TW201714948A - Curable composition and cured product thereof - Google Patents

Abstract

The present invention provides a curable composition which is capable of forming a cured product having a high refractive index and a cured product thereof. The curable composition contains: a polyfunctional (meth) acrylate and a monofunctional (meth) acrylate represented by the following formula (1). wherein, R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group, R3 represents an alkyl group, Ar1 represents a condensed polycyclic arene ring, a represents an integer of 1 to 4, and b represents 0 or an integer of 1 or more.

Description

Hardening composition and hardened substance thereof

The present invention relates to a novel hardenable composition capable of forming a cured product having a high refractive index and a cured product thereof.

Since a cured product having a three-dimensional network structure is formed by a polymerization reaction, a polyfunctional (meth) acrylate having a plurality (two or more) of (meth) acrylonitrile groups in the molecule has been utilized in various types. field. Among them, a polyfunctional (meth) acrylate having an anthracene skeleton has excellent optical properties derived from an anthracene skeleton (for example, a 9,9-bisarylfluorene skeleton, etc.) (for example, high refractive index, high transparency) It can be used as an optical material. A polyfunctional (meth) acrylate having an anthracene skeleton is generally known as 9,9-bis[(meth)acrylomethoxy(poly)alkoxyallyl]fluorene or the like. However, polyfunctional (meth) acrylates (especially, polyfunctional (meth) acrylates having an anthracene skeleton) are often used for monotonicity in order to improve workability when relatively high viscosity is used. A reactive diluent such as methyl acrylate is used in combination.

For example, in International Publication No. 2013/022065 (Patent Document 1), it has been disclosed that adjusting the average of the number of additions of an oxyalkylene group to a specific range of 9,9-bis[(meth)acrylofluorene An oxypolyalkoxyphenyl]anthracene, a hardenable composition containing the cerium compound, and the like. The compound having an anthracene skeleton and the curable composition containing the compound have been described as excellent in handleability and curability, and have high refractive index and scratch resistance in the cured product. In particular, an aryloxyalkyl (meth)acrylate of an aromatic (meth) acrylate is described [for example, (meth)acrylic acid C _6-10 aryloxy C such as phenoxyethyl (meth)acrylate _{A 1-10} alkyl ester or the like is a monofunctional (meth) acrylate which is excellent in both high refractive index and excellent handleability, and can effectively maintain scratch resistance. In the examples of this document, the average number of 9,9-bis[4-((meth)propenyloxypolyethoxy)phenyl]anthracene (additional ethoxy groups in one molecule) was prepared. A curable composition of various monofunctional or polyfunctional acrylates such as 10.9) and an aromatic acrylate (for example, phenoxyethyl acrylate or the like). Such a curable composition and a cured product thereof have high workability and exhibit high refractive index and scratch resistance in a cured product, but further improvement is required in the field of optical materials.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: International Publication No. 2013/022065 (Application Patent Range, Paragraph [0013] [0107] [0111] [0112], Examples)

Accordingly, it is an object of the present invention to provide novel curability in which a cured product having a high refractive index can be formed even if a reactive diluent is contained. A composition, a cured product thereof, and a method for producing the cured product.

Another object of the present invention is to provide a novel hardenable composition having high workability (low viscosity) and capable of forming a cured product having a high refractive index and a cured product thereof.

Still another object of the present invention is to provide a curable composition which can form a cured product which also has excellent scratch resistance (softness) and a cured product thereof.

Still another object of the present invention is to provide a method and a low viscosity agent which are effective in low viscosity even in the case of a highly viscous polyfunctional (meth) acrylate.

In order to achieve the above-mentioned problems, the present inventors have found that a polyfunctional (meth) acrylate and a condensed polycyclic aryl group-containing monofunctional (meth) acrylate as a reactive diluent have been found. The ester combination can form a cured product having a high refractive index even if it contains a reactive diluent, and can make a high-viscosity polyfunctionality even if the monofunctional (meth) acrylate is solid at room temperature ( The methyl acrylate is low in viscosity and improves workability, and the present invention has been completed.

In other words, the curable composition of the present invention contains a polyfunctional (meth) acrylate and a novel first monofunctional (meth) acrylate represented by the following formula (1).

Wherein R ¹ represents a hydrogen atom or a methyl group; R ² is a linear or branched alkylene group; R ³ is an alkyl group; Ar ¹ is a condensed polycyclic aromatic hydrocarbon ring; a is an integer from 1 to 4; b is 0. Or an integer of 1 or more.

The ratio of the polyfunctional (meth) acrylate to the first monofunctional (meth) acrylate represented by the above formula (1) may be the former/the latter (weight ratio) = 99/1 to 1/99 ( For example: 80/20 to 5/95, etc.). The first monofunctional (meth) acrylate represented by the above formula (1) may be a (meth)acrylic condensed polycyclic C _10-14 aryloxy C _2-4 alkyl ester.

The polyfunctional (meth) acrylate comprising: selected from the group consisting of the following formula (2)

Wherein rings Z ¹ and Z ² and rings Z ³ and Z ⁴ represent an arene ring; R ^4a and R ^4b and R ^5a and R ^{5b are} each the same or different non-reactive substituent; R ^6a and R ^6b are a straight or branched alkyl group; R ^7a and R ^7b are a hydrogen atom or a methyl group; k1 and k2 are an integer of 0 or more; m1 and m2 are an integer of 0 or more; n1 and n2 are 0 or An integer of 1 or more; p1 and p2 are integers of 1 or more.

The (meth) acrylate, alicyclic or aromatic epoxy (meth) acrylate, urethane (meth) acrylate and polyester (meth) acrylate containing an anthracene skeleton are shown. At least one of the high viscosity polyfunctional (meth) acrylates of the group.

In the above formula (2), the rings Z ¹ and Z ² and the rings Z ³ and Z ⁴ may each be a benzene ring or a naphthalene ring; k1 and k2 may also be 0; and R ^5a and R ^5b may also be C _1-6 An alkyl group or a C _6-10 aryl group; m1 and m2 may also be an integer of 0 or 1 to 2; R ^6a and R ^6b may also be a linear C _2-6 alkylene group; n1 and n2 may also be 1 An integer of up to 10; p1 and p2 may also be 1.

Further, the polyfunctional (meth) acrylate may contain at least a fluorene (meth) acrylate represented by the formula (2) and an urethane (meth) acrylate. The ratio of the (meth) acrylate containing an anthracene skeleton to the ethyl urethane (meth) acrylate represented by the formula (2) is about 50 mg/50 to about 99/1 of the former/the latter (weight ratio).

Further, the polyfunctional (meth) acrylate may contain, in addition to the high-viscosity polyfunctional (meth) acrylate, a diphenol-based or bisphenol-based alkylene oxide adduct (Part 2) Base) acrylate. The ratio of the high viscosity polyfunctional (meth) acrylate to the di(meth) acrylate of the biphenol or bisphenol alkylene oxide adduct may be the former / the latter (weight ratio) = 50 / 50 to 99/1 or so.

The aromatic epoxy (meth) acrylate may also be an aromatic epoxy (meth) acrylate represented by the following formula (3).

Wherein R ⁸ each represents a hydrogen atom, an alkyl group or an aryl group, and two R ⁸ groups may be bonded to each other to form a hydrocarbon ring which may have an alkyl group; R ^9a and R ^{9b are} each an alkyl group or an aryl group; ^10a and R ^10b are a linear or branched alkylene group; R ^11a and R ^11b are a hydrogen atom or a methyl group; q1 and q2 are integers from 0 to 4; r1 and r2 are integers of 0 or more; t is 0. Or 1.

The urethane (meth) acrylate may be a polyester urethane (meth) acrylate, a polyether urethane (meth) acrylate, a polycarbonate urethane (A) Base) acrylate and the like.

Further, the viscosity (at 25 ° C) of the polyfunctional (meth) acrylate is a high viscosity, and may be, for example, 3,000 mPa ‧ s or more.

The curable composition may further contain an alkylthio group (meth)acrylate, an arylthio (meth)acrylate, an arylalkylthio (meth)acrylate, and an arylthio(meth)acrylate. A second monofunctional (meth) acrylate (monofunctional (meth) acrylate containing a sulfur atom) of at least one selected from the group consisting of alkyl esters. The ratio of the first monofunctional (meth) acrylate to the second monofunctional (meth) acrylate may be about the former/the latter (weight ratio) = about 80/20 to 20/80.

The curable composition may further contain a third monofunctional (meth) acrylate represented by the following formula (4).

Wherein R ¹² represents a hydrogen atom or a methyl group; R ¹³ is an alkylene group; R ¹⁴ is an alkyl group; Ar ² is a benzene ring or a ring-condensed aromatic hydrocarbon ring; c is an integer of 1 to 4; and d is 0 or more. The integer.

The ratio of the first monofunctional (meth) acrylate represented by the above formula (1) to the third monofunctional (meth) acrylate represented by the above formula (3) may be the former/the latter (weight ratio) ) = 80/20 to 20/80 or so.

The curable composition may further contain a polymerization initiator.

The present invention also includes a cured product obtained by curing the curable composition, and further comprising a method of applying the active energy to the curable composition to cure the cured product.

Moreover, the present invention is a low viscosity agent for lowering the viscosity of the polyfunctional (meth) acrylate, and also includes a low viscosity agent containing the first monofunctional (meth) acrylate. The low viscosity agent may further contain the second monofunctional (meth) acrylate.

The present invention also encompasses a method of adding the above-mentioned first monofunctional (meth) acrylate to a polyfunctional (meth) acrylate to reduce the viscosity of the polyfunctional (meth) acrylate.

Further, the present invention also encompasses the aforementioned first monofunctional (meth) acrylate of the novel compound.

Furthermore, in the present specification, "(poly)alkoxy" means an alkane Both oxy and polyalkoxy.

The curable composition of the present invention contains a polyfunctional (meth) acrylate and a monofunctional (meth) acrylate (first monofunctional (meth) acrylate) containing a condensed polycyclic aryl group. Therefore, even if a reactive diluent (monofunctional (meth) acrylate or the like) is contained, a cured product having a high refractive index can be formed. Therefore, the amount of the expensive polyfunctional (meth) acrylate can be effectively reduced. In addition, the first monofunctional (meth) acrylate can function as a low viscosity agent to improve the workability (low viscosity) of the curable composition, and can also form a cured product having a high refractive index. Further, the cured product can have both high refractive index and scratch resistance (softness).

Fig. 1 is a graph showing the refractive index before hardening of the composition ratio of the compositions of Comparative Examples 1 to 5 and Examples 1 to 5.

Fig. 2 is a graph showing the viscosity of the diluent blending ratio with respect to the compositions of Comparative Examples 1 to 5 and Examples 2 to 5.

Figure 3 is a graph showing the viscosity (calculated value) of the composition reaching the target refractive index in the BPEFA/reactive diluent blending system.

The curable composition of the present invention contains a polyfunctional (meth) acrylate and a first monofunctional (meth) acrylate having a condensed polycyclic aryl group as a reactive diluent. The first monofunctional (meth) acrylate is a novel compound.

<The first monofunctional (meth) acrylate having a condensed polycyclic aryl group>

The first monofunctional (meth) acrylate having a condensed polycyclic aryl group is a compound represented by the following formula (1).

Wherein R ¹ represents a hydrogen atom or a methyl group; R ² is a linear or branched alkylene group; R ³ is an alkyl group; Ar ¹ is a condensed polycyclic aromatic hydroxy ring; a is an integer from 1 to 4; b is An integer of 0 or more.

In the above formula (1), the group R ¹ is a hydrogen atom or a methyl group. Further, the group R ² is a linear or branched alkyl group, and the linear alkyl group may, for example, be a linear C _2-6 alkyl group such as an ethyl group, a trimethylene group or a tetramethylene group. Preferably, the linear C _2-4 alkyl group is a straight chain C _2-3 alkyl group, particularly an ethyl group; and in the case of a branched alkyl group, for example, a propyl group, 1, A branched C _3-6 alkylene group such as a 2-butanediyl group or a 1,3-butanediyl group (preferably, a branched C _3-4 alkylene group, particularly a propyl group). In such a group R ² , a linear or branched C _2-6 alkylene group (for example, a linear or branched C _2-4 alkyl group) is preferred, and a linear or branched C _2-3 stretch is preferred. An alkyl group (especially an ethyl group and a propyl group) is more preferred. The number of repetitions a of the radical (R ² O) may be selected from an integer of from about 1 to about 4, for example, an integer of from about 1 to about 3, more preferably 1 or 2, and still more preferably. When the number of repetitions a is too large, there is a concern that the refractive index of the cured product is lowered. Further, when a is 2 or more, two or more groups R ² may be the same or different.

In the above formula (1), the ring Ar ¹ is a condensed polycyclic aromatic hydrocarbon ring, and examples thereof include a condensed bicyclic aromatic hydrocarbon ring (for example, a condensed bicyclic C _10-16 aromatic hydrocarbon ring such as a naphthalene ring), and a condensed tricyclic aromatic hydrocarbon ring (for example, hydrazine). A ring, a phenanthroline ring, etc., etc. condense a di- to tetracyclic aromatic hydrocarbon ring or the like. The preferred ring Ar ¹ may, for example, be a condensed polycyclic C _10-16 aromatic hydrocarbon ring such as a naphthalene ring or an anthracene ring (preferably a condensed polycyclic C _10-14 aromatic hydrocarbon ring), and more preferably a naphthalene ring. In the aforementioned formula (1), relative to ring Ar group of ^{1 [-O- (R 2 O)} a -CO-CR 1 = CH 2] of the bonding position is not particularly limited, and for example, ^a naphthalene ring Ar In the case of a ring, it may be bonded at any position of the 1-position or the 2-position, but it is preferable to bond the 2-position.

