JP2010254732A - Curable composition and cured product of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable composition that excels in heat resistance and low shrinkage property, etc., and can be cured by irradiation of active light (such as an ultraviolet ray and an electron beam), and to provide a cured product (such as a cured film) using the composition. <P>SOLUTION: This photocurable composition is an ene-thiol-based curable composition which includes an ethylenic unsaturated compound (such as multifunctional (meth)acrylate) and a thiol compound (such as a polythiol compound) as curable components, wherein the photocurable composition includes, as at least one curable component of the curable components, ≥20 wt.% of a compound having a 9,9-bisarylfluorene skeleton (such as di(meth)acrylate) on the basis of the total amount. The ratio of a mercapto group of the thiol compound to 1 mol of an ethylenic unsaturated bond of the ethylenic unsaturated compound is 0.1-1.5 mol. The curable composition may include a photopolymerization initiator. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is an ene / thiol-based curable composition and its cured product (cured film, etc.), particularly excellent in heat resistance and low shrinkage, and can be cured by irradiation with actinic rays (ultraviolet rays, electron beams, etc.). The present invention relates to a photocurable composition and a cured product thereof (such as a cured film).

  A photocurable composition that can be cured by irradiation with ultraviolet rays or an electron beam does not require a solvent and can reduce the burden on the environment. Such a photocurable resin composition has a component containing an ethylenically unsaturated group such as a photocurable oligomer (epoxy acrylate, polyester acrylate, polyurethane acrylate, etc.) or a photocurable monomer (polyfunctional acrylate, etc.). In the ultraviolet curable resin composition, a photopolymerization initiator is used.

  However, when a resin composition containing a component containing an ethylenically unsaturated group is cured, the shrinkage is large. For this reason, when a cured coating film is formed, a substrate such as paper is curled or the adhesion of the cured coating film to a substrate such as metal tends to be lowered. Moreover, since the said photocurable resin composition utilizes radical reaction, hardening is easy to be inhibited with oxygen.

  In recent years, an ene / thiol-based curable composition in which a component having an ethylenically unsaturated group and a compound having a mercapto group are combined has been proposed, and the curable composition can suppress shrinkage due to curing.

  Japanese Unexamined Patent Publication No. 2006-89623 (Patent Document 1) discloses a cationic electrodeposition coating composition containing an unsaturated group and cationic group-containing epoxy resin and a thiol group and cationic group-containing epoxy resin. It is also described that it may contain an initiator, an unsaturated group-containing compound and / or a thiol group-containing compound. In this cationic electrodeposition coating composition, the content of the blocked isocyanate curing agent can be greatly reduced by utilizing the ene-thiol reaction.

  Japanese Patent Application Laid-Open No. 2008-13690 (Patent Document 2) discloses an electron beam curable composition containing a compound having an ethylenically unsaturated double bond and a polyfunctional thiol compound or a disulfide compound in a predetermined ratio. Yes. Furthermore, in JP2009-58582A (Patent Document 3), a photopolymerizable compound (such as a ring-opening addition reaction product of a carboxyl group-containing acrylic resin and an alicyclic epoxy compound having a polymerizable group), A photocurable resin composition containing a photopolymerization initiator and a thiol chain transfer agent (mercapto organic acid derivative and thioglycolic acid derivative) is applied onto a substrate, pre-baked, selectively exposed, and then subjected to alkali development. Thus, it is disclosed to form a resist pattern.

  However, it is difficult for these curable resin compositions to improve heat resistance. In addition, the optical properties of the cured coating film cannot be improved.

  JP 2006-154775 A (Patent Document 4) includes (A) a binder resin having a carboxyl group (such as a bisphenol-type epoxy acrylate resin having a carboxyl group), (B) a compound having an ethylenically unsaturated group, ( C) Photopolymerization initiator system containing a thiol compound having a 9,9-bisphenylfluorene skeleton (such as 9,9-bis [4- (mercaptoalkylcarbonyloxy) alkyloxyphenyl] fluorenes), (D) a black pigment And (E) a color filter black matrix resist composition containing an organic solvent is disclosed. In this patent document, in a system excluding the organic solvent (E), (A) a binder resin having a carboxyl group; 10 to 30% by mass, (B) a compound having an ethylenically unsaturated group; 2 to 20% by mass (C) Photopolymerization initiator system: 2 to 15% by mass, (D) Black pigment: 40 to 80% by mass, and the photopolymerization initiator system (C) contains 20 to 70% by mass of the thiol compound. It is described that it contains in the ratio. In this document, when (C) the photopolymerization initiator system contains a thiol compound having a fluorene skeleton, a photo radical generator, and a sensitizer, and a novel thiol compound having a fluorene skeleton is used, the light shielding property is improved. It is described that the development margin can be improved with high sensitivity and high sensitivity.

  However, even the resist composition has low heat resistance and optical characteristics, and low shrinkage cannot be reduced while maintaining high heat resistance.

JP 2006-89623 A (Claims, paragraph [0007]) JP 2008-13690 A (Claims) JP 2009-58582 A (Claims) JP 2006-154775 A (claims, paragraphs [0011] [0029])

  Accordingly, an object of the present invention is to provide a curable composition (or curable resin composition) that can achieve both high thermal characteristics and low shrinkage, and a cured product thereof (such as a cured film).

  Another object of the present invention is to provide a curable composition (or curable resin composition) having a high refractive index and capable of forming a cured product having excellent optical properties, and a cured product thereof (such as a cured film). There is.

  Still another object of the present invention is to provide a photocurable composition (or photocurable resin composition) capable of forming a cured film having high heat resistance and optical properties by irradiation with light rays such as ultraviolet rays and electron beams, and curing thereof. It is to provide a product (cured film or the like).

  As a result of intensive studies to solve the above problems, the present inventors have found that in an ene / thiol curing system in which a specific compound having an ethylenically unsaturated double bond and a specific thiol compound are combined, When a compound having a 9,9-bisarylfluorene skeleton is used as at least one component (curable component) of the compound and the thiol compound, thermal properties such as heat resistance are improved and shrinkage is reduced. The inventors found that increasing the content of the compound having a 9,9-bisarylfluorene skeleton as the curing component can further improve the thermal characteristics and the optical characteristics, thereby completing the present invention.

  That is, the curable composition (or curable resin composition) of the present invention contains an ethylenically unsaturated compound and a thiol compound as a curing component to form an ene / thiol-based curable composition. At least one component of the ethylenically unsaturated compound and the thiol compound includes a compound having a 9,9-bisarylfluorene skeleton. In such a composition, the ethylenically unsaturated compound may be a polyfunctional compound having a plurality of ethylenically unsaturated bonds, for example, a polyfunctional (meth) acrylic compound having a plurality of (meth) acryloyl groups. .

  More specifically, the ethylenically unsaturated compound may be a compound represented by the following formula (1) or (1a).

(In the formula, rings Z ₁ and Z ₂ are the same or different and are aromatic hydrocarbon rings, R _2a and R _2b are the same or different and represent a hydrogen atom or a methyl group, and R _4a and R _4b are the same or different. Represents a halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, cycloalkyloxy group, aryloxy group, aralkyloxy group, acyl group, nitro group, cyano group or substituted amino group, R _5a and R _5b is the same or different and represents a halogen atom, a cyano group or an alkyl group, X _1a and X _1b are the same or different linking groups (for example, a linking group containing an ester bond or a urethane bond), and m is 1 to 3. An integer, q represents an integer of 0 or 1 to 3, and r represents an integer of 0 or 1 to 3)

(In the formula, R _1a and R _1b are alkylene groups, n represents 0 or an integer of 1 to 10, Z ₁ and Z ₂ , R _4a and R _4b , R _5a and R _5b , m, q and r are the same as above. Same as)
The thiol compound may be a polythiol compound having a plurality of mercapto groups. For example, the thiol compound may be a compound represented by the following formula (2), (2a) or (2b).

