JP5571968B2 - Curable composition and cured product thereof - Google Patents

Description

  The present invention relates to a curable composition that can be cured by irradiation with actinic rays (such as ultraviolet rays and electron beams), a cured product thereof (such as a cured film), and a method for producing the cured product.

  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 includes an ethylenically unsaturated group-containing component such as a photocurable resin (epoxy acrylate, polyester acrylate, polyurethane acrylate, etc.) and a photocurable monomer (polyfunctional acrylate, etc.). In the ultraviolet curable resin composition, a photopolymerization initiator is used.

  A compound having a 9,9-bisphenylfluorene skeleton such as bisphenolfluorene (BPF) is known to have excellent functions such as a high refractive index and high heat resistance. Photopolymerizable resin made from a compound having such a fluorene skeleton [for example, 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene, 9,9-bis [4- (2- (meth) acryloyl) When a (meth) acrylate having a fluorene skeleton such as oxyethoxy) phenyl] fluorene] is used, an attempt has been made to obtain a cured product having characteristics such as a high refractive index and high hardness.

  For example, JP-A-4-325508 (Patent Document 1) discloses a copolymer of a radically polymerizable composition mainly composed of 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene. A plastic lens material having a refractive index of 1.60 or more is disclosed.

  However, a photopolymerizable resin having such a fluorene skeleton is usually a solid or very high-viscosity liquid at room temperature, and a cured product such as a film is obtained using such a photopolymerizable resin. For this, it is necessary to make it liquefied by dissolving it in a solvent component or by heating and melting it. In order to make it liquefied, a method of adding a polymerizable diluent which is liquid at room temperature is also conceivable, but (1) since the concentration of the fluorene skeleton in the photopolymerizable resin becomes small, characteristics such as refractive index and heat resistance can be obtained. (2) It is difficult to select a polymerizable diluent that is compatible with the photopolymerizable resin having a fluorene skeleton, and (3) depending on the type of the polymerizable diluent, the photocurability is lowered. .

  JP-A-2005-187661 (Patent Document 2) discloses a resin composition composed of a resin component composed of a compound having a fluorene skeleton and a sulfur-containing compound. However, in the examples of this document, a molded product obtained by melt-kneading a polyester resin having a fluorene skeleton and a component such as bis (4-methacryloylthiophenyl) sulfide (both solid components at room temperature). However, there is no description of an example using a photopolymerizable resin such as 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene as the resin component.

JP-A-4-325508 (Claims) Japanese Patent Laying-Open No. 2005-187661 (Claims and Examples)

  Accordingly, an object of the present invention is to provide a curable composition that can efficiently achieve both a high refractive index and excellent curability (particularly photocurability), a cured product thereof, and a method for producing the cured product.

  Another object of the present invention is to provide a curable composition having excellent handling properties even when it is composed of an ethylenically unsaturated compound having a fluorene skeleton (specifically, a 9,9-bisarylfluorene skeleton), a cured product thereof, and a cured product. It is in providing the manufacturing method of a thing.

  Still another object of the present invention is to provide a curable composition capable of forming a cured film having a high refractive index without melting, a cured product thereof, and a method for producing the cured product.

  Another object of the present invention is to provide a method capable of easily and efficiently producing a cured product (cured film or the like) having a high refractive index without passing through a melting step.

  As a result of intensive studies to solve the above problems, the present inventors have combined a compound having a specific fluorene skeleton having an ethylenically unsaturated bond with a thio (meth) acrylate compound, so that a high refractive index and excellent In particular, by selecting a specific thio (meth) acrylate compound, it can be mixed uniformly without using a solvent, and has a suitable viscosity and a curable composition with excellent handling properties. And such a curable composition is excellent in photopolymerizability and has a high refractive index similar to (or even higher than) a compound having a fluorene skeleton alone. The present inventors have found that a cured product can be easily formed and completed the present invention.

  That is, the curable composition (or curable resin composition) of the present invention comprises an ethylenically unsaturated compound (1) having a 9,9-bisarylfluorene skeleton and a thio (meth) acrylate compound (2). It is a curable composition containing.

  The compound (1) is a compound having a plurality of (meth) acryloyl groups {for example, 9,9-bis [((meth) acryloyloxyalkoxy) phenyl] fluorene, 9,9-bis [alkyl-((meth) Acryloyloxyalkoxy) phenyl] fluorene, 9,9-bis [aryl-((meth) acryloyloxyalkoxy) phenyl] fluorene, 9,9-bis [di or tri ((meth) acryloyloxyalkoxy) phenyl] fluorene, and 9,9-bis [((meth) acryloyloxyalkoxy) naphthyl] fluorene, etc.}.

  The compound (2) may contain an aliphatic polythio (meth) acrylate compound. Moreover, the said compound (2) may contain the liquid compound at normal temperature (for example, 15-25 degreeC). Typically, the curable composition of the present invention may contain a compound represented by the following formula (2a) as the compound (2).

(Wherein R is a hydrogen atom or a methyl group, X ¹ and X ² are the same or different and a divalent aliphatic hydrocarbon group, Y is an oxygen atom or a sulfur atom, and p is an integer of 0 or more)
In the curable composition of the present invention, the ratio of the compound (1) to the compound (2) may be, for example, the former / the latter (weight ratio) = 99/1 to 10/90.

