WO2013022065A1

WO2013022065A1 - Multifunctional (meth)acrylate having fluorene skeleton and curable composition containing same

Info

Publication number: WO2013022065A1
Application number: PCT/JP2012/070351
Authority: WO
Inventors: 渓子三ノ上; 佐季子福西; 信輔宮内; 長嶋　太一; 光宏服部; 祐一郎安田
Original assignee: 大阪ガスケミカル株式会社
Priority date: 2011-08-11
Filing date: 2012-08-09
Publication date: 2013-02-14
Also published as: TW201311744A; JP6158084B2; TWI530508B; CN103890018A; JPWO2013022065A1; KR20140049584A; KR101868665B1; CN103890018B

Abstract

Provided is a fluorene skeleton-containing multifunctional (meth)acrylate which has a good balance between excellent scratch resistance and high refractive index. In formula (1), the average of m1 + m2 is regulated to 8.5-17. (In the formula, each of R^1a and R^1b represents a non-radically polymerizable substituent; each of R^2a and R^2b represents an alkylene group; each of R^3a and R^3b represents a hydrogen atom or a methyl group; each of R^4a and R^4b represents a non-radically polymerizable substituent; each of k1 and k2 represents an integer of 0-4; each of m1 and m2 represents an integer of 0 or more; each of n1 and n2 represents an integer of 1-4; and each of p1 and p2 represents an integer of 0-4. In this connection, n1 + p1 ≤ 5 and n2 + p2 ≤ 5.)

Description

Multifunctional (meth) acrylate having fluorene skeleton and curable composition thereof

The present invention relates to a novel multifunctional (meth) acrylate having scratch resistance, a curable composition containing this multifunctional (meth) acrylate, and a cured product thereof.

As a curable material that can be used as an optical material, a polyfunctional (meth) acrylate having a fluorene skeleton (particularly a 9,9-bisarylfluorene skeleton) that is a material having a high refractive index and heat resistance (for example, 9 , 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene and the like) have been proposed.

However, such a polyfunctional (meth) acrylate having a fluorene skeleton is not sufficient in scratch resistance (or flexibility) in a cured product even if a high refractive index can be realized. In addition, the viscosity is high and handling properties are often insufficient.

Regarding the structure of the polyfunctional (meth) acrylate having a fluorene skeleton, for example, JP-A-2007-91870 (Patent Document 1) discloses a polyfunctional (meth) acrylate as a constituent of the polymerizable composition. Following formula (1)

(In the formula, R ^1a , R ^1b , R ^2a and R ^2b represent a substituent, R ^3a and R ^3b represent an alkylene group, R ^4a and R ^4b represent a hydrogen atom or a methyl group, and k 1 and k 2 represent Identical or different and represent an integer of 0 to 4, m1 and m2 are identical or different and represent an integer of 0 to 3, n1 and n2 are identical or different and represent an integer of 0 or 1 and p1 and p2 are the same Or, it is different and represents an integer of 1 to 4, where m1 + p1 and m2 + p2 are each an integer of 1 to 5)
The compound represented by these is disclosed.

In Examples of this document, only an example in which n1 and n2 corresponding to the number of oxyalkylene groups (R ^3a , R ^3b ) (or the number of added moles of alkylene oxide) in Formula (1) is 1 is described. Has been. However, such a polyfunctional (meth) acrylate is inferior in scratch resistance.

JP 2007-91870 A (Claims, Examples)

Accordingly, an object of the present invention is to provide a multifunctional (meth) acrylate having a novel fluorene skeleton having scratch resistance, a curable composition containing the multifunctional (meth) acrylate, and a cured product thereof. is there.

Another object of the present invention is to provide a polyfunctional (meth) acrylate having a novel fluorene skeleton capable of achieving both a high refractive index and scratch resistance, a curable composition containing this polyfunctional (meth) acrylate, and curing thereof. To provide things.

Still another object of the present invention is to provide a polyfunctional (meth) acrylate having a novel fluorene skeleton capable of balancing handling and curability in a well-balanced manner, a curable composition containing the polyfunctional (meth) acrylate, and its It is to provide a cured product.

In conventional polyfunctional (meth) acrylates having a fluorene skeleton, the number of additions of oxyalkylene groups is defined in a wide range, but its significance is not known. In reality, as described above, from the viewpoint of high refractive index and hard coat properties, which are desired characteristics, there are no known examples in which the number of oxyalkylene groups added is increased. .

Under such circumstances, the present inventors have intensively studied to achieve the above problems, and as a result, surprisingly, excellent scratch resistance can be imparted by setting the number of oxyalkylene groups added within a specific range. Moreover, the expected decrease in the refractive index by increasing the number of oxyalkylene groups added and the characteristics that are usually considered difficult to achieve at the same time, that is, excellent scratch resistance and high refractive index, are at a high level. In addition, a polyfunctional (meth) acrylate that can be realized by the above-mentioned method is obtained, and such a polyfunctional (meth) acrylate has a relatively low viscosity and good curability, and further improves handling properties (low The present inventors have found that a curable composition capable of maintaining excellent scratch resistance and high refractive index can be obtained even when used in combination with other monomers, for example, for increasing the viscosity.