(Wherein Y _1a and Y _1b are the same or different linking groups, p represents 0 or 1, Z ₁ and Z ₂ , R _4a and R _4b , R _5a and R _5b , m, q and r are as defined above. the same)

(Wherein R _3a and R _3b represent an alkylene group, R _1a and R _1b , Z ₁ and Z ₂ , R _4a and R _4b , R _5a and R _5b , m, n, q and r are the same as above. )
In the composition, the content of the compound having a 9,9-bisarylfluorene skeleton may be 20% by weight or more based on the solid content in order to function as a curing component. Moreover, a thiol compound (for example, polythiol having a plurality of mercapto groups) with respect to 1 mol of the ethylenically unsaturated bond of an ethylenically unsaturated compound (for example, a polyfunctional ethylenically unsaturated compound having a plurality of ethylenically unsaturated bonds) The ratio of the mercapto group in the compound) may be about 0.1 to 1.5 mol.

  The curable composition includes a polyfunctional ethylenically unsaturated compound having a plurality of ethylenically unsaturated bonds [in particular, a polyfunctional (meth) acrylic compound having a plurality of (meth) acryloyl groups] and a cured product (cured). A monofunctional ethylenically unsaturated compound having a single ethylenically unsaturated bond in the molecule [in particular, a monofunctional (meth) acrylic compound having a (meth) acryloyl group] May be included. Furthermore, the curable composition may contain a polymerization initiator (for example, a photopolymerization initiator).

  The present invention, together with the curable composition, a cured product (cured film or the like) obtained by curing the curable composition, and a cured product (cured) that imparts active energy (heat or light energy) to the curable composition for curing. And the like.

  In this specification, 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.

  In the present invention, since a compound having a 9,9-bisarylfluorene skeleton is used in the ene / thiol-based curable composition, thermal properties such as heat resistance can be improved and shrinkage can be greatly reduced. In addition, a cured product having a high refractive index and excellent optical characteristics can be formed. Furthermore, a cured product (cured film or the like) having high heat resistance and optical properties can be generated by irradiation with light of active energy (heat or light energy), particularly ultraviolet rays or electron beams.

  The curable composition of the present invention contains an ethylenically unsaturated compound and a thiol compound as curing components, and 9,9-bisarylfluorene having an ethylenically unsaturated bond as at least one of these components. A 9,9-bisarylfluorene compound having a compound and / or a mercapto group.

[Ethylenically unsaturated compound]
The ethylenically unsaturated compound only needs to have at least one ethylenically unsaturated bond, and may be a monofunctional unsaturated compound having one ethylenically unsaturated bond in the molecule. At least a polyfunctional unsaturated compound having an ethylenically unsaturated bond. A monofunctional unsaturated compound and a polyfunctional unsaturated compound can be used in combination.

Monofunctional unsaturated compounds include compounds having an allyl group (such as allyl alcohol), compounds having a vinyl group [styrene monomers, N-vinylpyrrolidone, vinyl ethers, etc.], compounds having a (meth) acryloyl group [ Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) _C1-24 alkyl (meth) acrylates such as acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoroisopro Fluoro C _1-10 alkyl (meth) acrylates such as pill (meth) acrylate; cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate; dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Bridged cyclic (meth) acrylates such as dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate; benzyl (meth) acrylate, etc. aralkyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl _{C 2-10} alkyl, such as hydroxybutyl (meth) acrylate (meth) acrylates; Phenoxyalkyl (meth) acrylates such as enoxyethyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate; glycidyl (meth) acrylate, dimethylamino (meth) acrylate, (meth) acrylamide, tetrahydro Furfuryl (meth) acrylate etc.] etc. can be illustrated. Monofunctional unsaturated compounds include, for example, (meth) acrylic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid and itaconic acid or their anhydrides, carboxyl group-containing compounds such as half esters thereof, and sulfonic acids It may be a group-containing compound or a phosphate group-containing compound such as (meth) acryloyloxyethyl acid phosphate. These monofunctional unsaturated compounds can be used alone or in combination of two or more.

As the polyfunctional unsaturated compound, a compound having an allyl group such as diallyl phthalate can be used, but polyfunctional (meth) acrylates having a plurality of (meth) acryloyl groups are often used. Polyfunctional (meth) acrylates can be classified into di (meth) acrylates and poly (meth) acrylates having three or more (meth) acryloyl groups. Examples of di (meth) acrylates include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate. , Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and other alkanediol di (meth) acrylates; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol Polyalkylene glycol di (meth) acrylates such as di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate; 2,2-bis (4- ( Bisphenols such as acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane Examples include di (meth) acrylates of C _2-4 alkylene oxide adducts (such as bisphenol A); and bridged cyclic (meth) acrylates such as tricyclodecane dimethanol di (meth) acrylate. Examples of poly (meth) acrylates include trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth). Alkane polyols such as acrylate and dipentaerythritol hexa (meth) acrylate; poly (meth) acrylates; alkane polyols such as trimethylolpropane and glycerin tri (meth) acrylates of C _2-4 alkylene oxide adducts; Examples thereof include tri (meth) acrylates having a triazine ring such as (hydroxyethyl) isocyanurate tri (meth) acrylate.

  Furthermore, the polyfunctional unsaturated compound includes a polyfunctional oligomer having an ethylenically unsaturated bond (for example, a (meth) acryloyl group) such as a polyvalent carboxylic acid and a polyol, (meth) acrylic acid and / or hydroxyalkyl ( Polyester (meth) acrylates produced by reaction with (meth) acrylate; epoxy compounds having a plurality of epoxy groups (polyhydric alcohol type, polycarboxylic acid type, bisphenol types such as bisphenol A, F, and S, novolak type, etc.) (Epoxy resin)) (epoxy (meth) acrylate) with (meth) acrylic acid ring-opening addition; reaction with polyisocyanate and polyol, and reaction with oligomer having terminal isocyanate group with hydroxyalkyl (meth) acrylate Polyurethane (meth) acrylic Such as over theft of any kind are included. In addition, an oligomer having a hydroxyl group (for example, epoxy (meth) acrylate having a hydroxyl group generated by a ring-opening reaction) reacts with a reactive compound having a carboxyl group or an acid anhydride group (for example, an acid anhydride). And a carboxyl group or the like may be introduced.

  These polyfunctional unsaturated compounds can also be used alone or in combination of two or more. As the ethylenically unsaturated compound, a compound having a (meth) acryloyl group is usually used in order to increase sensitivity. In order to increase the strength, hardness, sensitivity, etc. of the cured product, it is usually a polyfunctional unsaturated compound having a plurality of ethylenically unsaturated bonds, particularly a polyfunctional (meth) acrylic compound having a plurality of (meth) acryloyl groups. Compounds, for example, polyfunctional oligomers and / or polyfunctional (meth) acrylates (such as di (meth) acrylates and poly (meth) acrylates) are often used.

  The ethylenically unsaturated compound preferably includes a 9,9-bisarylfluorene compound having an ethylenically unsaturated bond. Such a compound can be represented by the following formula (1).