  The curable composition of the present invention may further contain a polymerizable diluent (for example, a (meth) acrylic monomer).

  The curable composition of the present invention may be a liquid composition (liquid composition) usually at room temperature.

  The present invention includes a cured product obtained by curing the curable composition. Moreover, the manufacturing method of the hardened | cured material which gives active energy to a curable composition and hardens | cures is also contained in this invention. In such a manufacturing method, a curable composition that is liquid at room temperature may be used, and a coating film may be formed and cured without undergoing a step of melting the curable composition.

  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.

  The curable composition of the present invention can efficiently achieve both a high refractive index and excellent curability (particularly photocurability). The curable composition of the present invention is usually an ethylenically unsaturated compound having a fluorene skeleton that is a solid or highly viscous liquid [for example, 9,9-bis [4- (2- (meth) acryloyloxyethoxy)]. [Phenyl] fluorene, etc.] can be made into a liquid composition having a relatively low viscosity by combination with a thio (meth) acrylate compound, and is excellent in handling properties. Furthermore, since it can be liquid, a cured film having a high refractive index can be formed without melting. Furthermore, in the method of the present invention, since a liquid curable composition can be formed with the above components, a cured product (cured film, etc.) having a high refractive index can be obtained easily and efficiently without going through a melting step. Can be manufactured.

[Curable composition]
The curable composition of the present invention may be referred to as an ethylenically unsaturated compound (1) having at least a 9,9-bisarylfluorene skeleton (simply an ethylenically unsaturated compound, compound (1), etc.) as a curing component. ) And a thio (meth) acrylate compound (2) (sometimes simply referred to as compound (2), etc.).

(Compound (1))
The ethylenically unsaturated compound (1) only needs to have a 9,9-bisarylfluorene skeleton and at least one ethylenically unsaturated bond, and is a monofunctional compound having one ethylenically unsaturated bond in the molecule. Although it may be an unsaturated compound, it is usually often a polyfunctional unsaturated compound having a plurality of ethylenically unsaturated bonds.

  Such compound (1) includes, for example, a compound represented by the following formula (1).

(Wherein, 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 each represents a hydrogen atom or a methyl group, and R _4a and R _4b are the same or different and are 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, R _1a and R _1b are the same or different linking groups (for example, a linking group containing an ester bond or a urethane bond), and m is an integer of 1 to 3. Q represents an integer of 0 or 1 to 3, and r represents 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 _1a and R _1b are linking groups that connect the rings Z ₁ and Z ₂ and the unsaturated bond, and are usually ester bonds (or bonds of both ester bonds and ether bonds) or urethane bonds (or urethane bonds and ethers). 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, the linking groups R _1a and R _1b are, when the rings Z ₁ and Z ₂ have a carboxyl group, a linking group or a carboxyl group having an ester bond generated by a reaction between the carboxyl group and the hydroxyalkyl (meth) acrylate. And a linking group having an ester bond produced by a reaction with glycidyl (meth) acrylate.

The connecting group _{R 1a} and _{R 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.

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.

  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 2 (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 in terms of photocurability and the like. Such an ethylenically unsaturated compound includes, for example, a compound having a plurality of (meth) acryloyl groups such as a compound represented by the following formula (1a).

(In the formula, R _1a and R _1b represent an alkylene group, n represents 0 or an integer of 1 to 10, Z ₁ and Z ₂ , R _2a and R _2b , R _4a and R _4b , R _5a and R _5b. , M, q and r are the same as above)
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. 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. R _1a and R _1b may be different types of groups, and the types of the groups R _1a and R _1b may be different depending on the number of coefficients n. The repeating number n of the oxyalkylene unit or the like 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. In particular, 1 may be used from the viewpoint of achieving both handling properties and high refractive properties.