That is, the polyfunctional (meth) acrylate of the present invention has the following formula (1)

(Wherein R ^1a and R ^1b are non-radically polymerizable substituents, R ^2a and R ^2b are alkylene groups, R ^3a and R ^3b are hydrogen atoms or methyl groups, and R ^4a and R ^4b are non-radical polymerizable substituents. , K1 and k2 are each an integer of 0 to 4, m1 and m2 are each an integer of 0 or more, n1 and n2 are each an integer of 1 to 4, and p1 and p2 are each an integer of 0 to 4. However, n1 + p1 ≦ 5, n2 + p2 ≦ 5.)
In the above formula (1), the average value of m1 + m2 is 8.5 to 17 polyfunctional (meth) acrylate.

In the above formula (1), n1 and n2 may each be 1, m1 and m2 may each be 1 or more, and the average value of m1 + m2 may be 8.5 to 16.5 (for example, 9 to 15) . In particular, in the formula (1), the average value of m1 + m2 may be 9.5 to 11.5 (for example, 10 to 11).

In the present invention, the polyfunctional (meth) acrylate represented by the formula (1) and the following formula (2)

(In the formula, R ^5a and R ^5b represent a hydrogen atom or a (meth) acryloyl group, and R ^1a , R ^1b , R ^2a , R ^2b , R ^4a , R ^4b , k1, k2, m1, m2, n1, n2, p1, p2 are the same. However with ^the, at least one of ^{R 5a} and ^{R 5b} is (meth) acryloyl ^groups, all of ^{R 5a} and ^{R 5b} are (meth) never becomes acryloyl group.)
The polyfunctional (meth) acrylate composition containing the compound represented by these is included.

In addition, such a polyfunctional (meth) acrylate composition has the following formula (A)

(In the formula, R ^1a , R ^1b , R ^2a , R ^2b , R ^4a , R ^4b , k1, k2, m1, m2, n1, n2, p1, and p2 are the same as above.)
It can obtain by making the compound (polyhydroxy compound) represented by and (meth) acrylic acid component react.

In the polyfunctional (meth) acrylate composition, the ratio of the compound represented by the formula (2) is represented by, for example, the polyfunctional (meth) acrylate represented by the formula (1) and the formula (2). The area ratio (area ratio or area%) by high performance liquid chromatography may be about 5 to 30% with respect to the total amount of the compound. Typically, in Formula (1) and Formula (2), n1 and n2 are each 1, m1 and m2 are each 1 or more, and the average value of m1 + m2 is 9 to 15, and Formula (2) The ratio of the compound represented by formula (1) is the ratio of the area by high performance liquid chromatography (area ratio) to the total amount of the polyfunctional (meth) acrylate represented by formula (1) and the compound represented by formula (2). Or area%) may be about 8 to 20%.

The multifunctional (meth) acrylate (or multifunctional (meth) acrylate composition, hereinafter the same) of the present invention has a low viscosity despite being a high refractive index. For example, at 25 ° C., the refractive index ( 589 nm) may be 1.53 or more, and the viscosity (25 ° C.) may be 20000 mPa · s or less.

The present invention includes a curable composition containing a curable component including the polyfunctional (meth) acrylate or the polyfunctional (meth) acrylate composition. In such a curable composition, the curable component may be composed only of a polyfunctional (meth) acrylate, and may further contain a non-fluorene-based monofunctional monomer (that is, multifunctional). (Meth) acrylate and non-fluorene-based monofunctional monomer may be used).

The non-fluorene monofunctional monomer may contain a monofunctional (meth) acrylate, typically a branched alkyl (meth) acrylate, an alicyclic (meth) acrylate, or an aromatic (meth) acrylate. And at least one monofunctional (meth) acrylate selected from sulfur-containing (meth) acrylates. In particular, the non-fluorene-based monofunctional monomer may contain at least one monofunctional (meth) acrylate selected from aromatic (meth) acrylate and sulfur-containing (meth) acrylate.

Non-fluorene monofunctional monomers are aryl (meth) acrylate, aralkyl (meth) acrylate, aryloxyalkyl (meth) acrylate, aryloxy (poly) alkoxyalkyl (meth) acrylate, alkylaryloxy (poly) alkoxy Monofunctional (meth) acrylate (A) selected from alkyl (meth) acrylate, arylthio (meth) acrylate, aralkylthio (meth) acrylate, and arylthioalkyl (meth) acrylate, and arylaryloxyalkyl (meth) Selected from acrylates, arylaryloxy (poly) alkoxyalkyl (meth) acrylates, and mono (meth) acrylates of bisphenols or their alkylene oxide adducts Functional (meth) acrylate (B) and may contain. In such a curable composition, the ratio of the monofunctional (meth) acrylate (A) to the monofunctional (meth) acrylate (B) is, for example, the former / the latter (weight ratio) = 97/3 to 30 It may be about / 70.

In the curable composition containing a non-fluorene monomer, the ratio of the polyfunctional (meth) acrylate (or the polyfunctional (meth) acrylate composition) to the non-fluorene monofunctional monomer is the former / the latter ( (Weight ratio) = 99/1 to 15/85, in particular 80/20 to 20/80 (for example 75/25 to 20/80). In the present invention, even when mixed with a non-fluorene monomer, the scratch resistance can be maintained at a high level.