In the above formula (1), the group R ³ may also be an alkyl group, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, and a t-butyl group. , pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl etc. straight-chain or branched C _1-12 alkyl group, and straight chain or branched chain C _{1- More} preferably, the decyl group is more preferably a linear or branched C _1-6 alkyl group (e.g., a linear or branched C _1-4 alkyl group). The number of substitutions b of the radical R ³ may be an integer of 0 or more, and may be, for example, an integer of from 0 to 4, more preferably an integer of from 0 to 2, more preferably 0 or 1, and more preferably 0. It is especially good. Further, when b is 2 or more, the types of the two or more groups R ³ may be the same or different. Further, the substitution position of the group R ³ is not particularly limited, for example, the ring Ar ¹ is a naphthalene ring, and the group [-O-(R ² O) _a -CO-CR ¹ =CH ₂ ] is bonded at the 2-position. Alternatively, it may be substituted at any of the 1-position and 3- to 8-position of the 2-naphthyl group.

Representative examples of the first monofunctional (meth) acrylate represented by the above formula (1) include, for example, a compound of a=1 and b=0 in the above formula (1), that is, (meth) Polycyclic poly(aryloxyalkyl) acrylates [eg 2-(2-naphthalenyloxy)ethyl (meth)acrylate, 2-(1-naphthalenyl)ethyl (meth)acrylate, (A) (meth)acrylic acid polycyclic C _10-14 aryloxy C _2-4 alkyl ester, etc.]; in the above formula (1), a compound of a ≧ 2 and b =0, that is, a polycyclohexyloxy(meth) acrylate (mono to tri) alkoxyalkyl ester [eg 2-(2-(2-(2-)) (naphthyloxy)ethoxy)ethyl ester, 2-(2-(2-naphthyloxy)propoxy)propyl (meth)acrylate, poly(cyclo)C _10-14 An aryloxy group (mono to tri) C _2-4 alkoxy C _2-4 alkyl ester, etc.]; in the above formula (1), a compound of a=1 and b=1, that is, (meth)acrylic acid Alkyl polycyclic aryloxyalkyl ester [e.g., (meth)acrylic acid C _1-12 alkyl such as 2-(4-t-butyl-1-naphthyloxy)ethyl (meth)acrylate condensation polycyclic C _10-16 aryloxy C _2-4 alkyl ester]; the formula (1), a ≧ 2 and b = 1 of the compound , that is, alkyl (poly) aryloxy (mono to tri) alkoxyalkyl (meth) acrylate [eg 2-(2-(2-(4-tert-butyl)) (1-naphthyloxy)ethoxy)ethoxy)ethyl ester, etc. (meth)acrylic acid C _1-12 alkyl polycyclic C _10-14 aryloxy (mono to tri) C _2-4 Alkoxy C _2-4 alkyl ester, etc.]. The first monofunctional (meth) acrylates represented by the above formula (1) may be used singly or in combination of two or more kinds. Preferably, the first monofunctional (meth) acrylate represented by the above formula (1) is a compound of a=1 and b=0 in the above formula (1), that is, (meth)acrylic acid condensed. Polycyclic aryloxyalkyl esters, poly(cyclo)C _10-14 aryloxy C _2-4 alkyl (meth) acrylate (eg 2-(2-naphthyloxy)ethyl (meth) acrylate More preferably, a (meth)acrylic acid naphthyloxy C _2-4 alkyl ester or the like). Since the first monofunctional (meth) acrylate represented by the above formula (1) has a polycyclic aryl group, it can maintain or enhance the cured product even if it is mixed in a large amount in the curable composition. Refractive index, and can also improve the viscosity reduction effect. Therefore, for example, it is possible to combine the characteristics of high refractive index and low viscosity, and it is possible to effectively reduce the blending ratio (or the amount of use) of the expensive polyfunctional (meth) acrylate. Meanwhile, in general, a liquid compound which exhibits high fluidity at a use temperature (for example, at room temperature of about 25 ° C) can be used as the reactive diluent, but unexpectedly, the first formula shown in the above formula (1) A monofunctional (meth) acrylate which is in the form of a powdery or viscous substance, and although it is a compound which does not exhibit fluidity, it can remarkably make a high viscosity polyfunctional (meth) acrylate low viscosity. Chemical. Therefore, the first monofunctional (meth) acrylate can also function as a low viscosity agent for lowering the viscosity of the polyfunctional (meth) acrylate. In the low-viscosity method of the polyfunctional (meth) acrylate, a low viscosity agent containing at least a first monofunctional (meth) acrylate and a polyfunctional (meth) acrylate are mixed. The method is not particularly limited, and the obtained curable composition can be effectively made low in viscosity and can maintain or increase the refractive index. The ratio of the first monofunctional (meth) acrylate to the polyfunctional (meth) acrylate may be the same as the ratio of the curable composition described later.

Further, the compound represented by the formula (1) can be obtained by a generally known method (for example, the method described in JP-A-2012-226040 (paragraph [0014], etc.), for example, a ring of a hydroxyl group-condensed polycyclic aromatic hydrocarbon. An alkylene carbonate or an alkylene carbonate addition product, an esterification catalyst such as sulfuric acid, p-toluenesulfonic acid-water, and the like, a polymerization inhibitor such as hydroquinone or 4-methoxyphenol, and toluene as required. In the presence of a solvent, it is prepared by a method of reacting a (meth)acrylic acid component (for example, (meth)acrylic acid or an ester-forming derivative thereof (for example, an acid halide, an acid anhydride, a lower alkyl ester, etc.)).

The hydroxy condensed polycyclic aromatic hydrocarbon may, for example, be a compound corresponding to the compound represented by the above formula (1) (for example, 1-naphthol or 2-naphthol). The alkylene oxide or the carbene carbonate may, for example, be an alkylene oxide or an alkylene carbonate (for example, ethylene oxide) exemplified in the alkyl group exemplified in the above R ² . The alkylene oxide or alkylene carbonate adduct of a representative hydroxy-condensed polycyclic aromatic hydrocarbon may, for example, be 2-(2-naphthalenyloxy)ethanol (NEO) or 2-(1-naphthyloxy)propanol, 2 A hydroxy (mono to tetra) C _2-4 alkoxy-C _10-14 condensed polycyclic aromatic hydrocarbon such as (2-(2-naphthyloxy)ethoxy)ethanol.

The ratio of the polyfunctional (meth) acrylate to the first monofunctional (meth) acrylate represented by the formula (1) is, for example, selected from the former/the latter (weight ratio) = 99/1 to 1/99. The range of left and right, for example, may be 90/10 to 3/97, preferably 80/20 to 5/95 (for example, 70/30 to 10/90), and 65/35 to 13/87 (for example, 60/40). It is better to 17/83), and it is particularly good at around 55/45 to 20/80 (for example, 50/50 to 22/78). When the ratio of the first monofunctional (meth) acrylate represented by the formula (1) is too low, there is a possibility that the high refractive index and/or the low viscosity are insufficient.

In addition, the ratio of the polyfunctional (meth) acrylate and the total amount of the first monofunctional (meth) acrylate represented by the formula (1) to the entire polymerizable component in the curable composition is, for example, 30 to 100% by weight (50 to 100% by weight), more preferably 60 to 100% by weight (for example, 70 to 100% by weight), and still more preferably 80 to 100% by weight (for example, 90 to 100% by weight). It is also possible to form substantially 100% by weight (only a polyfunctional (meth) acrylate and a first monofunctional (meth) acrylate represented by the formula (1)).

<Polyfunctional (meth) acrylate>

The polyfunctional (meth) acrylate type is not particularly limited as long as it has a plurality (two or more) of (meth) acrylonitrile groups. The number of (meth)acrylonitrile groups per molecule is, for example, 2 to 10, preferably 2 to 6 and more preferably 2 to 4 (for example, 2). When the number of (meth) acrylonitrile groups is too large, the scratch resistance of the cured product is reduced.

Representative polyfunctional (meth) acrylates include, for example, polyfunctional (meth) acrylates having a 9,9-bisarylfluorene skeleton; aliphatic epoxy (meth) acrylates, [ For example, a di(meth) acrylate or a polypropylene glycol diepoxypropyl group of an alkanediol diepoxypropyl ether such as a di(meth)acrylate of 1,6-hexanediol diepoxypropyl ether. a di(meth)acrylate such as a polyalkylene glycol diepoxypropyl ether such as an ether di(meth)acrylate; an alicyclic epoxy (meth) acrylate; an aromatic epoxy group; (meth) acrylate; ethyl urethane (meth) acrylate; polyester (meth) acrylate; alkyl diol di (meth) acrylate [eg diethylene glycol di(meth)acrylate , C _2-10 alkanediol di(meth)acrylate, etc., such as butylene glycol di(meth)acrylate; polyalkylene glycol di(meth)acrylate [eg di(di)methacrylate) a poly(di(meth)acrylic acid C _2-10 alkanediol ester such as a glycol ester or the like]; a di(meth)acrylate of a biphenol or a bisphenol (or an alkylene oxide adduct thereof); a low molecular weight polyol compound having from 3 to 6 hydroxyl groups (Meth) acrylate [eg trimethylolpropane tri (meth) acrylate, neopentyl alcohol tri (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol Penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.]. These polyfunctional (meth) acrylates can be used individually or in combination of 2 or more types.

Among these polyfunctional (meth) acrylates, even a relatively high-viscosity (meth) acrylate can be effectively made low-viscosity by the first monofunctional (meth) acrylate. Thus, the polyfunctional (meth) acrylate can be a viscous or solid at room temperature (eg, 25 ° C). The viscosity (25 ° C) of the polyfunctional (meth) acrylate is, for example, 1000 mPa ‧ s or more, preferably 3,000 mPa ‧ s or more, more preferably 5,000 mPa ‧ s or more. The upper limit of the viscosity is not particularly limited, and may be, for example, about a measurement limit value (for example, 352 Pa‧s) of the viscosity meter described in the examples described later. Among the above polyfunctional (meth) acrylates, it is preferred to contain a polyfunctional (meth) acrylate selected from the group consisting of a 9,9-bisaryl fluorene skeleton (for example, hydrazine represented by the formula (2) Skeletal (meth) acrylate, etc.), alicyclic epoxy (meth) acrylate, aromatic epoxy (meth) acrylate, ethyl urethane (meth) acrylate, and polyester ( At least one of the group of methyl acrylates. Among these high-viscosity polyfunctional (meth) acrylates, usually, a polyfunctional (meth) acrylate having a 9,9-bisarylfluorene skeleton is used (for example, the formula (2) is shown. The (meth) acrylate having an anthracene skeleton, an aromatic epoxy group (meth) acrylate, or an urethane (meth) acrylate.

A polyfunctional (meth)acrylate having a 9,9-bisarylfluorene skeleton is excellent in various properties such as optical properties (for example, high refractive index, low birefringence, transparency, etc.), mechanical properties, and heat resistance. Therefore, it is suitable to improve the properties of the resulting cured product. Furthermore, in the present specification, "having a 9,9-bisaryl fluorene skeleton" means at least a 9,9-bisaryl tibia in a molecular structure. The frame is used for at least one of the two benzene rings which are also included in the anthracene ring forming the skeleton, and has a skeleton in which an aromatic hydrocarbon ring is condensed (for example, a bisarylbenzindole skeleton, a bisaryldibenzofluorene skeleton, etc.) The meaning. A polyfunctional (meth) acrylate having a 9,9-bisarylfluorene skeleton, which may be a compound represented by the following formula (2) (sometimes referred to as a (meth) acrylate having an anthracene skeleton .).

Wherein rings Z ¹ and Z ² and rings Z ³ and Z ⁴ represent an arene ring; R ^4a and R ^4b and R ^5a and R ^{5b are} each the same or different non-reactive substituent; R ^6a and R ^6b are a straight or branched alkyl group; R ^7a and R ^7b are a hydrogen atom or a methyl group; k1 and k2 are an integer of 0 or more; m1 and m2 are an integer of 0 or more; n1 and n2 are 0 or 1. The above integer; p1 and p2 are integers of 1 or more.

In the above formula (2), examples of the aromatic hydrocarbon ring represented by the ring Z ¹ and Z ² include a monocyclic aromatic hydrocarbon ring such as a benzene ring, a polycyclic aromatic hydrocarbon ring, and the like, and a polycyclic aromatic hydrocarbon ring system containing a condensed polycyclic aromatic hydrocarbon. Ring (condensed polycyclic aromatic hydrocarbon ring), cyclic assembly aromatic hydrocarbon ring (cyclic assembly aromatic hydrocarbon ring), and the like.

The condensed polycyclic aromatic hydrocarbon ring system may, for example, be a condensed polycyclic aromatic hydrocarbon ring exemplified in the description of the ring Ar ¹ in the above formula (1), and is preferably the same as the ring Ar ¹ described above.

Examples of the ring-collecting aromatic hydrocarbon ring system include a biaryl ring (for example, a biphenyl ring, a binaphthyl ring, a phenylnaphthalene ring (1-phenylnaphthalene ring, a 2-phenylnaphthalene ring, etc.), a C _6-12 aromatic hydrocarbon ring, or the like. And a triaryl hydrocarbon ring (for example, a tris(C _6-12 aromatic hydrocarbon ring such as a bistriphenyl ring) or the like. A preferred ring-assembled aromatic hydrocarbon ring system may, for example, be a C _6-10 aromatic hydrocarbon ring or the like, and particularly preferably a biphenyl ring.

The two rings Z ¹ and Z ² bonded to the 9-position of the 茀 can be the same or different, and usually, the same. Among the rings Z ¹ and Z ² , a benzene ring, a naphthalene ring, a biphenyl ring or the like is preferred, and a benzene ring is particularly preferred.

Further, the position at which the ring Z ¹ and Z ² in the 9-position of the oxime is bonded is not particularly limited. For example, when the ring Z ¹ and Z ² are a naphthalene ring, the group corresponding to the ring Z ¹ and Z ² bonded at the 9-position of the fluorene may be a 1-naphthyl group or a 2-naphthyl group. Further, when the rings Z ¹ and Z ² are biphenyl rings, the groups corresponding to the rings Z ¹ and Z ² bonded to the 9-position of the oxime may be 2-biphenyl or 3-biphenyl. 4-biphenyl and the like.