(In the formula, rings Z ₁ and Z ₂ are the same or different and are aromatic hydrocarbon rings, R _2a and R _2b are the same or different and represent a hydrogen atom or a methyl group, and R _4a and R _4b are the same or different. Represents a halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, cycloalkyloxy group, aryloxy group, aralkyloxy group, acyl group, nitro group, cyano group or substituted amino group, R _5a and R _5b is the same or different and represents a halogen atom, a cyano group or an alkyl group, X _1a and X _1b are the same or different linking groups (for example, a linking group containing an ester bond or a urethane bond), and m is 1 to 3 , Q is 0 or an integer of 1 to 3, and r is an integer of 0 or 1 to 3)
In the formula (1), examples of the aromatic hydrocarbon ring represented by Z ₁ and Z ₂ include C _6-14 aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring, and an indene ring. Can be illustrated. Preferred Z ₁ and Z ₂ are a benzene ring or a naphthalene ring.

R _2a and R _2b may be either a hydrogen atom or a methyl group, but are preferably a hydrogen atom from the viewpoint of curability and sensitivity.

Examples of the halogen atom represented by R _4a and R _4b include a fluorine atom and a chlorine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, t Examples include linear or branched C _1-8 alkyl groups (particularly, C _1-6 alkyl groups) such as a butyl group. Examples of the cycloalkyl group include C _5-10 cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include a phenyl group, an alkylphenyl group (tolyl group, xylyl group, t-butyl group). A C _6-10 aryl group such as a naphthyl group, and the like, and examples of the aralkyl group include a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group and a phenethyl group. As an alkoxy group, _C1-8 alkoxy groups (especially _C1-6 alkoxy group), such as a methoxy group, an ethoxy group, a propoxy group, n-butoxy group, an isobutoxy group, t-butoxy group, etc. can be illustrated, for example. Examples of the cycloalkyloxy group include C _5-10 cycloalkyloxy groups such as a cyclohexyloxy group, and examples of the aryloxy group include C _6-10 aryloxy groups such as a phenoxy group, and an aralkyloxy group. Examples thereof include C _6-10 aryl-C _1-4 alkyloxy groups such as a benzyloxy group. Examples of the acyl group include C _1-6 acyl groups such as an acetyl group, and examples of the substituted amino group include a dialkylamino group. Preferred substituents R _4a and R _4b are C _1-4 alkyl groups (particularly methyl group) such as methyl group and ethyl group, C _1-4 alkoxy groups (particularly methoxy group) such as phenyl group, methoxy group and ethoxy group. Etc. The substitution position of R _4a and R _4b is not particularly limited. For example, when rings Z ₁ and Z ₂ are benzene rings, they are usually 2-position, 3-position or 4-position, When Z ₁ and Z ₂ are naphthalene rings, they are often 4-position, 5-position, 6-position or 7-position.

Examples of the halogen atom represented by R _5a and R _5b include a fluorine atom and a chlorine atom, and examples of the alkyl group include linear or branched C _1-8 alkyl groups such as a methyl group and an ethyl group ( In _{particular, C 1-6} alkyl group), and others. A preferred alkyl group is a methyl group.

X _1a and X _1b are linking groups linking the rings Z ₁ and Z ₂ and the unsaturated bond, and usually an ester bond (or a bond of both an ester bond and an ether bond) or a urethane bond (or a urethane bond and an ether). A linking group containing both bonds). This linking group includes a hydroxyl group and a carboxyl group-containing unsaturated compound ((meth) acrylic acid, maleic anhydride, when the rings Z ₁ and Z ₂ have a hydroxyl group (terminal hydroxyalkyloxy group in the alkylene oxide adduct). A linking group having an ester bond formed by a reaction with the unsaturated polycarboxylic acid or acid anhydride thereof such as an acid, a hydroxyl group (terminal hydroxyalkyloxy group in an alkylene oxide adduct), and a terminal isocyanate group It may be a linking group having a urethane bond produced by a reaction with a (meth) acrylate-based compound having. As a (meth) acrylate compound having a terminal isocyanate group, it is formed by a reaction of diisocyanate with the hydroxyalkyl (meth) acrylate or a reaction of diisocyanate, diol and hydroxyalkyl (meth) acrylate, and is a free isocyanate at the terminal. Compounds having a group and a (meth) acryloyl group, such as 2- (meth) acryloyloxyethyl isocyanate, 6- (meth) acryloyloxyhexyl isocyanate, 2,2-bis ((meth) acryloyloxymethyl) ethyl isocyanate, etc. (Meth) acryloyloxyalkyl isocyanate, 4- (meth) acryloyloxyphenyl isocyanate, and the like. In addition, the coupling group produced | generated by reaction with a silane coupling agent which has a hydroxyl group and an ethylenically unsaturated bond [(meth) acryloyl group, vinyl group, etc.] may be sufficient.

In addition, when the rings Z ₁ and Z ₂ have a carboxyl group, the linking group includes a linking group having an ester bond formed by a reaction between the carboxyl group and the hydroxyalkyl (meth) acrylate, a carboxyl group, and glycidyl (meta ) A linking group having an ester bond generated by reaction with acrylate may be used.

The connecting group _{X 1a} and _{X 1b} can be substituted at any position of the ring _{Z 1} and _{Z 2,} for example, when ring _{Z 1} and _{Z 2} is a benzene ring, typically the 3-position or 4-position In the case where rings Z ₁ and Z ₂ are naphthalene rings, they are often 4-position, 5-position, 6-position or 7-position.

  The coefficient m is an integer of 1 to 3, particularly 1 or 2. The coefficient q represents an integer of 0 or 1 to 3, and is usually 0 to 3 (for example, 0 or 1). The coefficient r represents 0 or an integer of 1 to 3, and is usually 0 or 1.

  The ethylenically unsaturated compound preferably has a (meth) acryloyl group as an unsaturated bond. Such an ethylenically unsaturated compound can be represented by the following formula (1a).

(In the formula, R _1a and R _1b are alkylene groups, n represents 0 or an integer of 1 to 10, Z ₁ and Z ₂ , R _4a and R _4b , R _5a and R _5b , m, q and r are the same as above. Same as)
Examples of the alkylene group represented by R _1a and R _1b include linear or branched C _2-6 alkylene groups such as an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group. R _1a and R _1b may be different types of alkylene groups, and the types of the alkylene groups R _1a and R _1b may be different depending on the number of coefficients n. A preferable alkylene group is a _C2-4 alkylene group, particularly a _C2-3 alkylene group (ethylene group, propylene group), and is usually an ethylene group in many cases. The repeating number n of the oxyalkylene unit is 0 or an integer of 1 to 10, usually 1 to 7, preferably 1 to 5 (for example, 1 to 3), more preferably an integer of about 1 or 2. Good.

