JP6231904B2 - Curable composition and cured product thereof - Google Patents

Description

  The present invention relates to a curable composition containing a polyfunctional (meth) acrylate and a monofunctional (meth) acrylate, and a cured product thereof.

  A curable component such as a heat or photo-curable resin forms a cured product on various substrates depending on the application. Therefore, such a curable component or cured product is required to have adhesion to the substrate, but depending on the combination of the curable component and the substrate, the adhesion may not be sufficient. For example, a cured product of a (meth) acrylic compound is widely used as an optical material and has a high light-transmitting substrate [for example, an inorganic substrate (glass, etc.), an organic substrate (polyethylene terephthalate, polycarbonate, cellulose triacetate, etc. ) Etc.], but generally has low adhesion to a substrate such as glass.

  In order to improve such adhesion, various additives are being developed. For example, JP 2009-167244 A (Patent Document 1) discloses an active energy ray-curable glass containing a specific radical polymerizable compound (for example, di (meth) acrylic acid polyethoxylated hydrogenated bisphenol A). It is described that a silane coupling agent (such as γ- (meth) acryloxypropyltrimethoxysilane) can be used as a component for improving the adhesion of the adhesive composition.

  However, with such conventional additives, even in a normal state, the adhesion of the cured product can be secured to some extent, but it is exposed to a high humidity environment (for example, a moist heat environment) or in an environment where moisture or humidity acts. Adhesion may be impaired by long-term storage or long-term use. In particular, when the curable component is a polyfunctional (meth) acrylate, the decrease in adhesion under such humidity or wet heat environment is significant.

  In addition, the characteristics of the curable component itself (for example, high refractive index, high heat resistance, etc.) will be reduced if significant changes are made to the formulation, such as using a large amount of additives to ensure sufficient adhesion. There is a risk of causing it. Furthermore, depending on the type of additive, sufficient compatibility and storage stability cannot be ensured, handling properties may be impaired, and good cured products may not be obtained, and the appearance may be impaired by bleeding out.

JP 2009-167244 A (claims, paragraph [0020], examples)

  Accordingly, an object of the present invention is to provide a curable composition capable of improving or improving moisture-resistant adhesion (particularly moist and heat-resistant adhesion) to a base material, and a cured product thereof, even if it is composed of a polyfunctional (meth) acrylate. It is to provide.

  Another object of the present invention is to provide a curable composition that can achieve both excellent properties such as a high refractive index and excellent moisture-proof adhesion to a substrate, and a cured product thereof.

  Still another object of the present invention is to provide an additive for improving or improving moisture-resistant adhesion of a cured product to a substrate and a method for improving or improving adhesion to a substrate using this additive. is there.

  Another object of the present invention is to provide an additive for improving or improving moisture adhesion to a substrate of a cured product without impairing compatibility with the curable component, and moisture resistance adhesion to a substrate using this additive. It is to provide a method for improving or improving the property.

  Conventionally, as additives (or modifiers) for improving moisture resistance and water resistance, various compounds (for example, silicon-based compounds such as the silane coupling agent of Patent Document 1 and fluorine-based compounds) have been known. However, among the curable components, particularly in relation to the polyfunctional (meth) acrylate, there is no one that can sufficiently improve the adhesion in an environment where moisture acts.

  On the other hand, (meth) acrylate having a phenoxybenzyl group can be used as a component for adjusting curability, hardness, viscosity, etc., and has excellent properties such as high refractive index among monofunctional (meth) acrylates. And is useful as a monofunctional (meth) acrylate for imparting or improving such excellent properties in combination with a polyfunctional (meth) acrylate. In particular, among polyfunctional (meth) acrylates, when combined with a polyfunctional (meth) acrylate having a fluorene skeleton, it can be maintained or improved without impairing properties such as a high refractive index derived from the fluorene skeleton, which is useful. It is an ingredient. Therefore, the present inventors evaluated the moisture adhesion in a combined system of a polyfunctional (meth) acrylate and a (meth) acrylate having a phenoxybenzyl group, but it was found that the moisture adhesion was still insufficient. .

  Under such circumstances, the present inventors have intensively studied to achieve the above-mentioned problems. As a result, among a number of additives or modifiers (surface modifiers), the carbodiimide compound and a polyfunctional compound as a curable component are used. Surprisingly, the moisture-resistant adhesion of the cured product to the substrate (adhesion in an environment in which moisture acts or in a high humidity environment) can be achieved by combining a functional (meth) acrylate and a (meth) acrylate having a phenoxybenzyl group. The present invention has been completed by finding that it can be improved or improved.

  That is, the curable composition (resin composition) of the present invention includes a polyfunctional (meth) acrylate (a compound having two or more (meth) acryloyloxy groups) and a monofunctional (meth) acrylate (meth). A curable composition comprising a curable component composed of an acrylate monomer and a carbodiimide compound, wherein the monofunctional (meth) acrylate comprises a monofunctional (meth) acrylate having a phenoxybenzyl group It is.

  In particular, the polyfunctional (meth) acrylate may contain a polyfunctional (meth) acrylate having a fluorene skeleton, and is typically a compound represented by the following formula (1) [for example, 9, 9 -Bis ((meth) acryloyloxyaryl) fluorenes, 9,9-bis ((meth) acryloyloxy (poly) alkoxyaryl) fluorenes, etc.].

(In the formula, ring Z represents an aromatic hydrocarbon ring, R ¹ represents a substituent, R ² represents an alkylene group, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a substituent, and k represents An integer of 0 to 4, m is an integer of 0 or more, n is an integer of 0 or more, and p is an integer of 1 or more.)
In the above formula (1), R ² may be, for example, a C _2-4 alkylene group such as an ethylene group or a propylene group, and m is 0 to 12 (eg, 1 to 10, preferably 1 to 4). The p may be about 1 to 3 (for example, 1 to 2, particularly 1). In particular, the total of two m may be 8 or less (for example, about 2 to 4) from the viewpoint of excellent characteristics while maintaining moisture-resistant adhesion.

  The (meth) acrylate having a phenoxybenzyl group may typically be phenoxybenzyl (meth) acrylate.

  In the (meth) acrylate monomer, the ratio of the polyfunctional (meth) acrylate and the monofunctional (meth) acrylate may be, for example, the former / the latter (weight ratio) = 99/1 to 10/90. .

  In the curable composition of the present invention, the carbodiimide compound may particularly include a polycarbodiimide compound, and particularly may include a polycarbodiimide compound having a terminal isocyanate group ratio of 2% by weight or more. The carbodiimide compound may be a compound that is liquid at room temperature (particularly a polycarbodiimide compound).

  The proportion of the carbodiimide compound may be, for example, about 0.005 to 30 parts by weight with respect to 100 parts by weight of the (meth) acrylate monomer. In particular, the ratio of the carbodiimide compound may be about 0.01 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylate monomer. In the present invention, even such a very small amount of carbodiimide compound can sufficiently improve the moisture resistance adhesion.

  The curable composition of the present invention may further contain a photopolymerization initiator.

  The present invention includes a method for producing a cured product that imparts active energy to the curable composition and cures the curable composition. Moreover, the hardened | cured material (or hardened | cured material obtained by the said manufacturing method) which the said curable composition hardened | cured is also contained in this invention. Such a cured product may be formed on a substrate. Therefore, the present invention also includes a laminate composed of a base material and the cured product formed on the base material.

  In the present invention, as described above, by adding a carbodiimide compound to a specific curable component, it is possible to improve the moisture resistance adhesion of the cured product to the substrate. Therefore, in the present invention, the monofunctional (meth) acrylate is composed of a (meth) acrylate monomer including a polyfunctional (meth) acrylate and a monofunctional (meth) acrylate, and the monofunctional (meth) acrylate has a phenoxybenzyl group ( An additive for improving or improving moisture-resistant adhesion to a substrate of a cured product containing a curable component containing (meth) acrylate, which includes an additive composed of a carbodiimide compound. The present invention also includes a monofunctional (meth) acrylate monomer comprising a polyfunctional (meth) acrylate and a monofunctional (meth) acrylate, wherein the monofunctional (meth) acrylate has a phenoxybenzyl group ( Also included is a method of adding or mixing the additive to a curable composition containing a curable component containing a (meth) acrylate, and improving or improving moisture-resistant adhesion to a substrate of a cured product obtained by curing the curable composition. .

  Although the curable composition of the present invention is composed of polyfunctional (meth) acrylate (and monofunctional (meth) acrylate), it has moisture-resistant adhesion (particularly moisture and heat-resistant adhesion) to a substrate. Can be improved or improved. In addition, even if the polyfunctional (meth) acrylate is composed of a polyfunctional (meth) acrylate having a fluorene skeleton, etc., it does not impair such moisture resistance adhesion, so it has a high refractive index and high heat resistance. It is possible to achieve both excellent properties such as excellent moisture resistance adhesion to the substrate.

  Moreover, the additive (moisture-resistant adhesion improvement agent or moisture-proof adhesion improvement agent) of this invention is useful as an additive for improving or improving the moisture-proof adhesion with respect to the base material of hardened | cured material as mentioned above. In particular, such an additive can improve or improve the moisture resistance adhesion of the cured product to the substrate without impairing the compatibility with the curable component. Therefore, even if such an additive is added, a uniform (and further transparent) cured product can be formed with good handling properties.

<Curable composition>
The curable composition (resin composition) of the present invention is a curable component composed of a (meth) acrylate monomer containing a polyfunctional (meth) acrylate and a specific monofunctional (meth) acrylate (curable resin, A curable resin component) and a carbodiimide compound.

[Multifunctional (meth) acrylate]
A polyfunctional (meth) acrylate (or poly (meth) acrylate) is a compound having two or more (meth) acryloyloxy groups. In the polyfunctional (meth) acrylate, the number of (meth) acryloyloxy groups is not limited as long as it is 2 or more. For example, 2 to 10, preferably 2 to 6, and more preferably 2 to 4. Good.

Specific polyfunctional (meth) acrylates include, for example, bifunctional (meth) acrylates {for example, alkylene glycol di (meth) acrylate [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, C _2-10 alkylene glycol di (meth) acrylate such as neopentyl glycol di (meth) acrylate], (poly) oxyalkylene glycol di (meth) acrylate [for example, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) a (Poly) oxy C _2-6 alkylene glycol di (meth) acrylate etc. such as acrylate], di (meth) acrylate of bisphenol A (or its C _2-3 alkylene oxide adduct), bridged cyclic (meth) acrylate (For example, tricyclodecane dimethanol di (meth) acrylate), alkanetri to hexaol di (meth) acrylate [for example, glycerin di (meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolpropane di (meth) C _3-10 alkanetri to hexaol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate etc.]}, trifunctional or higher (meth) acrylate {e.g., polyhydric alcohol ( or As C _2-3 alkylene oxide adduct) of (meth) acrylate, for example, glycerin tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate Polyols such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. (Meth) acrylate}, (poly) urethane (meth) acrylate, (poly) ester (meth) acrylate, epoxy (meth) acrylate, fluorene Etc. having a rated (meth) acrylate.

  Polyfunctional (meth) acrylates may be used alone or in combination of two or more.