In the above formula (2), the aromatic hydrocarbon ring represented by the ring Z ³ and Z ⁴ may, for example, be a monocyclic aromatic hydrocarbon ring such as a benzene ring or a condensed polycyclic aromatic hydrocarbon ring (condensed polycyclic aromatic hydrocarbon ring). The condensed polycyclic aromatic hydrocarbon ring system is, for example, a condensed polycyclic aromatic hydrocarbon ring exemplified in the ring Ar ^{1 of the} above formula (1), and is preferably the same as the ring Ar ¹ described above. Among such aromatic hydrocarbon rings, preferred rings Z ³ and Z ⁴ may, for example, be a benzene ring or a naphthalene ring.

The ring Z ³ and the Z ⁴ system may also form a condensed ring skeleton together with the 5-membered ring therebetween. For example, in the rings Z ³ and Z ⁴ , a benzofluorene skeleton in which one ring is a benzene ring and the other ring is a naphthalene ring may be formed. The two sides are the dibenzopyrene skeleton of the naphthalene ring. Further, when the rings Z ³ and Z ⁴ are condensed polycyclic aromatic hydrocarbon rings, the ring Z ³ and Z ⁴ and the bonding position of the 5-membered ring therebetween (or, in the rings Z ³ and Z ⁴ , The position of the two adjacent carbon atoms shared by the 5-member ring is not particularly limited as long as it can be bonded (or shared), for example, the 1,2-position, the 2,3-position of the naphthalene ring, or The carbon atom at any position of the 3,4-position is shared with the aforementioned 5-membered ring. That is, in the ring Z ³ and Z ⁴ , when one of the rings is a naphthalene ring and the other is a benzene ring, and both of them are naphthalene rings, the condensed ring skeleton structure in the above formula (2) (only, R ^{4a is} omitted) And R ^4b , k1 and k2) may be any of the structures shown by the following formulas (a) to (i).

Particularly preferred rings Z ³ and Z ⁴ are benzene rings, ring Z ³ and Z ⁴ and a fused ring skeleton formed by a 5-membered ring therebetween, especially in the case of a ring of Z ³ and Z ^{4 which} is a benzene ring. good.

In the above formula (2), the non-reactive substituent (or non-radical polymerizable substituent) R ^4a and R ^4b may, for example, be a hydrocarbon group [for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, or the like). a straight or branched C _1-6 alkyl group such as an isopropyl group, a butyl group or a tributyl group; an aryl group (for example, a C _6-10 aryl group such as a phenyl group, etc.), a cyano group or a halogen atom ( For example, a fluorine atom, a chlorine atom, a bromine atom or the like).

In these groups R ^4a and R ^4b , an alkyl group (for example, a linear or branched C _1-4 alkyl group (particularly, a C _1-3 alkyl group such as a methyl group)), a cyano group or a halogen atom is used. Preferably, an alkyl group is more preferred.

The substitution numbers k1 and k2 of the radicals R ^4a and R ^{4b are} integers of 0 or more, and are selected by the rings Z ³ and Z ⁴ . The substitution numbers k1 and k2 are usually selected from an integer of about 0 to 6, for example, an integer of about 0 to 4 (for example, 0 to 3), and more preferably an integer of about 0 to 2, and 0 or 1 is It is even better, especially with 0 being even better. Further, the substitution numbers k1 and k2 in the rings Z ³ and Z ⁴ may be the same or different from each other, and the types of the groups R ^4a and R ^4b may be the same or different from each other. When k1 and k2 are 2 or more, the types of the two or more groups R ^4a and R ^4b in the Z ³ and Z ⁴ of each ring may be the same or different from each other. Further, the substitution positions of the groups R ^4a and R ^{4b are} not particularly limited. For example, when the rings Z ³ and Z ⁴ and the 5-membered ring therebetween form an anthracene ring, they may be 2-position to 7-position of the anthracene ring ( 2-bit, 3-position and 7-position, etc.).

In the above formula (2), the non-reactive substituent (or non-radical polymerizable substituent) R ^5a and R ^5b may, for example, be a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom). a hydrocarbon group {for example, a linear or branched C _1-10 alkyl group such as an alkyl group (methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, t-butyl, etc.), which is linear or A branched C _1-6 alkyl group is preferred, and a linear or branched C _1-4 alkyl group or the like is more preferred; a cycloalkyl group (for example, a C _5-10 cycloalkyl group such as a cyclopentyl group or a cyclohexyl group). An aryl group [e.g., phenyl, alkylphenyl (e.g., methylphenyl (tolyl), dimethylphenyl (xylyl), etc.), biphenyl, naphthyl, etc., C _6-12 aryl An aralkyl group (e.g., a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group or a phenethyl group), etc., an alkoxy group (e.g., a methoxy group, an ethoxy group, a propoxy group) a linear or branched C _1-10 alkoxy group such as a n-butoxy group, an isobutoxy group or a third butoxy group, or a cycloalkoxy group (for example, a C _5-10 cycloalkoxy group such as a cyclohexyloxy group). An aryloxy group (for example, a C _6-10 aryloxy group such as a phenoxy group) or an aralkyloxy group (for example, a C _6-10 aryl-C _1-4 alkoxy group such as a benzyloxy group). Alkylthio group Methylthio, ethylthio, propylthio, n-butylthio, tertiary butylthio C _1-10 alkylthio group), a cycloalkyl group (e.g. cyclohexyl, etc. C _5-10 cycloalkyl group Sulfur-based or the like, an arylthio group (for example, a C _6-10 arylthio group such as a thiophenoxy group), or an aralkylthio group (for example, a C _6-10 aryl-C _1-4 alkylthio group such as a phenylthio group) etc.), acyl (e.g. C _1-6 acyl acetyl group, etc.), a nitro group, a cyano group, a substituted amino group [e.g. dialkylamino (e.g. dimethylamino, etc. Second C _1-4 alkoxy Alkylamino group, etc.), a dialkylcarbonylamino group (for example, a di(C _1-4 alkyl-carbonyl)amino group such as a diethylguanidino group), etc.].

Examples of such radicals R ^5a and R ^5b include a halogen atom, a hydrocarbon group (alkyl group, cycloalkyl group, aryl group, arylalkyl group), alkoxy group, fluorenyl group, nitro group, and cyano group. Substituting an amine group or the like. Preferred groups R ^5a and R ^5b are an alkyl group (such as a linear or branched C _1-6 alkyl group such as a methyl group), an aryl group (such as a C _6-14 aryl group such as a phenyl group), or an alkoxy group. group are straight-chain or branched C1- ₄ alkoxy group, etc.), particularly useful for example as alkyl (especially methyl and other straight-chain or branched-chain C _1-4 alkyl), aryl (such as phenyl C _{6 -10} aryl, etc.). Further, when the groups R ^5a and R ^5b are aryl groups, the groups R ^5a and R ^5b may form the ring assembly aromatic hydrocarbon ring together with the rings Z ¹ and Z ² . Further, the types of the radicals R ^5a and R ^5b may be the same or different. When the number of substitutions m1 and m2 is 2 or more, the types of the two or more groups R ^2a and R ^2b substituted by the same ring Z ¹ and Z ² may be the same or different.

The number of substitutions m1 and m2 of the radicals R ^5a and R ^5b may be an integer of 0 or more, and may be appropriately selected depending on the types of the rings Z ¹ and Z ² . For example, it may be an integer of about 0 to 8, and an integer of about 0 to 4 (for example, 0 to 3) is preferable, and an integer of about 0 to 2 (for example, 0 or 1) is more preferable, particularly 0. Better yet. Further, the substitution numbers m1 and m2 may be the same or different from each other. In particular, when m1 and m2 are 1, the rings Z ¹ and Z ² may be a benzene ring, a naphthalene ring or a biphenyl ring, and the groups R ^5a and R ^5b may be a methyl group. Further, the substitution positions of the groups R ^5a and R ^5b are not particularly limited as long as the base [-(OR ^6a ) _n1 -OC(=O)-CR ^7a =CH ₂ ] and the group [-(OR ^6b ) _n2 - OC(=O)-CR ^7b =CH ₂ ] (may be referred to as a position other than the substitution position of the (meth)acryl-containing group).

In the above formula (2), the alkylene groups R ^6a and R ^{6b each} comprise a linear or branched alkylene group. The representative alkylene group R ^6a and R ^6b may, for example, be a linear or branched alkyl group exemplified in the description relating to the group R ^{2 of the} above formula (1), and the preferred aspect is also the group R ^{2 .} the same. Further, the types of the alkyl groups R ^6a and R ^6b which are substituted between the respective (meth)acryl-containing groups substituted on the same or different rings Z ¹ and Z ² may be the same or different, usually, For the same. Further, when the number of repetitions n1 and n2 is 2 or more, the types of the alkylene groups R ^6a and R ^{6b in} the same (meth)acryloyl group-containing group may be different, but the same is preferable.

The number of repetitions n1 and n2 of the oxygen alkyl group (OR ^6a and OR ^6b ) may be selected from a range of 0 or more integers (for example, an integer of from 0 to 20), for example, an integer of from about 1 to 15, and An integer of from 1 to 10 (e.g., from 2 to 8) is preferred, and an integer of from about 3 to 7 (e.g., from 4 to 6) is more preferably. Further, in each of the (meth)acrylonitrile group-containing groups substituted on the same or different rings Z ¹ and Z ² , n1 and n2 may be the same or different. In addition, in the present specification, unless otherwise stated, "the number of repeats of the oxygen-extended alkyl group" (and the "counter number of oxygen-extended alkyl groups (total addition number)") described later are used for inclusion in the molecule of the compound 1. The average of the number of oxygen alkyl groups (integer) and the number of oxygen alkyl groups in the molecular assembly of the compound (or the average value, the arithmetic mean) [ie, the average addition mole number) The meaning of both. Therefore, the number of repetitions n1 and n2 may be an average value (additional average or arithmetic mean) in the molecular assembly of the compound represented by the above formula (2), and the range may be about the same as the range of the previous integer.

In addition, the total number of repetitions n1 and n2 means the total number of oxygen-extended alkyl groups in the molecule of the (meth)acrylate containing an anthracene skeleton represented by the above formula (2) (the total number of additions), and sometimes Just called n1+n2. Further, when n1+n2 is 2 or more in p1 and/or p2, it means that only the total number of n1 and n2 of the numbers of p1 and p2 exists. N1+n2 may, for example, be selected from a range of integers from about 0 to 30, for example, may be an integer of from about 1 to 25 (e.g., from 2 to 20), and an integer of from about 3 to 18 (e.g., from 4 to 16) is preferred. More preferably, an integer of from 5 to 14 (e.g., from 6 to 12) is more preferably, and an integer of from about 7 to 11 (e.g., from 8 to 10) is more preferably. Further, n1+n2 may be an integer as described above, but may be an average addition mole number in a molecular assembly of a (meth)acrylate containing an anthracene skeleton represented by the above formula (2), and the range thereof is, for example, It may be the same as the range of the aforementioned integer. When the value of n1+n2 is too small, the viscosity of the curable composition tends to increase, and the workability is lowered. Moreover, there is also a problem that the scratch resistance of the cured product is lowered. However, in the present invention, since even a large amount of mixing Since the first monofunctional (meth) acrylate represented by the above formula (1) can maintain or increase the refractive index, even if the value of n1 + n2 is relatively small, the workability (reduced viscosity) can be effectively improved. . When the value of n1+n2 is too large, the content of the 9,9-bisarylindole skeleton per unit amount (for example, unit weight) of the hardened material (for example, the number of moles) is also decreased, so that there is a high ratio from the aforementioned skeleton. Excellent characteristics such as refractive index and high heat resistance are reduced. Further, n1+n2 can be measured by a conventional method, for example, in the preparation of a (meth)acrylate containing an anthracene skeleton represented by the above formula (2), from a 9,9-bisarylfluorene skeleton as a raw material. The ratio of the amount of the hydroxy compound to the amount of the alkylene oxide or the alkylene carbonate consumed in the reaction can be calculated by a method of calculating the value of the addition average or the arithmetic mean (for example, the method described in Patent Document 1). Determination.

In the above formula (2), the groups R ^7a and R ^7b are a hydrogen atom or a methyl group. In the (meth)acrylonitrile group-containing group substituted on the same or different rings Z ¹ and Z ² , the groups R ^7a and R ^7b may be the same or different, and are usually the same.

In the above formula (2), the substitution numbers p1 and p2 of the (meth)acrylenyl group-containing group are an integer of 1 or more, for example, an integer of 1 to 4, and preferably an integer of 1 to 3, It is more preferable to have 1 or 2 (especially 1). When p1 and p2 are too large, scratch resistance is lowered. Further, the substitution numbers p1 and p2 may be the same or different in each of the rings Z ¹ and Z ² .