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 such as fluorene; 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) phenyl] fluorene - bis [((meth) acryloyloxy alkoxy) phenyl] fluorene {e.g., 9,9-bis [((meth) acryloyloxy _{C 2-4} alkoxy) phenyl] fluorene}; 9,9-bis [3-methyl - 4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (2- (meth) 9,9-bis [alkyl-((meth) acryloyl) such as acryloyloxypropoxy) phenyl] fluorene, 9,9-bis [3,5-dimethyl-4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene Oxyalkoxy) phenyl] fluorene {eg, 9,9-bis [mono or di C _1-4 alkyl-((meth) acryloyloxy C _2-4 alkoxy) phenyl] fluorene}; 9,9-bis [3-phenyl 9,9-bis [aryl-((meth) acryloyloxyalkoxy) phenyl] fluorene such as -4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene {eg 9,9-bis [phenyl-(( meth) acryloyloxy _{C 2-4} alkoxy) phenyl] fluorene}; 9,9-bi 9, such as [3,5-di (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3,4,5-tris (2- (meth) acryloyloxyethoxy) phenyl] fluorene 9-bis [di or tri ((meth) acryloyloxyalkoxy) phenyl] fluorene {eg, 9,9-bis [di or tri ((meth) acryloyloxy C _2-4alkoxy ) phenyl] fluorene; in these compounds Compounds in which rings Z ₁ and Z ₂ are naphthyl groups {for example, 9,9-bis [5- (2- (meth) acryloyloxyethoxy) -1-naphthyl] fluorene, 9,9-bis [6- (2 -9,9-bis [(((meth) acryloyloxyalkoxy) such as-(meth) acryloyloxyethoxy) -2-naphthyl] fluorene In In these compounds _{(R 1a} O) or _{(R 1b} O); Shi) naphthyl] fluorene [e.g., 9,9-bis [((meth) acryloyloxy _{C 2-4} alkoxy) naphthyl] fluorene, etc.], etc.} A compound in which an alkoxy group represented by a polyalkoxy group (poly C _2-4 alkoxy group such as diethoxy or triethoxy group) is substituted {for example, 9,9-bis [4- (2- (2- (meth) acryloyl) Oxyethoxy) ethoxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (2- (2- (meth) acryloyloxyethoxy) ethoxy) phenyl] fluorene, 9,9-bis [3,5- Dimethyl-4- (2- (2- (meth) acryloyloxyethoxy) ethoxy) phenyl] fluorene, 9,9-bis [3-phenyl-4 -(2- (2- (2- (meth) acryloyloxyethoxy) ethoxy) phenyl) fluorene, 9,9-bis [3,4-di (2- (2- (meth) acryloyloxyethoxy) ethoxy) phenyl] fluorene, 9,9-bis {6- [2- (2- (meth) acryloyloxyethoxy) ethoxy] -2-naphthyl} fluorene etc. can be exemplified.

  You may use a compound (1) individually or in combination of 2 or more types.

  The compound (1) may be a liquid or a solid at normal temperature (for example, about 15 to 30 ° C.). The viscosity of the liquid compound (1) at 25 ° C. may be, for example, 1000 mPa · s or more, preferably 5000 mPa · s or more, more preferably about 10,000 mPa · s or more.

  In the present invention, even if the curable composition is composed of a solid or highly viscous liquid compound (1), the liquid composition (low viscosity) may be used in combination with the thio (meth) acrylate compound (2). Liquid). In addition, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene and the like are usually solid or highly viscous liquid at normal temperature.

  The viscosity of the highly viscous liquid compound (1) may be, for example, about 50000 mPa · s or more, preferably 70000 mPa · s or more, more preferably about 100,000 mPa · s or more at 25 ° C.

  The refractive index of the compound (1) can be selected from the range of, for example, 1.55 or more at 25 ° C. and 589 nm, preferably 1.57 or more (for example, 1.58 to 1.75), preferably 1 .59 or more (for example, 1.595 to 1.72), more preferably 1.6 or more (for example, 1.605 to 1.68), particularly 1.61 or more (for example, 1.615 to 1.66). It may be.

  Furthermore, the glass transition temperature of the compound (1) may be, for example, about 100 to 400 ° C., preferably about 130 to 350 ° C., more preferably about 150 to 300 ° C. (for example, 180 to 270 ° C.).

(Compound (2))
The compound (2) may be a compound having at least one thio (meth) acryloyl group (CH ₂ ═CHC (═O) S— or CH ₂ ═C (CH ₃ ) C (═O) S—). A monofunctional compound having a single thio (meth) acryloyl group in the molecule (monothio (meth) acrylate compound) or a polyfunctional compound having a plurality of thio (meth) acryloyl groups (polythio (meth) acrylate) Compound). In a preferred embodiment, compound (2) often contains at least a polythio (meth) acrylate compound. In addition, you may combine a polythio (meth) acrylate compound and a monothio (meth) acrylate compound.

As a monothio (meth) acrylate compound, for example, alkylthio (meth) acrylate (for example, C _1-10 alkylthio (meth) acrylate such as methylthio (meth) acrylate), arylthio (meth) acrylate (for example, phenylthio (meth) acrylate) , Tolylthio (meth) acrylate, 2-naphthylthio (meth) acrylate, C _6-10 arylthio (meth) acrylate such as chlorophenylthio (meth) acrylate), aralkylthio (meth) acrylate (for example, benzylthio (meth) acrylate, etc.) C _6-10 aryl C _1-4 alkylthio (meth) acrylate, etc.). These monothio (meth) acrylate compounds may be used alone or in combination of two or more.

  Examples of the polythio (meth) acrylate compound include di ((meth) acryloylthio) arene [for example, di ((meth) acryloylthio) benzene such as 1,4-di (meth) acryloylthiobenzene; Di (meth) acryloylthiobiphenyl and the like], di ((meth) acryloylthioaryl) sulfide {for example, di (4- (meth) acryloylthiophenyl) sulfide [or S, S ′-(thiodip-phenylene) bis ( Thio (meth) acrylate)], bis (3,5-dimethyl-4- (meth) acryloylthiophenyl) sulfide, bis (3,5-dibromo-4- (meth) acryloylthiophenyl) sulfide, and the like (( Aromatic polythio (meth) acrylates such as (meth) acryloylthiophenyl) sulfide} Compounds include aliphatic polythiol (meth) acrylate compound.