The curable component may further contain a non-fluorene bifunctional (meth) acrylate. In such a curable composition, the ratio of the polyfunctional (meth) acrylate (or polyfunctional (meth) acrylate composition) to the non-fluorene bifunctional (meth) acrylate is, for example, the former / the latter (Weight ratio) may be about 99/1 to 50/50.

The curable component may further contain another fluorene-based monomer, for example, a compound represented by the following formula (3).

(In the formula, R ⁶ is a direct bond or a divalent hydrocarbon group, R ⁷ is a substituent, m 3 is an integer of 0 or more, q is 0 or 1, R ^1a , R ^1b , R ^2a , R ^3a , k1 and k2 are the same as above.)
In such a curable composition, the ratio between the polyfunctional (meth) acrylate (or polyfunctional (meth) acrylate composition) and the compound represented by the formula (3) is the former / the latter (weight ratio). ) = About 95/5 to 30/70.

The present invention includes a cured product obtained by curing the curable composition. Since such a cured product has a high refractive index and excellent scratch resistance, the cured product for optical use that requires them, such as a prism sheet (for example, a prism sheet for a liquid crystal display) A cured product (or a touch panel sheet) for use in a prism sheet) or a touch panel (for example, a liquid crystal display touch panel) may be used.

The present invention further includes a method for producing the cured product in which active energy is applied to the curable composition to be cured.

In the present invention, the scratch resistance of a cured product containing a polyfunctional (meth) acrylate having a fluorene skeleton can be improved. Therefore, the present invention includes the following formula (1A)

(Wherein R ^1a and R ^1b are non-radically polymerizable substituents, R ^2a and R ^2b are alkylene groups, R ^3a and R ^3b are hydrogen atoms or methyl groups, and R ^4a and R ^4b are non-radical polymerizable substituents. , K1 and k2 are each an integer of 0 to 4, m1 and m2 are each an integer of 0 or more, n1 and n2 are each an integer of 1 to 4, and p1 and p2 are each an integer of 0 to 4. However, n1 + p1 ≦ 5, n2 + p2 ≦ 5.)
Is a method for improving or improving the scratch resistance of a cured product obtained by curing a curable composition comprising a curable component composed of a polyfunctional (meth) acrylate represented by formula (1A): m1 + m2 A method for improving or improving the scratch resistance is also included, in which the average value is adjusted to 8.5 to 17.

In this method, the scratch resistance may be improved or improved while the refractive index (589 nm) at 25 ° C. is 1.53 or more and the viscosity (25 ° C.) is 20000 mPa or less.

In the present specification, “polyfunctional (meth) acrylate represented by formula (1)” means “aggregate” or “molecular aggregate” of compounds belonging to the category of formula (1), and m1 + m2 Such a value may mean an average value in such an “aggregate” or “molecular aggregate”.

In the present invention, scratch resistance can be imparted to a polyfunctional (meth) acrylate having a fluorene skeleton. Moreover, such a polyfunctional (meth) acrylate can maintain a high refractive index, and can achieve both a high refractive index and scratch resistance. In particular, such excellent scratch resistance and high refractive index are not unexpectedly damaged (or high levels) even in combination with other curable monomers (for example, non-fluorene (meth) acrylate). Therefore, a curable composition that can realize scratch resistance and high refractive index can be easily formed according to a desired viscosity (handling property). Moreover, in the polyfunctional (meth) acrylate of this invention, handling property can be improved (viscosity reduction), without impairing sclerosis | hardenability, and it can be compatible with handling property and sclerosis | hardenability.

<Multifunctional (meth) acrylate>
The polyfunctional (meth) acrylate (polyfunctional (meth) acrylate aggregate) of the present invention has the following formula (1):

(Wherein R ^1a and R ^1b are non-radically polymerizable substituents, R ^2a and R ^2b are alkylene groups, R ^3a and R ^3b are hydrogen atoms or methyl groups, and R ^4a and R ^4b are non-radical polymerizable substituents. , K1 and k2 are each an integer of 0 to 4, m1 and m2 are each an integer of 0 or more, n1 and n2 are each an integer of 1 to 4, and p1 and p2 are each an integer of 0 to 4. However, n1 + p1 ≦ 5, n2 + p2 ≦ 5.)
In the above formula (1), the average value of m1 + m2 is a polyfunctional (meth) acrylate represented by (or a compound represented by the above formula (1) or an aggregate of polyfunctional (meth) acrylates). The polyfunctional (meth) acrylate is adjusted to a specific range with respect to the entire polyfunctional (meth) acrylate (aggregate).

In the formula (1), the groups R ^1a and R ^1b may be non-radical polymerizable groups such as cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), carboxyl group, hydrocarbon, etc. Group [for example, alkyl group, aryl group (C _6-10 aryl group such as phenyl group) and the like], and the like. Examples of the alkyl group include C _1-12 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-8 alkyl group, particularly a C _1-1 such as a methyl group). ₄ alkyl group) and the like. When k1 or k2 is plural (2 to 4), the plural groups R ^1a or R ^1b may be different from each other or the same. In addition, the groups R ¹ and R ^1b may be the same or different. Moreover, the bonding position (substitution position) of the groups R ^1a and R ^1b is not particularly limited, and examples thereof include the 2nd, 7th, 2nd and 7th positions of the fluorene ring. The preferred substitution number k1 or k2 is 0 to 1, in particular 0. The substitution numbers k1 and k2 may be the same or different.