Containing (meth) Bing Xixi group of the group, may be substituted in the ring Z ¹ and Z ² position on, for example, when ring Z ¹ and Z ² is a benzene ring, can be at the 2- to 6-position of the appropriate When the positions of p1 and p2 are 1, the substitution is made at any position of the 2-position, 3-position, 4-position (especially 3-position or 4-position) of the phenyl group. When p1 and p2 are 2, there are many cases in which the 2-position and 4-position, 3-position and 4-position, 3-position and 5-position (especially 3-position and 5-position) are substituted. When p1 and p2 are 3 or more, the substitution position is not particularly limited. Further, when the ring Z ¹ and Z ² are a naphthalene ring, the substitution is carried out at any of the 5- to 8-positions of the naphthyl group. For example, when p1 and p2 are 1, relative to the quinone 9- And replacing the 1-position or the 2-position of the naphthalene ring (substituted by the relationship of 1-naphthyl or 2-naphthyl), and the 1,5-position, 2,6-position, etc. with respect to the substitution position The relationship (especially the relationship of the 2,6-position) is mostly replaced by a group containing a (meth)acryl fluorenyl group. Further, when p1 and p2 are 2 or more, the substitution position is not particularly limited. Further, in the ring-assembled aromatic hydrocarbon ring Z ¹ and Z ² , the substitution position of the (meth)acryl-containing group is not particularly limited. For example, when p1 and p2 are 1, the bond may be bonded. The 9-position aromatic hydrocarbon ring and/or the aromatic hydrocarbon ring adjacent to the aromatic hydrocarbon ring are substituted. For example, the 3- or 4-position of the biphenyl ring Z ¹ and Z ² may be bonded to the 9-position of the oxime. When the 3-position of the biphenyl ring Z ¹ and Z ² is bonded to the 9-position of the fluorene, the substitution position of the (meth)acryl fluorenyl group may be the 2-position of the biphenyl ring, 4- Any of the bit, 5-bit, 6-position, 2'-position, 3'-position, and 4'-position, usually, also in the 6-position, 3'-position, and 4'-position, and It is preferable to replace it at the position of any of the 6-position and the 4'-position (especially the 6-position). When the 4-position of the biphenyl ring Z ¹ and Z ² is bonded to the 9-position of the fluorene, the substitution position of the (meth) fluorenyl group-containing group may be at the 2-position of the biphenyl ring, 3 Any of the -bit, 2'-position, 3'-position, and 4'-position, usually, in the 2-bit, 3'-position, 4'-position, and in the 2-position, The position on any of the 4'-positions (especially the 2-position) is preferred. Further, when p1 and p2 are 2 or more, the substitution position is not particularly limited.

The (meth) acrylate-containing (meth) acrylate represented by the above formula (2) is exemplified by the compound of the above formula (2), wherein the ring Z ³ and Z ⁴ are a benzene ring, that is, the following formula (2a)

Wherein rings Z ¹ and Z ² , R ^4a and R ^4b , R ^5a and R ^5b , R ^6a and R ^6b , R ^7a and R ^7b , k1 and k2, m1 and m2, n1 and n2, and p1 and p2 It also contains the preferred aspect and is the same as the above formula (2). The compound shown. More specifically, in the above formula (2a), the quinones in which p1 and p2 are 1, may, for example, be 9,9-bis[(meth)acryloxyphenyl]anthracene, 9,9-double [(Meth)acryloxy(poly)alkoxyphenyl]anthracene, 9,9-bis[(methyl)propenyloxynaphthyl]anthracene, 9,9-bis[(methyl Acryloxy (poly)alkoxynaphthyl] anthracene or the like. Further, such anthraquinones are as long as 9,9-bis[(meth)acrylomethoxyaryl]fluorene skeleton or 9,9-bis[(meth)acryloxyloxy group having a corresponding correspondence. a (poly)alkoxyaryl]anthracene skeleton, which is used in a compound having a non-reactive substituent also contained in two benzene rings constituting an anthracene skeleton, and/or rings Z ¹ and Z ² (in the above formula (2a) In the case where k1 and k2, and/or m1 and m2 are compounds of 1 or more).

9,9-bis[(meth)acryloxyphenyl]anthracene, in the above formula (2a), ring Z ¹ and Z ² are a benzene ring, n1 and n2 are 0, and p1 and p2 are 1 The compound may, for example, be 9,9-bis[(meth)acryloxyphenyl]anthracene (for example, 9,9-bis[4-(methyl)propenyloxyphenyl]anthracene, 9,9 - bis[3-(meth)acryloxyphenyl]anthracene); 9,9-bis[(meth)acryloxy-mono- or dialkylphenyl]anthracene (eg 9,9- Bis[4-(methyl)propenyloxy-3-methylphenyl]anthracene, 9,9-bis[4-(methyl)propenyloxy-3-tert-butylphenyl]anthracene, 9,9-bis[(meth)acryloyloxy-mono or di-C ₁ such as 9,9-bis[4-(methyl)propenyloxy-3,5-dimethylphenyl]anthracene _-4 alkylphenyl]anthracene, etc.; 9,9-bis[(meth)acrylomethoxy-arylphenyl]anthracene (eg 9,9-bis[4-(methyl)propenyloxy) 9,9-bis[(meth)acryloxy-C _6-10 arylphenyl]anthracene or the like such as -3-phenylphenyl]anthracene.

9,9-bis[(meth)acryloxycarbonyl (poly)alkoxyphenyl]anthracene, in the above formula (2a), ring Z ¹ and Z ² are a benzene ring, and n1 and n2 are 1 A compound having a ratio of 1 to 6 (preferably 1 to 6) and p1 and p2 is 1, for example, 9,9-bis[(meth)acryloxycarbonyl (poly)alkoxyphenyl]fluorene (for example) 9,9-bis[4-(2-(methyl)acryloxyethoxyethoxy)phenyl]anthracene, 9,9-bis[4-(2-(methyl)propenyloxypropoxy) Benzene] 9,9-bis[4-(2-(2-(methyl)propenyloxyethoxy)ethoxy)phenyl]indole, etc. 9,9-bis[(A) Acetylene methoxy (mono to ten) C _2-4 alkoxy phenyl] fluorene); 9,9-bis[(meth) propylene oxy (poly) alkoxy-mono or dialkyl Phenyl]anthracene (eg 9,9-bis[4-(2-(methyl)propenyloxyethoxy)-3-methylphenyl]indole, 9,9-bis[4-(2- (Meth)acryloxypropoxypropoxy)-3-t-butylphenyl]anthracene, 9,9-bis[4-(2-(2-(methyl)propenyloxyethoxy) 9,9-bis[(meth)acryloxyl (mono to ten) C _{2 -4} alkoxy-single or di-C ₁ such as ethoxy)-3,5-dimethylphenyl]anthracene _-4 alkylphenyl]anthracene, etc.; 9,9-bis[(meth)acryloxy(poly)alkoxy-arylphenyl]anthracene (for example: 9,9-bis[4] -(2-(Methyl)acryloxyethoxyethoxy)-3-phenylphenyl]anthracene, 9,9-bis[4-(2-(methyl)propenyloxypropoxy)- 3-phenylphenyl]anthracene, 9,9-bis[4-(2-(2-(methyl)acryloxyethoxyethoxy)ethoxy)-3-phenylphenyl]indole 9,9-bis[(meth)acryloxycarbonyl (mono to deca) C _2-4 alkoxy-C _6-10 arylphenyl] hydrazine, etc.).

9,9-bis[(meth)propenyloxynaphthyl]anthracene is in the above formula (2a), ring Z ¹ and Z ² are naphthalene rings, n1 and n2 are 0, and p1 and p2 are 1 The compound may, for example, be 9,9-bis[(meth)propenyloxynaphthyl]anthracene (for example, 9,9-bis[6-(methyl)propenyloxy-2-naphthyl]anthracene, 9 , 9-bis[5-(methyl)propenyloxy-1-naphthyl 1 oxime, etc.).

9,9-bis[(meth)acryloxyl (poly)alkoxynaphthyl] anthracene is in the above formula (2a), ring Z ¹ and Z ² are naphthalene rings, and n1 and n2 are 1 to 10 (preferably 1 to 6), and a compound wherein p1 and p2 are 1, and may, for example, be 9,9-bis[(meth)acryloxy(poly)alkoxynaphthyl]anthracene (for example, 9, 9-bis[6-(2-(methyl)acryloxyethoxyethoxy)-2-naphthyl]anthracene, 9,9-bis[5-(2-(methyl)propenyloxypropoxyl) 9-naphthyl]anthracene, 9,9-bis[6-(2-(2-(methyl)acryloxyethoxyethoxy)ethoxy)-2-naphthyl]anthracene , 9-bis[(meth)acryloxyl (mono to deca) C _2-4 alkoxynaphthyl] anthracene, etc.).

These (meth) acrylates containing an anthracene skeleton may be used singly or in combination of two or more kinds. Preferably, the (meth) acrylate containing an anthracene skeleton is in the above formula (2a), the rings Z ¹ and Z ² are a benzene ring, and n1 and n2 are 1 to 10 (preferably 1 to 6), p1 and The compound wherein p2 is 1 may, for example, be 9,9-bis[(meth)acryloxycarbonyl (poly)alkoxyphenyl]anthracene or the like, and among them, 9,9-bis[(methyl) is preferred. Propylene oxime (poly)alkoxyphenyl]anthracene (for example, 9,9-bis[4-(2-(methyl)propenyloxyethoxy)phenyl]anthracene, 9,9-bis[ 9,9-bis[(meth)acryloxyl (single to ten) C ₂ such as 4-(2-(2-(methyl)propenyloxypropoxy)propoxy)phenyl]anthracene _-4 alkoxyphenyl]anthracene); 9,9-bis[(meth)acrylomethoxy(poly)alkoxy-mono or dialkylphenyl]anthracene (eg 9,9-bis[4] -(2-(Methyl)acryloxyethoxyethoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-(methyl)propenyloxypropoxy)- 3-tert-butylphenyl]anthracene, 9,9-bis[4-(2-(2-(methyl)propenyloxyethoxy)ethoxy)-3,5-dimethylbenzene 9,9-bis[(meth)acryloxyl (mono to ten)C _2-4 alkoxy-mono or di-C _1-4 alkylphenyl] hydrazine, etc.; 9-bis[(meth)acryloxy(poly)alkoxy-arylphenyl]anthracene (eg 9,9-bis[4-(2-(methyl) Acryloxyethoxy)-3-phenylphenyl]anthracene, 9,9-bis[4-(2-(2-(methyl)propenyloxypropoxy)propoxy)- 9,9-bis[(meth)acryloxycarbonyl (mono to deca) C _2-4 alkoxy-C _6-10 arylphenyl] anthracene, etc. such as 3-phenylphenyl]anthracene .

In addition, the (meth) acrylate containing the oxime skeleton can be prepared by a commercially available product, and can be prepared by a conventional method (for example, the method described in Patent Document 1).

The alicyclic epoxy (meth) acrylate may be a polyfunctional epoxy (meth) acrylate having at least one alicyclic hydrocarbon ring (aliphatic ring), and the alicyclic ring may be used. For example, a C _5-8 cycloalkane ring (e.g., a cyclopentane ring, a cyclohexyl ring, etc.), a C _7-10 di or tricycloalkane ring (e.g., a norbornane ring, an adamantane ring, etc.), and the like. A typical alicyclic epoxy (meth) acrylate may, for example, be a C _5-10 aliphatic group such as 1,4-cyclohexane dimethanol diglycidyl ether di(meth)acrylate. A bis(meth) acrylate such as an epoxy compound of a ring. These alicyclic epoxy (meth) acrylates may be used singly or in combination of two or more kinds.

The aromatic epoxy group (meth) acrylate may be a polyfunctional epoxy (meth) acrylate having at least an aromatic ring, and the aromatic ring may, for example, be a benzene ring or a naphthalene ring. _10-14 condensed polycyclic aromatic hydrocarbon ring and the like. The aromatic epoxy (meth) acrylate is suitable for obtaining a cured product having a high refractive index because it has the aforementioned aromatic ring. Representative aromatic epoxy (meth) acrylates, for example, di(methyl) diglycidyl ethers of biphenols or bisphenols (or alkylene oxide adducts thereof) Poly(meth)acrylate of acrylate or novolak type epoxy resin. These aromatic epoxy (meth) acrylates may be used singly or in combination of two or more kinds.

Preferred aromatic epoxy (meth) acrylates, for example, di-glycidyl ether (epoxy compound) of a biphenol or a bisphenol (or an alkylene oxide adduct thereof) (Meth) acrylate. Examples of the biphenols include p,p'-biphenol, m,m'-biphenol, o,o'-biphenol, and the like. Examples of the bisphenols include bisphenol A, bisphenol F, bisphenol B, bisphenol AP, bisphenol AF, and bisphenol S. The alkylene oxide may, for example, be a C _2-4 alkylene oxide such as ethylene oxide or propylene oxide, and preferably a C _2-3 alkylene oxide. Further, the alkylene oxide adduct may be an adduct of an alkylene carbonate corresponding to the exemplified alkylene oxide.

The di(meth) acrylate of the diglycidyl ether of a typical biphenol or bisphenol (or an alkylene oxide adduct thereof), for example, is represented by the following formula (3). Group epoxy (meth) acrylate.

Wherein R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, respectively, and two of R ⁸ may be bonded to each other to form a hydrocarbon ring which may have an alkyl group; and R ^9a and R ^9b are each an alkyl group or an aryl group; R ^10a and R ^10b are each a linear or branched alkyl group; R ^11a and R ^11b are each a hydrogen atom or a methyl group; q1 and q2 are each an integer of 0 to 4; and r1 and r2 are each 0 or 1 respectively. Integer; t is 0 or 1.

In the above formula (3), the alkyl group of R ⁸ may also be a linear or branched C _1-6 alkyl group such as a methyl group, an ethyl group, an isopropyl group or a tributyl group, and may be a straight chain or a branched chain. Chain C _1-4 alkyl (especially methyl) and the like. The aryl group of R ⁸ may also be a C _6-10 aryl group (particularly a phenyl group) such as a phenyl group or a naphthyl group. The types of R ⁸ may be the same or different. Further, the hydrocarbon ring formed by bonding two R ⁸ groups to each other may be a C _5-8 cycloalkane ring such as a cyclopentane ring or a cyclohexene ring. The alkyl group substituted with a hydrocarbon ring may, for example, be an alkyl group as exemplified in the above-mentioned alkyl group of R ⁸ , and may be the same as the preferred embodiment. The number of substitutions and the position of substitution of the alkyl group substituted with a hydrocarbon ring are not particularly limited. The aforementioned substitution number is, for example, an integer of 0 to 3, and is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly 0. When the hydrocarbon ring is a cyclohexane ring, the aforementioned substitution position may be substituted, for example, at any position from the 3-position to the 5-position.