As a typical compound represented by the formula (1a), for example, 9,9-bis [(meth) acryloyloxyphenyl] such as 9,9-bis [4-((meth) acryloyloxy) phenyl] fluorene 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) phenyl] fluorene, etc. 9-bis [((meth) acryloyloxy C _2-4 alkoxy) phenyl] fluorenes; 9,9-bis [3-methyl-4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9 -Bis [3-methyl-4- (2- (meth) acryloyloxypropoxy) phenyl] fluorene, 9,9-bis [3,5-dimethyl 9,9-bis [mono or di C _1-4 alkyl- (2- (meth) acryloyloxy C _2-4 alkoxy) phenyl] fluorene such as -4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene 9,9-bis [di (2- (meth) acryloyloxy C _2-4 alkoxy) phenyl] such as 9,9-bis [3,5-di (2- (meth) acryloyloxyethoxy) phenyl] fluorene; Fluorenes; 9,9-bis [tri (2- (meth) acryloyloxy C _2-4 ) such as 9,9-bis [3,4,5-tris (2- (meth) acryloyloxyethoxy) phenyl] fluorene Alkoxy) phenyl] fluorenes; in these compounds, the C _2-4 alkoxy group represented by (R _1a O) or (OR _1b ) is poly (C _{2 -4} alkoxy) group (diethoxy, triethoxy group, etc.) substituted compounds (9,9-bis [(meth) acryloyloxy C _2-4 alkoxy) phenyl] fluorenes; 9,9-bis [4- (2 -(2- (meth) acryloyloxyethoxy) ethoxy) phenyl] fluorene, 9,9-bis [3,5-dimethyl-4- (2- (2- (meth) acryloyloxyethoxy) ethoxy) phenyl] fluorene, etc. 9,9-bis [((meth) acryloyloxy C _2-4 alkoxy C _2-4 alkoxy) phenyl] fluorenes, etc.); and in these compounds, a phenyl group is present on the phenyl groups of rings Z ₁ and Z _2. Compound substituted with biphenyl group (9,9-bis [3-phenyl-4- (2- (meth) acryloyloxyethoxy) ) Phenyl] fluorene such as 9,9-bis [phenyl - (meth) acryloyloxy _{C 2-4} alkoxyphenyl] fluorenes, etc.); compounds in these compounds the ring _{Z 1} and _{Z 2} is a naphthyl group (9, 9-bis [5 or 6- (2- (meth) acryloyloxyethoxy) -2-naphthyl)] fluorene, 9,9-bis [5 or 6- (2- (meth) acryloyloxyethoxy) -1-naphthyl )] 9,9-bis [((meth) acryloyloxy C _2-4 alkoxy) naphthyl] fluorenes) and the like.

  The ethylenically unsaturated compound is a polyfunctional ethylenically unsaturated compound having a plurality of ethylenically unsaturated bonds in the molecule (particularly a polyfunctional (meth) acrylic compound having a plurality of (meth) acryloyl groups in the molecule). In order to adjust properties such as the flexibility of the cured product and the handling properties (such as viscosity) of the composition (including the ethylenically unsaturated compound), it is preferable to include one compound in the molecule. A monofunctional ethylenically unsaturated compound having an ethylenically unsaturated bond (in particular, a monofunctional (meth) acrylic compound having one (meth) acryloyl group in the molecule) may be contained. The weight ratio of the polyfunctional unsaturated compound to the monofunctional unsaturated compound is the former / the latter = 25/75 to 100/0 (for example, 30/70 to 95/5), preferably 40/60 to 100/0 ( For example, it is about 45/55 to 90/10), and may be about 50/50 to 100/0 (for example, 60/40 to 80/20).

[Thiol compound]
The thiol compound only needs to have at least one mercapto group, and may be a monofunctional compound (monofunctional thiol compound) having one mercapto group in the molecule, but usually has a plurality of mercapto groups. It contains at least a polyfunctional compound (polythiol compound or polyfunctional thiol compound).

  Examples of the thiol compound include alkane polythiols such as 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol; 1,4-dimercapto-3-thia-butane, 1,6-dimercapto -4-thia-hexane, 1,8-dimercapto-4-thia-octane, 1,6-dimercapto-2,4-dithia-hexane, 1,8-dimercapto-2,4-dithia-octane, 1,12 -Polyalkanedithiols such as dimercapto-4,8-dithia-dodecane (or polythioxyalkylenedithiol); dimercaptobenzene, trimercaptobenzene, 1,4-di (mercaptomethyl) benzene, 1,4-bis ( Aromatic polythiols such as 2-mercaptoethyl) benzene; mercapto group-containing carboxylic acid Esters of polyhydric alcohol; and heterocyclic polythiols such as 2,4,6-trimercapto-1,3,5-triazine can be exemplified. These thiol compounds can be used alone or in combination of two or more.

Examples of the mercapto group-containing carboxylic acid include thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, 4-mercaptobutyric acid, 2-mercaptoisobutyric acid, 3-mercaptoisobutyric acid, 2 Linear or branched chain mercapto group-containing C _1- such as -mercapto-3-methylbutyric acid, 3-mercaptovaleric acid, 4-mercaptovaleric acid, 5-mercaptovaleric acid, 3-mercapto-4-methylvaleric acid ₁₀ alkanecarboxylic - carboxylic acid (preferably a mercapto group-containing _{C 1-6} alkane - carboxylic acid), a mercapto group-containing _{C 4-10} cycloalkane such as thio cyclohexanecarboxylic acid - carboxylic acid, containing a mercapto group such as thiosalicylic acid _{C 6-} Examples thereof include ₁₂ arene-carboxylic acid. Mercapto group-containing carboxylic acids can be used alone or in combination of two or more. Examples of the polyhydric alcohol include alkylene glycols (ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1, Linear or branched C _2-10 alkanediols such as 5-pentanediol and 1,6-hexanediol), polyalkylene glycols such as diethylene glycol, polyethylene glycol and dipropylene glycol, cyclohexanediol and cyclohexanedi Alicyclic or bridged alicyclic cycloalkanediols such as methanol and norbornane dimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol Alkane polyols such as 1,3,5-tris (2-hydroxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5- Triazine ring-containing polyols such as tris (2-hydroxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (such as tris (hydroxyalkyl) isocyanurates), 2 Bisphenols such as 1,2-bis (4-hydroxyethoxyphenyl) propane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyethoxyphenyl) fluorene, or alkylene oxide adducts thereof Is mentioned.

  Among the esters of mercapto group-containing carboxylic acid and polyhydric alcohol (mercapto group-containing esters), as thioglycolate ester, for example, ethylene glycol dithioglycolate, butanediol dithioglycolate, neopentyl glycol dithioglycolate, Alkanediol dithioglycolate such as hexanediol dithioglycolate; alkane polyol polythioglycolate such as trimethylolpropane trithioglycolate, pentaerythritol trithioglycolate, pentaerythritol tetrathioglycolate, dipentaerythritol hexathioglycolate Polyalkylene glycol dithioglycolates such as diethylene glycol dithioglycolate; 1,4-cyclohexanediol dithiol Alicyclic or bridged alicyclic cycloalkane polyol polythioglycolates such as glycolate and 1,4-cyclohexanedimethanol dithioglycolate; 1,3,5-tris [2- (mercaptomethylcarbonyloxy) ethyl ] Triazine ring-containing polythioglycolates such as isocyanurate; 2,2-bis [4- (2- (mercaptoacetyloxy) ethoxy) phenyl] propane, 9,9-bis [4- (mercaptoacetyloxy) phenyl Bisphenols such as fluorene (bis (4-hydroxyphenyl) alkanes, bis (4-hydroxyphenyl) cycloalkanes, bis (4-hydroxyphenyl) ethers, bis (4-hydroxyphenyl) sulfides, bis ( 4-hydroxyphenyl) sulfones, etc. Or as poly thioglycollate such an alkylene oxide adduct thereof can be exemplified.

  Mercapto group-containing esters include mercaptopropionic acid esters (3-mercaptopropionic acid esters, 3-mercapto-3-phenylpropionic acid esters, etc.) corresponding to the above thioglycolates (mercaptoacetic acid esters), Mercaptobutyric acid esters (3-mercaptobutyric acid esters, 2-mercaptoisobutyric acid esters, 3-mercapto-3-methylbutyric acid esters, etc.), mercapto valeric acid esters (3-mercapto valeric acid esters, 4-mercapto Mercaptoalkanecarboxylic acid esters such as valeric acid esters and 3-mercapto-4-methylvaleric acid esters) are also included. These mercapto group-containing esters can be used alone or in combination of two or more.