  Examples of the aliphatic polythio (meth) acrylate compound include a compound represented by the following formula (2a).

(Wherein R is a hydrogen atom or a methyl group, X ¹ and X ² are the same or different and a divalent aliphatic hydrocarbon group, Y is an oxygen atom or a sulfur atom, and p is an integer of 0 or more)
In the above formula (2a), examples of the aliphatic hydrocarbon group represented by X ¹ and X ² include alkylene groups (for example, C ₁ such as methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, etc.). _-8 alkylene group, preferably C _1-6 alkylene group, more preferably C _1-4 alkylene group), cycloalkylene group (for example, C _5-10 cycloalkylene group such as cyclohexylene group), arene dialkylene group ( For example, a saturated aliphatic hydrocarbon group such as a C _6-10 arene di C _1-4 alkylene group such as a xylylene group). Preferred aliphatic hydrocarbon groups are alkylene groups (such as C _2-4 alkylene groups), especially ethylene groups.

In the formula (2a), Y may be either a sulfur atom or an oxygen atom. When p is 2 or more, the compound represented by the formula (2a) is a sulfur atom. unit ^(-X 1 -Y-) and Y may have a combination of a unit ^(-X 1 -Y-) is an oxygen atom. From the viewpoint of refractive index, particularly preferred Y is a sulfur atom.

  Further, in the formula (2a), p may be, for example, 0 to 10, preferably 0 to 6 (for example, 0 to 5), and more preferably about 0 to 3.

Representative aliphatic polythio (meth) acrylate compounds (or compounds represented by formula (2a)) include S, S-alkylenebis (thio (meth) acrylate) [for example, S, S-ethylenebis (thio S, S—C _1-6 alkylenebis (thio (meth) acrylate) such as (meth) acrylate), preferably S, S—C _2-4 alkylenebis (thio (meth) acrylate)], S, S— (Thiodialkylene) bis (thio (meth) acrylate) [e.g., S, S-thiodiC _1-6 alkylenebis (thio (meth)) such as S, S- (thiodiethylene) bis (thio (meth) acrylate) Acrylate), preferably S, S-thiodiC _2-4 alkylenebis (thio (meth) acrylate)], S, S- [thiobis (dialkylene sulfide)] bis ( Thio (meth) acrylate) {e.g., S, S- [thiobis (diC _1-6 alkylenesulfide)] bis (thio (S, S- [thiobis (diethylenesulfide)] bis (thio (meth) acrylate)) meth) acrylate), preferably S, S-, etc. [thiobis (di _{C 2-4} alkylene sulfides)] bis (thio (meth) acrylate)}, di ((meth) acryloylthio alkyl) arene [e.g., xylylenedithiol Di ((meth) acryloylthio C _1-4 alkyl) C _6-10 arene] such as di (meth) acrylate], S, S- (oxydialkylene) bis (thio (meth) acrylate) [eg, S, S - S such as (oxydiethylene) bis (thio (meth) acrylate), S- (oxydi _{C 2-4} alkylene) bis And thio (meth) acrylate), etc.] and the like.

  The polythio (meth) acrylate compounds may be used alone or in combination of two or more.

Preferred polythio (meth) acrylate compounds include aliphatic polythio (meth) acrylate compounds, especially S, S-alkylene bis (thio (meth) acrylate), S, S- (thiodialkylene) bis (thiol). (Meth) acrylate), S, S- [thiobis (dialkylene sulfide)] bis (thio (meth) acrylate) and the like in formula (2a), X ¹ and X ² are alkylene groups (for example, ethylene groups, etc.) C _2-4 alkylene group), a compound in which Y is a sulfur atom, and p is about 0 to 3 are preferred.

  As will be described later, the aliphatic polythio (meth) acrylate compound is usually liquid at normal temperature (for example, 15 to 25 ° C.) and has a rigid fragrance despite having an aliphatic skeleton. It is excellent in compatibility with the compound (1) having a group skeleton, and a uniform liquid mixture (liquid composition) is often formed by combination with the compound (1). Moreover, since such a liquid mixture is also excellent in photopolymerizability, an aliphatic polythio (meth) acrylate compound can be preferably used in the present invention. On the other hand, the aromatic polythio (meth) acrylate compound is usually a solid compound at normal temperature and often cannot form a liquid mixture with the compound (1) alone.

  Therefore, it is preferable that the polythio (meth) acrylate compound contains at least an aliphatic polythio (meth) acrylate compound. When the aliphatic polythio (meth) acrylate compound is included, the ratio of the aliphatic polythio (meth) acrylate compound to the whole polythio (meth) acrylate compound is 30 mol% or more (for example, 40 to 100 mol%), preferably 50 mol. % Or more (for example, 60 to 100 mol%), more preferably 70 mol% or more (for example, 80 to 100 mol%).

  As described above, the thio (meth) acrylate compound is preferably composed of a polythio (meth) acrylate compound, and may be composed of a polythio (meth) acrylate compound and a monothio (meth) acrylate compound.