R ^9a and R ^9b may, for example, be an alkyl group, an aryl group or the like exemplified in the item of R ⁸ , and may be the same in a preferred embodiment. The substitution numbers q1 and q2 of R ^9a and R ^{9b are} integers of 0 to 4, for example, an integer of 0 to 3, and preferably an integer of 0 to 2, more preferably 0 or 1, and particularly 0. . Further, the types of R ^9a and R ^9b may be the same or different, and when q1 and q2 are 2 or more, the types of R ^9a and R ^9b bonded to two or more of the same benzene rings may be the same or different. different. The substitution position of R ^9a and R ^9b is not particularly limited, and may be substituted at any position (2-position, 3-position, etc.) of the benzene ring.

The linear or branched alkyl group represented by R ^10a and R ^10b may, for example, be exemplified in the item of R ² (and R ^6a and R ^{6b of the} above formula (2)) of the above formula (1). Straight or branched alkyl groups, etc., also include preferred embodiments and may be the same. Further, the types of R ^10a and R ^10b may be the same or different from each other. Further, when the number of repetitions r1 and r2 of the oxygen alkyl group (OR ^10a and OR ^10b ) is 2 or more, the types of two or more of R ^10a and R ^10b may be different from each other, but it is preferably the same.

The total count of r1 and r2, and r1 and r2 [the total number of oxygen-extended alkyl groups (total number of additions) may be simply referred to as r1 + r2. The values (integer or average) exemplified in the items of n1 and n2, and n1+n2 of the above formula (2) are also preferably the same. When the value of r1+r2 is too small, the viscosity of the curable composition tends to increase, and the workability is lowered. However, in the present invention, even if a large amount of the first monofunctional (meth) acrylate represented by the above formula (1) is mixed, the refractive index can be maintained or increased, so even if the value of r1 + r2 is relatively small, Effectively improve operability (reduced viscosity). When the value of r1+r2 is too large, since the aromatic ring content (for example, the number of moles) is also lowered, the excellent characteristics such as high refractive index are lowered. Further, the r1+r2 system can measure the method exemplified in the item of n1+n2 of the above formula (2) as a reference.

R ^11a and R ^11b may be the same or different from each other, and are generally the same.

t is 0 or 1, and 1 is preferred.

Representative aromatic epoxy (meth) acrylate represented by the above formula (3), which is exemplified by the compound of the formula (3), t = 0 (for example, p,p'-biphenyl Di(meth)acrylate of di-epoxypropyl ether, etc.); in the above formula (3), q1=q2=0, r1=r2=0, compound of t=1 [for example, two R ^{8 are} each a compound of a hydrogen atom or an alkyl group (e.g., a bisphenol (epoxypropyl ether) bis(meth)acrylate such as bisphenol A, bisphenol F, bisphenol E or bisphenol B) a compound in which at least one of R ⁸ is an aryl group (for example, a bisphenolic compound such as bisphenol AP or bisphenol BP); and two R ^{8 are} bonded to each other to form A compound having a hydrocarbon ring of an alkyl group (for example, a bisphenol (such as bisphenol Z or a bisphenolic epoxy compound such as bisphenol TMC), or the like].

The aromatic epoxy group (meth) acrylate represented by the above formula (3) may be used singly or in combination of two or more kinds. Among the aromatic epoxy (meth) acrylates represented by the above formula (3), a compound wherein q1 = q2 = 0 and r1 = r2 = 0, wherein a compound of t = 1 is also preferred, in particular, It is more preferable that two R ⁸ compounds each having a hydrogen atom or an alkyl group (for example, bis(meth)acrylate of bisphenol A diglycidyl ether).

The urethane (meth) acrylate-based backbone skeleton (the backbone of the urethane oligomer or the urethane polymer portion) is a unit derived from a reactant of a polyol component and a polyisocyanate component. Formed. The polyol component may be a low molecular weight polyol component (for example, an alkyl diol such as ethylene glycol), and a high molecular weight polyol component is preferred from the viewpoint of improving scratch resistance in the cured product. Further, the high molecular weight polyol component may be a polymer or an oligomer having a small number of repeating units. The weight average molecular weight (Mw) of the high molecular weight polyol component can be measured by gel permeation chromatography (GPC) or the like, and converted into standard polystyrene, for example, may be selected from 300 or more (for example, 400 to 50,000). Range, for example, 500 to 10,000 (example For example, 600 to 5000), preferably 700 to 3000 (for example, 800 to 2000). When the molecular weight (weight average molecular weight) of the polyol component is too low, the scratch resistance of the cured product is lowered. When the molecular weight is too high, the viscosity is high, and the workability is lowered. In the present invention, by combining with the above-mentioned first monofunctional (meth) acrylate, even a relatively high-viscosity polyfunctional (meth) acrylate can be effectively made low in viscosity.

The high molecular weight polyol component may, for example, be a polyether polyol, a polyester polyol or a polycarbonate polyol. The polyether polyol (particularly polyether diol) may, for example, be a polyalkylene oxide [or a polyalkylene glycol such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4- Separate or copolymer of C _2-6 alkylene oxide such as butylene oxide (tetrahydrofuran) (for example, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyethylene oxide-polypropylene oxide) a polyoxyalkylene C _2-6 alkanediol such as a segment copolymer, particularly polytetramethylene ether glycol), etc., an alkylene oxide adduct of bisphenol A or hydrogenated bisphenol A (for example, relative to hydroxyl group 1) Mohr, addition of a C _2-4 alkylene oxide of about 1 to 5 moles of an adduct). These polyether polyols can be used singly or in combination of two or more kinds.

The polyester polyol (particularly a polyester diol) contains a diol component and a dicarboxylic acid component [dicarboxylic acid or a derivative thereof (for example, a lower alkyl ester (such as a C _1-2 alkyl ester such as a methyl ester) a reactant of an acid halide, an acid anhydride, or the like, a hydroxyalkanecarboxylic acid (3-hydroxybutyric acid, etc.), and/or a lactone (C _3-10 lactone such as ε-caprolactone or δ-valerolactone) Separate or copolymer (poly-ε-caprolactone or the like), the above diol component, a copolymer of a dicarboxylic acid component and a hydroxyalkanecarboxylic acid and/or a lactone, etc. The dicarboxylic acid component may, for example, be aromatic. a dicarboxylic acid (for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, etc.), an alicyclic dicarboxylic acid (such as cyclohexanedicarboxylic acid, etc.), an aliphatic dicarboxylic acid (for example) a linear C _4-12 dicarboxylic acid such as adipic acid or sebacic acid, or the like, and a derivative of such a dicarboxylic acid, etc. Further, the diol component may be an alkanediol (for example, ethylene glycol). , propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc., C _2-10 alkanediol, etc.), polyoxygen a polyether diol such as an alkanediol (for example, a polyalkylene glycol such as diethylene glycol) or an alicyclic diol (for example, 1,4-cyclohexanediol or cyclohexane) Each of the diol component and the dicarboxylic acid component may be used alone or in combination of two or more. The specific polyester polyol includes a polyester diol having a terminal hydroxyl group, for example, polyadipate. Ethylene glycol ester, diethylene glycol adipate, polypropylene adipate, polymethylene adipate, polyhexamethylene adipate, copolymers thereof and the like. These polyester polyols may be used singly or in combination of two or more kinds.

The polycarbonate polyol (particularly, a polycarbonate diol) may, for example, be a polyol (a low molecular weight polyol, a polyether polyol, a polyester polyol or the like exemplified above) and a dialkyl carbonate (for example). For example, a polycarbonate diol (for example, polyhexamethylene carbonate diol) obtained by a reaction of dimethyl carbonate or the like or a carbonated ester (for example, ethylene carbonate). These polyol components may be used singly or in combination of two or more kinds.

The polyisocyanate component is not particularly limited, and examples thereof include aliphatic polyisocyanates (for example, hexamethylene diisocyanate (HDI), 1,3,6-hexamethylene triisocyanate, etc.); alicyclic polyisocyanates [for example, Carbaryl diisocyanate (IPDI), hydrogenated xylene diisocyanate (hydrogenated XDI), hydrogenated diphenylmethane-4,4'-diisocyanate (hydrogenated MDI), etc.; araliphatic polyisocyanate [eg xylene diisocyanate ( XDI), tetramethyl xylene Isocyanate (TMXDI), etc.; aromatic polyisocyanate (eg, tolyl diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), toluidine diisocyanate (TODI) , p-phenylene diisocyanate, etc.; a prepolymer having an isocyanate group at the end [for example, a urethane prepolymer having a reaction of a polyol component (for example, a diol component) exemplified above and a polyisocyanate component (for example, a diisocyanate component) Polymer] and the like. Further, the polyisocyanate component may be a modified substance [or a derivative such as a polymer (dimer, trimer (such as a trimeric isocyanate ring) or the like), a carbodiimide, a biuret, or Urea formate, uretdione, polyamine modified, etc.]. These polyisocyanate components can be used individually or in combination of 2 or more types.

Typical urethane (meth) acrylates include polyester urethane (meth) acrylate, polyether urethane (meth) acrylate, and polyol component. Polycarbonate type urethane (meth) acrylate or the like. These ethyl urethane (meth) acrylates may be used singly or in combination of two or more kinds. These ethyl urethane (meth) acrylates are effective for improving the scratch resistance of the cured product, and the polyester urethane (meth) acrylate and/or polyether amine is contained therein. Ethyl formate (meth) acrylate is preferred.

The polyester (meth) acrylate contains a preferred aspect and the like, and can be prepared by reacting the same polyester polyol as described above with (meth)acrylic acid. The polyester polyol may also be derived from an aliphatic monomer component (for example, an aliphatic diol component (C _2-12 alkanediol such as butanediol, etc.) from the viewpoint of improving scratch resistance in the cured product. And an aliphatic dicarboxylic acid component [C _4-20 alkanecarboxylic acid such as adipic acid or dodecanedioic acid or a derivative thereof (acid halide, acid anhydride, lower alkyl ester), etc.], an aliphatic lactone component A unit such as (ε-caprolactone or the like) or an aliphatic hydroxycarboxylic acid component (3-hydroxybutyric acid, 5-hydroxyvaleric acid or the like) is formed. These polyester polyols may be used alone or in combination of two or more.

Further, an alicyclic epoxy (meth) acrylate, an aromatic epoxy (meth) acrylate, an urethane (meth) acrylate, or a polyester (meth) acrylate may also be used. Sale.

The content of the high-viscosity polyfunctional (meth) acrylate may be, for example, selected from the range of 10% by weight or more, and may be, for example, 30% by weight or more, based on the total of the polyfunctional (meth) acrylate. 50% by weight or more is more preferably 60% by weight or more (for example, 80% by weight or more), and particularly, substantially 100% by weight. When the ratio of the high-viscosity polyfunctional (meth) acrylate is too low, there is a possibility that the viscosity is not effectively lowered.

Further, these high-viscosity polyfunctional (meth) acrylates may be used singly or in combination of two or more kinds depending on the application, and various characteristics (for example, refractive index, scratch resistance, heat resistance, and the like) may be adjusted. Equilibrium of mechanical properties, etc.). In general, a cured product having a high refractive index tends to have high steel properties and lacks flexibility. However, in the present invention, it is possible to highly combine high refractive index and scratch resistance (softness). For example, the polyfunctional (meth) acrylate may contain at least a polyfunctional (meth) acrylate having a 9,9-bisarylfluorene skeleton excellent in optical characteristics such as a high refractive index (for example, the above formula ( 2) The (meth) acrylate containing an anthracene skeleton, etc.) and the urethane (meth) acrylate excellent in scratch resistance of a cured product. Such a polyfunctional (meth) acrylate can form a cured product which has a high refractive index and excellent scratch resistance in a well-balanced manner. Polyfunctional (meth) propyl with 9,9-bisaryl fluorene skeleton The ratio of the olefinic acid ester (for example, the (meth) acrylate containing an anthracene skeleton represented by the formula (2), etc.) to the ethyl urethane (meth) acrylate may be, for example, selected from the former/the latter (weight ratio). a range of from about 50/50 to about 99/1, for example, from 53/47 to 90/10, and preferably from 55/45 to 80/20, from 58/42 to 70/30 (for example, 60/40 to 65) /35) The left and right are better. When the polyfunctional (meth) acrylate having a 9,9-bisarylfluorene skeleton is too small, the refractive index of the cured product is lowered.

The polyfunctional (meth) acrylate may contain, in addition to the high-viscosity polyfunctional (meth) acrylate, a dialkyl group as an alkylene oxide adduct of a biphenol or a bisphenol. )Acrylate. Such a polyfunctional (meth) acrylate can be easily balanced to improve the low viscosity in the curable composition, and the high refractive index and scratch resistance in the cured product.

Examples of the di(meth)acrylate of the alkylene oxide adduct of a biphenol or a bisphenol, and the biphenols, bisphenols, and alkylene oxides are, for example, the above-mentioned biphenols or bisphenols ( And the biphenols, bisphenols, and alkylene oxides exemplified in the di(meth)acrylate of the di-epoxypropyl ether of the alkylene oxide adduct thereof, or the like, also include a preferred state. The same is true. The total number (total number of additions) (integral or average addition mole number) of the alkylene oxide added from the alkylene oxide (or oxyalkylene ester) may be, for example, selected from the range of about 1 to 30, for example 2 to 25, preferably 3 to 20, more preferably 5 to 15 (for example, 8 to 12). When the total number of oxygen alkyl groups is too low, there is a possibility that the scratch resistance cannot be improved.