In the above formula (1), examples of the alkylene group represented by the groups R ^2a and R ^2b include C _2-6 alkylene such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group. A group, preferably a C _2-4 alkylene group, more preferably a C _2-3 alkylene group, particularly an ethylene group. When m1 or m2 is 2 or more, the alkylene group may be composed of different alkylene groups, and usually may be composed of the same alkylene group. Further, the groups R ² and R ^2b may be the same or different and may usually be the same. In addition, m1 and m2 which are the substitution numbers of the oxyalkylene group corresponding to these alkylene groups may be the same or different.

The number of oxyalkylene groups (OR ^2a and OR ^2b ) (addition moles) m1 and m2 may be any integers of 0 or more, for example, selected from the range of about 0 to 30 (eg, 0 to 25). Usually 1 or more (eg 1 to 22), preferably 2 or more (eg 2 to 20), more preferably 2 to 15 (eg 2 to 10), especially 3 to 8 (eg 3 to 7). ) Degree.

Here, in the polyfunctional (meth) acrylate of the present invention, the total of m1 and m2 with respect to the entire polyfunctional (meth) acrylate (molecular assembly of the compound represented by the formula (1)) is within a specific range. adjust. The sum of m1 and m2 (m1 + m2) can be selected from the range of 8.5 to 17 (for example, 8.5 to 16.7) as an average (arithmetic average or arithmetic average). 5 to 16.5 (eg, 8.6 to 16.3), preferably 8.8 to 16.2 (eg, 8.9 to 16), and more preferably 9 to 15.8 (eg, 9.1). To 15.6), especially 9.2 to 15.5 (eg 9.3 to 15.2), usually 9 to 15 (eg 9 to 14.5, preferably 9.3 to 14). May be. In particular, the average of m1 + m2 is, for example, 9 to 13 (eg, 9.3 to 12.5), preferably 9.5 to 12 (eg, 9.7 to 11.7), and more preferably 10 to 11. It may be about 5 (for example, 10.2 to 11.3), and usually about 9.5 to 11.5 (for example, 10 to 11). If the value of m1 + m2 is too large, a cured product having a sufficient refractive index cannot be obtained.

Each value of m1 and m2 can be selected from an average (arithmetic average or arithmetic average), for example, in the range of 4.1 to 8.5 (eg, 4.2 to 8.4). 4.3 to 8.3 (eg 4.3 to 8.2), preferably 4.4 to 8.1 (eg 4.4 to 8), more preferably 4.5 to 7.9 (eg 4.5 to 7.8), particularly 4.6 to 7.8 (for example, 4.8 to 7.6).

The average (arithmetic average or arithmetic average) can be measured by a conventional method, and the measurement method is not particularly limited. For example, a polyhydroxy compound (a compound represented by the formula (A) described below) described below can be used. At the time of synthesis, it is easily obtained as an arithmetic average or arithmetic average value from the ratio of the amount of the starting compound (compound represented by the formula (B) described later) and the amount of the consumed alkylene oxide. be able to.

In the formula (1), the groups R ^3a and R ^3b may be different from each other, but they may usually be the same group (that is, a hydrogen atom or a methyl group).

In the formula (1), the group [CH ₂ ═C (R ^3a ) —CO— (OR ^2a ) _m1 —O—] or [CH ₂ ═C (R ^3b ) —CO— (OR ^2a ) _m1 —O— ] (Sometimes referred to as a (meth) acryloyl group-containing group or the like), the number of substitutions n1 and n2 may be 1 to 4, for example, 1 to 3, preferably 1 to 2, particularly 1. Also good. The numbers of substitutions n1 and n2 may be the same or different and are usually the same in many cases. Further, the substitution position of the (meth) acryloyl group-containing group is not particularly limited, and it may be substituted at an appropriate substitution position on the benzene ring. For example, the (meth) acryloyl group-containing group may be substituted at an appropriate position (especially at least the 4th position) of the 2-6th position of the benzene ring substituted at the 9th position of fluorene.

The polyfunctional (meth) acrylate is typically a compound in which n1 = n2 = 1 and the (meth) acryloyl group-containing group is substituted at the 4-position of the benzene ring substituted at the 9-position of fluorene, that is, The compound represented by a formula may be sufficient.

(In the formula, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , R ^4a , R ^4b , k1, k2, m1, m2, p1, and p2 are the same as above.)
The substituents R ^4a and R ^4b are usually non-radically polymerizable substituents such as alkyl groups (for example, C _1-12 alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl groups, preferably _{C 6,} such as _{C 5-8} cycloalkyl group etc.), an aryl group (e.g., phenyl group, tolyl group, xylyl group, naphthyl group, such as _{C 1-8} an alkyl group), a cycloalkyl group (cyclohexyl group is _-10 and aryl group), a hydrocarbon group such as an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group); an alkoxy group (methoxy group, such as an ethoxy group _{C 1- 8} alkoxy groups), cycloalkoxy groups (C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups), aryloxy A group such as a group (C _6-10 aryloxy group such as phenoxy group), an aralkyloxy group (C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group) or the like —OR ⁵ [wherein R ⁵ Represents a hydrocarbon group (such as the hydrocarbon group exemplified above). A group such as an alkylthio group (such as a C _1-8 alkylthio group such as a methylthio group) —SR ⁵ (wherein R ⁵ is as defined above); an acyl group (such as a C _1-6 acyl group such as an acetyl group) ); Alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); nitro group; cyano group; substituted amino group (for example, And a dialkylamino group such as a dimethylamino group).