Among thiol compounds, esters of polyhydric alcohols selected from alkane diols, alkane polyols, triazine ring-containing polyols, bisphenols or their alkylene oxide adducts, and mercapto group-containing C _1-6 alkane-carboxylic acids Is often used. Such thiol compounds include, for example, butanediol dithiopropionate, hexanediol dithiopropionate, trimethylolpropane trithiopropionate, pentaerythritol trithiopropionate in addition to the thioglycolates exemplified above. Mercaptopropionates such as benzoate, pentaerythritol tetrathiopropionate, dipentaerythritol hexathiopropionate, trihydroxyethyl isocyanurate trithiopropionate; 3-mercapto corresponding to these mercaptopropionates -3-phenylpropionic acid esters; 2-mercaptoisobutyric acid esters and 3-mercaptobutyric acid esters corresponding to the mercaptopropionic acid esters (1,4-bis (3- Lucaptobutyryloxy) butane, pentaerythritol tetra (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione), 3-mercapto-3-methylbutyric acid esters, 3-mercapto-4-methylvaleric acid esters and the like.

  In addition, thioesters of mercapto group-containing carboxylic acid and polyhydric alcohol can be prepared according to a conventional esterification method.

The thiol compound may be a polyfunctional thiol having a molecular weight in the oligomer or polymer region. For example, the mercapto group-containing carboxylic acid (linear or branched mercapto group-containing C) may be added to an epoxy compound such as a bisphenol type epoxy resin. _1-6 alkane-carboxylic acid or the like) may be a reaction product obtained by ring-opening addition, and a polyurethane oligomer (diisocyanate component is reacted with a hydroxyl group of a mercapto group-containing alkanol (mercaptoethanol or the like) to form a terminal. A polyurethane oligomer having a mercapto group formed by a reaction between a compound having an isocyanate group and a diol component), a polysulfide polymer having a mercapto group at the terminal (such as a sulfide polymer having an aliphatic ether chain), such as a polyether Liquid resin in which a mercapto group is introduced into a ter chain (poly C _2-4 alkylene ether chain, etc., “Polythiol” manufactured by Toray Industries, Inc.), a disulfide bond and an ether chain (C _1-4 alkylene ether chain in the main chain) Etc.) or liquid rubber (manufactured by Toray Industries, Inc., “thiocol”).

  The thiol compound preferably includes a 9,9-bisarylfluorene compound having a mercapto group. Such a compound can be represented by the following formula (2).

(Wherein Y _1a and Y _1b are the same or different linking groups, p represents 0 or 1, Z ₁ and Z ₂ , R _4a and R _4b , R _5a and R _5b , m, q and r are as defined above. the same)
In the compound represented by the formula (2), the linking groups Y _1a and Y _1b are linking groups for linking the rings Z ₁ and Z ₂ and the mercapto group, and usually include a linking group containing an ether bond (such as an alkyleneoxy group). ), Or a linking group containing the same linking group as the linking groups X _1a and X _1b [an ester bond (or both an ester bond and an ether bond) or a urethane bond (or both a urethane bond and an ether bond)) ]. The coefficient p is 0 (direct coupling) or 1.

In the compound represented by the formula (2), preferable rings Z ₁ and Z ₂ , substituents R _4a , R _4b , R _5a and R _5b , and coefficients m, q and r are represented by the formula (1). It is the same as the compound.

  The thiol compound preferably has an alkyleneoxy group and an ester bond (or a bond of both an ester bond and an ether bond). Such a compound can be represented by the following formula (2a) or (2b).

(Wherein R _3a and R _3b represent an alkylene group, R _1a and R _1b , Z ₁ and Z ₂ , R _4a and R _4b , R _5a and R _5b , m, n, q and r are the same as above. )
_Examples of the alkylene group represented by R _3a and R _3b include methylene group, ethylene group, ethylidene group, trimethylene group, propylene group, tetramethylene group, ethylethylene group, 2-methyltrimethylene group, 2,2-dimethyltrimethyl group. Examples thereof include a linear or branched C _1-6 alkylene group such as a methylene group.

In the compound represented by the formula (2a) or (2b), alkylene groups R _1a and R _1b , rings Z ₁ and Z ₂ , substituents R _4a , R _4b , R _5a and R _5b , repeating number n, and coefficient m, q and r are the same as in the compound represented by the formula (1a).

As a representative compound in which the coefficient p is 0 (direct bond) in the formula (2) (or a typical compound in which n = 0 in the formula (2a)), for example, 9,9-bis (4-mercapto) 9,9-bis (mercaptophenyl) fluorenes such as phenyl) fluorene; 9,9-bis (3-methyl-4-mercaptophenyl) fluorene, 9,9-bis (2-methyl-4-mercaptophenyl) fluorene 9,9-bis (mono- or di-C _1-4 alkyl-mercaptophenyl) fluorenes such as 9,9-bis (3,5-dimethyl-4-mercaptophenyl) fluorene; 9,9-bis (phenyl-mercaptophenyl) fluorenes such as phenyl-4-mercaptophenyl) fluorene; 9,9-bis (5 or 6-mercapto-2) Examples include 9,9-bis (mercaptonaphthyl) fluorenes such as -naphthyl) fluorene and 9,9-bis (5- or 6-mercapto-1-naphthyl) fluorene.

As a typical compound represented by the formula (2a), for example, 9,9-bis [4- (2-mercaptoethoxy) phenyl] fluorene, 9,9-bis [4- (2-mercaptopropoxy) phenyl ] 9,9-bis (mercapto C ₂₋ ) such as fluorene, 9,9-bis [4- (3-mercaptopropoxy) phenyl] fluorene, 9,9-bis [4- (4-mercaptobutoxy) phenyl] fluorene _4- alkoxyphenyl) fluorenes; 9,9-bis [3-methyl-4- (2-mercaptoethoxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (3-mercaptopropoxy) phenyl] fluorene 9,9-bis [3-methyl-4- (4-mercaptobutoxy) phenyl] fluorene, 9,9-bis [3,5-dimethyl-4- (2 9,9-bis (mono- or di-C _1-4 alkyl-mercapto C _2-4 alkoxyphenyl) fluorenes such as -mercaptoethoxy) phenyl] fluorene; in these compounds (R _1a O) or (OR _1b ) A compound (9,9-bis (mercapto C _2-4 alkoxy C _2-4 alkoxyphenyl) in which the represented C _2-4 alkoxy group is substituted with a poly (C _2-4 alkoxy) group (diethoxy, triethoxy group, etc.) ) Fluorenes, 9,9-bis (mono or di C _1-4 alkyl-mercapto C _2-4 alkoxy C _2-4 alkoxyphenyl) fluorenes, etc.); in these compounds the phenyl groups of the rings Z ₁ and Z ₂ A compound in which a phenyl group is substituted to form a biphenyl group (9,9-bis [3-phenyl-4- (2-mercapto Butoxy) phenyl] 9,9-bis fluorene [phenyl - (mercapto _{C 2-4} alkoxy) phenyl] fluorenes, etc.); compounds in these compounds the ring _{Z 1} and _{Z 2} is a naphthyl group (9, 9 -9,9- such as bis [5 or 6- (2-mercaptoethoxy) -2-naphthyl)] fluorene, 9,9-bis [5 or 6- (2-mercaptoethoxy) -1-naphthyl)] fluorene Bis [mercapto C _2-4 alkoxy) naphthyl)] fluorenes) and the like.