The di(meth)acrylate of the alkylene oxide adduct of the representative biphenols or bisphenols may, for example, be a di(meth)acrylate of a biphenol-based alkylene oxide adduct [for example, Compared with 1 mol of p, p'-biphenol, addition of a di(meth)acrylate such as an adduct of about 10 mol of alkylene oxide, etc., is added to 1 mol of biphenol. a di(meth)acrylate of an adduct of C _2-4 alkylene oxide of about 2 to 25 mol; etc.; a di(meth)acrylate of a bisphenol-based alkylene oxide adduct [for example, relative In 1 mole of bisphenol A, an addition of about 10 moles of ethylene oxide adduct of di(meth)acrylate, compared to 1 mole of bisphenol F, an addition of 10 moles An adduct of a C _2-4 alkylene oxide having an adduct of about 2 to 25 mols is added to a bisphenol (meth) acrylate such as an adduct of propylene oxide to the left and right. Di(meth)acrylate, etc.].

The di(meth)acrylates of the alkylene oxide adducts of the biphenols or bisphenols may be used singly or in combination of two or more kinds. Among the di(meth)acrylates of the alkylene oxide adducts of the biphenols or bisphenols, the di(meth)acrylates of the bisphenol alkylene oxide adducts are preferred. Adding a di(meth)acrylate of an adduct of C _2-3 alkylene oxide of about 3 to 20 moles in 1 mole of bisphenol (for example, relative to 1 mole of bisphenol A) It is more preferable to add an bis(meth) acrylate having an adduct of about 10 moles of ethylene oxide. Further, commercially available products may also be used as the di(meth)acrylate of the alkylene oxide adduct of the biphenol or bisphenol.

The ratio of the high-viscosity polyfunctional (meth) acrylate to the di(meth) acrylate of the alkylene oxide or the bisphenol alkylene oxide adduct, for example, may be selected from the former/the latter (weight ratio) a range of from about 50/50 to about 99/1, for example, from 53/47 to 90/10, and preferably from 55/45 to 80/20, from 58/42 to 70/30 (for example, 60/40 to 65) /35) The left and right are better. Bisphenol When the ratio of the di(meth)acrylate of the alkylene oxide-like adduct is too high, the effect of lowering the viscosity cannot be obtained.

<Other monofunctional polymeric components>

The curable composition of the present invention may contain, in addition to the polyfunctional (meth) acrylate and the first monofunctional (meth) acrylate represented by the above formula (1), other monofunctional groups. A polymeric component (or monomer). The curable composition may adjust or improve handling properties (low viscosity), refractive index, and scratch resistance (softness) depending on the use, by containing other monofunctional polymerizable components. The other monofunctional polymerizable component is one having one polymerizable group (or polymerizable unsaturated bond) (for example, an alkenyl group (for example, a vinyl group, an allyl group, etc.), a (meth) acrylonitrile group, or the like. The compound may be, for example, a monofunctional vinyl monomer [for example, an α-olefin monomer (for example, ethylene or propylene); a styrene monomer (for example, styrene, α-methylstyrene, ethylene). A vinyl-based monomer (for example, vinyl acetate or the like; N-vinylpyrrolidone or the like), a monofunctional (meth)acrylic monomer, or the like. These monofunctional polymerizable components may be used singly or in combination of two or more kinds. Among these monofunctional polymerizable components, a monofunctional (meth)acrylic monomer is preferred.

The monofunctional (meth)acrylic monosystem can be, for example, (meth)acrylic acid, (meth)acrylamide, N-substituted (meth)acrylamide (for example, N-hydroxymethyl (methyl)) A acrylamide, N,N-dimethyl(meth)acrylamide or the like, (meth)acrylonitrile or the like, and a monofunctional (meth)acrylate is often used.

The monofunctional (meth) acrylate may, for example, be an aliphatic monofunctional (meth) acrylate [for example, methyl (meth) acrylate, butyl (meth) acrylate, or (meth) acrylate 2 - Ethylhexyl ester or the like (C _1-20 alkyl (meth)acrylate, etc.]; alicyclic monofunctional (meth) acrylate [e.g. (meth)acrylic acid C _5-10 such as cyclohexyl (meth) acrylate a cross-linked cyclic (meth) acrylate such as a cycloalkyl ester, dicyclopentenyl (meth) acrylate or isodecyl (meth) acrylate; etc.; an aromatic monofunctional (meth) acrylate (only, The monofunctional (meth) acrylate represented by the above formula (1) is not contained.); a monofunctional (meth) acrylate containing a sulfur atom or the like. These monofunctional (meth) acrylates may be used singly or in combination of two or more kinds. Among these monofunctional (meth) acrylates, the curable composition is improved from the viewpoint of improving the handleability of the curable composition and the high refractive index and scratch resistance of the cured product. Preferably, it contains a monofunctional (meth) acrylate containing a sulfur atom (sometimes referred to simply as a second monofunctional (meth) acrylate), and a second monofunctional (meth) acrylate may also be used. Has an aromatic ring. Further, from the viewpoint of improving the workability of the curable composition and further increasing the refractive index of the cured product, the curable composition contains an aromatic monofunctional (meth) acrylate (sometimes only It is preferably referred to as a third monofunctional (meth) acrylate.) The third monofunctional (meth) acrylate may also contain a sulfur atom. A preferred monofunctional (meth) acrylate may have an aromatic ring and be a monofunctional (meth) acrylate having a sulfur atom.

The second monofunctional (meth) acrylate containing a sulfur atom may, for example, be an alkylthio(meth)acrylate (for example, (meth)acrylic acid C _1-6 alkane such as methyl methacrylate. Sulfuryl esters and the like, arylthio (meth)acrylates (for example, C _6-10 arylthioesters such as (meth)acrylic acid phenylthiolate), and aralkyl sulfides (meth)acrylate a base ester (for example, (meth)acrylic acid such as (meth)acrylic acid C _6-10 aryl C _1-6 alkylthioester, etc.), (meth)acrylic acid aryl thioester (for example, (methyl) a phenylthioethyl acrylate or the like (such as a C _6-10 arylthio C _2-6 alkyl (meth)acrylate). These second monofunctional (meth) acrylates containing a sulfur atom may be used singly or in combination of two or more kinds. Among these second monofunctional (meth) acrylates having a sulfur atom, the operability of the curable composition and the refractive index and scratch resistance in the cured product can be improved in a particularly balanced manner. In general, a (meth)acrylic acid C _6-10 arylthio C _2-4 is preferred as the arylthioalkyl (meth) acrylate, particularly, phenylthioethyl (meth) acrylate. Alkyl esters are more preferred. A commercially available product or the like can also be used as the second monofunctional (meth) acrylate containing a sulfur atom.

Further, the ratio of the first monofunctional (meth) acrylate to the second monofunctional (meth) acrylate may be, for example, selected from the former/the latter (weight ratio) = 100/0 to 20/80 ( For example, a range of about 80/20 to 20/80), for example, 70/30 to 25/75, and preferably 65/35 to 30/70 (for example, 60/40 to 35/65), 55/45. It is better to be around 40/60 (for example, 50/50 to 40/60). When the ratio of the first monofunctional (meth) acrylate is too low, workability and a decrease in the refractive index of the cured product are observed.

The aromatic monofunctional (meth) acrylate (third monofunctional (meth) acrylate) may, for example, be an aryl (meth) acrylate (for example, phenyl (meth) acrylate). a mono (meth) acrylate of an arylalkyl (meth) acrylate (such as benzyl (meth) acrylate) or a bisphenol (or an alkylene oxide adduct thereof) (for example, bisphenol A) a mono(meth)acrylate of an ethylene oxide adduct, or a (meth)acrylate containing an anthracene skeleton (for example, 9-(meth)acryloxymethylhydrazine), and the following formula ( 4)

Wherein R ¹² represents a hydrogen atom or a methyl group; R ¹³ is an alkylene group; R ¹⁴ is an alkyl group; Ar ² is a benzene ring or a ring-condensed aromatic hydrocarbon ring; c is an integer of 1 to 4; and d is 0 or more. The integer. Monofunctional (meth) acrylates and the like are shown. These third monofunctional (meth) acrylates may be used singly or in combination of two or more kinds. In the third monofunctional (meth) acrylate, the operability of the curable composition is improved, and the refractive index of the cured product is particularly increased, and the formula (4) is contained. The third monofunctional (meth) acrylate is preferred.

In the above formula (4), the group R ¹² is a hydrogen atom or a methyl group. Further, the group R ¹³ is a linear or branched alkyl group, and for example, an alkylene group exemplified in the above-mentioned group R ² (and the groups R ^6a and R ^6b ) can be exemplified, and the preferred aspect is also the above-mentioned group R. ² (and base R ^6a and base R ^6b ) are the same. The number of repetitions c of the group (R ¹³ O) may be selected from an integer of about 1 to 4, for example, an integer of about 1 to 3, more preferably 1 or 2, still more preferably 1 or more. When the number of repetitions c is too large, there is a tendency to lower the refractive index of the cured product. Further, when c is 2 or more, two or more groups R ¹³ may be the same or different.

In the above formula (4), the ring Ar ² is a benzene ring or a ring-assembled aromatic hydrocarbon ring, and the ring-assembled aromatic hydrocarbon ring system is, for example, a ring-assembled aromatic hydrocarbon ring exemplified in the above-mentioned ring Z ¹ and Z ² , and the like. It is also the same as the ring-assembled aromatic hydrocarbon ring of the aforementioned rings Z ¹ and Z ² . Among these rings Ar ² , a benzene ring or a biphenyl ring (particularly a biphenyl ring) is preferred. In the above formula (4), the bonding position with respect to the group of the ring Ar ² [-O-(R ¹³ O) _c -CO-CR ¹² =CH ₂ ] is not particularly limited, for example, in the ring Ar ² When it is a biphenyl ring, it may be bonded to any position of the 2- to 6-position of the biphenyl ring, but it is preferably bonded at the 2-position.

In the above formula (4), the group R ¹⁴ is an alkyl group. For example, in the above formula (1), the alkyl group represented by the group R ³ or the like is preferably the same as the group R ³ . The substitution number d of the radical R ¹⁴ may be an integer of 0 or more, for example, an integer of about 0 to 4, and preferably an integer of about 0 to 2, more preferably 0 or 1, particularly Is 0. Further, when d is 2 or more, the types of the two or more groups R ¹⁴ may be the same or different. Further, the substitution position of the group R ¹⁴ is not particularly limited. For example, the ring Ar ² is a benzene ring, and the bonding position of the group [-O-(R ¹³ O) _c -CO-CR ¹² =CH ₂ ] is 1- In the case of a position, it may be substituted at any of the 2- to 6-positions of the 1-phenyl group, for example, at any of the 3- to 5-positions (for example, at the 4-position). Further, the ring Ar ² is a biphenyl ring, and the group [-O-(R ¹³ O) _c -CO-CR ¹² =CH ₂ ] is bonded at the 2-position, and may be in the 2-position of the 2-biphenyl group. The 6-position and the 2'- to 6'-position are substituted.

A representative example of the third monofunctional (meth) acrylate represented by the above formula (4) is that, in the above formula (4), c=1 and d=1, and Ar ² is a benzene ring. a compound, that is, an alkylphenoxyalkyl (meth)acrylate [such as 2-(nonylphenoxy)ethyl (meth)acrylate, etc. (meth)acrylic acid C _1-12 alkylphenoxy a C _2-4 alkyl ester or the like]; in the above formula (4), c=1 and d=1, and Ar ² is a compound of a ring-assembled aromatic hydrocarbon ring, that is, a plurality of alkyl (meth)acrylic acid rings are aggregated. Cycloaryloxyalkyl esters [e.g., 2-(mercaptobiphenoxy)ethyl (meth)acrylate, etc. (meth)acrylic acid C _1-12 alkyl C _6-10 aryl C _6-10 aryloxy a C _2-4 alkyl ester or the like]; in the above formula (4), c≧2 and d=1, and Ar ² is a compound of a benzene ring, that is, an alkylphenoxy group (meth)acrylate (single) To a) alkoxyalkyl ester [e.g., 2-(2-(nonylphenoxy)ethoxy)ethyl (meth)acrylate, etc. (meth)acrylic acid C _1-12 alkylphenoxy ( Mono to tri) C _2-4 alkoxy C _2-4 alkyl ester, etc.]; in the above formula (4), c ≧ 2 and d =1, and Ar ² is a compound of a ring-condensed aromatic hydrocarbon ring, that is, (meth)acrylic acid alkyl-ring assembly polycyclic aryloxy (single Iii) alkoxyalkyl ester [e.g. (meth) acrylate, 2- (2- (biphenyl-nonyl-yl) ethoxy) ethyl (meth) acrylic acid C _1-12 alkyl C _6-10 Aryl C _6-10 aryloxy (mono to tri) C _2-4 alkoxy C _2-4 alkyl ester, etc.]; in the above formula (4), c=1 and d=0, and Ar ² is a compound of a benzene ring, that is, a phenoxyalkyl (meth)acrylate [e.g., 2-phenoxyethyl (meth)acrylate, 2-phenoxypropyl (meth)acrylate, etc. a phenoxy C _2-4 alkyl acrylate or the like]; in the above formula (4), c=1 and d=0, and Ar ² is a compound of a ring assembly aromatic ring, that is, a (meth)acrylic acid ring A polycyclic aryloxyalkyl ester [for example, 2-(o-phenylphenoxy)ethyl (meth)acrylate, 2-(m-phenylphenoxy)ethyl (meth)acrylate, ( (meth)acrylic acid C _6-10 aryl C _6-10 aryloxy C _2-4 alkyl ester such as 2-(p-phenylphenoxy)propyl acrylate; the above formula (4) Wherein c≧2 and d=0, and Ar ² is a compound of a benzene ring, that is, a phenoxy (mono to tri) alkoxyalkyl (meth)acrylate [for example, (meth)acrylic acid 2- (2-phenoxyethoxy)ethyl ester, 2-(2-phenoxypropoxy)propyl (meth)acrylate, etc. (Meth)acrylic acid phenoxy (mono to tri) C _2-4 alkoxy C _2-4 alkyl ester, etc.]; in the above formula (4), c ≧ 2 and d = 0, and Ar ² is a ring a compound which aggregates an aromatic hydrocarbon ring, that is, a (meth)acrylic acid ring assembly polycyclic aryloxy (mono to tri) alkoxyalkyl ester [for example, 2-(2-(o-phenylbenzene) (meth) acrylate) (oxy)ethoxy)ethyl ester, 2-(2-(m-phenylphenoxy)propoxy)propyl (meth)acrylate, etc. (meth)acrylic acid C _6-10 aryl C _{6- 10} aryloxy (mono to tri) C _2-4 alkoxy C _2-4 alkyl ester, etc.].