  Preferred polyfunctional (meth) acrylates include polyfunctional (meth) acrylates having a fluorene skeleton. The (meth) acrylate having such a fluorene skeleton has excellent properties such as excellent optical properties (high refractive index, etc.) and high heat resistance, and a cured product reflecting such properties is obtained. In particular, the moisture-resistant adhesion is not sufficient. However, in the present invention, by combining with a carbodiimide compound, even if the curable component is composed of a polyfunctional (meth) acrylate having such a fluorene skeleton, the moisture-resistant adhesion can be improved or improved at a high level.

  Therefore, in this invention, you may comprise suitably polyfunctional (meth) acrylate with the polyfunctional (meth) acrylate which has a fluorene skeleton.

  A polyfunctional (meth) acrylate having a fluorene skeleton [or a fluorene compound having two or more (meth) acryloyloxy groups] has a fluorene skeleton together with a (meth) acryloyl group (or (meth) acryloyloxy group). doing.

  Examples of such a fluorene skeleton include fluorene (fluorene skeleton having no substituent at the 9-position), 9-substituted fluorene (for example, 9-alkylfluorene, 9-monoarylfluorene, 9,9-bisarylfluorene, etc.). And fluorene having a hydrocarbon group. A typical fluorene skeleton is a 9,9-bisarylfluorene skeleton. Note that the fluorene skeleton may have a substituent in fluorene or a substituent substituted at the 9-position of fluorene.

  The substitution position (bonding position) of the (meth) acryloyl group (or a group containing the (meth) acryloyl group) is not particularly limited, and may be the fluorene skeleton itself or bonded to the substituent located at the 9th position of fluorene. You may do it.

  The polyfunctional (meth) acrylate having a fluorene skeleton is not particularly limited as long as it has two or more (meth) acryloyloxy groups, (poly) urethane (meth) acrylate, (poly) ester (meth) acrylate, epoxy ( A meth) acrylate may be used, but typically, 9,9-bisarylfluorenes having two or more (meth) acryloyloxy groups, for example, a compound represented by the following formula (1), etc. included.

(In the formula, ring Z represents an aromatic hydrocarbon ring, R ¹ represents a substituent, R ² represents an alkylene group, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a substituent, and k represents An integer of 0 to 4, m is an integer of 0 or more, n is an integer of 0 or more, and p is an integer of 1 or more.)
In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z include a benzene ring and a condensed polycyclic arene (or condensed polycyclic aromatic hydrocarbon) ring. As the condensed polycyclic arene (or condensed polycyclic aromatic hydrocarbon) ring, for example, a condensed bicyclic arene ring (for example, a C _8-20 condensed bicyclic arene ring such as an indene ring or a naphthalene ring), Examples thereof include fused bicyclic to tetracyclic arene rings such as fused tricyclic arene rings (eg, anthracene ring). The two rings Z may be the same or different rings, and may usually be the same ring.

  A typical ring Z is a benzene ring or a naphthalene ring.

In the formula (1), examples of the group R ¹ include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [eg, an alkyl group, an aryl group (C ₆ such as a phenyl group). Non-reactive substituents such as an _-10 aryl group), etc., and in particular, an alkyl group is often used. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, such as _{C 1-12} alkyl group _{(e.g., C 1-8} alkyl groups, especially methyl groups, such as t- butyl group _{C 1- 4} alkyl group) and the like. In addition, when k is plural (two or more), the groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on the two benzene rings constituting the fluorene may be the same or different. Further, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number k is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

In the formula (1), examples of the alkylene group represented by the group R ² include C _2-6 alkylene groups such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group, Is a C _2-4 alkylene group, more preferably a C _2-3 alkylene group. When m is 2 or more, the alkylene group may be composed of different alkylene groups, and usually may be composed of the same alkylene group. In the two rings Z, the groups R ² may be the same or different, and may usually be the same.

The number (addition mole number) m of oxyalkylene groups (OR ² ) can be selected, for example, from a range of about 0 to 25 (for example, 0 to 20) according to the application and desired performance, and is usually 0 to 18 (E.g. 0-15), preferably 0-12 (e.g. 0-10), more preferably 0-8 (e.g. 0-7), especially 1 or more (e.g. 1-10, preferably 1-6). More preferably, it may be 1-4). Two m's may be the same or different.

  In the formula (1), the total of two m is, for example, 0 to 30 (for example, 0 to 25), preferably 0 to 20 (for example, 0 to 18), more preferably 0 to 16 (for example, 0-14) may be sufficient and 2 or more may be sufficient especially.

  In the formula (1), various properties (hardness, viscosity, refractive index, etc. in the cured product) vary depending on the sum of two m. Therefore, the sum of the two m values may be adjusted according to desired characteristics. For example, in the formula (1), the sum of two m is relatively small to about 8 or less (for example, 2 to 6, preferably 2 to 5, more preferably 2 to 4, particularly about 2 to 3). Also good. Thus, when the sum of two m is made small, it is easy to obtain a hard cured product with a high refractive index and high heat resistance. In addition, although moisture resistance adhesiveness may fall easily, so that the sum of m becomes small, even if it is a polyfunctional (meth) acrylate which has such a fluorene skeleton in this invention, moisture resistance adhesiveness is improved. Or it can be improved.

  On the other hand, in the formula (1), the sum of two m is relatively large [for example, 6 or more (for example, 6.5 to 20), preferably 7 to 18 (for example, 7 to 16), and more preferably 8 to 14 (for example, 8.5 to 12), particularly 9 to 12 (for example, about 9.5 to 11.5)]. When the sum of the two m is increased in this way, it is easy to obtain a cured product having softness or flexibility while having a relatively high refractive index and heat resistance.

  The compound represented by the formula (1) may be an assembly of compounds having the same value of m, or an assembly of compounds having different values of m. In the latter case, the value of m and the sum of the two m are average values (arithmetic average or arithmetic average).

In the formula (1), the substitution number p of the group containing the group R ² (sometimes referred to as a (meth) acryloyloxy group-containing group) may be 1 or more (for example, 1 to 6). It may be 1-4, preferably 1-3, more preferably 1-2, especially 1. In addition, the substitution number p may be the same or different in each ring Z, and is usually the same in many cases. The substitution position of the (meth) acryloyl group-containing group is not particularly limited as long as it is substituted at an appropriate substitution position on ring Z. For example, when the ring Z is a benzene ring, the (meth) acryloyloxy group-containing group may be substituted at an appropriate position (especially at least the 4-position) at positions 2 to 6 of the benzene ring. When it is a condensed polycyclic hydrocarbon ring, it may be substituted at least with a hydrocarbon ring different from the hydrocarbon ring bonded to the 9th position of fluorene (for example, the 5th and 6th positions of the naphthalene ring).

Examples of the substituent R ⁴ substituted on the ring Z include an alkyl group (eg, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, preferably a C _1-8 alkyl group). ), A cycloalkyl group (such as a C _5-8 cycloalkyl group such as a cyclohexyl group), an aryl group (eg, a C _6-10 aryl group such as a phenyl group, tolyl group, xylyl group, naphthyl group, etc.), Hydrocarbon groups such as aralkyl groups (such as C _6-10 aryl-C _1-4 alkyl groups such as benzyl group and phenethyl group); alkoxy groups (such as C _1-8 alkoxy groups such as methoxy group and ethoxy group), cyclo Alkoxy groups (C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups), aryloxy groups (C _6-1 such as phenoxy groups) ₀ aryloxy group), aralkyloxy group (C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group) and the like -OR [wherein R is a hydrocarbon group (the hydrocarbon group exemplified above) Etc.) A group such as an alkylthio group (such as a C _1-8 alkylthio group such as a methylthio group) -SR (wherein, R is as defined above); an acyl group (such as a C _1-6 acyl group such as an acetyl group); Alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); hydroxyl group; mercapto group; halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); nitro group; cyano group; Examples thereof include amino groups (for example, dialkylamino groups such as dimethylamino group).

Preferred group R ⁴ includes, for example, a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _{6 -10} aryl group), an aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group) and the like, and an alkoxy group (C _1-4 alkoxy group etc.). In particular, R ⁴ is preferably an alkyl group [C _1-4 alkyl group (especially methyl group) or the like], an aryl group [eg C _6-10 aryl group (especially phenyl group)] or the like.

In the same ring Z, when n is plural (2 or more), the groups R ⁴ may be different from each other or the same. In the two rings Z, the groups R ⁴ may be the same or different. Moreover, the preferable substitution number n can be selected according to the kind of the ring Z, for example, 0-8, Preferably it is 0-4 (for example, 0-3), More preferably, it may be 0-2. In different rings Z, the number of substitutions n may be the same or different from each other, and may usually be the same.

  The polyfunctional (meth) acrylate having a typical fluorene skeleton (or the compound represented by the formula (1)) includes 9,9-bis ((meth) acryloyloxyaryl) fluorenes, 9,9- Bis ((meth) acryloyloxy (poly) alkoxyaryl) fluorenes are included.

As 9,9-bis ((meth) acryloyloxyaryl) fluorenes, for example, 9,9-bis ((meth) acryloyloxyphenyl) fluorene [for example, 9,9-bis (4- (meth) acryloyloxy) Phenyl) fluorene and the like], 9,9-bis (alkyl- (meth) acryloyloxyphenyl) fluorene [9,9-bis (4- (meth) acryloyloxy-3-methylphenyl) fluorene, 9,9-bis ( 9,9-bis (mono or diC _1-4 alkyl- (meth) acryloyloxyphenyl) fluorene etc.] such as 4- (meth) acryloyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis ( Aryl (meth) acryloyloxyphenyl) fluorene [9,9-bis (4- (meth) acryloylo 9,9-bis (mono- or di-C _6-8 aryl- (meth) acryloyloxyphenyl) fluorene, etc.] such as xyl-3-phenylphenyl) fluorene, 9,9-bis (poly (meth) acryloyloxyphenyl) Fluorene {for example, 9,9-bis [2,4-di ((meth) acryloyloxy) phenyl] fluorene, 9,9-bis [3,4-di ((meth) acryloyloxy) phenyl] fluorene, 9,9-bis ((9,9-bis (di or tri (meth) acryloyloxyphenyl) fluorene} such as 9-bis [3,4,5-tri ((meth) acryloyloxy) phenyl] fluorene) (Meth) acryloyloxyphenyl) fluorenes (compound in which ring Z is a benzene ring and m is 0 in formula (1)); 9,9-bis ((Meth) acryloyloxynaphthyl) fluorene [eg, 9,9-bis [6- (2- (meth) acryloyloxynaphthyl)] fluorene, 9,9-bis [1- (5- (meth) acryloyloxynaphthyl) )] 9,9-bis ((meth) acryloyloxynaphthyl) fluorenes (compound in which the ring Z is a naphthalene ring and m is 0 in the formula (1)).