As a representative compound represented by the formula (2b), for example, 9,9-bis [4- (2-mercaptoethylcarbonyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-mercapto) Propylcarbonyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-mercaptoisopropylcarbonyloxyethoxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (2-mercaptopropylcarbonyloxyethoxy) ) Phenyl] fluorene, 9,9-bis [3-methyl-4- (2-mercaptoisopropylcarbonyloxyethoxy) phenyl] fluorene, 9,9-bis [3,5-dimethyl-4- (2-mercaptopropylcarbonyl) Oxyethoxy) phenyl] fluorene, 9,9-bis [3,5-di ( 9,9-bis [mono, di or tri (9) such as -mercaptopropylcarbonyloxyethoxy) phenyl] fluorene, 9,9-bis [3,4,5-tris (2-mercaptopropylcarbonyloxyethoxy) phenyl] fluorene Mercapto C _2-6 alkylcarbonyloxy C _2-4 alkoxy) phenyl] fluorenes: In the same manner as the compound represented by the formula (1a) or (2a), in these compounds, (R _1a O) or (OR _1b ) represented by _{C 2-4} alkoxy group is a poly _{(C 2-4} alkoxy) group (diethoxy, compounds substituted with triethoxy etc. group) (9,9-bis [mercapto _{C 2-6} alkylcarbonyloxy _{C 2 -4} alkoxy _C2-4 alkoxyphenyl] fluorenes); And a compound in which a phenyl group is substituted on the phenyl group of the rings Z ₁ and Z ₂ to form a biphenyl group (9,9-bis [phenyl-mercapto C _2-6 alkylcarbonyloxy C _2-4 alkoxyphenyl) In these compounds, compounds in which rings Z ₁ and Z ₂ are naphthyl groups (9,9-bis [mercapto C _2-6 alkylcarbonyloxy C _2-4 alkoxynaphthyl] fluorenes etc.)) Etc. can be exemplified.

[Curable composition]
The ethylenically unsaturated compound and thiol compound are used as a curing component. That is, a thiol compound having a 9,9-bisarylfluorene skeleton also functions as a component that cures by an ene / thiol reaction, not as a component of a photopolymerization initiator in the present invention. In particular, when a compound having a 9,9-bisarylfluorene skeleton is used as a curing component, thermal properties and optical properties can be improved and low shrinkage can be imparted. Therefore, in the present invention, in order to realize thermal properties such as heat resistance and dimensional stability (low shrinkage), at least one of the ethylenically unsaturated compound and the thiol compound is 9,9-bisarylfluorene. Including compounds having a skeleton. That is, the composition of the present invention may be a combination of an ethylenically unsaturated compound having a 9,9-bisarylfluorene skeleton and a thiol compound (polyfunctional thiol compound not having a bisarylfluorene skeleton), It may be a combination of an ethylenically unsaturated compound (polyfunctional unsaturated compound not having a bisarylfluorene skeleton) and a thiol compound having a 9,9-bisarylfluorene skeleton, or a 9,9-bisarylfluorene skeleton It may be a combination of an ethylenically unsaturated compound having a thiol compound having a 9,9-bisarylfluorene skeleton.

  In the present invention, the content of the compound having a 9,9-bisarylfluorene skeleton can be selected from a wide range as long as thermal properties such as heat resistance and optical properties can be improved. 20% by weight or more (for example, 20 to 100% by weight), preferably 25 to 90% by weight (for example, 30 to 80% by weight), and more preferably 35 to 70% by weight (minute). For example, it is about 40 to 60% by weight) and may be about 30 to 50% by weight (for example, 35 to 45% by weight). If the content of the compound having a 9,9-bisarylfluorene skeleton is increased, the heat resistance and optical properties of the cured product (or cured molded product) can be greatly improved.

  The ratio of thiol compound (especially polythiol compound having a plurality of mercapto groups) to ethylenically unsaturated compound (especially polyfunctional ethylenically unsaturated compound having a plurality of ethylenically unsaturated bonds) It can be selected from a range of about 0.1 to 1.5 (for example, 0.15 to 1.3) of the mercapto group of the thiol compound with respect to 1 mol of the ethylenically unsaturated bond. .25 (e.g., 0.25 to 1.25), preferably 0.3 to 1.2 (e.g., 0.4 to 1), more preferably 0.4 to 0.9 (e.g., 0.5 to 0). .8) may be sufficient. In order to effectively express the characteristics of the compound having a 9,9-bisarylfluorene skeleton, the ratio may be about 0.4 to 1.1 (for example, 0.45 to 1). When the ethylenically unsaturated compound and / or thiol compound is composed of a plurality of components, the ethylenically unsaturated bond and mercapto group can be calculated using a weighted average.

  The weight ratio between the ethylenically unsaturated compound and the thiol compound can be selected from a wide range according to the molecular weight and the number of functional groups of each component, and the ratio of the thiol compound to 100 parts by weight of the ethylenically unsaturated compound is 1 to It can be selected from a range of about 1000 parts by weight (particularly 10 to 500 parts by weight), and is usually 1 to 500 parts by weight (for example, 5 to 500 parts by weight), preferably 10 to 250 parts by weight (for example, 15 to 200 parts by weight). ), More preferably 20 to 200 parts by weight (for example, 30 to 150 parts by weight), particularly 40 to 130 parts by weight (for example, 50 to 125 parts by weight). In general, as the ratio of the thiol compound increases, the shrinkage rate decreases and the flexibility increases in many cases.

[Polymerization initiator]
When active energy (heat or light energy) is allowed to act on the curable composition of the present invention, the composition is cured by a reaction between an unsaturated bond and a mercapto group. Therefore, a polymerization initiator is not necessarily required, but the curable composition of the present invention may contain a polymerization initiator, and the polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or light. It may be a polymerization initiator (photo radical generator). A preferred polymerization initiator is a photopolymerization initiator.

[Photopolymerization initiator]
Examples of the photopolymerization initiator or photo radical generator include benzoins (benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl 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, -Hydroxy-2-methyl-propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.); butyrylphenones [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-propane- 1-one etc.]; aminoacetophenones [2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 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-phenylpropan-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′-bis (dimethylamino) benzophenone (Michlerske) ), 3,3-dimethyl-4-methoxybenzophenone, N, N′-dialkylaminobenzophenone such as benzyl); ketals (acetophenone dimethyl ketal, benzyldimethyl 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, etc.); acridines (1,3-bis- (9-acridinyl) propane, 1,7- Su- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, etc.); 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 (benzyldiphenyl) And acylphosphine oxides (2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like); titanocene photopolymerization initiators; oxime esters and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  The photopolymerization initiator can be obtained as a commercial product, for example, trade names “Irgacure” “Darocur” (manufactured by Ciba Specialty Chemicals), trade name “Syracure” (manufactured by Union Carbide), and the like.

  Examples of thermal polymerization initiators include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxide (such as lauroyl peroxide), and dialoyl peroxide (benzoyl peroxide). Oxide, benzoyl toluyl peroxide, toluyl peroxide, etc.)], peracid esters (percarboxylic acid alkyl esters such as t-butyl peracetate, t-butyl peroxyoctate, t-butyl peroxybenzoate, etc.), Organic peroxides such as ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds [2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyro) Nitrile) 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc.], azoamide compound {2,2′-azobis {2-methyl -N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like}, azoamidine compounds {2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, etc.}, azoalkane compounds [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis (4-cyano) Azo compounds, etc.], and azo compounds having an oxime skeleton [2,2′-azobis (2-methylpropionamidooxime, etc.)]. You may use a thermal-polymerization initiator individually or in combination of 2 or more types.