Preferred groups R ^4a and R ^4b include, for example, a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, , C _6-10 aryl group), aralkyl group (eg C _6-8 aryl-C _1-2 alkyl group)], alkoxy group (C _1-4 alkoxy group etc.) and the like. In particular, R ^4a and R ^4b are preferably an alkyl group [C _1-4 alkyl group (especially methyl group) etc.], an aryl group [eg C _6-10 aryl group (especially phenyl group)], etc. .

In addition, when p1 or p2 is plural, the groups R ^4a or R ^4b may be different from each other or the same. The groups R ^4a and R ^4b may be the same or different. Further, the preferred substitution numbers p1 and p2 may be, for example, 0 to 3, preferably 0 to 2, and more preferably 0 to 1, respectively. The substitution numbers p1 and p2 may be the same or different from each other, and may be usually the same.

[Production method of polyfunctional (meth) acrylate]
Although polyfunctional (meth) acrylate is not specifically limited, Usually, following formula (A)

(Method for producing polyhydroxy compound)
The polyhydroxy compound (compound represented by the formula (A)) is not particularly limited, but usually a compound represented by the following formula (B) and an alkylene oxide or alkylene carbonate corresponding to the group OR ^2a or the group OR ^2b It can obtain by making it react. In such a method, a polyhydroxy compound (an assembly of polyhydroxy compounds) having a range of values (or molecular weights) of m1, m2, and m1 + m2 in the formula (1) is usually obtained.

(Wherein, x1 and x2 represent 0 or 1, and R ^1a , R ^1b , R ^2a , R ^2b , R ^4a , R ^4b , k1, k2, n1, n2, p1, and p2 are the same as described above.)
Examples of the polyhydroxy compound include conventional methods [for example, a method of reacting 9-fluorenone and phenol in the presence of an acid catalyst (for example, the method described in Patent Document 1), 9-fluorenone and phenoxy. Those synthesized by a method of reacting with alkanols (for example, 2-phenoxyethanol etc.) may be used, or commercially available products may be used.

In addition, in the formula (B), when a compound where x1 = x2 = 1 is used, it is easy to efficiently suppress the coloring of the polyhydroxy compound (moreover, polyfunctional (meth) acrylate).

Specific polyhydroxy compounds include, for example, 9,9-bis (hydroxyphenyl) fluorene [eg, 9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis (alkyl-hydroxyphenyl) fluorene [For example, 9,9-bis (mono or di-C) such as 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene _1-4 alkyl-hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxyphenyl) fluorene [for example, 9,9-bis (9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, etc. mono- or _{di-C 6-10} aryl - hydroxyphenyl) fluorene], 9,9-bis (polyhydroxyalkyl A compound in which x1 = x2 = 0 in the above formula (B), such as enyl) fluorene [eg, 9,9-bis (3,4-dihydroxyphenyl) fluorene, etc.]; 9,9-bis (hydroxyalkoxyphenyl) In the above formula (B) such as fluorene {eg, 9,9-bis (hydroxyC _2-4 alkoxyphenyl) fluorene such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene}, x1 = Examples thereof include compounds where x2 = 1.

^Examples of the alkylene oxide corresponding to the group OR ^2a or the group OR ^2b include C _2-6 alkylene oxide such as ethylene oxide, propylene oxide and butylene oxide, preferably C _2-4 alkylene oxide, more preferably C _2-3 alkylene oxide ( In particular, ethylene oxide) may be mentioned. ^Examples of the alkylene carbonate corresponding to the group OR ^2a or the group OR ^2b include C _2-6 alkylene carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, preferably C _2-4 alkylene carbonates, more preferably C _2-3 alkylene carbonates. (Especially ethylene carbonate). When alkylene oxide or alkylene carbonate is reacted, an oxyalkylene unit (group OR ^2a or group OR ^2b ) can be introduced through the hydroxyl group of the compound represented by the formula (B). When alkylene carbonate is used, oxyalkylene units are introduced by decarboxylation after addition of alkylene carbonate.

The amount of alkylene oxide or alkylene carbonate corresponding to group ^{OR 2a} or a group ^{OR 2b} can be adjusted according to the value of the m1 in formula (1), m2, m1 + m2. For example, in theory, in the formula (B), with respect to 1 mol of the compound where x1 = x2 = 0, about (m1 + m2) × (n1 + n2) mol of alkylene oxide or alkylene carbonate may be used. In the formula (B), with respect to 1 mole of the compound where x1 = x2 = 1, about (m1 + m2-2) × (n1 + n2) mole of alkylene oxide or alkylene carbonate may be used. Specifically, in the formula (B), 8.5 to 17 mol, preferably 8.5 to 16.5 mol, per 1 mol of the compound where n1 = n2 = 1 and x1 = x2 = 0. More preferably, about 9 to 15 moles may be used. In the formula (B), 6.5 to 15 moles per 1 mole of the compound where n1 = n2 = 1 and x1 = x2 = 1, Preferably about 6.5 to 14.5 mol, more preferably about 7 to 13 mol may be used.