The 9,9-bis ((meth) acryloyloxy (poly) alkoxyaryl) fluorenes correspond to the 9,9-bis ((meth) acryloyloxyaryl) fluorenes, and m is 1 in the formula (1). Compounds that are above, for example, 9,9-bis ((meth) acryloyloxyalkoxyphenyl) fluorene [eg 9,9-bis (4- (2- (meth) acryloyloxyethoxy) phenyl) fluorene, etc. 9-bis ((meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene and the like], 9,9-bis ((meth) acryloyloxydialkoxyphenyl) fluorene (eg, 9,9-bis {4- [2- 9,9-bi, such as (2- (meth) acryloyloxyethoxy) ethoxy] phenyl} fluorene etc. Scan {[2- (2- (meth) acryloyloxy _{C 2-4 alkoxy) C 2-4} alkoxy] phenyl} fluorene), 9,9-bis (alkyl - (meth) acryloyloxy-alkoxyphenyl) fluorene [e.g., 9,9-bis (4- (2- (meth) acryloyloxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxyethoxy) -3,5-dimethyl 9,9-bis (mono- or di-C _1-4 alkyl (meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene etc.] such as phenyl) fluorene, 9,9-bis (aryl- (meth) acryloyloxyalkoxyphenyl) ) Fluorene [9,9-bis (4- (2- (meth) acryloyloxyethoxy) -3-phenyl] 9,9-bis (mono- or di-C _6-8 aryl (meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene etc.], 9,9-bis [di- or tri ((meth) acryloyloxy) Alkoxy) phenyl] fluorene [e.g., 9,9-bis [2,4-di (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3,4-di (2- (meth)) 9,9-bis [di or tri ((meth) acryloyl) such as acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3,4,5-tri (2- (meth) acryloyloxyethoxy) phenyl] fluorene oxy _{C 2-4} alkoxy) phenyl] fluorene] such as 9,9-bis ((meth) acryloyloxy (poly) Arukokishifu Nyl) fluorenes (compounds wherein in formula (A1) ring Z is a benzene ring and m is 1 or more (for example, 1 to 10, preferably 1 to 8, more preferably 1 to 6)); 9,9- 9,9-bis ((meth) acryloyloxy (poly) such as bis ((meth) acryloyloxyalkoxynaphthyl) fluorene [for example, 9,9-bis ((meth) acryloyloxy C _2-4 alkoxynaphthyl) fluorene, etc.] ) Alkoxynaphthyl) fluorenes (compounds in which ring Z is a naphthalene ring and m is 1 or more (for example, 1 to 10, preferably 1 to 8, more preferably 1 to 6) in the formula (A1)). It is done.

  Polyfunctional (meth) acrylates having a fluorene skeleton may be used alone or in combination of two or more.

  As the polyfunctional (meth) acrylate having a fluorene skeleton, a commercially available product may be used, or one synthesized by a conventional method may be used.

  The polyfunctional (meth) acrylate may be composed only of a polyfunctional (meth) acrylate having a fluorene skeleton, and other polyfunctional (meth) acrylates (polyfunctional (meth) acrylates having no fluorene skeleton). , A polyfunctional (meth) acrylate other than the polyfunctional (meth) acrylate having a fluorene skeleton) may be used in combination. When combining, the ratio of the polyfunctional (meth) acrylate having a fluorene skeleton and the other polyfunctional (meth) acrylate is the former / the latter (molar ratio) = 99.9 / 0.1 / 1/99, preferably Is 99.5 / 0.5 to 10/90 (eg 99/1 to 30/70), more preferably 99/1 to 40/60 (eg 98/2 to 50/50), in particular 95/5. About 60/40 (for example, 90 / 10-70 / 30) may be sufficient.

  In addition, when it comprises with the polyfunctional (meth) acrylate which has a fluorene skeleton, the ratio of the polyfunctional (meth) acrylate which has a fluorene skeleton with respect to the whole polyfunctional (meth) acrylate is 1 mol% or more (for example, 5 For example, 10 mol% or more (for example, 20 mol% or more), preferably 30 mol% or more (for example, 40 mol% or more), more preferably 50 mol% or more (for example, 60 mol% or more), particularly 70 mol% or more.

  The form of the polyfunctional (meth) acrylate is not particularly limited, and may be, for example, solid or liquid at normal temperature. The polyfunctional (meth) acrylate having a fluorene skeleton often becomes a solid or a liquid depending on the number of m in the formula (1) and the like. For example, as m is smaller, It tends to be solid.

[Monofunctional (meth) acrylate]
The monofunctional (meth) acrylate (mono (meth) acrylate) includes at least a monofunctional (meth) acrylate having a phenoxybenzyl group.

  In addition, the monofunctional (meth) acrylate having a phenoxybenzyl group is used for the purpose of handling property, curability, and imparting a high refractive index as described above. In combination, moisture resistance adhesion is still insufficient. In particular, in combination with a polyfunctional (meth) acrylate having a fluorene skeleton, the moisture-resistant adhesion is often insufficient. The reason for this is not clear, but the reactivity (polymerization reactivity) and affinity between the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate having a rigid fluorene skeleton are different. It is considered that one of the factors is that there is some difference compared to the case of the polyfunctional (meth) acrylate.

  However, in the present invention, even when such a polyfunctional (meth) acrylate having a fluorene skeleton and a monofunctional (meth) acrylate having a phenoxybenzyl group are combined, sufficient moisture resistance adhesion is imparted to the cured product. can do.

  The monofunctional (meth) acrylate having a phenoxybenzyl group is not particularly limited as long as it has a phenoxybenzyl group, and examples thereof include a compound represented by the following formula.

(In the formula, a represents an integer of 0 or more, and R ² and R ³ are the same as above.)
In the above formula, a may be an integer of 0 or more, for example, 0 to 10 (for example, 0 to 8), preferably 0 to 6 (for example, 0 to 4), more preferably 0 to 2 (for example, 0 to 1), in particular 0.

In the above formula, R ² and R ³ are the same as above (that is, R ² is an alkylene group, and R ³ is a hydrogen atom or a methyl group). Preferable R ² includes a C _2-4 alkylene group (particularly an ethylene group) such as an ethylene group and a propylene group. When a is 2 or more, the plurality of R ² may be the same or different alkylene groups.

  Representative monofunctional (meth) acrylates having a phenoxybenzyl group include phenoxybenzyl (meth) acrylate (o-phenoxybenzyl (meth) acrylate, m-phenoxybenzyl (meth) acrylate, p-phenoxybenzyl (meth) At least one selected from acrylates) and the like.

  The monofunctional (meth) acrylate having a phenoxybenzyl group may be used alone or in combination of two or more.

(Other monofunctional (meth) acrylates)
The monofunctional (meth) acrylate may be composed of at least a (meth) acrylate having a phenoxybenzyl group, or may be composed of only a (meth) acrylate having a phenoxybenzyl group. For adjustment and the like, other monofunctional (meth) acrylate [monofunctional (meth) acrylate that is not (meth) acrylate having a phenoxybenzyl group] may be included as necessary. In the present invention, even when such other monofunctional (meth) acrylate is contained, the moisture-resistant adhesion is not impaired.

  Other monofunctional (meth) acrylates include aliphatic (meth) acrylate ((meth) acrylate having an aliphatic skeleton), aromatic (meth) acrylate ((meth) acrylate having an aromatic skeleton), sulfur-containing Examples include (meth) acrylate.

Monofunctional aliphatic (meth) acrylates include alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate , T-butyl (meth) acrylate, isobutyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) ) Acrylate, C _1-20 alkyl (meth) acrylate such as stearyl (meth) acrylate], alicyclic (meth) acrylate {e.g. cycloalkyl (meth) acrylate [e.g. (meth) acrylate (Meth) acrylic acid C _5-8 cycloalkyl such as cyclohexyl silylate; (meth) acrylic polycyclic cycloalkyl such as bornyl (meth) acrylate and isobornyl (meth) acrylate], bridged cyclic (meth) acrylate [For example, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate etc.], etc.}, haloalkyl (meth) acrylates (e.g., trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, halo _{C 1-10} alkyl, such as hexafluoroisopropyl (meth) acrylate (meth Acrylate), hydroxyalkyl (meth) acrylate (e.g., hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl _{C 2-10} alkyl (meth) acrylates such as hydroxybutyl (meth) acrylate), alkoxyalkyl (meth ) Acrylates (eg C _1-10 alkoxy C _1-10 alkyl (meth) acrylates such as methoxyethyl (meth) acrylate), polyalkylene glycol mono (meth) acrylates [eg di to tetraethylene glycol mono (meth) acrylates such as (poly) such as oxy _{C 2-6} alkylene glycol mono (meth) acrylate, aliphatic epoxy (meth) acrylate {e.g., 2-hydroxy-3-alkoxypropyl ( Data) acrylates [e.g., 2-hydroxy-3-butoxypropyl (meth) acrylate, 2-hydroxy-3-pentadecyloxy propyl (meth) 2-hydroxy _{-3-C 2-20} alkoxy-propyl, such as acrylates (meth) Acrylate] etc.} Mono (meth) acrylate of an aliphatic polyol having 3 or more hydroxyl groups in one molecule {eg aliphatic triol mono (meth) acrylate [eg glycerol mono (meth) acrylate, trimethylolethane mono (meth) acrylate, alkane triol mono (meth) acrylates such as trimethylolpropane mono (meth) acrylates (e.g., C _3-10 alkane triol mono (meth) acrylate), etc.], etc.}, aminoalkyl (meth) acrylates [For example, N, N- dimethylaminoethyl acrylate such as N- substituted aminoalkyl (meth) acrylate, etc.], glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate.