  The ratio of the polymerization initiator can be selected from a range of, for example, about 0.1 to 10 parts by weight (for example, 0.5 to 10 parts by weight) with respect to 100 parts by weight of the total amount of the ethylenically unsaturated compound and the thiol compound. For example, it may be about 1 to 10 parts by weight (for example, 1 to 5 parts by weight), preferably about 1 to 5 parts by weight (for example, 1 to 3 parts by weight).

  In addition, you may combine a photoinitiator 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) benzophenone such as 4,4-bis (dimethylamino) benzophenone (Michler's ketone), 4,4′-diethylaminobenzophenone], triphenylphosphine, etc. Examples include phosphine, toluidines such as N, N-dimethyltoluidine, anthracene such as 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. It is done. 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 of the present invention may contain a resin, for example, a water-insoluble resin (such as an acrylic resin), a water-soluble resin (such as polyvinyl alcohol or cellulose ether), or an alkali-soluble resin, if necessary. For example, an alkali-soluble resin may be included in order to form a predetermined pattern by alkali development using a lithography technique. Examples of the alkali-soluble resin may include a carboxyl group-containing acrylic resin and a carboxyl group-containing epoxy resin.

The carboxyl group-containing acrylic resin can be composed of a copolymer of the above-described unsaturated polyvalent carboxylic acid such as (meth) acrylic acid or the acid anhydride thereof and a copolymerizable monomer. Examples of the monomer include the above-described monofunctional unsaturated compounds [for example, C _1-24 alkyl (meth) acrylates such as methyl (meth) acrylate; cycloalkyl (meth) acrylates; ) 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) , Vinyl toluene, etc.), fatty acid vinyl esters (vinyl acetate, vinyl propionate, pivalic acid) Vinyl etc.). A copolymerizable monomer can be used individually or in combination of 2 or more types.

The weight average molecular weight of the carboxyl group-containing acrylic resin may be, for example, about 0.5 × 10 ⁴ to 50 × 10 ⁴ , preferably about 1 × 10 ^{4 to} 5 × 10 ^{4 in} terms of polystyrene. The acid value of the carboxyl group-containing acrylic resin may be about 15 to 400 mgKOH / g, preferably about 30 to 300 mgKOH / g, and more preferably about 40 to 200 mgKOH / g.

  Carboxyl group-containing epoxy resin consists of a hydroxyl group-containing product (epoxy (meth) acrylate) produced by a ring-opening addition reaction between an epoxy resin such as a bisphenol-type epoxy resin and (meth) acrylic acid, and an epoxy (meth) produced. Reaction of hydroxyl group of acrylate with acid anhydride (maleic anhydride, succinic anhydride, phthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, etc.) Can be obtained.

The weight average molecular weight of the carboxyl group-containing epoxy resin (carboxyl group-containing epoxy (meth) acrylate) is, for example, 0.2 × 10 ^{4 to} 5 × 10 ⁴ , preferably 0.3 × 10 ⁴ to 1 × 10 in terms of polystyrene. ^It may be about ⁴ . The acid value of the carboxyl group-containing epoxy (meth) acrylate may be about 15 to 250 mgKOH / g, preferably about 30 to 200 mgKOH / g, more preferably about 50 to 150 mgKOH / g.

  The amount of the resin used can be selected, for example, from a range of about 1 to 500 parts by weight with respect to 100 parts by weight of the total amount of the ethylenically unsaturated compound and thiol compound, and is usually 10 to 250 parts by weight, preferably 25 to 200 parts by weight. It may be about 50 to 100 parts by weight, more preferably about 50 to 100 parts by weight.

[solvent]
Furthermore, the curable composition may contain a solvent in order to improve applicability. Examples of the solvent include alcohols (alkyl alcohols such as ethanol, propanol, isopropanol, butanol and isobutanol, glycols such as ethylene glycol and propylene glycol), hydrocarbons (aliphatic hydrocarbons such as hexane, Alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (such as methylene chloride and chloroform), ethers (chain ethers such as dimethyl ether and diethyl ether, Cyclic ethers such as dioxane and tetrahydrofuran), esters (methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, ethyl butyrate, etc.), ketones (acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclohexa) , N-methyl-2-pyrrolidone, etc.), cellosolves (such as methyl cellosolve, ethyl cellosolve, butyl cellosolve), carbitols (such as methyl carbitol, ethyl carbitol, butyl carbitol), propylene glycol monoalkyl ethers (such as Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-butyl ether, etc.), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, butylcarbi Tall acetate, etc.), amides (N, N-dimethylformamide, N, N- Such as methyl acetamide), sulfoxides (dimethyl sulfoxide, etc.), nitriles (acetonitrile, and benzonitrile), include organic solvents such as N- methylpyrrolidone. The organic solvent can be used alone or as a mixed solvent.

  In addition, the composition of this invention may contain various additives, if necessary. Examples of additives include thermal polymerization inhibitors (hydroquinone, hydroquinone monoethyl ether, etc.), antifoaming agents, coatability improvers, thickeners, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers). Etc.), plasticizers, surfactants, dissolution accelerators, colorants, fillers, antistatic agents, silane coupling agents, leveling agents, dispersants, dispersion aids and the like. The additives may be used alone or in combination of two or more.

  The solid (or non-volatile) concentration of the composition containing the solvent may be, for example, about 0.5 to 60% by weight, preferably about 2 to 40% by weight (for example, 5 to 30% by weight). The viscosity of the composition containing the solvent may be, for example, 5 to 500 mPa · s, preferably 10 to 100 mPa · s, and more preferably about 20 to 50 mPa · s at a temperature of 25 ° C.

  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. Therefore, the curable composition of the present invention is useful for forming a cured product using thermal energy and / or light energy as active energy. The cured product may have a three-dimensional structure and is usually a cured film in many cases. The cured film may be a film pattern (particularly a thin film pattern). A cured film can be formed by applying a curable composition to a base material or a substrate, drying if necessary, and then exposing to heat or actinic rays. It can be formed by selectively exposing to light and developing the generated latent image pattern.

  The base material or the substrate can be selected depending on the application, and may be a porous material such as wood, a metal such as aluminum or copper, a ceramic such as glass or quartz, a plastic such as polymethyl methacrylate or polycarbonate. The coating method is not particularly limited. For example, flow coating method, spin coating method, spray coating method, screen printing method, casting method, bar coating method, curtain coating method, roll coating method, gravure coating method, dipping method, slit method. It may be.

  In the curable composition containing a solvent, after apply | coating, it can dry (for example, dry at about 40-150 degreeC), and can 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 10 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 exposure step, the entire surface may be exposed depending on the application, or a patterned latent image may be formed by selective exposure using a photomask or the like. For exposure, radiation (gamma rays, X-rays, etc.), ultraviolet rays, visible rays, etc. can be used, and usually ultraviolet rays are often used. As the light source, for example, in the case of ultraviolet rays, a Deep UV lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a halogen lamp, a laser light source (light source such as a helium-cadmium laser or an excimer laser), etc. it can. Irradiation light amount (irradiation energy) varies depending on the thickness of the coating film, for example, be selected from 50~10000mJ / cm ² in the range of about, 75~2000mJ / cm ^2, more preferably 100~1000mJ / cm ² (e.g., 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.

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

  A developed coating pattern can be formed by developing the generated latent image pattern. Developers include water, alkaline aqueous solutions (eg, tetramethylammonium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc.), acidic aqueous solutions, hydrophilic solvents (eg, alcohols such as methanol, ethanol, isopropanol, Ketones such as acetone, ethers such as dioxane and tetrahydrofuran, cellosolves, cellosolve acetates, etc.), and a mixture 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. In the following examples and comparative examples, the properties of the cured films were measured as follows.