The reaction between the compound represented by the formula (B) and alkylene oxide or alkylene carbonate may be carried out in the absence of a catalyst, but can usually be carried out in the presence of a catalyst. Examples of the catalyst include a base catalyst and an acid catalyst, and usually a base catalyst can be used. Base catalysts include metal hydroxides (alkali metals such as sodium hydroxide or alkaline earth metal hydroxides), metal carbonates (alkali metals such as sodium carbonate or alkaline earth metal carbonates, sodium hydrogen carbonate, etc.) Inorganic bases such as alkali metals or alkaline earth metal hydrogen carbonates of the above; metal alkoxides (such as alkali metal alkoxides such as sodium methoxide), amines [eg, tertiary amines (eg, trialkylamines such as triethylamine, Aromatic tertiary amines such as N, N-dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole, etc.], carboxylic acid metal salts (sodium acetate, calcium acetate and other alkali metal acetates or alkaline earths) Organic bases such as metal salts). The catalyst (base catalyst) may be used alone or in combination of two or more.

The amount of the catalyst used can be adjusted according to the type of the catalyst. For example, 0.001 to 1 part by weight (for example, 0.003 to 0.005 parts by weight) with respect to 1 part by weight of the compound represented by the formula (B). 5 parts by weight), preferably 0.005 to 0.3 parts by weight, more preferably about 0.01 to 0.1 parts by weight.

The reaction may be performed in a solvent. The solvent is not particularly limited and can be selected according to the raw material to be used. For example, when using an alkylene oxide, an ether solvent (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, Anisole, etc.), halogen solvents (halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride), hydrocarbon solvents (aromatic hydrocarbons such as benzene, toluene, xylene, etc.). When alkylene carbonate is used, in addition to the solvents exemplified above, alcohols (C _1-4 alcohols such as methanol and ethanol, (poly) C ₂ such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol) are used. _-3 alkylene glycol, etc.) may be used. The solvents may be used alone or in combination of two or more. The amount of the solvent used is, for example, about 1 to 30 parts by weight, preferably about 1.5 to 20 parts by weight, and more preferably about 2 to 10 parts by weight with respect to 1 part by weight of the compound represented by the formula (B). It may be.

The reaction is often carried out, for example, at about 0 to 170 ° C., preferably 10 to 150 ° C., more preferably about 20 to 130 ° C., depending on the type of compound to be added (alkylene oxide, alkylene carbonate) and the like. In particular, when alkylene carbonate is used, in order to efficiently perform the decarboxylation reaction, for example, the reaction is often performed at 70 to 150 ° C., preferably about 80 to 120 ° C. The reaction time is, for example, 30 minutes to 48 hours, usually 1 to 24 hours, preferably about 2 to 10 hours.

The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed at normal pressure or under pressure. Moreover, you may react, removing the gas (carbon dioxide etc.) which generate | occur | produces as needed.

The target product (compound represented by formula (A)) may be purified from the reaction mixture after completion of the reaction using a conventional purification method (extraction, crystallization, etc.).

(Reaction between polyhydroxy compound and (meth) acrylic acid component)
As the (meth) acrylic acid component, a (meth) acryloyl group {that is, [CH ₂ ═C (R ^3a ) —CO—] and [CH ₂ ═C () in the formula (1) is reacted with a polyhydroxy compound. R ^3b ) —a group represented by —CO—] is not particularly limited as long as it is a compound capable of introducing a group, such as (meth) acrylic acid, (meth) acrylic acid derivatives [eg, (meth) acrylic acid lower alkyl esters (eg, C _1-4 alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate), (meth) acrylic acid halides (for example, (meth) acrylic acid chloride) Etc.), (meth) acrylic anhydride, etc.].

The proportion of the (meth) acrylic acid component is, for example, 0.7 mol or more (for example, 0.8 to 10 mol), preferably 0 with respect to 1 mol of the hydroxyl group of the compound represented by the formula (A). It may be 0.9 mol or more (for example, 0.95 to 8 mol), more preferably 1 mol or more (for example, 1.1 to 5 mol). In addition, when obtaining the composition containing the compound (compound represented by below-mentioned formula (2)) which is not completely (meth) acrylated as described later, (meth) acrylic acid used for the reaction time and reaction You may adjust the quantity of a component.

In the reaction, a catalyst (such as an acid catalyst or a base catalyst) may be used as appropriate. The acid catalyst is not particularly limited as long as it is an esterification acid catalyst. For example, inorganic acid (sulfuric acid, hydrochloric acid, phosphoric acid, etc.), organic acid [sulfonic acid (methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, etc.) And alkane sulfonic acids, and arene sulfonic acids such as p-toluene sulfonic acid etc.], etc.], and solidified acids [supporting an acid (an inorganic acid such as sulfuric acid, phosphoric acid, heteropoly acid, organic acid) on a carrier] Solid acid (such as solid phosphoric acid)], cation exchange resin, metal oxide (such as ZnO), metal halide (such as CuCl ₂ ), metal salt catalyst [metal sulfate (such as NiSO ₄ ), metal phosphorus Acid salts (such as phosphates of transition metals such as Zr and Ti), metal nitrates (such as Zn (NO ₃ ) ₂ · 6H ₂ O), etc.], natural minerals (acid clay, bentonite, kao, etc.) Also included are solid acid catalysts such as phosphorus and montmorillonite). The acid catalysts may be used alone or in combination of two or more.