Examples of the monofunctional aromatic (meth) acrylate include aryl (meth) acrylate (for example, C _6-10 aryl (meth) acrylate such as phenyl (meth) acrylate), aralkyl (meth) acrylate (for example, benzyl) C _6-10 arylC _1-4 alkyl (meth) acrylate such as (meth) acrylate), aryloxyalkyl (meth) acrylate (for example, C _6-10 aryloxy C _1-10 such as phenoxyethyl (meth) acrylate) Alkyl (meth) acrylate), arylaryloxyalkyl (meth) acrylate (for example, C _6-10 aryl C _6-10 aryloxy C _1-10 alkyl such as 2- (o-phenylphenoxy) ethyl (meth) acrylate ( Meta) Acrelay ), Aryloxy (poly) alkoxyalkyl (meth) acrylates [for example, phenoxy _{C 6-10} aryloxy, such as ethoxyethyl (meth) acrylate _{(poly) C 2-4} alkoxy _{C 2-4} alkyl (meth) acrylate, Alkylaryloxy (poly) alkoxyalkyl (meth) acrylates [eg C _4-20 alkyl C _6-10 aryloxy (poly) C _2-4 alkoxy C ₂₋ such as nonylphenoxy (poly) ethoxyethyl (meth) acrylate) ₄ alkyl (meth) acrylate], arylaryloxy (poly) alkoxyalkyl (meth) acrylate [for example, C _6-10 aryl C _6-10 aryloxy (poly) such as phenylphenoxy (poly) ethoxyethyl (meth) acrylate) C _2-4 alkoxy _C2-4 alkyl (meth) acrylate], bisphenols or alkylene oxide adducts thereof (for example, C _2-4 alkylene oxide adducts such as ethylene oxide adduct, propylene oxide adduct (for example, 2 to 2). An adduct of about 10 alkylene oxides), the same applies hereinafter) mono (meth) acrylate, aromatic epoxy (meth) acrylate {for example, 2-hydroxy-3-aryloxypropyl (meth) acrylate [for example, 2 2-hydroxy-3-C _{6-10 aryloxypropyl} (meth) acrylate such as hydroxy-3-phenoxypropyl (meth) acrylate; 2-hydroxy-3- (2-phenylphenoxy) propyl (meth) acrylate and the like 2-hydroxy-3 -(C _6-10 aryl C _6-10 aryl) oxypropyl (meth) acrylate] and the like}, (meth) acrylate having a fluorene skeleton {for example, 9- (meth) acryloyloxyfluorene, 9- (meth) acryloyloxy 9- (meth) acryloyloxyfluorenes such as 9-alkylfluorene and 9- (meth) acryloyloxy-9-arylfluorene; 9- (meth) acryloyloxymethylfluorene such as 9- (meth) acryloyloxymethylfluorene 9- (meth) acryloyloxyphenyl-9-phenylfluorene [for example, 9- (4- (meth) acryloyloxyphenyl) -9-phenylfluorene, etc.], 9- (alkyl- (meth) acryloyloxyphenyl) -9-phenylfluoro [For example, 9- (4- (meth) acryloyloxy-3-methylphenyl) -9-phenylfluorene, 9- (4- (meth) acryloyloxy-3,5-dimethylphenyl) -9-phenylfluorene, etc. 9- (mono- or di-C _1-4 alkyl- (meth) acryloyloxyphenyl) -9-phenylfluorene], 9- (aryl- (meth) acryloyloxyphenyl) -9-phenylfluorene [e.g. 9- ( 9- (such as 9- (mono or di-C _6-10 aryl- (meth) acryloyloxyphenyl) -9-phenylfluorene] such as 4- (meth) acryloyloxy-3-phenylphenyl) -9-phenylfluorene (Meth) acryloyloxyphenyl-9-phenylfluorenes; 9- (meth) acryloyloxy Poly) alkoxy-phenyl-9-phenyl fluorene [e.g., 9- (4- (2- (meth) acryloyloxy ethoxy) phenyl) -9-phenyl-fluorene 9- (meth) acryloyloxy _{(poly) C 2-4} 9- (meth) acryloyloxy (poly) alkoxyphenyl-9-phenylfluorenes} such as alkoxyphenyl-9-phenylfluorene], arylthio (meth) acrylate, aralkylthio (meth) acrylate, arylthioalkyl (described later) And (meth) acrylate.

Examples of the sulfur-containing (meth) acrylate include 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} and aryl _{C 1-4} alkylthio (meth) acrylate), arylthioalkyl (meth) acrylate (e.g., phenyl thio (meth) _{C 6-10,} such as acrylate Riruchio such _{C 2-10} alkyl (meth) acrylate), and the like. In addition, arylthio (meth) acrylate, aralkylthio (meth) acrylate, and arylthioalkyl (meth) acrylate can also be classified as aromatic (meth) acrylate.

  Other monofunctional (meth) acrylates may be used alone or in combination of two or more.

These other monofunctional (meth) acrylates may be properly used depending on the application. For example, among other monofunctional (meth) acrylates, from the viewpoint of improving handling properties, aliphatic (meth) acrylate [particularly branched alkyl (meth) acrylate (particularly branched C such as isoamyl (meth) acrylate) _3-10 alkyl (meth) acrylates, preferably branched C _3-6 alkyl (meth) acrylates, alicyclic (meth) acrylates, and the like] can be suitably used.

  In addition, from the viewpoint of balancing optical characteristics such as a high refractive index and excellent handling properties in a balanced manner, aromatic (meth) acrylates, sulfur-containing (meth) acrylates, and the like can be suitably used.

  Among other monofunctional (meth) acrylates, in particular, monofunctional (meth) acrylate having an aryloxy group (for example, phenoxy group) and monofunctional (meta) having an arylthio group (for example, phenylthio group). ) Acrylate and the like can be suitably used from the viewpoint of refractive index as described above, but the reason is not clear, but the polyfunctional (meth) acrylate [in particular, the polyfunctional (having a fluorene skeleton ( When combined with (meth) acrylate], the system that does not contain the carbodiimide compound of the present invention often has poor moisture adhesion.

  Therefore, in the present invention, a monofunctional (meth) acrylate having an aryloxy group [for example, aryloxyalkyl (meth) acrylate (for example, phenoxyethyl (meth) acrylate), arylaryloxyalkyl (meth) acrylate (for example, 2- (o-phenylphenoxy) ethyl (meth) acrylate), aryloxy (poly) alkoxyalkyl (meth) acrylate, alkylaryloxy (poly) alkoxyalkyl (meth) acrylate, arylaryloxy (poly) alkoxyalkyl (meta) ) Acrylate 2-hydroxy-3-aryloxypropyl (meth) acrylate, etc.], monofunctional (meth) acrylate having an arylthio group [for example, arylthio (meth) acrylate, aryl Thioalkyl (meth) acrylate, etc.] may be suitably used.

  The viscosity of the other monofunctional (meth) acrylate is not particularly limited, and may be selected from a range of about 300 mPa · s or less (eg, 200 mPa · s or less) at 25 ° C., for example, 100 mPa · s or less. (For example, 0.01 to 100 mPa · s), preferably 50 mPa · s or less (for example, 0.1 to 50 mPa · s), more preferably 30 mPa · s or less (for example, 0.3 to 30 mPa · s). 20 mPa · s or less [e.g., 0.01 to 20 mPa · s, preferably 0.05 to 10 mPa · s, more preferably 0.1 to 5 mPa · s (e.g., 0.5 to 3 mPa · s). ]].

  Among other monofunctional (meth) acrylates, the viscosity of monofunctional (meth) acrylate having an aryloxy group is 10 to 300 mPa · s, preferably 30 to 250 mPa · s at 25 ° C. Preferably, it may be about 50 to 200 mPa · s, particularly about 70 to 180 mPa · s.

  Moreover, the refractive index of other monofunctional (meth) acrylates may be 1.4 or more at 25 ° C. and 589 nm, for example, 1.4 to 1.65, preferably 1.41 to It may be about 1.62, more preferably about 1.42 to 1.6. In particular, the refractive index of the monofunctional (meth) acrylate may be 1.5 or more, for example, 1.5 to 1.65, preferably 1.51 to 1.62, more preferably 1.515. It may be about -1.6, especially 1.53 or more (for example, about 1.54-1.6, preferably about 1.55-1.59).

  Among other monofunctional (meth) acrylates, the refractive index of monofunctional (meth) acrylate having an aryloxy group is, for example, 1.57 to 1.67 at 25 ° C. and 589 nm, preferably It may be 1.571 to 1.64, more preferably 1.573 to 1.62, particularly about 1.575 to 1.61.

  When other monofunctional (meth) acrylate is used in combination, the ratio of the monofunctional (meth) acrylate having a phenoxybenzyl group and the other monofunctional (meth) acrylate is the former / the latter (weight ratio) = It can be selected from the range of about 99.9 / 0.1 to 5/95 (for example, 99.5 / 0.5 to 10/90), for example, 99/1 to 15/85 (for example, 97/3 to 20). / 80), preferably 95/5 to 25/75 (eg 93/7 to 30/70), more preferably 90/10 to 35/65 (eg 88/12 to 40/60), in particular 85 / It may be about 15 to 45/55.

  The ratio of the polyfunctional (meth) acrylate and the monofunctional (meth) acrylate is the former / the latter (weight ratio) = 99.9 / 0.1 to 1/99 (for example, 99.5 / 0.5 to 5/95), for example, 99/1 to 10/90 (for example, 97/3 to 12/88), preferably 95/5 to 15/85 (for example, 93/7 to 17 / 83), more preferably 90/10 to 20/80 (eg 88/12 to 25/75), particularly 85/15 to 30/70 (eg 83/17 to 33/67), particularly preferably 80 / It may be about 20 to 35/65 (for example, 75/25 to 38/62), and usually 99/1 to 20/80 (for example, 95/5 to 25/75, preferably 90/10 to 35 / 65) or so.

  Moreover, the ratio of polyfunctional (meth) acrylate and monofunctional (meth) acrylate is the former / the latter (molar ratio) = 99/1 to 0.5 / 99.5 (for example, 97/3 to 1 / 99), for example, 95 / 5-3 / 97 (for example, 90 / 10-5 / 95), preferably 85 / 15-7 / 93 (for example, 80 / 20-8 / 92) More preferably, 75/25 to 10/90 (for example, 70/30 to 12/88), particularly 65/35 to 15/85 (for example, 60/40 to 18/82), particularly preferably 55/45. It may be about 20/80 (for example, 50/50 to 25/75).

[Other curable components]
The curable component (radical polymerizable component, radical polymerizable monomer) may be composed of a (meth) acrylate monomer, and other curable components ((meth) acrylate monomer) as long as the effects of the present invention are not impaired. A curable component that does not belong to the category of (meth) acrylate monomers).

Other curable components (non- (meth) acrylate monomers) include polyfunctional monomers (for example, monomers having two or more radical polymerizable groups such as divinylbenzene), monofunctional monomers {for example, (meth) acrylic Monomers [for example, (meth) acrylic acid, (meth) acrylamide, N-substituted (meth) acrylamide (N, N-diC _1-4 alkyl (meth) acrylamide such as N, N-dimethyl (meth) acrylamide, etc.] And the like], styrene monomers (eg, styrene, α-methylstyrene, vinyltoluene, etc.), vinyl ester monomers (eg, vinyl acetate, etc.), N-vinylpyrrolidone, etc.]. Other curable components may be used alone or in combination of two or more.

  When using another curable component, the ratio of the other curable component to the entire curable component is, for example, 50% by weight or less (for example, 0.01 to 40% by weight), preferably 30% by weight or less (for example, 0.05 to 25% by weight), more preferably 20% by weight or less (for example, 0.1 to 15% by weight), and particularly 10% by weight or less (for example, 0.2 to 5% by weight). .

  In addition, the ratio of polyfunctional (meth) acrylate with respect to the whole curable component can be selected from the range of 1 weight% or more (for example, 5 weight% or more), for example, 10 weight% or more (for example, 15 weight% or more). It may be 20% by weight or more (for example, 25% by weight or more), more preferably 30% by weight or more (for example, 35% by weight or more), particularly 40% by weight or more.

[Carbodiimide compound]
The carbodiimide compound is a compound having a carbodiimide skeleton or a carbodiimide group (—N═C═N—) in the molecule. Such a carbodiimide compound may have at least one carbodiimide group and may have two or more carbodiimide groups. Further, in the carbodiimide compound, the carbodiimide group is not particularly limited, but may be usually bonded to a hydrocarbon group (or hydrocarbon skeleton).

  Representative carbodiimide compounds can be broadly classified into monocarbodiimide compounds (compounds having one carbodiimide group) and polycarbodiimide compounds (compounds having two or more carbodiimide groups).

  Examples of the monocarbodiimide compound include compounds represented by the following formula (2A).