  In the thio (meth) acrylate compound including such a polythio (meth) acrylate compound, the ratio of the polythio (meth) acrylate compound is, for example, 30 mol% or more (for example, 40%) with respect to the entire thio (meth) acrylate compound. To 100 mol%), preferably 50 mol% or more (for example, 60 to 100 mol%), more preferably 70 mol% or more (for example, 80 to 100 mol%).

  In addition, when combining a polythio (meth) acrylate compound and a monothio (meth) acrylate compound, these ratios are former / latter (molar ratio) = 99 / 1-70 / 30, Preferably 98 / 2-50 / 50 More preferably, it may be about 95/5 to 70/30. In addition, a monothio (meth) acrylate compound can also be used as a polymerizable diluent (polymerizable monomer).

  The thio (meth) acrylate compound may be liquid or solid at normal temperature (for example, about 15 to 25 ° C.). In the present invention, a thio (meth) acrylate compound that is liquid at normal temperature (in particular, a polythio (meth) acrylate compound that is liquid at normal temperature) can be suitably used. Of the thio (meth) acrylate compounds, aliphatic polythiol (meth) acrylate compounds [for example, S, S- (thiodialkylene) bis (thio (meth) acrylate), etc.] are liquid at room temperature. In many cases, aromatic polythio (meth) acrylate compounds [S, S ′-(thiodi-p-phenylene) bis (thio (meth) acrylate) and the like] are solid at room temperature.

  Such a liquid thio (meth) acrylate compound is not only effective for obtaining a liquid curable composition but also depending on the type (for example, an aliphatic polythio (meth) acrylate compound). In other cases, the compound is excellent in compatibility with the compound (1), and is useful for obtaining a liquid curable composition in which the compound (1) and the compound (2) are uniformly mixed. Can do.

  The viscosity of the thio (meth) acrylate compound that is liquid at room temperature is, for example, 1 to 1000 mPa · s, preferably 3 to 500 mPa · s, more preferably 5 to 300 mPa · s (for example, 10 to 100 mPa · s) at 25 ° C. s) degree may be sufficient.

  The refractive index of the thio (meth) acrylate compound can be selected from the range of 1.4 or more (for example, 1.4 to 1.8) at 25 ° C. and 589 nm, preferably 1.45 to 1.75, Preferably, it may be 1.5 to 1.72, more preferably 1.52 to 1.7, particularly about 1.55 to 1.65.

  In particular, the refractive index of a polythio (meth) acrylate compound (such as an aliphatic polythio (meth) acrylate compound) is, for example, 1.5 to 1.7, preferably 1.52 to 1.67 at 25 ° C. and 589 nm. More preferably, it may be about 1.53 to 1.65, particularly about 1.54 to 1.62 (for example, 1.55 to 1.6).

  As the thio (meth) acrylate compound, a commercially available product may be used, and a conventional method [for example, a method of reacting the corresponding thiol with (meth) acrylic acid or a derivative thereof (such as an acid halide)] It is also possible to use a synthetic product produced by the above method.

  The ratio of the compound (1) to the thio (meth) acrylate compound (2) is, for example, the former / the latter (weight ratio) = 99/1 to 10/90 (for example, 98/2 to 15/85), preferably Is 97/3 to 20/80 (for example, 95/5 to 25/75), more preferably 93/7 to 30/70, particularly 90/10 to 40/60 (for example, 88/12 to 45/55). It may be about 95/5 to 30/70 (for example, 90/10 to 35/65).

(Other polymerizable unsaturated compounds)
If necessary, the curable composition of the present invention is a polymerizable unsaturated compound (not belonging to the category of the compound (1) and the compound (2)) as long as the effects of the present invention are not impaired. (Unsaturated compound).

  Examples of other polymerizable unsaturated compounds (or polymerizable components or polymerizable monomers) include monofunctional unsaturated compounds and polyfunctional unsaturated compounds. The polymerizable unsaturated compound may be constituted by combining a monofunctional unsaturated compound and a polyfunctional unsaturated compound.