Examples of the base include metal carbonate (alkali metal or alkaline earth metal carbonate such as sodium carbonate, alkali metal or alkaline earth metal hydrogen carbonate such as sodium hydrogen carbonate), carboxylate metal salt (sodium acetate, Inorganic bases such as alkali metal acetates or alkaline earth metal salts such as calcium acetate), metal hydroxides (alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide) Amines [eg tertiary amines (trialkylamines such as triethylamine, triisopropylamine and tributylamine, aromatic tertiary amines such as N, N-dimethylaniline, and heterocyclic tertiary amines such as pyridine; And an organic base such as amine). The bases may be used alone or in combination of two or more.

The amount of the catalyst (acid catalyst, base) used depends on the type of the catalyst, but for example 0.01 to 10 mol, preferably 0, with respect to 1 mol of the compound represented by the formula (A). .05 to 5 mol, more preferably about 0.1 to 3 mol.

Further, the reaction may be carried out in the presence of a polymerization inhibitor (thermal polymerization inhibitor) as necessary. Polymerization inhibitors include hydroquinones (eg, hydroquinone; hydroquinone monoalkyl ethers such as hydroquinone monomethyl ether (methoquinone)), catechols (eg, alkyl catechols such as t-butylcatechol), amines (eg, diphenylamine) And 2,2-diphenyl-1-picrylhydrazyl, 4-hydroxy-2,2,6,6-tetramethylpiperazine-1-oxyl and the like. The polymerization inhibitors may be used alone or in combination of two or more.

The amount of the polymerization inhibitor used is, for example, 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid component. It may be about a part.

The reaction may be performed in the absence of a solvent or in a solvent. Solvents (organic solvents) include hydrocarbons (aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene), halogenated hydrocarbons (methylene chloride, chloroform, etc.) And carbon tetrachloride), ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, anisole and the like), ketones (dialkyl ketones such as acetone and methyl ethyl ketone), and the like. The solvents may be used alone or in combination of two or more. In addition, when the said catalyst is a liquid, you may use the said catalyst as a solvent.

The reaction temperature and reaction time can be appropriately selected according to the type of (meth) acrylic acid component to be used. The reaction time is, for example, 30 minutes to 48 hours, usually 1 to 36 hours, preferably 2 to 24 hours. In addition, as described later, when obtaining a composition containing a compound that is not completely (meth) acrylated (a compound represented by the following formula (2)), the reaction temperature and reaction time may be adjusted. .

The reaction may be performed while refluxing, or may be performed while removing by-product water and alcohols. The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (such as nitrogen or a rare gas), and may be performed under normal pressure, increased pressure, or reduced pressure. In particular, when the reaction is performed under reduced pressure, coloring can be reduced and the reaction time can be shortened.

The produced compound (compound represented by the formula (1)) can be separated by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. It may be separated and purified by

[Multifunctional (meth) acrylate composition]
The reaction mixture obtained by reacting the compound represented by the formula (A) with the (meth) acrylic acid component as described above contains a product (polyfunctionality represented by the formula (1) ( In addition to (meth) acrylate), some or all of the hydroxyl groups of the compound represented by formula (A) may contain a compound that remains without reacting with the (meth) acrylic acid component. Such a compound (compound represented by the following formula (2)) may be separated from the compound represented by the above formula (1), but is usually multifunctional represented by the above formula (1). As a composition with (meth) acrylate, it can be used as it is. That is, even if the composition (polyfunctional (meth) acrylate composition) of the polyfunctional (meth) acrylate represented by the formula (1) and the compound represented by the following formula (2) is formed. Good. In such a composition, it is easy to realize a lower viscosity (improvement of handling properties), and by adjusting the amount of the compound represented by the following formula (2), the scratch resistance can be improved in combination with the plastic effect. There are cases where it can be improved more advantageously or effectively.

(In the formula, R ^5a and R ^5b represent a hydrogen atom or a (meth) acryloyl group, and R ^1a , R ^1b , R ^2a , R ^2b , R ^4a , R ^4b , k1, k2, m1, m2, n1, n2, p1, p2 are the same. However with ^the, at least one of ^{R 5a} and ^{R 5b} is (meth) acryloyl ^groups, all of ^{R 5a} and ^{R 5b} are (meth) never becomes acryloyl group.)
In addition, since the compound represented by Formula (2) is a component normally produced | generated (byproduct) in the manufacture process of the polyfunctionality (meth) acrylate represented by Formula (1), in formula, R ^The same except for ^5a and R ^5b . For example, also in the formula (2), the average value of m1 + m2 is selected from the same range as described above.

In the formula (2), among the n1 + n2 R ^5a and R ^5b , the number of (meth) acryloyl groups may be 1 or more and smaller than n1 + n2. For example, when (i) n1 = n2 = 1, the number of (meth) acryloyl groups is 1, and (ii) when n1 = n2 = 2, the number of (meth) acryloyl groups is 1 to 3, (Iii) When n1 = n2 = 3, the number of (meth) acryloyl groups is 1-5. In the formula (2), when n1 + n2 is 3 or more, the number of (meth) acryloyl groups is the average value of the whole compound represented by the formula (2) as in the case of the polyfunctional (meth) acrylate. Represented as:

A typical polyfunctional (meth) acrylate composition includes a polyfunctional (meth) acrylate in which n1 and n2 are each 1 in the formula (1), and n1 and n2 in the formula (2). Examples thereof include compositions each containing 1, a compound in which R ^5a is a hydrogen atom and R ^5b is a (meth) acryloyl group (that is, a monofunctional (meth) acrylate compound represented by the following formula (2A)). .