^{R 5 -N = C = N-} R 6 (2A)
(In the formula, R ⁵ and R ⁶ represent a hydrocarbon group which may have a substituent.)
In the above formula (2A), the hydrocarbon groups R ⁵ and R ⁶ include, for example, an aliphatic hydrocarbon group [for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group). , A hexyl group, a 2-ethylhexyl group, an octyl group, a dodecyl group, etc., a C _1-30 alkyl group, preferably a C _1-20 alkyl group, more preferably a C _1-12 alkyl group, etc.) Group], an alicyclic hydrocarbon group [for example, a cycloalkyl group (for example, a C _5-10 cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, preferably a C _5-8 cycloalkyl group, etc.) such as a hydrocarbon group, an aromatic hydrocarbon group [for example, an aryl group (e.g., phenyl group, a tolyl group, C _6-15, such as a naphthyl group Aryl group, preferably a _{C 6-10} aryl group)], aromatic aliphatic hydrocarbon group [for example, an aralkyl group (e.g., benzyl group, etc. _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group), etc. ] Etc. can be illustrated.

The hydrocarbon groups R ⁵ and R ⁶ may have a substituent. Examples of the substituent include those exemplified in the section of the substituent R ^{4 in} the formula (1), for example, a hydrocarbon group (an alkyl group, a cycloalkyl group, an aryl group, etc.), an alkoxy group, an alkylthio group, an acyl group, an alkoxy group. Examples thereof include a carbonyl group, a halogen atom, a hydroxyl group, a nitro group, a cyano group, and a substituted amino group.

The groups R ⁵ and R ⁶ may be the same group or different groups.

Specific monocarbodiimide compounds include, for example, aliphatic monocarbodiimide compounds {for example, dialkylcarbodiimide compounds [for example, 1,3-dimethylcarbodiimide, 1,3-diisopropylcarbodiimide, 1-isopropyl-3-t-butylcarbodiimide, Substituents such as 1,3-dihexylcarbodiimide, 1,3-dioctylcarbodiimide, 1-isopropyl-3-dodecylcarbodiimide, 1,3-dioctyldecylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide which may have di _{C 1-30} alkyl carbodiimides, preferably di _{C 1-20} alkyl carbodiimides, more preferably _{di-C 1-12} alkyl carbodiimides, etc.], alkyl aralkyl carbodiimide Compound [for example, _{C 1-10} alkyl _{-C 6-10} aryl _{C 1-4} alkyl carbodiimides such as benzyl isopropyl carbodiimide] such}, alicyclic monocarboxylic carbodiimide compound {e.g., dicycloalkyl carbodiimide compound [e.g., 1 , 3-dicyclohexylcarbodiimide and the like optionally having a substituent such as diC _5-10 cycloalkylcarbodiimide]}, aromatic monocarbodiimide compound {eg, diarylcarbodiimide compound [eg, N, N′-diphenylcarbodiimide] N, N′-dio-tolylcarbodiimide, N, N′-bis (2,6-dimethylphenyl) carbodiimide, N, N′-bis (2,4,6-trimethylphenyl) carbodiimide, N, N ′ -Bis (2,6-diethylphenyl) carbo Imido, N, N′-bis (2-ethyl-6-isopropylphenyl) carbodiimide, N, N′-bis (2,6-diisopropylphenyl) carbodiimide, N, N′-bis (2,4,6-tri Isopropylphenyl) carbodiimide, N, N′-bis (2-isobutyl-6-isopropylphenyl) carbodiimide, N, N′-bis (2,6-di-t-butylphenyl) carbodiimide, N-phenyl-N′-tolyl Carbodiimide, N, N′-di-β-naphthylcarbodiimide, N, N′-di (p-nitrophenyl) carbodiimide, N, N′-di (p-aminophenyl) carbodiimide, N, N′-di (p - hydroxyphenyl) optionally di _{C 6-20} aryl carbodiimides may have a substituent such as a carbodiimide, preferably di _{C 6-10} arylene Carbodiimide], arylcycloalkyl carbodiimide compound (e.g., N- tolyl -N'- cyclohexyl carbodiimide optionally _{C 6-10} aryl _{-C 5-8} cycloalkyl carbodiimides have a substituent, etc.)}, and the like It is done.

  The monocarbodiimide compounds may be used alone or in combination of two or more.

  The polycarbodiimide compound is not particularly limited as long as it has two or more carbodiimide groups. For example, a compound (oligomer or polymer type carbodiimide compound) having a skeleton (constituent unit, repeating unit) represented by the following formula (2B) ) And the like.

− (N═C═N—R ⁷ ) _q − (2B)
(In the formula, R ⁷ is a divalent hydrocarbon group which may have a substituent, and q represents an integer of 2 or more.)
In the above formula (2B), as the hydrocarbon group R ⁷ , a divalent hydrocarbon group corresponding to R ⁵ or R ⁶ , for example, an aliphatic hydrocarbon group [for example, an alkylene group (for example, a methylene group) A C _1-30 alkylene group such as an ethylene group, a propylene group, a trimethylene group, a tetramethylene group or a hexamethylene group, preferably a C _1-20 alkylene group, more preferably a C _1-12 alkylene group, etc.] A cyclic hydrocarbon group {eg, a cycloalkylene group (eg, a C _5-10 cycloalkylene group such as cyclohexylene group), an alkylene-cycloalkylene group (eg, a C _1-10 alkylene-C such as methylene-cyclohexylene group) _5-10 such as a cycloalkylene group), dicycloalkyl alkanediyl group (for example, dicyclohexyl Di _{C 5-10} cycloalkyl _{-C 1-6} alkane such as Tan-4,4'-diyl group - diyl group), etc.}, an aromatic hydrocarbon group {e.g., an arylene group [e.g., a phenylene group (1, 4-phenylene group, etc.), C _6-20 arylene group such as tolylene group, naphthylene group, etc., preferably C _6-10 arylene group], diarylalkanediyl group (for example, diphenylmethane-4,4′-diyl group, etc.) DiC _6-10 aryl-C _1-6 alkanediyl group and the like), dialkylarene diyl group (for example, diC _1-6 alkyl-C _6-10 arene-diyl group such as α, α′-xylylene group, etc.) Etc.}.

The hydrocarbon group R ⁷ may have a substituent. Examples of the substituent include the same substituents as those exemplified in the above R ⁵ or R ⁶ section.

In addition, the group R ⁷ may be the same group or different groups in the repeating unit.

  In the formula (2B), the number of repeating units (average number of repeating units) q may be 2 or more (for example, about 2 to 100), for example, 2 to 50 (for example, 2 to 40), preferably 2 -30 (for example, 2-25), More preferably, about 2.5-20 (for example, 3-18) may be sufficient.

  The molecular weight (number average molecular weight) of the polycarbodiimide compound can be selected from a range of 200 or more (for example, 250 to 50,000), for example, 300 to 30000 (for example, 400 to 20000), preferably 500 to 15000 (for example, 600 to 12000), more preferably about 700 to 10000 (for example, 800 to 8000). From the viewpoint that a cured product having excellent transparency can be formed, for example, 200 to 3500, preferably 300 to 3000, More preferably, it is about 500-2500 (especially 800-2000).

Specific examples of the polycarbodiimide compound include aliphatic polycarbodiimide compounds {for example, polyalkylene carbodiimide [for example, poly (C _2-20 alkylene carbodiimide) such as polyhexamethylene carbodiimide], preferably poly (C _2-10 alkylene). carbodiimide), etc.], etc.}, alicyclic polycarbodiimide compound {e.g., polydicyclopentadiene alkylalkane carbodiimides such as poly (4,4'-dicyclohexylmethane carbodiimide) such as poly _{(di-C 5-10} cycloalkyl _{-C 1- 10} alkane carbodiimide), etc.], etc.}, the aromatic polycarbodiimide compound {e.g., polyarylene carbodiimide [e.g., poly m- phenylene carbodiimide, poly p- phenylene carbodiimide, Poritori Down carbodiimide, poly (diisopropyl phenylene carbodiimide), poly _{(C 6-20} arylene carbodiimide), such as (methyl diisopropyl phenylene carbodiimide), preferably poly _{(C 6-10} arylene carbodiimide), etc.], polydiene arylalkanoic carbodiimide [for example, Poly (diC _6-10 aryl-C _1-10 alkanecarbodiimide) and the like] such as poly (4,4′-diphenylmethanecarbodiimide) and the like.

  Polycarbodiimide compounds may be used alone or in combination of two or more.

  The terminal group of the polycarbodiimide compound (compound represented by formula (2B)) is not particularly limited, and may be, for example, a group derived from a raw material such as an isocyanate group, and part or all of the terminal is blocked. Alternatively, it may be a protected group [for example, a group in which a terminal isocyanate group is blocked with a blocking agent (for example, amine, alcohol, monoisocyanate, etc.)]. In addition, since a polycarbodiimide compound is usually obtained by reacting (polymerizing) an isocyanate compound (for example, a diisocyanate compound), the terminal group may form an isocyanate group.

  When the polycarbodiimide compound has a terminal isocyanate group, the ratio of the isocyanate group to the whole polycarbodiimide compound is, for example, 0.1 to 30% by weight, preferably 0.2 to 20% by weight, and more preferably 0.3 to It may be about 15% by weight. In particular, in the present invention, the proportion of the terminal isocyanate group is relatively large [for example, 1% by weight or more (for example, 1.5 to 30% by weight), preferably 2% by weight or more (for example, 2.5 to 20% by weight). ), More preferably 3% by weight or more (for example, 4 to 15% by weight), particularly 5% by weight or more (for example, 6 to 12% by weight), usually about 3 to 15% by weight (for example, 5 to 10% by weight). ]] A polycarbodiimide compound may be suitably used.

  Of these carbodiimide compounds, polycarbodiimide compounds are preferred. Therefore, the carbodiimide compound may be composed of at least a polycarbodiimide compound.

  When the carbodiimide compound is composed of at least a polycarbodiimide compound, the ratio of the polycarbodiimide compound to the entire carbodiimide compound can be selected from a range of 1% by weight or more (for example, 5% by weight or more), for example, 10% by weight or more. (For example, 15% by weight or more), preferably 20% by weight or more (for example, 25% by weight or more), more preferably 30% by weight or more (for example, 35% by weight or more), particularly 40% by weight or more. , 50% by weight or more (for example, 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more).

  The carbodiimide compound may be in any form such as solid or liquid at normal temperature (for example, 25 ° C.). In particular, in order to form a uniform curable composition (or cured product) without a solvent, a liquid carbodiimide compound can also be suitably used.

  In particular, the viscosity of the liquid polycarbodiimide compound is, for example, 500,000 mPa · s or less (eg, 500 to 300,000 mPa · s), preferably 200,000 mPa · s or less (eg, 3000 to 100,000 mPa · s), more preferably at 25 ° C. Is 70000 mPa · s or less (for example, 5000 to 60000 mPa · s), particularly from the point of being able to form a cured product having excellent transparency, and is 50000 mPa · s or less (for example, 8000 to 40000 mPa · s, preferably 10,000 to 35000 mPa · s, More preferably, it may be about 15000 to 30000 mPa).