The third monofunctional (meth) acrylates represented by the above formula (4) may be used singly or in combination of two or more kinds. A preferred third monofunctional (meth) acrylate is, for example, a compound of the formula (4) wherein c=1 and d=0, and Ar ² is a cyclic aromatic hydrocarbon ring, that is, (A) The acrylic ring is a polycyclic aryloxyalkyl ester or the like; more preferably, for example, a C _6-10 aryl C _6-10 aryloxy C _2-4 alkyl (meth) acrylate (for example, (methyl) a phenylphenoxy C _2-4 alkyl (meth) acrylate such as 2-(o-phenylphenoxy)ethyl acrylate or the like).

Further, as the compound represented by the formula (4), a commercially available product may be used, and an ester of sulfuric acid or the like may be obtained by a generally known method, for example, an alkylene oxide or an alkylene carbonate adduct of a polycyclic aromatic hydrocarbon in a phenol or a hydroxyl ring. The polymerization catalyst, a polymerization inhibitor such as hydroquinone, and a method of reacting with (meth)acrylic acid in the presence of a solvent as needed are prepared.

Further, the ratio of the first monofunctional (meth) acrylate represented by the formula (1) to the third monofunctional (meth) acrylate represented by the formula (4) may be selected from the former/the latter ( Weight ratio) = a range of about 100/0 to 20/80 (for example, 80/20 to 20/80), for example, 70/30 to 25/75, and 65/35 to 30/70 (for example, 60/40) Preferably, it is preferably from about 55/45 to 40/60 (e.g., from 50/50 to 43/57). The first monofunctionality represented by formula (1) (A When the ratio of the acrylate is too small, there is workability and a decrease in the refractive index of the cured product.

Further, in the low viscosity agent of the present invention, in addition to the first monofunctional (meth) acrylate, the other monofunctional polymerizable component may be contained (for example, the second monofunctional ( Methyl) acrylate, a third monofunctional (meth) acrylate (particularly a second monofunctional (meth) acrylate), etc.]. Further, the other monofunctional polymerizable component may be the same as described above, including a preferred embodiment (a representative compound, a ratio with a first monofunctional (meth) acrylate, etc.).

<Components other than polymerizable ingredients>

(polymerization initiator)

The curable composition may further contain a polymerization initiator in addition to the polymerizable component (or monomer component). The polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photoradical generator).

The thermal polymerization initiator may be exemplified by an organic peroxide [e.g., a dialkyl peroxide (e.g., di-tert-butyl peroxide, etc.), a dioxonium peroxide type (e.g., lauricyl peroxide, peroxidation). Benzopyridinyl, etc., peracid (or perester) (such as hydrogenated peroxylated tert-butyl, hydrogenated cumene, tert-butyl peracetate, etc.), ketone peroxides, peroxycarbonate An ester, a peroxyaldehyde or the like], an azo compound (for example, an azonitrile compound such as 2,2'-azobis(isobutyronitrile), an azoamine compound, an azomethamine compound, etc.] . These thermal polymerization initiators may be used singly or in combination of two or more.

The photopolymerization initiator may, for example, be a benzoin (for example, a benzoin alkyl ether such as benzoin or benzoin ethyl ether) or an acetophenone (for example, acetophenone or 2-hydroxy-). 2-methyl-1-phenylpropan-1-one, etc.), aminoacetophenones {eg 2-methyl-1-[4-(methylthio)phenyl]-2-folininyl Aminopropan-1-one, etc., anthraquinones (eg, hydrazine, 2-methylhydrazine, etc.), thioxanthone (eg, 2,4-dimethylthiaxanone, 2,4- Diethyl thioxanthone, 2-chlorothiazolone, etc.), ketals (such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.), benzophenones (such as benzophenone) Wait), Ketones, etc. These photopolymerization initiators may be used singly or in combination of two or more kinds.

The ratio of the polymerization initiator (heat and/or photopolymerization initiator) may be 0.1 to 15 parts by weight, and 0.5 to 10 parts by weight (for example, 1 to 8) based on 100 parts by weight of the total amount of the polymerizable component. It is preferably in the form of parts by weight, preferably about 2 to 5 parts by weight.

The photopolymerization initiator may also be combined with a photosensitizer. The photo sensitizer may be, for example, a tertiary amine such as a trialkylamine, a trialkanolamine (for example, triethanolamine or the like), or an N,N-dimethylaminobenzoic acid ethyl ester [for example, Ethylamino)benzoic acid, etc.], N,N-dimethylaminobenzoic acid amyl ester [e.g., p-(dimethylamino)benzoic acid, etc.] a dialkylamine such as bis(dialkylamino)diphenyl ketone or 4-(dimethylamino)diphenyl ketone such as ester or 4,4-bis(diethylamino)diphenyl ketone A light sensitizer such as a bisphenyl ketone or the like. Such photo sensitizers may be used singly or in combination of two or more kinds.

The proportion of the photosensitizer may be 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, still more preferably 10 to 100 parts by weight, based on 100 parts by weight of the above polymerization initiator.

(solvent)

Further, the curable composition may contain a solvent as needed. The solvent is not particularly limited, and examples thereof include hydrocarbons (for example, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene); and halogenated hydrocarbons. (e.g., dichloromethane, chloroform, 1,2-dichloroethane, etc.); ethers (e.g., dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran, dioxane, etc.); ketones (for example) a dialkyl ketone such as acetone or methyl ethyl ketone or a cyclic ketone such as cyclohexanone; an ester (for example, an acetate such as methyl acetate, ethyl acetate or butyl acetate); Esters (for example, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate (poly) alkanediol monoalkyl ether acetate, etc.); sulfoxides (eg dimethyl amide)碸, etc.); guanamines (such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.); nitriles (such as acetonitrile, etc.). These solvents may be used singly or in combination of two or more kinds.

(other additives)

Further, the curable composition may also contain conventional additives such as coloring agents, stabilizers (heat stabilizers, antioxidants, ultraviolet absorbers, etc.), fillers, antistatic agents, flame retardants, surfactants, plasticizers. , polymerization inhibitors, and the like. These additives may be used singly or in combination of two or more.

<hardened matter>

The curable composition of the present invention can be easily cured by imparting active energy (or active energy ray) to form a cured product. The aforementioned active energy system may use thermal energy and/or light energy (for example, ultraviolet rays, X-rays, etc.).

When heat treatment is performed by using heat energy, the heating temperature is, for example It may be 50 to 200 ° C, preferably 60 to 150 ° C, and more preferably 70 to 120 ° C.

Further, when the light irradiation with light (e.g., ultraviolet rays), the use of visible light energy is appropriately selected, for example, 50 to 10000mJ / cm ^2, and 70 to 8000mJ / cm ² preferably, 100 to 5000mJ / cm ² (for example, 500 to 3000 mJ/cm ² ) is preferable.

The shape of the cured product is not particularly limited, and may be a cured product having a three-dimensional structure (for example, a lens), or a cured product (or a cured film) of a two-dimensional structure (for example, a film or a sheet), or a cured product of a one-dimensional structure. (eg linear, rod, tubular, etc.).

The method for producing the cured product is not particularly limited. For example, a method for producing a cured product of a three-dimensional structure or a one-dimensional structure may be formed by molding or casting (injecting) the curable composition into a predetermined mold according to the shape of the cured product. , manufactured by hardening treatment (heating and/or light irradiation). Further, in the method for producing a cured product having a two-dimensional structure, for example, the curable composition may be applied to a substrate or a substrate (for example, an inorganic material such as a metal (for example, aluminum) or a ceramic (for example, titanium oxide, glass, quartz, or the like). An organic material such as a plastic (for example, a cycloolefin resin or a polycarbonate resin) or a porous body such as wood is formed into a film-form coating film (or a film), and then subjected to a curing treatment.

<Characteristics of hardening composition and cured product>

Since the curable composition of the present invention contains a polyfunctional (meth) acrylate and a first monofunctional (meth) acrylate represented by the above formula (1), it has a low viscosity and is excellent in handleability. Further, a cured product having a high refractive index can be formed.

The viscosity (temperature: 25 ° C) of the curable composition may be, for example, about 1 to 500,000 mPa ‧ (for example, 50 to 100,000 mPa ‧ s) depending on the type of the polyfunctional (meth) acrylate, etc., for example, may be selected from A range of about 1 to 50,000 mPa ‧ (for example, 5 to 25,000 mPa ‧ s), for example, 10 to 20,000 mPa ‧ s (for example, 20 to 10,000 mPa ‧ s), and 30 to 6000 mPa ‧ s (for example, 50 to 2000 mPa ‧ s) Preferably, it is preferably about 70 to 1000 mPa‧s (for example, 90 to 300 mPa‧s). Further, in the present invention, even a polyfunctional (meth) acrylate having an extremely high viscosity can be effectively reduced in viscosity by being combined with a first monofunctional (meth) acrylate. Therefore, the viscosity (temperature: 60 ° C) of the curable composition may be, for example, selected from the range of about 100 mPa ‧ s (for example, 0.1 to 50 Pa ‧ s), for example, 30 Pa ‧ s or less (for example, 1 to 27 Pa ‧ s), It is preferably about 25 Pa ‧ or less (for example, 10 to 23 Pa ‧ s). Further, the viscosity can be measured by a method or the like described in Examples to be described later.

The refractive index (pre-hardening refractive index) (temperature 25 ° C, wavelength 589 nm) of the curable composition before hardening is, for example, selected from the range of about 1.5 to 1.7, for example, 1.52 to 1.65 (for example, 1.53 to 1.62), and It is preferably 1.54 to 1.61, more preferably about 1.55 to 1.60.

In addition, the curable composition tends to have a higher refractive index by hardening, and a curable composition obtained by heating and mixing 3 parts by weight of the photopolymerization initiator is prepared by using 100 parts by weight of the polymerizable component. A refractive index (temperature: 25 ° C, wavelength: 589 nm) of a cured product (for example, a hardened product such as the method described in the Examples of Examples to be described later) which is hardened by ultraviolet irradiation (500 mJ/cm ² ), for example, may be selected from The range of about 1.5 to 1.7 is, for example, 1.52 to 1.66, and preferably 1.54 to 1.63, more preferably about 1.56 to 1.6. Further, the refractive index can be measured by a method or the like described in the examples below.

Example

Hereinafter, the present invention will be described in more detail based on the examples, but the present invention is not limited by the examples. The evaluation methods and raw materials are shown below.

(viscosity)

Using a TV-22 type viscometer (cone-plate type, "TVE-22L" manufactured by Toki Sangyo Co., Ltd.), according to the selectivity of the rotor for measuring viscosity (0.1:1°34'×R24, 0.7:3°×R7.7), The viscosity at 25 ° C was measured at a number of revolutions of 0.5 to 20 rpm.

Further, the viscosity at 60 ° C was measured using an E-type melt viscosity meter ("CAP2000+" manufactured by BROOK FIELD).

(refractive index)

The refractive index at a temperature of 25 ° C and 589 nm was measured using a multi-wavelength Abbe refractometer (manufactured by ATAGO Co., Ltd., DR-M2 <circulating constant temperature water tank 60-C3>).

(scratch resistance)

The surface tester HEIDON-14DR (manufactured by Shinto Scientific Co., Ltd.) was used, and the steel wool #0000 was installed at the front end of the pencil hardness tester, and the load was 250 g vertical load on the hardened material (50 mm × 15 mm × 2 mm), and then at a speed 1 mm/s was moved on the hardened material, and it was visually confirmed whether or not there was damage. After this operation was performed on the five cured materials, the scratch resistance was evaluated on the basis of the following.

○: All hardened materials were free from scratches.

△: Even if there is one scratched cured product, the initial recovery property can be confirmed.

×: There was a scratch and the recovery could not be confirmed.

(raw material)

BPEFA: 9,9-bis[4-(2-acryloxyethoxy)phenyl]anthracene, manufactured by Osaka Gas Chemical Company

BPEF-9EOA: manufactured by Osaka Gas Chemical Co., Ltd., with an average of 9 moles of ethylene oxide relative to 9,9-bis[4-(2-hydroxyethoxy)phenyl]indole 1 molar. Diacrylate of the adduct

UV-3200B: Made by Japan Synthetic Chemical Industry Co., Ltd., difunctional urethane acrylate

FA-321A: Diacrylate manufactured by Hitachi Chemical Co., Ltd., relative to 1 mole of bisphenol A, oxyethane with an average of 10 moles of addition addition.

Epoxy ester 3000A: Acrylic acid adduct of bisphenol A diglycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd.

KAYARAD UX-5000: Manufactured by Nippon Kasei Co., Ltd., 6-functional ester urethane acrylate

POA: 2-phenoxyethyl acrylate

NEOA: 2-(2-naphthyloxy)ethyl acrylate (prepared according to Synthesis Example 1 described later)

PTEA: manufactured by Miwon Speciality Chemical Co., Ltd., propylene Phenylthioethyl ester

OPPEOA: manufactured by Nippon Kasei Co., Ltd., o-phenylphenoxyethyl acrylate

Irgacure 184: Photopolymerization starter manufactured by BASF Japan AG.