Monofunctional unsaturated compounds include non- (meth) acrylic monomers {for example, compounds having an allyl group (such as allyl alcohol), compounds having a vinyl group [styrene monomers, N-vinylpyrrolidone, vinyl ethers, etc.} , (Meth) acrylic monomers (or compounds having a (meth) acryloyl group) {for example, (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) Alkyl (meth) acrylates such as acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate (for example, , _1-24 alkyl (meth) acrylate); trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, haloalkyl (meth) acrylates such as hexafluoroisopropyl (meth) acrylate (e.g., halo _{C 1-10} alkyl ( (Meth) acrylate); cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate; dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) Bridged cyclic (meth) acrylate such as acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate; Aralkyl (meth) acrylate such as benzyl (meth) acrylate Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate (eg, hydroxy C _2-10 alkyl (meth) acrylate); phenoxyethyl (meta ) Phenoxyalkyl (meth) acrylates such as acrylate (eg phenoxy C _1-10 alkyl (meth) acrylate); alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate (eg C _1-10 alkoxy C _{1- 10} alkyl (meth) acrylate); glycidyl (meth) acrylate, dimethylamino (meth) acrylate, (meth) acrylamide, tetrahydrofurfuryl (meth) acrylate, 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 the di (meth) acrylate include alkylene glycol di (meth) acrylate [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- C _2-10 alkylene glycol di (meth) acrylate such as hexanediol di (meth) acrylate], polyalkylene glycol di (meth) acrylate [diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, poly C _2-4 alkylene glycol di (meth) acrylates such as polypropylene glycol di (meth) acrylate Etc.], di bisphenol A (or _{C 2-3} alkylene oxide adducts) (meth) acrylates [for example, 2,2-bis (4- (meth) acryloyloxy diethoxy phenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, etc.], bridged cyclic (meth) acrylate (for example, tricyclodecane dimethanol Examples thereof include di (meth) acrylate and the like. 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) acrylate. Alkane polyols such as dipentaerythritol hexa (meth) acrylate; poly (meth) acrylates; alkane polyols such as trimethylolpropane and glycerol; tri (meth) acrylates of C _2-4 alkylene oxide adducts; tris (2-hydroxyethyl) isocyanate Examples thereof include tri (meth) acrylate having a triazine ring such as nurate 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) acrylate produced by reaction with (meth) acrylate; epoxy compound having a plurality of epoxy groups (polyhydric alcohol type, polycarboxylic acid type, bisphenol type such as bisphenol A, F, S, novolak type, etc.) Epoxy (meth) acrylate obtained by ring-opening addition of (meth) acrylic acid to epoxy resin; polyurethane produced by reaction of polyisocyanate and polyol, and oligomer having terminal isocyanate group reacted with hydroxyalkyl (meth) acrylate (Meta) Acrelay Etc. are also included. In addition, an oligomer having a hydroxyl group (for example, epoxy (meth) acrylate having a hydroxyl group generated by a ring-opening reaction) is a reactive compound having a carboxyl group or an acid anhydride group (for example, an acid anhydride). You may make it react and introduce | transduce a carboxyl group etc.

  These polyfunctional unsaturated compounds can be used alone or in combination of two or more.

  In addition, the polymerizable unsaturated compound (especially monofunctional unsaturated compound) liquid at normal temperature can also be utilized as a polymerizable diluent of the curable composition. In the curable composition of the present invention, the liquid curable composition can be formed only by the combination of the compound (1) and the compound (2) as described above, but the handling property is further improved. For this reason (or to lower the viscosity), a polymerizable diluent may be used.

  Therefore, the polymerizable unsaturated compound may be composed at least of a polymerizable unsaturated compound (or polymerizable diluent) that is liquid at normal temperature. When a monofunctional unsaturated compound (for example, a monofunctional unsaturated compound as a polymerizable diluent) and a polyfunctional unsaturated compound are used in combination, the weight ratio of these compounds is the former / the latter = 25 / 75 to 99/1 (for example, 30/70 to 95/5), preferably 40/60 to 100/0 (for example, 45/55 to 90/10), and 50/50 to 90/10 (for example, 60/40 to 80/20).

  The ratio of the polymerizable unsaturated compound is, for example, 1 to 150 parts by weight (for example, 1 to 100 parts by weight), preferably 2 to 100 parts by weight of the total amount of the compound (1) and the compound (2). It may be about 70 parts by weight, more preferably about 3 to 50 parts by weight, and usually about 3 to 60 parts by weight (for example, 5 to 55 parts by weight).

  The ratio of the polymerizable unsaturated compound is, for example, about 1 to 1000 parts by weight, preferably about 5 to 700 parts by weight, and more preferably about 10 to 600 parts by weight with respect to 100 parts by weight of the compound (2). It may be about 15 to 500 parts by weight (for example, about 20 to 400 parts by weight).

(Polymerization initiator)
The curable composition of the present invention may contain a polymerization initiator, and such a polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photo radical generator). It may be. A preferred polymerization initiator is a 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.]; 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.); ) 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) pentane, etc.); triazines (2,4,6-tris (trichloromethyl) -s-triazine, 2- ( 4-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, etc.); sulfides (benzyldiphenyl sulfide, etc.); acylphosphine oxides Examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide; titanocene photopolymerization initiators; oxime esters. 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 (particularly the photopolymerizable initiator) is, for example, 0.1 to 20 parts by weight (for example, 0.3) with respect to 100 parts by weight of the total amount of the compound (1) and the compound (2). To 15 parts by weight), preferably 0.5 to 12 parts by weight (for example, 0.7 to 10 parts by weight), and more preferably about 1 to 10 parts by weight (for example, 2 to 7 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) benzophenones 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.], aromatic vinyl compounds (eg, 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 compound (1) and the compound (1), and usually 10 to 250 parts by weight, preferably It may be about 25 to 200 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. In addition, in the curable composition of this invention, since handling property can be improved by the combination of a compound (1) and a compound (2) as mentioned above, a solvent is not required, but application property is improved further. Therefore, a solvent may be included as long as the effect of the present invention is not impaired. The solvent does not include a liquid polymerizable unsaturated compound (polymerizable diluent).

  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 solvent can be used alone or as a mixed solvent.

  In the curable composition containing a solvent, the proportion of the solvent is, for example, 0.1 to 100 parts by weight, preferably 1 to 100 parts by weight with respect to 100 parts by weight of the total amount of the compound (1) and the compound (2). It may be about 50 parts by weight, more preferably about 2 to 30 parts by weight.