  The ratio of the carbodiimide compound can be selected from the range of 0.001 to 50 parts by weight (for example, 0.003 to 40 parts by weight) with respect to 100 parts by weight of the (meth) acrylate monomer (or curable component), for example. For example, 0.005 to 30 parts by weight (for example, 0.007 to 25 parts by weight), preferably 0.01 to 20 parts by weight (for example, 0.02 to 15 parts by weight), and more preferably 0.03 to 10 parts by weight. Parts by weight (for example, 0.04 to 7 parts by weight), particularly 0.05 to 5 parts by weight (for example, 0.07 to 3 parts by weight), and usually 0.1 to 10 parts by weight (for example, 0.2-7 parts by weight, preferably 0.3-5 parts by weight). In particular, in the present invention, for example, 5 parts by weight or less (for example, 0.001 to 4 parts by weight), preferably 3 parts by weight or less (for example, for 100 parts by weight of (meth) acrylate monomer [or curable component] (for example, 0.005 to 2 parts by weight), more preferably 1 part by weight or less (for example, 0.01 to 0.7 parts by weight), usually 0.01 to 3 parts by weight (for example, 0.2 to 3 parts by weight, Even a very small amount of carbodiimide compound (preferably 0.3 to 2 parts by weight) can improve moisture resistance adhesion. Therefore, the moisture-resistant adhesion of the cured product can be improved while maintaining excellent characteristics derived from the curable component at a high level.

  Moreover, the ratio of a carbodiimide compound can be selected from the range of 0.0005-30 weight part (for example, 0.001-25 weight part) with respect to 100 weight part of polyfunctional (meth) acrylate, for example, 0.003 to 20 parts by weight (for example, 0.005 to 15 parts by weight), preferably 0.007 to 10 parts by weight (for example, 0.01 to 8 parts by weight), more preferably 0.02 to 5 parts by weight (For example, 0.03 to 4 parts by weight) or about 3 parts by weight or less (for example, 0.0005 to 2.5 parts by weight), preferably 2 parts by weight or less (for example, 0.001 to 1 part). 0.5 parts by weight), more preferably 0.7 parts by weight or less (for example, 0.005 to 0.6 parts by weight), particularly 0.5 parts by weight or less (for example, 0.007 to 0.3 parts by weight)] It can also be.

  Furthermore, the ratio of the carbodiimide compound can be selected, for example, from a range of 0.0005 to 30 parts by weight (for example, 0.001 to 25 parts by weight) with respect to 100 parts by weight of the monofunctional (meth) acrylate. 0.003 to 20 parts by weight (for example, 0.005 to 15 parts by weight), preferably 0.007 to 10 parts by weight (for example, 0.01 to 8 parts by weight), more preferably 0.02 to 5 parts by weight (For example, 0.03 to 4 parts by weight) or about 3 parts by weight or less (for example, 0.0005 to 2.5 parts by weight), preferably 2 parts by weight or less (for example, 0.001 to 1 part). 0.5 parts by weight), more preferably 0.7 parts by weight or less (for example, 0.005 to 0.6 parts by weight), particularly 0.5 parts by weight or less (for example, 0.007 to 0.3 parts by weight)] It can also be.

  In addition, the ratio of the carbodiimide compound is 0.0001 to 100 mol (for example, carbodiimide group (—N═C═N—) in the carbodiimide compound with respect to 100 mol of the (meth) acryloyloxy group in the (meth) acrylate monomer. , 0.0005 to 50 mol), for example, 0.001 to 30 mol (for example, 0.005 to 20 mol), preferably 0.01 to 10 mol (for example, 0.02 to 8 mol). Mol), more preferably 0.03 to 5 mol (for example, 0.04 to 3 mol), and particularly 0.05 to 1 mol (for example, 0.05 to 0.5 mol).

(Polymerization initiator)
The curable composition may further contain a polymerization initiator (radical polymerization initiator) as necessary. Such a polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photo radical generator). 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 (benzyl diphenyl sulfide, etc.); acylphosphine oxides ( 2,4,6-trimethylbenzoyldiphenylphosphine oxide); titanocene photopolymerization initiators; oxime esters and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  In addition, a photoinitiator can be obtained as a commercial item, for example, a brand name "Irgacure" "Darocur" (Ciba Japan Co., Ltd. product), a brand name "Syracure" (made by Union Carbide), etc.

  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, preferably 0.5 to 15 parts per 100 parts by weight of the curable component [or (meth) acrylate monomer]. The weight may be about 0.7 to 10 parts by weight (for example, 1 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, preferably 1 to 100 parts by weight, more preferably 5 to 75 parts by weight (particularly 10 parts by weight) with respect to 100 parts by weight of the photopolymerization initiator. (About 50 parts by weight).

(Other ingredients)
The curable composition of the present invention further contains conventional additives [eg, pigments, colorants, thickeners, sensitizers, antifoaming agents, leveling agents, coatability improvers, lubricants, stabilizers (antioxidants). And other components such as a UV absorber, a plasticizer, a surfactant, a filler, an antistatic agent, etc.]. These other components may be used alone or in combination of two or more.

  The curable composition of the present invention may contain a known additive as a component for improving moisture resistance and water resistance, a component for improving adhesion to a substrate (surface treatment agent, etc.) and the like. Good. The (meth) acrylate monomer in the present invention usually cannot sufficiently improve or improve the moisture-resistant adhesion with such a known additive, but contains such an additive as long as it contains a carbodiimide compound. However, the moisture-resistant adhesion is not impaired.

  Such a curable composition of this invention can be prepared by mixing each component.

[Hardened product]
The curable composition (resin composition) of the present invention is easily cured by applying active energy (active energy rays). 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 may be cured by applying at least light energy (light irradiation).

  The cured product may have a three-dimensional structure, and in particular, may be a cured film. The cured film may be a film pattern (particularly a thin film pattern). The cured product can be formed by applying a curable composition (resin composition) on a substrate (or on a substrate), drying as necessary, and then exposing it to heat or actinic rays, and the pattern (film pattern) is The coating film formed on the base material or the substrate can be selectively exposed with actinic rays and developed to develop the generated latent image pattern.

  The material of the base material or the substrate can be selected depending on the application, and inorganic materials [for example, metals (aluminum, copper, etc.), ceramics (zirconium oxide, titanium oxide, etc.), transparent inorganic materials (glass, quartz, magnesium fluoride, Calcium fluoride, etc.)], organic materials {eg, resins [eg, cyclic olefin resins, styrene resins, (meth) acrylic resins (polymethyl methacrylate, etc.), acrylonitrile resins, polyester resins, polyamides] Resin, polycarbonate resin, cellulose ester (such as triacetyl cellulose)], wood, etc.}.

  Moreover, since the curable composition of the present invention has a high refractive index and high transparency, it is suitable for optical applications. Among these substrates, a transparent substrate or a transparent film can be coated to be transparent. Substrate or transparent film {for example, transparent inorganic substrate (for example, glass substrate or glass substrate), transparent organic substrate [for example, cyclic olefin resin, styrene resin, (meth) acrylic resin (polymethacrylic acid] Methyl, etc.), acrylonitrile resins, polyester resins, polyamide resins, polycarbonate resins, substrates or films formed of cellulose esters (triacetyl cellulose, etc.), etc.] Good.

  The thickness of the base material can be selected according to the use and is not particularly limited. The thickness of the film-like or plate-like base material is, for example, 1 μm to 10 mm (for example, 5 to 7000 μm), preferably 10 to 5000 μm, Preferably, it may be about 30 to 3000 μm (for example, 50 to 1000 μm), or about 1 to 1000 μm (for example, 10 to 500 μm, preferably 30 to 300 μm).

  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.

  After apply | coating a curable composition, you may dry (for example, dry at about 40-150 degreeC). Although the thickness of a coating film changes with uses, it can select from the range of about 0.01-1000 micrometers, for example, 1-500 micrometers, Preferably it is 5-400 micrometers, More preferably, it may be about 10-300 micrometers.

  The curable composition is usually liquid or solid (or highly viscous liquid) at room temperature, but the solid curable composition can be applied by melting it by heating or dissolving it in a solvent. A film can be formed. Even when the curable composition of the present invention is solid at room temperature, it can be easily melted and applied by heating at a relatively low temperature, and the phase of a (meth) acrylate monomer and a carbodiimide compound is often obtained. Since the solubility is often relatively high, the coating film may be formed without using a solvent (without solvent). In addition, when forming a coating film in a solvent-free system as compared with a solvent system, the curable composition is less likely to permeate the base material, and the adhesiveness to the base material may be easily reduced. In some cases, the moisture-resistant adhesion may be further reduced, but in the present invention, the moisture-resistant adhesion can be improved even with a coating film or a cured film formed in such a solvent-free system.

  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 addition, hardened | cured material can also be obtained 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, etc.) may be performed before exposure, with exposure, or after exposure. The heating temperature may be, for example, 60 to 200 ° C, preferably 65 to 150 ° C, more preferably about 70 to 120 ° C.

  When a pattern-like latent image is formed, a developed coating pattern can be formed by developing the 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 various properties. In particular, the present invention has excellent optical properties (high refractive index, high transparency, etc.), high heat resistance, etc. by configuring the curable component with a polyfunctional (meth) acrylate having a fluorene skeleton. A cured product can be obtained efficiently. For example, the refractive index of the cured product of the present invention can be selected from a range of about 1.50 or more (for example, 1.51 to 1.75) at 25 ° C. and 589 nm, and 1.52 or more (for example, 1.525). 1.7), preferably 1.53 or more (e.g. 1.535 to 1.68), more preferably 1.54 or more (e.g. 1.545 to 1.65), in particular 1.55 or more (e.g. , 1.56-1.64). In particular, in the present invention, the refractive index at 25 ° C. and 589 nm of the cured product is, for example, 1.56 or more (for example, 1.575 to 1.75) by using (meth) acrylate having a fluorene skeleton. , Preferably 1.58 or more (for example, 1.59 to 1.7), more preferably 1.6 or more (for example, 1.61 to 1.68), particularly 1.61 or more (for example, 1.615 to 1.67) or so.

  As described above, in the cured product of the present invention, moisture resistance adhesion to a substrate can be improved or improved while maintaining or imparting excellent characteristics by combining a (meth) acrylate monomer and a carbodiimide compound. In other words, it can be said that the carbodiimide compound acts or functions as an additive for improving or improving the moisture resistance adhesion of the cured product containing the curable component to the substrate. Therefore, the present invention includes such an additive and a method for improving or improving moisture-resistant adhesion to a substrate using the additive.

  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 examples, the various components (and their abbreviations) used are as follows.

[Multifunctional (meth) acrylate]
BPEFA: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (synthesized in Synthesis Examples described later)
BPEF-9EO-A: 9.0 mol of ethylene oxide (EO) with respect to 1 mol of 9,9- (4-hydroxyphenyl) fluorene (BPF) (total of m in Formula (1) is 9.0 mol) (Synthesized in the same manner as in Reference Example 1 of JP2013-53310A).

