phenoxyethyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd. "Light Acrylate PO-A"
Photopolymerization initiator: “Irgacure 184” manufactured by BASF Japan Ltd.

[APHA (Hazen color number)]
A sample solution having a concentration of 50% by weight was prepared with propylene glycol monomethyl ether acetate (PGMEA), and APHA was measured using a color difference turbidimeter (“COH-300A” manufactured by Nippon Denshoku Industries Co., Ltd.).

[Haze]
A sample solution having a concentration of 50% by weight was prepared with propylene glycol monomethyl ether acetate (PGMEA), and haze (%) was measured using a color difference turbidimeter (“COH-300A” manufactured by Nippon Denshoku Industries Co., Ltd.).

[Heating loss]
Using a thermogravimetric / differential heat simultaneous measuring device TG-DTA (“TG / DTA6200” manufactured by SII Co., Ltd.), the temperature at which the temperature is increased at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere and the weight decreases by 5%. Was measured.

[Refractive index]
Using a multi-wavelength Abbe refractometer (manufactured by Atago Co., Ltd., DR-M2 <use of circulating water bath 60-C3>), the temperature was maintained at 25 ° C., and the refractive index at 589 nm was measured.

[Glass transition temperature Tg (° C)]
About 10 mg of the obtained sample was weighed in an aluminum pan for DSC measurement, and a cured product was produced by irradiating 2,000 mJ / cm ² using an ultraviolet irradiation device (H015-L31: manufactured by Eye Graphics Co., Ltd.). Under a nitrogen atmosphere, DSC (DSC 6220: manufactured by SII) was heated at 10 ° C./min, and the glass transition temperature was measured in the range of 30 to 300 ° C.

[curl]
Cut the obtained coating film into 5 cm square, place the top in contact with the flat surface, measure the height of the four corners from the flat surface (the height of the float from the flat surface), and average the value The curl index.

[Transmissivity (%)]
Using “UV-3600” manufactured by Shimadzu Corporation, the transmittance of the sample (cured film) was measured at a wavelength of 400 nm.

Example 1
(1) Synthesis of 9,9-bis [6- [2- (2-mercaptopropionyloxy) ethoxy] -2-naphthyl] fluorene

  BNEF 108.75 g (201.90 mmol), 2-mercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 49.29 g (464.39 mmol), p-toluenesulfonic acid monohydrate (manufactured by Junsei Chemical Co., Ltd.) 1.63 g (8.57 mmol) and 174.0 g of toluene (manufactured by Junsei Kagaku Co., Ltd.) were charged into a 500 mL eggplant flask and equipped with a Dean-Stark apparatus and a condenser. The contents were heated at an internal temperature of 110 ° C. with stirring. After 5 hours from the start of the reaction, the mixture was allowed to cool, and the reaction solution was neutralized with 400 mL of a 10 wt% aqueous sodium hydrogen carbonate solution. Further, the reaction solution was washed three times with ion-exchanged water, then dehydrated and dried with anhydrous magnesium sulfate (manufactured by Junsei Kagaku Co., Ltd.), and toluene was distilled off to obtain a purity of 96.5 by high performance liquid chromatography. % Target compound (thiol compound A) 136.28 g (yield 90.8%). The obtained thiol compound A was a colorless and transparent solid at room temperature. When the refractive index (25 ° C., 589 nm) was measured, it was a high refractive index of 1.65.

¹ H-NMR (CDCl ₃ -300 MHz): δ (ppm) = 7.82 (d, 2H, J = 7.5 Hz), 7.07-7.63 (m, 18H), 4.27-4. 55 (m, 8H), 3.53-3.58 (m, 2H), 2.18 (d, 2H, J = 8.4 Hz), 1.53 (d, 6H, J = 6.9 Hz)

(2) Preparation of photopolymerizable composition 58 g (81.13 mmol) of thiol compound A obtained in the synthesis step (1), 42 g (76.84 mmol) of BPEFA, 3 g of a photopolymerization initiator, and propylene glycol monomethyl 42 g of ether acetate (PGMEA) was mixed to prepare a photopolymerizable composition.