(Synthesis Example 1)

In a 500 mL three-necked flask equipped with a Dean-Stark condensing and dehydrating unit, 29.4 g (0.26 mol) of 2-(2-naphthalenyloxy)ethanol (NEO), 24.6 g (0.34 mol) of acrylic acid, and 4-methoxyphenol were added. 0.56 g (0.0046 mol) and 256 g of toluene. The reaction system was replaced with nitrogen, and the temperature was raised to 60 ° C. After the components were dissolved, p-toluenesulfonic acid monohydrate and 6.24 g (0.033 mol) were added. After substituting nitrogen again, the temperature was raised to 115 ° C and refluxed for 3 hours.

The obtained solution was washed with 20% by weight of saline, and then neutralized with a 10% by weight aqueous sodium hydroxide solution and 20% by weight of saline solution, and it was confirmed that the aqueous layer had a pH of 10 or more. Then, 500 ppm of 4-methoxyphenol was further added to the organic layer to homogenize the solution. The solution was washed twice with 20% by weight saline, washed three times with distilled water, and after the aqueous layer was determined to have pH 7, the organic layer was concentrated and filtered over Celite. After filtration, the filtrate was concentrated to dryness to give a powdery white solid NEOA.

The NEOA has a refractive index (25 ° C, 589 nm) of 1.59 and a melting point of 62 ° C. Further, the melting point can be measured by a differential scanning calorimeter (DSC) ("EXSTAR DSC6220" manufactured by SII Nanotechnology Co., Ltd.).

(Comparative Examples 1 to 5 and Examples 1 to 5)

Each polymerizable component (as a multifunctional) in the ratio shown in Table 1 below The BPEFA of the (meth) acrylate and the POA or NEOA as a reactive diluent are mixed to prepare a curable composition, and the refractive index and viscosity before hardening are measured. The measurement results are shown in Table 1 and Figs. 1 to 2.

As is apparent from Table 1 and Figs. 1 to 2, in the examples, although a large amount of diluent was contained in the examples, a relatively high refractive index was maintained, and the viscosity was lowered to the same extent. Further, in the normal temperature (for example, about 25 ° C), the POA system is the same as the general reactive diluent, and is a transparent liquid, but NEOA is a powdery white solid which does not exhibit fluidity at all, and is mixed with the BPEFA of the viscous material. After it became liquid, it showed low viscosity, which was a very unexpected result.

Further, the equations shown in Figs. 1 and 2 indicate that the ratio of the respective reactive diluents is x, and the refractive index or viscosity is y, according to Comparative Examples 1 to 5 and Examples 1 to 5. The trend line of the measured value. Furthermore, the trend line is "Microsoft" manufactured by Microsoft Corporation. The Excel (Microsoft Office Standard 2010) calculation uses a linear trend for the refractive index system and a power trend for the viscosity. In order to make it easier to understand and compare the results obtained by the comparative examples and the examples, based on these trend lines (or the expression of the trend line), the preparation of the BPEFA and the reactive diluents is calculated for each reactive diluent. In the system, the blending ratio of the target refractive index (before curing) described in Table 2 below and the viscosity of the curable composition in the blending ratio are achieved. The results of the calculation are shown in Table 2 and Figure 3.

As can be seen from Tables 2 and 3, in the BPEFA/NEOA blending system, the viscosity of the curable composition at which the target refractive index is achieved is low, and it is particularly known that the target refractive index is larger and the viscosity is higher than that of the BPEFA/POA blending system. The difference has become enormous. Further, it has been found that in the BPEFA/NEOA blending system, the ratio of the reactive diluent is large in the blending ratio of the target refractive index, and the ratio of use of the BPEFA can be reduced.

(Comparative Example 6 and Examples 6 to 12)

Each of the polymerizable components was mixed at a ratio shown in the following Table 3 to prepare a curable composition, and the viscosity and the refractive index (before curing) were measured.

To 100 parts by weight of each of the curable composition (polymerizable component) prepared, 3 parts by weight of a photopolymerization initiator was added, and the mixture was heated and melted. Each of the obtained curable compositions was applied onto a TAC (cellulose acetate) film to a thickness of 200 μm using a thin coater, and UV irradiation (500 mJ/cm ² ) was performed once to prepare a cured product. Each of the obtained cured products was in the form of a film having a film thickness of 100 μm, and the cured product was used to measure the refractive index (after curing).

At the same time, the metal mold is placed on the glass to which the release agent is attached by spraying, and each of the hardening compositions in which the photopolymerization initiator is mixed is injected onto the mold to sandwich the glass treated with the same treatment. The metal mold was repeatedly irradiated with UV (500 mJ/cm ² ) four times to prepare a cured product having a size of 50 mm × 15 mm × 2 mm. The scratch resistance was measured using the obtained cured product.

The blending ratio and evaluation results are shown in Table 3. Further, the numbers in () in Table 3 mean the parts by weight of the respective constituent components in the curable composition (hereinafter, Table 4 is also the same).

As is clear from Table 3, although Comparative Example 6 is a high refractive index, since the viscosity is high, the workability is insufficient, and the operability and the high refractive index cannot be achieved. On the other hand, in Example 6, the scratch resistance was maintained while having excellent workability and high refractive index.

Further, in Examples 7 to 8, since the soft difunctional (meth) acrylate is contained, or the operability is maintained, and the high refractive index and scratch resistance are combined, the balance of the characteristics is also Excellent. In particular, UV-3200B mixed in Example 7 exhibited a relatively high viscosity even at a viscosity of 40,000 to 60,000 mPa·s at 60 ° C.

Further, in Examples 9 to 12, a combination of another monofunctional acrylate (a second monofunctional (meth) acrylate containing a sulfur atom or a third monofunctionality represented by the above formula (3) (A Base) Acrylate) for better operability and high refractive index. In particular, in the tenth embodiment, not only high operability and high refractive index but also scratch resistance can be improved.

(Comparative Examples 7 to 9 and Examples 13 to 15)

Each of the polymerizable components was mixed at a ratio shown in the following Table 4 to prepare a curable composition, and the viscosity (temperature: 25 ° C) and the refractive index (before curing) were measured. Further, in Comparative Examples 7 to 8 and Examples 13 to 14, the viscosity of the curable composition at 60 ° C was measured together.

At the same time, a cured product of each of the prepared curable compositions (a film-like cured product having a thickness of 100 μm and a cured product having a size of 50 mm × 15 mm × 2 mm) was produced by the same method as Comparative Example 6 and Examples 6 to 12. , using these hardened materials, measuring the refractive index (after hardening) and scratch resistance Sex. The blending ratio and the evaluation results are shown in Table 4.

As is clear from the results of Table 4, in all of Examples 13 to 15, the addition of 10% by weight of NEOA can greatly improve the workability and also increase the refractive index. Further, Examples 13 and 15 using ethyl urethane (meth) acrylate were also excellent in scratch resistance.

[Industrial availability]

The curable composition of the present invention is excellent in properties such as low viscosity, high refractive index, and scratch resistance, and thus can be used in various applications. For example, it can be suitably used for: 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, etc.), and a coating agent (for example, LED ( a lens for optical coating such as a coating material for a light-emitting diode or a hard coating agent, or a lens (for example, a photographing lens (for example, a photographic lens for a DVD (digital versatile disc)), or a microlens (for example, a liquid crystal projector) a microlens or the like, an eyeglass lens or the like, a polarizing film (for example, a polarizing film for a liquid crystal display), an antireflection film (or an antireflection film such as an antireflection film for a display device, etc.), a film for a touch panel, and a flexible film Film for a substrate, film for display [for example, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction type electronic emission device display), FED (electric field emission display), NED (nano-emitting display), cathode ray tube (Braun tube), electronic paper (such as thin display) film (filter, protective film, etc.), etc., fuel cell film, optical fiber, optical waveguide , hologram, etc. In particular, the curable composition of the present invention is suitable for use in optical materials, and the shape of such an optical material may be, for example, a film (or a sheet), a plate, a lens, a tube, or the like.

Further, the first monofunctional (meth) acrylate of the present invention can also be used as a low viscosity agent for lowering the viscosity of the polyfunctional (meth) acrylate.

Since the picture in this case is a test chart, it is not a representative figure of this case. Therefore, there is no designated representative map in this case.

Claims (19)

A curable composition comprising: a polyfunctional (meth) acrylate; and a first monofunctional (meth) acrylate represented by the following formula (1); Wherein R ¹ represents a hydrogen atom or a methyl group; R ² is a linear or branched alkylene group; R ³ is an alkyl group; Ar ¹ is a condensed polycyclic aromatic hydrocarbon ring; a is an integer from 1 to 4; b is 0. Or an integer of 1 or more. The sclerosing composition according to claim 1, wherein the first monofunctional (meth) acrylate is a (meth)acrylic condensed polycyclic C _10-14 aryloxy C _2-4 alkyl ester. . The sclerosing composition according to claim 1 or 2, wherein the polyfunctional (meth) acrylate comprises a (meth) acrylate selected from the group consisting of the oxime skeleton represented by the following formula (2). At least one high viscosity multi-functional group of alicyclic or aromatic epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate (meth) acrylate; Wherein rings Z ¹ and Z ² and rings Z ³ and Z ⁴ represent an arene ring; R ^4a and R ^4b and R ^5a and R ^{5b are} each the same or different non-reactive substituent; R ^6a and R ^6b are a straight or branched alkyl group; R ^7a and R ^7b are a hydrogen atom or a methyl group; k1 and k2 are an integer of 0 or more; m1 and m2 are an integer of 0 or more; n1 and n2 are 0 or 1. The above integer; p1 and p2 are integers of 1 or more. The sclerosing composition according to claim 3, wherein the polyfunctional (meth) acrylate is at least a (meth) acrylate containing an anthracene skeleton represented by the formula (2), and a urethane Ester (meth) acrylate. The curable composition according to claim 3 or 4, which further comprises a di(meth)acrylate of an alkylene oxide adduct of a biphenol or a bisphenol. The hardenable composition according to any one of claims 3 to 5, wherein in the formula (2), the rings Z ¹ and Z ² and the rings Z ³ and Z ^{4 are} each a benzene ring or a naphthalene ring; K1 and k2 are 0; R ^5a and R ^5b are C _1-6 alkyl or C _6-10 aryl; m1 and m2 are 0 or an integer of 1 to 2; R ^6a and R ^6b are linear C _2-6 An alkyl group; n1 and n2 are integers of 1 to 10; p1 and p2 are 1; and the aromatic epoxy (meth) acrylate is an aromatic epoxy group represented by the following formula (3) (methyl group) )Acrylate; Wherein R ⁸ each represents a hydrogen atom, an alkyl group or an aryl group, and two R ⁸ groups may be bonded to each other to form a hydrocarbon ring which may have an alkyl group; R ^9a and R ^{9b are} each an alkyl group or an aryl group; ^10a and R ^10b are a linear or branched alkylene group; R ^11a and R ^11b are a hydrogen atom or a methyl group; q1 and q2 are integers from 0 to 4; r1 and r2 are integers of 0 or more; t is 0. Or 1; ethyl urethane (meth) acrylate is polyester urethane (meth) acrylate, polyether urethane (meth) acrylate or polycarbonate urethane (Meth) acrylate. The curable composition according to any one of claims 1 to 6, wherein the viscosity of the polyfunctional (meth) acrylate (at 25 ° C) is 3,000 mPa ‧ s or more. The curable composition according to any one of claims 1 to 7, wherein the ratio of the polyfunctional (meth) acrylate to the first monofunctional (meth) acrylate is the former/the latter (weight ratio) = 80/20 to 5/95. The curable composition according to any one of claims 4 to 8, wherein the (meth) acrylate containing an anthracene skeleton and the ethyl urethane (meth) acrylate represented by the formula (2) The ratio is the former/the latter (weight ratio) = 50/50 to 99/1. The curable composition according to any one of claims 5 to 9, wherein the high viscosity polyfunctional (meth) acrylate and the biphenol or bisphenol alkylene oxide adduct are the second The ratio of (meth) acrylate is the former/the latter (weight ratio) = 50/50 to 99/1. The sclerosing composition according to any one of claims 1 to 10, which further comprises an alkylthio (meth) acrylate selected from the group consisting of At least one sulfur-containing second monofunctional group of the group consisting of aryl aryl acrylate, aryl alkyl thioalkyl (meth) acrylate, and aryl thioalkyl (meth) acrylate ( Methyl) acrylate; and the ratio of the first monofunctional (meth) acrylate to the second monofunctional (meth) acrylate is the former/the latter (weight ratio) = 80/20 to 20/80. The curable composition according to any one of claims 1 to 11, further comprising a third monofunctional (meth) acrylate represented by the following formula (4); Wherein R ¹² represents a hydrogen atom or a methyl group; R ¹³ is an alkylene group; R ¹⁴ is an alkyl group; Ar ² is a benzene ring or a ring-condensed aromatic hydrocarbon ring; c is an integer of 1 to 4; and d is 0 or more. The ratio of the first monofunctional (meth) acrylate to the third monofunctional (meth) acrylate is the former/the latter (weight ratio) = 80/20 to 20/80. The curable composition according to any one of claims 1 to 12, further comprising a polymerization initiator. A cured product obtained by hardening a curable composition according to any one of claims 1 to 13. A method of producing a cured product according to claim 14, wherein the curable composition according to any one of claims 1 to 13 is subjected to active energy to be hardened. A low viscosity agent used to make polyfunctional (meth) acrylates low A viscosity-lower low viscosity agent containing the first monofunctional (meth) acrylate described in claim 1 or 2. The low-viscosity agent according to claim 16, wherein the second monofunctional (meth) acrylate described in claim 11 is further included. A method for reducing the viscosity of a polyfunctional (meth) acrylate by adding a first monofunctionality (methyl) as described in claim 1 or 2 to a polyfunctional (meth) acrylate. )Acrylate. A monofunctional (meth) acrylate which is the first monofunctional (meth) acrylate described in claim 1 or 2.