[Monofunctional (meth) acrylate]
POBA: m-phenoxybenzyl acrylate [manufactured by Kyoeisha Chemical Co., Ltd., “POBA”, viscosity (25 ° C.) 20 mPa · s, refractive index (25 ° C., 589 nm) 1.566]
OPP: o-phenylphenol monoethoxy acrylate [or 2- (o-phenylphenoxy) ethyl acrylate, manufactured by Nippon Kayaku Co., Ltd., viscosity (25 ° C.) 163 mPa · s, refractive index (25 ° C., 589 nm) 1.577 ]
[Additive]
V-05: Polycarbodiimide, “Carbodilite V-05” manufactured by Nisshinbo Chemical Co., Ltd., NCO content 8.2%, liquid at room temperature, viscosity at 25 ° C. 23000 mPa · s [E-type viscometer (Toki Sangyo Co., Ltd.) TVE-22L), measured under conditions of a rotor 3 ° × R7.7 rotation speed 1 rpm], an average degree of polymerization of about 3, and a molecular weight of about 1000 to 1500.
HMV-15CA: Polycarbodiimide, “Carbodilite HMV-15CA” manufactured by Nisshinbo Chemical Co., Ltd., solid at normal temperature, average polymerization degree of about 15, no terminal NCO group, molecular weight of about 4000 to 5000
LA-1: Polycarbodiimide, “Carbodilite LA-1” manufactured by Nisshinbo Chemical Co., Ltd., solid at room temperature, average polymerization degree of about 15, terminal NCO group, molecular weight of about 4000 to 5000
BYK-307: Polyether-modified polydimethylsiloxane, “BYK-307” manufactured by Big Chemie Japan Co., Ltd.
BYK-333: Polyether-modified polydimethylsiloxane, “BYK-333” manufactured by Big Chemie Japan Co., Ltd.
MTMO: 3-Mercaptopropyltrimethoxysilane, manufactured by EVONIC INDUSTRIES, “Dynasylan MTMO”
KBM5103: 3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., “KBM5103”
RS-75: a fluorine-based surface modifier having a UV reactive group, manufactured by DIC Corporation, “Megafac RS-75”
(Synthesis example)
BPEFA was synthesized as follows.

  Charged 100 g of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd., BPEF), 258 g of acrylic acid, 30 g of p-toluenesulfonic acid, 1500 g of toluene, and 1 g of hydroquinone monomethyl ether The dehydration esterification reaction was performed while obtaining a theoretical dehydration amount while refluxing at 100 to 115 ° C. Thereafter, the reaction solution was neutralized with alkali and washed with 10% saline. After washing, toluene was removed to obtain 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (BPEFA).

(Comparative Example 1)
57.00 parts by weight of BPEFA, 43.00 parts by weight of POBA [BPEFA / POBA (molar ratio) = 38/62], 3 parts by weight of photopolymerization initiator (manufactured by BASF Japan Ltd., “IRGACURE184”) at 60 ° C. The resin composition (curable composition) was prepared by thoroughly mixing in a heated shaker.

The obtained resin composition was applied to one side of a polyethylene terephthalate film (trade name “Cosmo Shine A-4300”, thickness 188 μm, manufactured by Toyobo Co., Ltd.), and irradiated with ultraviolet light with an integrated light amount of 500 mJ / cm ² with a high-pressure mercury lamp. Then, a cured product (thickness 20 μm) was obtained. The coating film and the cured film were uniform and transparent.

  The refractive index (25 ° C., 589 nm) of the cured film was 1.622. The refractive index was measured using a multi-wavelength Abbe refractometer (manufactured by Atago, DR-M2 <using circulating thermostatic bath 60-C3>) at a temperature of 25 ° C. (hereinafter the same). ).

  And the heat-and-moisture-resistant adhesiveness of the obtained cured film was evaluated as follows.

  First, the cured film was wet-heat treated for 24 hours under conditions of a temperature of 65 ° C. and a humidity of 95%. A 100-mass lattice pattern was formed by cutting into the cured film after the wet heat treatment, and a cross-cut test was performed in accordance with JISK5600-5-6. The mass was peeled off). Note that the cross-cut test was performed at three locations on the same cured film, and when there were differences in the number of remaining cells at the three locations, the average value of the three locations was assumed to have a large number of remaining cells.

(Comparative Example 2)
In Comparative Example 1, BPEFA was replaced with 57.00 parts by weight, 48.00 parts by weight, POBA was replaced with 43.00 parts by weight, and 52.00 parts by weight (BPEFA / POBA (molar ratio) = 30/70). A cured product (thickness 20 μm) was obtained in the same manner as Comparative Example 1 except that it was used. The coating film and the cured film were uniform and transparent.

  It was 1.620 when the refractive index of the cured film was measured similarly to the comparative example 1.

  Further, when a cross-cut test was performed in the same manner as in Comparative Example 1, 21 squares remained in the lattice pattern (that is, 79 squares were peeled off).

Example 1
In Comparative Example 1, a cured film was obtained in the same manner as Comparative Example 1 except that 1.00 part by weight of polycarbodiimide (V-05) was further mixed. Even when polycarbodiimide was mixed, the coating film and the cured film were uniform and transparent.

  The refractive index of the cured film was 1.619, and even when V-05 was added, there was almost no change and a high refractive index could be maintained.

  And when the cross-cut test was done like the comparative example 1 in the obtained cured film, 100 mass remains (namely, there is no peeling at all), and the ratio of BPEFA and POBA is the same. It was found that the adhesion after wet heat treatment (moisture and heat adhesion) was improved.

(Example 2)
In Comparative Example 1, a cured film was obtained in the same manner as Comparative Example 1, except that 0.30 part by weight of polycarbodiimide (V-05) was further mixed. Even when polycarbodiimide was mixed, the coating film and the cured film were uniform and transparent.

  The refractive index of the cured film was 1.620, and even when V-05 was added, there was almost no change and a high refractive index could be maintained.

  And when the cross-cut test was done like the comparative example 1 in the obtained cured film, 100 mass remains (namely, there is no peeling at all), and the ratio of BPEFA and POBA is the same. It was found that the adhesion after wet heat treatment (moisture and heat adhesion) was improved.

(Example 3)
In Comparative Example 2, a cured film was obtained in the same manner as Comparative Example 2 except that 1.00 part by weight of polycarbodiimide (V-05) was further mixed. Even when polycarbodiimide was mixed, the coating film and the cured film were uniform and transparent.

  The refractive index of the cured film was 1.618, and even when V-05 was added, there was almost no change, and a high refractive index could be maintained.

  And when the cross-cut test was done like the comparative example 1 in the obtained cured film, 100 squares remain | survived (namely, there is no peeling at all) and the ratio of BPEFA and POBA is the same. It was found that the adhesion after wet heat treatment (moisture and heat adhesion) was improved.

Example 4
In Comparative Example 2, a cured film was obtained in the same manner as Comparative Example 2, except that 0.50 part by weight of polycarbodiimide (V-05) was further mixed. Even when polycarbodiimide was mixed, the coating film and the cured film were uniform and transparent.

  The refractive index of the cured film was 1.618, and even when V-05 was added, there was almost no change, and a high refractive index could be maintained.

  And when the cross-cut test was done like the comparative example 1 in the obtained cured film, 100 squares remain | survived (namely, there is no peeling at all) and the ratio of BPEFA and POBA is the same. It was found that the adhesion after wet heat treatment (moisture and heat adhesion) was improved.

(Example 5)
In Comparative Example 2, a cured film was obtained in the same manner as in Comparative Example 2, except that 0.05 part by weight of polycarbodiimide (V-05) was further mixed. Even when polycarbodiimide was mixed, the coating film and the cured film were uniform and transparent.

  The obtained cured film was subjected to a cross-cut test in the same manner as in Comparative Example 1. As a result, 100 squares remained (that is, there was no peeling), and the amount of polycarbodiimide was 0.05 parts by weight. It was found that the adhesion after wet heat treatment (moisture and heat adhesion) was improved as compared with Comparative Example 2 in which the ratios of BPEFA and POBA were the same despite the small amount.

(Reference Example 1)
In Comparative Example 1, 0.30 part by weight of polycarbodiimide (HMV-15CA) was further mixed, but it became cloudy and a uniform and transparent resin composition could not be obtained.

(Reference Example 2)
In Comparative Example 1, 0.30 part by weight of polycarbodiimide (LA-1) was further mixed, but it became cloudy and a uniform and transparent resin composition could not be obtained.

(Reference Example 3)
In Comparative Example 2, 0.30 part by weight of polycarbodiimide (HMV-15CA) was further mixed, but it became cloudy and a uniform and transparent resin composition could not be obtained.

(Reference Example 4)
In Comparative Example 2, 0.30 part by weight of polycarbodiimide (LA-1) was further mixed, but it became cloudy and a uniform and transparent resin composition could not be obtained.

(Reference Example 5)
Compared to Comparative Example 1, except that 0.10 parts by weight of polyether-modified polydimethylsiloxane (BYK-307) was further mixed, in anticipation of the improvement effect of moisture and heat resistance to the substrate due to the improvement in water repellency. A cured film was obtained in the same manner as in Example 1. In addition, even if BYK-307 was mixed, the coating film and the cured film were uniform and transparent.

  And when the cross-cut test was done like the comparative example 1 in the obtained cured film, 60 squares remain | survived (namely, 40 squares have peeled), Compared with the comparative example 1, after wet heat processing Adhesion (moisture and heat adhesion) did not improve at all, but rather decreased.

(Reference Example 6)
Compared to Comparative Example 1, except that 0.10 parts by weight of polyether-modified polydimethylsiloxane (BYK-333) was further mixed, in anticipation of the improvement effect of moisture and heat resistance to the substrate due to the improvement in water repellency. A cured film was obtained in the same manner as in Example 1. Even when BYK-333 was mixed, the coating film and the cured film were uniform and transparent.

  And in the obtained cured film, when the cross-cut test was done similarly to the comparative example 1, 52 squares remain | survived (namely, 48 masses have peeled), Compared with the comparative example 1, after wet heat processing Adhesion (moisture and heat adhesion) did not improve at all, but rather decreased.

(Reference Example 7)
A cured film was prepared in the same manner as in Comparative Example 1 except that in Example 1, Comparative Example 1 was further mixed with 1.00 parts by weight of 3-mercaptopropyltrimethoxysilane (MTMO). Obtained. Even when MTMO was mixed, the coating film and the cured film were uniform and transparent.

  And when the cross-cut test was done like the comparative example 1 in the obtained cured film, 31 squares remain | survived (namely, 69 squares have peeled), Compared with the comparative example 1, after wet heat processing Adhesion (moisture and heat adhesion) did not improve at all, but rather decreased.

(Reference Example 8)
A cured film was obtained in the same manner as in Comparative Example 1 except that acryloxypropyltrimethoxysilane (KBM5103) was mixed in an amount of 1.00 parts by weight in Comparative Example 1 in anticipation of the effect of improving adhesion to the substrate. Got. Even when KBM5103 was mixed, the coating film and the cured film were uniform and transparent.

  And in the obtained cured film, when the cross-cut test was done similarly to the comparative example 1, 43 squares remain | survived (namely, 57 masses have peeled), Compared with the comparative example 1, after wet heat processing Adhesion (moisture and heat adhesion) did not improve at all, but rather decreased.