(3) Preparation of cured film After applying this photocurable composition (coating agent) to a release substrate to form a coating film having a thickness of about 100 μm, an ultraviolet irradiation machine (H015-L31: Eye Graphics Co., Ltd.) The product was irradiated at 500 mJ / cm ² to produce a cured film, and various physical properties were measured.

(Example 2)
5.93 g (8.29 mmol) of thiol compound A, 3.09 g (5.66 mmol) of BPEFA, 1.07 g (5.57 mmol) of PO-A, 0.30 g of photopolymerization initiator, propylene glycol monomethyl ether acetate (PGMEA) ) 4.26 g was mixed to prepare a photopolymerizable composition, a cured film was prepared in the same manner as in Example 1, and various physical properties were measured.

(Example 3)
A mixture of 4.38 g (6.13 mmol) of thiol compound A, 5.71 g (6.05 mmol) of BPEF-9EOA, 0.30 g of a photopolymerization initiator, and 5.71 g of propylene glycol monomethyl ether acetate (PGMEA) A polymerizable composition was prepared, a cured film was prepared in the same manner as in Example 1, and various physical properties were measured.

Example 4
5.83 g (8.16 mmol) of thiol compound A, 4.18 g (8.16 mmol) of FA-324A, 0.31 g of photopolymerization initiator, and 4.19 g of propylene glycol monomethyl ether acetate (PGMEA) were mixed to produce light. A polymerizable composition was prepared, a cured film was prepared in the same manner as in Example 1, and various physical properties were measured.

(Comparative Example 1)
(1) Synthesis of 9,9-bis [4- [2- (2-mercaptopropionyloxy) ethoxy] phenyl] fluorene

  BPEF 104.4 g (238.08 mmol), 2-mercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 58.12 g (547.58 mmol), p-toluenesulfonic acid monohydrate (manufactured by Junsei Chemical Co., Ltd.) 1 .90 g (9.99 mmol) and 77.2 g of toluene (manufactured by Junsei Chemical Co., Ltd.) were charged into the flask in the same manner as in Synthesis Example 1, but the target compound (thiol) was 93.8% pure by high performance liquid chromatography. Compound B) 135.53 g (yield 92.6%) was obtained. The obtained thiol compound B was a transparent viscous liquid at room temperature. The refractive index (25 ° C., 589 nm) was measured and found to be 1.62.

¹ H-NMR (CDCl ₃ -300 MHz): δ (ppm) = 7.74 (d, 2H, J = 7.5 Hz), 6, 73-7.25 (m, 14H), 4.11-4. 45 (m, 8H), 3.45-3.55 (m, 2H), 2.14 (d, 2H, = 8.4 Hz), 1.49 (d, 6H, J = 6.9 Hz)

(2), (3) Preparation of photopolymerizable composition and cured film 53 g (86.21 mmol) of thiol compound B obtained in the synthesis step (1), 47 g (85.99 mmol) of BPEFA, and initiation of photopolymerization A cured film was prepared in the same manner as in Example 1 except that 3 g of the agent (“Irgacure 184”) and 47 g of propylene glycol monomethyl ether acetate (PGMEA) were mixed to prepare a photopolymerizable composition.

  Table 2 shows the results of evaluation of various properties of the thiol A obtained in Example 1 and the thiol B, BNEFA and BPEFA obtained in Comparative Example 1. Furthermore, Table 3 shows the results of evaluating the cured films obtained in Examples 1 to 3 and Comparative Example 1.

  As is clear from the results in Table 2, thiol A and thiol B were not significantly different in appearance properties (APHA and haze). Further, thiol A had a higher refractive index than that of thiol B, and the heat loss was improved by 8 ° C.

  Comparing Example 1 and Comparative Example 1 having a similar composition, from Tables 2 and 3, the thiol compound A of Example 1 not only has a high refractive index, but also has a 5% weight loss temperature in the monomer. Despite not much different from the thiol compound B of Comparative Example 1, the cured film has a glass transition temperature as high as about 25 ° C. Moreover, the thiol compound A of Example 1 has high transparency such as APHA = 8 and haze = 1.8, the transparency of the cured film is as high as 86%, and the evaluation of curl is 0.0 mm. I didn't curl. Therefore, the thiol compound A of Example 1 is suitable as a resin material for the optical member. Furthermore, since the thiol compound A of Example 1 can be obtained as a colorless and transparent solid (powder body), the handleability can be greatly improved.