[Refractive index]
A multi-wavelength Abbe refractometer (manufactured by Atago, DR-M2 <circulating constant temperature water bath 60-C3 use>) was used, and the refractive index at 589 nm was measured while maintaining a temperature of 25 ° C. In addition, about the refractive index, it evaluated by the reference | standard of "(circle)": Refractive index 1.58 or more and "x": Refractive index less than 1.58.

[Transmissivity (%)]
Using a color difference turbidity measuring instrument (manufactured by Nippon Denshoku Industries Co., Ltd., COH-300A), in a test tube (manufactured by Maruemu Co., Ltd., A-24 (24 × 200), straight port) or 10 × 10 mm quartz cell A sample was placed and measured. Note that the transmittance evaluation criteria were “◯”: 89% or more and “×”: less than 89%.

[Glass transition temperature Tg (° C)]
About 10 mg of the obtained sample was weighed on an aluminum pan for DSC measurement, and irradiated with 2,000 mJ / cm ² using an ultraviolet irradiation machine (H015-L31: manufactured by Eye Graphics Co., Ltd.) to produce a cured product. Thereafter, 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]
The coating film obtained in Example 1 was cut into a 5 cm square, placed with the top in contact with the flat surface, the heights of the four corners from the flat surface were measured, and the average value was used as the curl index. .

[Example 1]
As the ethylenically unsaturated compound, 50 parts by weight of 9,9-bis (4-acryloyloxyethoxyphenyl) fluorene (Osaka Gas Chemical Co., Ltd., Ogsol EA-0200) and phenoxyethyl acrylate (Kyoeisha Chemical Co., Ltd.) , Light acrylate POA) 50 parts by weight. 100 parts by weight of ethylenically unsaturated compound, 10 parts by weight of pentaerythritol tetra (3-mercaptobutyrate) (manufactured by Showa Denko KK, Karenz MT PE1), and photopolymerization initiator (manufactured by Ciba Specialty Chemicals) , Irgacure 184) was mixed with 3 parts by weight at room temperature to prepare a coating agent, and this coating agent was applied to a release substrate to form a coating film having a thickness of about 100 μm. Then, it irradiated with 500 mJ / cm < ² > using the ultraviolet irradiation machine (H015-L31: Eye Graphics Co., Ltd. product), produced the cured film, and measured various physical properties.

[Examples 2 to 5]
The coating film was cured in the same manner as in Example 1 except that the ethylenically unsaturated compound and thiol compound used in Example 1 were used in the proportions shown in Table 1, and various physical properties were measured.

[Comparative Example 1]
Instead of the ethylenically unsaturated compound used in Example 1, ethylene oxide-modified bisphenol A diacrylate (2,2-bis [4- (acryloyloxyethoxyethoxy) phenyl] propane, manufactured by Hitachi Chemical Co., Ltd., FA The coating film was cured in the same manner as in Example 1 except that -324A) was used, and various physical properties were measured.

[Comparative Example 2]
The coating film was cured in the same manner as in Example 1 except that ethylene oxide-modified bisphenol A type diacrylate and thiol compound were used in the proportions shown in Table 1, and various physical properties were measured.

  The results are shown in Table 1.

  The refractive indexes of Examples 1 to 5 were as high as 1.58 to 1.61, and the refractive indexes of Comparative Examples 1 and 2 were 1.55 to 1.56. Moreover, the transmittance | permeability of the Example and the comparative example was 89.0-90.8%.

  As is apparent from Table 1, compared to the comparative example, a cured film having a high refractive index and high heat resistance was obtained in the examples. Further, from the comparison between Example 2 and Comparative Example 1, when compared at the same glass transition temperature, the Example had less curl and low shrinkage.

  Since the curable composition and the cured product (or cured molded product) of the present invention contain a compound having a 9,9-bisarylfluorene skeleton as a curing component, 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, since it contains a compound having a 9,9-bisarylfluorene skeleton, a cured product (cured coating film, etc.) having a high refractive index and a small birefringence can be formed. Therefore, the curable composition of the present invention is useful for forming various thin films having high heat resistance and low shrinkage using a coating technique and a lithography technique. In particular, it is useful for forming a cured product (cured molded product such as a thin film) having improved optical characteristics such as refractive index. The cured film may be formed in a pattern. If necessary, the cured film or the cured film pattern may be peeled off from the substrate or used as an optical film together with the substrate.

Claims (13)

  A curable composition comprising an ethylenically unsaturated compound and a thiol compound as a curing component, wherein at least one of the ethylenically unsaturated compound and the thiol compound has a 9,9-bisarylfluorene skeleton. A curable composition comprising:   The curable composition according to claim 1, wherein the ethylenically unsaturated compound is a polyfunctional compound having a plurality of ethylenically unsaturated bonds, and the thiol compound is a polythiol compound having a plurality of mercapto groups.   The curable composition according to claim 1 or 2, wherein the ethylenically unsaturated compound is a polyfunctional (meth) acrylic compound having a plurality of (meth) acryloyl groups.   The curable composition according to any one of claims 1 to 3, wherein the content of the compound having a 9,9-bisarylfluorene skeleton is 20% by weight or more based on the solid content. The curable composition according to any one of claims 1 to 4, wherein the ethylenically unsaturated compound is a compound represented by the following formula (1).

(In the formula, rings Z ₁ and Z ₂ are the same or different and are aromatic hydrocarbon rings, R _2a and R _2b are the same or different and represent a hydrogen atom or a methyl group, and R _4a and R _4b are the same or different. Represents a halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, cycloalkyloxy group, aryloxy group, aralkyloxy group, acyl group, nitro group, cyano group or substituted amino group, R _5a and R _5b is the same or different and represents a halogen atom, a cyano group or an alkyl group, X _1a and X _1b are the same or different linking groups, m is an integer of 1 to 3, q is an integer of 0 or 1 to 3, Represents an integer of 0 or 1-3) The curable composition according to any one of claims 1 to 5, wherein the ethylenically unsaturated compound is a compound represented by the following formula (1a).

(In the formula, R _1a and R _1b are alkylene groups, n represents 0 or an integer of 1 to 10, Z ₁ and Z ₂ , R _4a and R _4b , R _5a and R _5b , m, q and r are the same as above. Same as) The curable composition according to any one of claims 1 to 6, wherein the thiol compound is a compound represented by the following formula (2).

(Wherein Y _1a and Y _1b are the same or different linking groups, p represents 0 or 1, Z ₁ and Z ₂ , R _4a and R _4b , R _5a and R _5b , m, q and r are as defined above. the same) The curable composition according to any one of claims 1 to 7, wherein the thiol compound is a compound represented by the following formula (2a) or (2b).

(Wherein R _3a and R _3b represent an alkylene group, R _1a and R _1b , Z ₁ and Z ₂ , R _4a and R _4b , R _5a and R _5b , m, n, q and r are the same as above. )   The curable composition according to any one of claims 1 to 8, comprising a mercapto group of a thiol compound at a ratio of 0.1 to 1.5 mol with respect to 1 mol of an ethylenically unsaturated bond of the ethylenically unsaturated compound.   Claim that the ethylenically unsaturated compound includes a polyfunctional (meth) acrylic compound having a plurality of (meth) acryloyl groups and a monofunctional (meth) acrylic compound having one (meth) acryloyl group in the molecule Item 10. The curable composition according to any one of Items 1 to 9.   Furthermore, the curable composition in any one of Claims 1-10 containing a photoinitiator.   Hardened | cured material which the curable composition in any one of Claims 1-11 hardened | cured.   The manufacturing method of the hardened | cured material which provides active energy to the curable composition in any one of Claims 1-11, and is hardened.