(Reference Example 9)
In Comparative Example 1, anticipation of improvement in wet heat resistance due to water repellency and surface modification, and 0.30 part by weight of a fluorine-based surface modifier (RS-75) having a UV reactive group However, it became cloudy (not compatible), and a uniform and transparent resin composition could not be obtained.

(Example 6)
In Comparative Example 1, the same procedure as in Comparative Example 1 was conducted except that 0.50 part by weight of polycarbodiimide (V-05) and 0.50 part by weight of 3-acryloxypropyltrimethoxysilane (KBM5103) were further mixed. A cured film was obtained. Even when V-05 and KBM5103 were mixed, the coating film and the cured film were uniform and transparent.

  The refractive index of the cured film was 1.620, and even when V-05 and KBM5103 were added, there was almost no change, and a high refractive index could be maintained.

  And when the cross-cut test was done like the comparative example 1 in the obtained cured film, 100 mass remains (namely, there is no peeling at all), and the ratio of BPEFA and POBA is the same. It was found that the adhesion after wet heat treatment (moisture and heat adhesion) was improved. From this result, it was found that even when other additives were added in addition to the carbodiimide compound, the wet heat resistance was not impaired.

(Reference Example 10)
In Comparative Example 1, 55.28 parts by weight of BPEFA was used instead of 57.00 parts by weight, and 44.72 parts by weight of OPP (BPEFA / OPP (molar ratio) = 38/62) was used instead of 43.00 parts by weight of POBA. A cured product (thickness 20 μm) was obtained in the same manner as Comparative Example 1 except that it was used. The coating film and the cured film were uniform and transparent.

  And when the crosscut test was done about the obtained cured film similarly to the comparative example 1, all the lattice patterns peeled (that is, it was a residual cell number 0).

  From this result, the cured film formed with BPEFA and POBA is slightly wet heat resistant compared to the cured film formed with OPP which is a monofunctional (meth) acrylate having an aromatic skeleton similar to BPEFA. It was found to be unique among the cured films formed of BPEFA and monofunctional (meth) acrylate.

  A summary of these results is shown in the table below.

  In the above example, since the number of remaining cells was 100 (that is, 0 cells were peeled off), as described below, the heat resistance after a severe wet heat treatment in which the wet heat treatment time was extended to 120 hours as follows. Adhesion was evaluated.

(Comparative Example 3)
In Comparative Example 1, except that the wet heat treatment time was changed from 24 hours to 120 hours, the cross cut test was performed in the same manner as in Comparative Example 1, and as a result, all the lattice patterns were peeled off (that is, the number of remaining cells) 0) and could not endure the extension of the treatment time.

(Comparative Example 4)
In Comparative Example 2, when the cross-cut test was performed in the same manner as Comparative Example 2 except that the wet heat treatment time was changed from 24 hours to 120 hours, all the lattice patterns were peeled off (that is, the number of remaining cells) 0) and could not endure the extension of the treatment time.

(Example 7)
In Example 1, except that the wet heat treatment time was changed from 24 hours to 120 hours, a cross-cut test was performed in the same manner as in Example 1. As a result, 100 cells remained (that is, there was no peeling at all). ), Even under severe wet heat conditions where the wet heat treatment time was 5 times longer, it was found that the wet heat and heat adhesion was not deteriorated and maintained at a high level.

(Example 8)
In Example 2, a cross-cut test was performed in the same manner as in Example 2 except that the wet heat treatment time was changed from 24 hours to 120 hours. As a result, 100 cells remained (that is, there was no peeling at all). ), Even under severe wet heat conditions where the wet heat treatment time was 5 times longer, it was found that the wet heat and heat adhesion was not deteriorated and maintained at a high level.

Example 9
In Example 3, a cross-cut test was performed in the same manner as in Example 3 except that the wet heat treatment time was changed from 24 hours to 120 hours. As a result, 100 cells remained (that is, no peeling occurred). ), Even under severe wet heat conditions where the wet heat treatment time was 5 times longer, it was found that the wet heat and heat adhesion was not deteriorated and maintained at a high level.

(Example 10)
In Example 3, a cross-cut test was performed in the same manner as in Example 3 except that the wet heat treatment time was changed from 24 hours to 120 hours. As a result, 100 cells remained (that is, no peeling occurred). ), Even under severe wet heat conditions where the wet heat treatment time was 5 times longer, it was found that the wet heat and heat adhesion was not deteriorated and maintained at a high level.

(Reference Example 11)
In Reference Example 7, when the cross-cut test was performed in the same manner as in Reference Example 7 except that the wet heat treatment time was changed from 24 hours to 120 hours, all the lattice patterns were peeled off (that is, the number of remaining cells) 0) and could not endure the extension of the treatment time.

(Reference Example 12)
In Reference Example 8, when the cross-cut test was performed in the same manner as in Reference Example 8 except that the wet heat treatment time was changed from 24 hours to 120 hours, all the lattice patterns were peeled off (that is, the number of remaining cells) 0) and could not endure the extension of the treatment time.

(Example 11)
In Example 6, a cross-cut test was performed in the same manner as in Example 6 except that the wet heat treatment time was changed from 24 hours to 120 hours. As a result, 100 cells remained (that is, there was no peeling at all). ), Even under severe wet heat conditions where the wet heat treatment time was 5 times longer, it was found that the wet heat and heat adhesion was not deteriorated and maintained at a high level.

(Comparative Example 5)
In Comparative Example 1, 61.40 parts by weight of BPEF-9EOA was used instead of 57.00 parts by weight of BPEFA, and 38.60 parts by weight of POBA instead of 43.00 parts by weight of POBA (BPEF-9EOA / POBA (molar ratio)). = 30/70) A cured product (thickness 20 µm) was obtained in the same manner as in Comparative Example 1 except that 30/70) was used. The coating film and the cured film were uniform and transparent.

  And when the crosscut test was done about the obtained cured film similarly to the comparative example 1, it was 98 of residual cell numbers.

Example 12
In Comparative Example 5, a cured film was obtained in the same manner as Comparative Example 5 except that 0.30 part by weight of polycarbodiimide (V-05) was further mixed. Even when polycarbodiimide was mixed, the coating film and the cured film were uniform and transparent.

  And when the cross-cut test was done like the comparative example 1 in the obtained cured film, 100 mass remains (namely, there is no peeling), and the adhesiveness after wet heat processing (moisture-heat-resistant adhesiveness) Was found to have improved.

  A summary of these results is shown in the table below.

The curable composition of the present invention includes, for example, an ink material, a light emitting material (for example, a light emitting material for organic EL), an organic semiconductor, a graphitization precursor, a gas separation membrane (for example, a CO ₂ gas separation membrane), OCA, and the like. (Optical adhesive layer), adhesives, coating agents (for example, optical overcoat agents such as LED (light emitting diode) element coating agents or hard coating agents), lenses [pickup lenses (eg, DVD (digital versatile) Pickup lens for disc), microlens (for example, microlens for liquid crystal projector), spectacle lens, etc.], polarizing film (for example, polarizing film for liquid crystal display), composite sheet, brightness enhancement film, prism sheet, Antireflection film (or antireflection film such as an antireflection film for display device), LCD panel film, flexible substrate film, display film [eg, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction electron-emitting device display), FED (field emission display) ), NED (nano-emissive display), cathode ray tube, electronic paper display (especially thin display) film (protective film, etc.)], color filter [eg, lens filter, display color filter, etc.], liquid crystal display Resist for devices [eg, photoresist for TFT array etching, pigment dispersion type photoresist, protective film, etc.], interlayer insulating film, solder resist, fuel cell film, optical fiber, optical waveguide, hologram It can be suitably used etc.. In particular, since the curable composition of the present invention has a high refractive index, it can be suitably used for optical material applications. Examples of the shape of the optical material include a film or sheet shape, a plate shape, a lens shape, and a tubular shape.

Claims (17)

A curable composition comprising a curable component composed of a polyfunctional (meth) acrylate and a (meth) acrylate monomer containing a monofunctional (meth) acrylate, and a carbodiimide compound, the monofunctional (meth) A curable composition comprising a monofunctional (meth) acrylate having a phenoxybenzyl group , wherein the polyfunctional (meth) acrylate comprises a polyfunctional (meth) acrylate having a fluorene skeleton. Thing . Polyfunctional (meth) acrylate having a fluorene skeleton, a curable composition of a is claim 1 Symbol placement compound represented by the following formula (1).

(In the formula, ring Z represents an aromatic hydrocarbon ring, R ¹ represents a substituent, R ² represents an alkylene group, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a substituent, and k represents An integer of 0 to 4, m is an integer of 0 or more, n is an integer of 0 or more, and p is an integer of 1 or more.) In formula (1), ^{R 2} is a _{C 2-4} alkylene group, m is 1 to 10, curable composition according to claim 2, wherein p is 1-3. The curable composition according to claim 3 , wherein in formula (1), R ² is a C _2-3 alkylene group, and the total of m is 8 or less. The curable composition according to any one of claims 1 to 4 , wherein the monofunctional (meth) acrylate having a phenoxybenzyl group is phenoxybenzyl (meth) acrylate. The ratio of a polyfunctional (meth) acrylate and a monofunctional (meth) acrylate is the former / the latter (weight ratio) = 99/1 to 10/90, The curability according to any one of claims 1 to 5 . Composition. The curable composition according to any one of claims 1 to 6 , wherein the carbodiimide compound includes a polycarbodiimide compound. The curable composition according to any one of claims 1 to 7 , wherein the carbodiimide compound contains a polycarbodiimide compound having a terminal isocyanate group ratio of 2% by weight or more. The curable composition according to any one of claims 1 to 8 , wherein the carbodiimide compound is liquid at normal temperature. Ratio of carbodiimide compound, the (meth) acrylate monomer 100 parts by weight, the curable composition according to any one of claims 1 to 9, which is 0.005 parts by weight. The ratio of a carbodiimide compound is 0.01-3 weight part with respect to 100 weight part of (meth) acrylate monomers, The curable composition in any one of Claims 1-10 . Further, the curable composition according to any one of claims 1 to 11 containing a photopolymerization initiator. The method according to claim 1 cured product is cured by applying an active energy curable composition according to any one of 12. Curable composition cured product obtained by curing according to any one of claims 1 to 12. The laminated body comprised with the base material and the hardened | cured material of Claim 14 formed on this base material. Consists of a polyfunctional (meth) acrylate containing a polyfunctional (meth) acrylate having a fluorene skeleton and a (meth) acrylate monomer containing a monofunctional (meth) acrylate, where the monofunctional (meth) acrylate is a phenoxybenzyl group An additive for improving or improving moisture-resistant adhesion to a substrate of a cured product containing a curable component containing a monofunctional (meth) acrylate having carbodiimide compounds. Consists of a polyfunctional (meth) acrylate containing a polyfunctional (meth) acrylate having a fluorene skeleton and a (meth) acrylate monomer containing a monofunctional (meth) acrylate, where the monofunctional (meth) acrylate is a phenoxybenzyl group The additive according to claim 16 is added to or mixed with a curable composition containing a curable component containing a monofunctional (meth) acrylate having a moisture resistance against a substrate of a cured product obtained by curing the curable composition. A method for improving or improving adhesion.