  When Example 1 was compared with Examples 2 to 4, the photopolymerizable composition of Example 2 had a lower viscosity than the photopolymerizable composition of Example 1 and was able to improve handleability. The cured film of Example 3 is superior in flexibility to the cured film of Example 1, and is suitable for optical film applications that require flexibility such as flexible display applications. In Example 4, by combining with a general-purpose bisphenol A acrylate resin, the transmittance could be improved without significantly reducing the refractive index.

  Since the curable composition and the cured product (or cured molded product) of the present invention contain a predetermined thiol compound, the glass transition temperature is high and the thermal characteristics are excellent. Moreover, since the shrinkage rate accompanying curing is small, a cured product (or cured molded product) having excellent dimensional accuracy can be formed, and adhesion to the substrate is also high. Furthermore, a cured product (cured coating film, etc.) having a high refractive index and small birefringence can be formed. Therefore, the curable composition of the present invention can be applied to various thin films having high heat resistance and low shrinkage, particularly cured products (such as thin films) having improved optical properties such as refractive index, using coating techniques and lithography techniques. It is useful for forming a cured molded product. In addition, you may peel a cured film from a base material as needed, or may utilize it as an optical film etc. with a base material.

Claims (11)

A thiol compound having a 9,9-bisarylfluorene skeleton represented by the following formula (1).

Wherein ring Z ₁ is a polycyclic arene ring; R ¹ and R ² are each independently a linear or branched alkylene group; m is an integer of 0 or 1 or more; n is an integer of 1 or more; R ⁴ and R ⁵ are substituents; p is 0 or an integer of 1 or more; k is an integer of 0 to 4) In the formula (1), ring Z ₁ is a condensed bicyclic or tricyclic arene ring, R ¹ is a linear or branched C _2-6 alkylene group, and R ² is a linear or branched chain A C _1-10 alkylene group, m is an integer of 0 to 5, n is an integer of 1 or 2, R ⁴ is an alkyl group or an alkoxy group, p is an integer of 0 to 3, R ⁵ is a cyano group, a halogen atom or an alkyl The thiol compound according to claim 1, wherein k is an integer of 0 to 3. In the formula (1), ring Z ₁ is a naphthalene ring, R ¹ is a linear or branched C _2-4 alkylene group, R ² is a linear or branched C _2-5 alkylene group, m 3 is 0 or 1, n is 1 or 2, R ⁴ is a C _1-4 alkyl group, p is an integer of 0 to 2, R ⁵ is a C _1-4 alkyl group, and k is 0 or 1. Thiol compounds.   In formula (1), n is 1, and group -SH is a primary or secondary mercapto group, The thiol compound in any one of Claims 1-3. A method for producing a compound represented by the formula (1) according to claim 1 by reacting a compound represented by the following formula (2) with a compound represented by the following formula (3).

(Wherein X ¹ represents a halogen atom or a group —OR ³ (R ³ is a hydrogen atom or a C _1-4 alkyl group), and ring Z ₁ , R ¹ , R ² , R ⁴ , R ⁵ , m, n , P, k are the same as in claim 1)   A curable composition comprising the thiol compound according to claim 1 and a compound having an ethylenically unsaturated bond.   The curable composition according to claim 6, wherein the compound having an ethylenically unsaturated bond includes a polyfunctional compound having a plurality of (meth) acryloyl groups. The compound having an ethylenically unsaturated bond is at least one selected from the group consisting of bisphenols or di (meth) acrylates of C _2-4 alkylene oxide adducts thereof and a compound represented by the following formula (4). The curable composition of Claim 6 or 7 containing a seed | species.

Wherein ring Z ₂ is a monocyclic or polycyclic arene ring; X ² is an allyl group or a (meth) acryloyl group; R ¹ , m, n, R ⁴ , R ⁵ , p, k are claims Same as 1)   The curable composition according to claim 7 or 8, wherein the compound having an ethylenically unsaturated bond further contains an aryloxyalkyl (meth) acrylate.   Furthermore, the curable composition in any one of Claims 6-9 containing a photoinitiator.   Hardened | cured material formed with the curable composition in any one of Claims 6-10.