  Moreover, the composition of this invention may contain the various additive 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.

  In addition, 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 this invention is excellent in sclerosis | hardenability (especially photocurability), and has high refractive property. For example, the refractive index of the curable composition (or the solid content of the curable composition) can be selected from a range of, for example, 1.5 or more at 25 ° C. and 589 nm, and preferably 1.52 or more (for example, 1. 53 to 1.75), preferably 1.54 or more (for example, 1.55 to 1.72), more preferably about 1.56 or more (for example, 1.57 to 1.68). It may be 58 or more (for example, 1.59 to 1.66).

  Moreover, in this invention, although it has the above high refractive properties, the curable composition excellent in handling property can be obtained by selecting a compound (2) etc. Therefore, the curable composition of the present invention may be usually liquid at normal temperature (for example, 15 to 25 ° C.). The viscosity of such a curable composition is, for example, 100000 mPa · s or less (eg, 5 to 90000 mPa · s), preferably 10 to 80000 mPa · s (eg, 20 to 75000 mPa · s), more preferably at 25 ° C. May be about 30 to 50000 mPa · s, or less than 30000 mPa · s (for example, 10 to 20000 mPa · s, preferably 20 to 10000 mPa · s, more preferably 30 to 7000 mPa · s, particularly 40 to 6000 mPa · s). It can also be a degree.

[Cured product]
The curable composition of the present invention is easily cured 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 (particularly, light energy) as active energy. The curable composition of the present invention is often excellent in photocurability and can be cured by applying at least light 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 coating, it can be dried (eg, dried at about 40 to 150 ° C.) to form a coating film (photosensitive layer or the like). Although the thickness of a coating film changes with uses, it may be about 0.01-10 micrometers, Preferably it is about 0.05-10 micrometers (especially 0.1-5 micrometers).

  The curable composition is usually in a liquid state at room temperature, and when such a liquid curable composition is used, a coating film can be formed without going through a step of melting the curable composition. it can.

  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. Since the curable composition of this invention is excellent in photopolymerizability, it can also obtain hardened | cured material by irradiation of actinic light, without heating.

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 helium-cadmium laser or excimer laser), etc. Can be used. 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, 75~5000mJ / cm ^2, more preferably 100~3000mJ / cm ² (e.g., 100 to 2000 mJ / cm ² ).

  If necessary, 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 mixtures thereof. The development can be performed using immersion, washing, spraying or spray development.

  As described above, a cured product (cured film or the like) is obtained. Such a cured product is excellent in thermal characteristics (for example, has a high glass transition temperature) and excellent in optical characteristics. For example, the refractive index of the cured product is, for example, 1.52 or more (for example, 1.54 to 1.8), preferably 1.55 or more (for example, 1.57 to 1.75) at 25 ° C. and 589 nm. More preferably, it is about 1.58 or more (for example, 1.59 to 1.7), and particularly 1.6 or more (for example, 1.6 to 1.66).

  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 characteristics of the curable composition and the cured film were measured as follows.

[viscosity]
Using a TV-22 type viscometer (cone plate type, manufactured by Toki Sangyo Co., Ltd., TVE-22L), using an optional rotor for high viscosity (07: 3 ° × R7.7), 1.0 to 20 rpm (depending on viscosity) Selection), the viscosity at 25 ° C. was measured.

[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.

( Reference Example 1)
9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd.), glass transition temperature 211 ° C., viscosity over 10,000 mPa · s (viscosity at 25 ° C.), refractive index (589 nm ) 1.616) 90 parts by weight, 10 parts by weight of S, S- (thiodiethylene) bis (thiomethacrylate) (manufactured by Sumitomo Seika Co., Ltd., “S2EG”), and photopolymerization initiator (Ciba Specialty) A coating agent was prepared by mixing 3 parts by weight of Irgacure 184 manufactured by Chemicals Co., Ltd. at room temperature, and this coating agent was applied to a release substrate to form a coating film having a thickness of about 100 μm. In addition, although the coating agent was a very viscous transparent liquid, each component was mixed uniformly, without phase-separating. Then, it irradiated with 500 mJ / cm < ² > using the ultraviolet irradiation machine (H015-L31: Eye Graphics Co., Ltd. product), and produced the cured film. The refractive index of the cured film was 1.625.

( Reference Example 2)
In Reference Example 1, except that 70 parts by weight of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene and 30 parts by weight of S, S- (thiodiethylene) bis (thiomethacrylate) were used. In the same manner as in Example 1, a coating agent was prepared and a cured film was produced. The property of the coating agent was a transparent liquid having a viscosity of 73000 mPa · s, and each component was uniformly mixed without phase separation. In addition, when the irradiation energy was 1000 mJ / cm ² , curing could be performed more efficiently. Moreover, the refractive index of the coating film before hardening was 1.606, and the refractive index of the cured film was 1.625.

( Reference Example 3)
In Reference Example 1, except that 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene was 50 parts by weight and S, S- (thiodiethylene) bis (thiomethacrylate) was 50 parts by weight. In the same manner as in Example 1, a coating agent was prepared and a cured film was produced. The property of the coating agent was a transparent liquid having a viscosity of 4300 mPa · s, and each component was uniformly mixed without phase separation. In addition, when the irradiation energy was 1000 mJ / cm ² , curing could be performed more efficiently. Moreover, the refractive index of the coating film before hardening was 1.597, and the refractive index of the cured film was 1.626.

(Reference Example 4 )
In Reference Example 1, except that 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene was not used and 10 parts by weight of S, S- (thiodiethylene) bis (thiomethacrylate) was used. In the same manner as in Example 1, a coating agent (transparent liquid having a viscosity of 25 mPa · s) was prepared, and a cured film was produced. The refractive index of the coating film before curing was 1.570, and the refractive index of the cured film was 1.626.

(Example 1 )
In Reference Example 1, polymerized with 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene instead of 90 parts by weight of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene Except for using 90 parts by weight of a mixture containing phenoxyethyl acrylate (“Viscoat 192” manufactured by Toagosei Co., Ltd.) as a functional diluent in a ratio of the former / the latter (weight ratio) = 50/50. In the same manner as in Example 1, a coating agent was prepared and a cured film was produced. The property of the coating agent was a transparent liquid having a viscosity of 600 mPa · s, and each component was uniformly mixed without phase separation. The refractive index of the coating film before curing was 1.568 , and the refractive index of the cured film was 1.599 .

(Example 2 )
In Example 1 , a coating agent was prepared in the same manner as in Example 4 except that the mixture was 70 parts by weight and S, S- (thiodiethylene) bis (thiomethacrylate) was 30 parts by weight. Was made. The property of the coating agent was a transparent liquid having a viscosity of 200 mPa · s, and each component was uniformly mixed without phase separation. In addition, when the irradiation energy was 1000 mJ / cm ² , curing could be performed more efficiently. Moreover, the refractive index of the coating film before hardening was 1.567 , and the refractive index of the cured film was 1.593 .

(Example 3 )
In Example 1 , a coating agent was prepared in the same manner as in Example 4 except that the mixture was 50 parts by weight and S, S- (thiodiethylene) bis (thiomethacrylate) was 50 parts by weight. Was made. The property of the coating agent was a transparent liquid having a viscosity of 50 mPa · s, and each component was uniformly mixed without phase separation. In addition, when the irradiation energy was 1000 mJ / cm ² , curing could be performed more efficiently. Moreover, the refractive index of the coating film before hardening was 1.566 , and the refractive index of the cured film was 1.600 .

  A table summarizing these results is shown below. In the table, “BPEFA” means 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene.

  Since the curable composition and the cured product (or cured molded product) of the present invention include an unsaturated compound having a 9,9-bisarylfluorene skeleton as a curing component, it has excellent thermal characteristics, high refractive index, It has excellent optical properties such as low birefringence. In addition, although it is usually composed of an unsaturated compound having a 9,9-bisarylfluorene skeleton that is solid or highly viscous, it can be efficiently reduced in viscosity by combination with a thio (meth) acrylate compound. Both handling and high refraction can be achieved. Therefore, the curable composition of the present invention is useful for forming various thin films using a coating technique or 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 (9)

A curable composition comprising an ethylenically unsaturated compound (1) having a 9,9-bisarylfluorene skeleton, an aliphatic thio (meth) acrylate compound (2), and a monofunctional (meth) acrylic monomer (3) It is a thing , Comprising: The said compound (1) is a curable composition containing the compound represented by a following formula (1a) .

(In the formula, rings Z ₁ and Z ₂ are the same or different and are aromatic hydrocarbon rings, R _1a and R _1b are alkylene groups, R _2a and R _2b are the same or different and each represents a hydrogen atom or a methyl group, R _4a And R _4b are the same or different and are 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 Represents an amino group, R _5a and R _5b are the same or different and represent a halogen atom, a cyano group or an alkyl group, m is an integer of 1 to 3, n is an integer of 1 to 10, q is 0 or 1 to 3. An integer, r represents 0 or an integer of 1 to 3) Compound (2) is an aliphatic polythio (meth) acrylate compound curable resin composition according to claim 1 Symbol mounting including.   The curable composition according to claim 1, wherein the compound (2) comprises a compound that is liquid at normal temperature. The curable composition according to any one of claims 1 to 3 , wherein the compound (2) comprises a compound represented by the following formula (2a).

(Wherein R is a hydrogen atom or a methyl group, X ¹ and X ² are the same or different and a divalent aliphatic hydrocarbon group, Y is an oxygen atom or a sulfur atom, and p is an integer of 0 or more) The ratio of a compound (1) and a compound (2) is former / latter (weight ratio) = 99/1-10/90, The curable composition in any one of Claims 1-4 . The curable composition according to any one of claims 1 to 5 , which is liquid at normal temperature. Hardened | cured material which the curable composition in any one of Claims 1-6 hardened | cured. The manufacturing method of the hardened | cured material which gives active energy to the curable composition in any one of Claims 1-6 , and is made to harden | cure. The manufacturing method according to claim 8 , wherein a coating film is formed and cured without using a step of melting the curable composition using a liquid curable composition at room temperature.