In the polyfunctional (meth) acrylate composition, the ratio (or concentration) of the compound represented by the formula (2) is the multifunctional (meth) acrylate represented by the formula (1) and the formula (2). ) In the range of 3 to 40% (eg, 4 to 35%), for example, 5 to 30% (eg, 6 to 27%), preferably 6.5. Even if it is about 26 to 26% (for example, 7 to 25%), more preferably about 7.5 to 22% (for example, 8 to 20%), especially about 8.5 to 18% (for example, 9 to 16%). Usually, it may be about 8 to 20% (for example, 8.5 to 17%, preferably 9 to 15.5%).

In the polyfunctional (meth) acrylate composition, the reaction rate of (meth) acrylation (that is, the (meth) acrylation rate of the compound represented by the formula (A)) is about 85 to 98%. The range can be selected, for example, 87 to 97.5% (for example, 87.5 to 97.5%), preferably 89 to 96.5% (for example, 89.5 to 96.5%), and more preferably It may be about 90 to 96% (for example, 90.5 to 96%), particularly about 91 to 95.5% (for example, 91.5 to 95.5%).

The (meth) acrylation reaction rate indicates the degree (index) of (meth) acrylation generally used in (meth) acrylic resins, and is a polyfunctional (meth) represented by the formula (1). It can be easily determined from the ratio (concentration) of acrylate and the ratio (concentration) of the compound represented by the formula (2). For example, to give a typical example, in the formulas (1) and (2), when n1 = n2 = 1, the ratio of the compound represented by the formula (1) is represented by A (%), and the formula When the ratio of the compound represented by (2) (a compound in which either of R ^5a and R ^5b is a (meth) acryloyl group) is B (%), [100 × A (%) + (100 × B (%)) / 2] / 100. In the formulas (1) and (2), when n1 = n2 = 2, the ratio of the compound represented by the formula (1) is A (%), and in the formula (2), R ^5a and The proportion of compounds in which one of R ^5b is a (meth) acryloyl group is B1 (%), and in the formula (2), the proportion of compounds in which two of R ^5a and R ^5b are (meth) acryloyl groups is B2 (%), In the formula (2), when the ratio of the compound in which three of R ^5a and R ^5b are (meth) acryloyl groups is B3 (%), [100 × A (%) + (100 × B1 (%)) / 4+ (100 × B2 (%) × 2) / 4 + (100 × B3 (%) × 3) / 4] / 100.

In addition, the ratio of the compound represented by Formula (1) and the compound represented by Formula (2) is a measurement of the hydroxyl value based on the usage-amount of the compound represented by Formula (A) used for the raw material ( Molar ratio, molar ratio), purity (area ratio) measurement by high performance liquid chromatography (HPLC), GPC measurement, NMR measurement, and the like.

The polyfunctional (meth) acrylate composition may further contain a solvent (solvent used in the reaction), an unreacted polyhydroxy compound (a compound represented by the formula (A)), and the like. Such a solvent or polyhydroxy compound may be separated and usually contained in a composition as it is because it is often a trace amount after purification. In such a polyfunctional (meth) acrylate composition, the ratio (or concentration) of the solid content (components other than the solvent) is, for example, 95% by weight or more, preferably 97% by weight or more, and more preferably 98% by weight. In particular, it may be 99% by weight or more (for example, 99.5% by weight or more).

<Characteristics and applications of polyfunctional (meth) acrylate>
The polyfunctional (meth) acrylate of the present invention (including a composition containing the compound represented by the formula (2) (including the polyfunctional (meth) acrylate composition), the same shall apply hereinafter)) has a high refractive index. Despite being, it has excellent scratch resistance after curing. For example, the refractive index of the polyfunctional (meth) acrylate at a wavelength of 589 nm is 1.52 or more (eg, 1.525 to 1.65), preferably 1.53 or more (eg, 1.535 to 1.6), more preferably 1.54 or more (eg 1.545 to 1.58), usually 1.53 to 1.58 (eg 1.535 to 1.575, preferably It may be about 1.54 to 1.57).

The properties of the polyfunctional (meth) acrylate of the present invention may be liquid at normal temperature (for example, 15 to 25 ° C.). Such a liquid polyfunctional (meth) acrylate has a relatively low viscosity despite its high refractive index as described above, and is excellent in handling properties. For example, the viscosity of the polyfunctional (meth) acrylate is, for example, 20000 mPa · s or less (eg, 50 to 17000 mPa · s), preferably 15000 mPa · s or less (eg, 100 to 13000 mPa · s) at 25 ° C. Preferably, it may be about 12000 mPa · s or less (for example, 200 to 11000 mPa · s), or may be 10,000 mPa · s or less (for example, 300 to 9000 mPa · s). In general, the viscosity of the polyfunctional (meth) acrylate may be about 400 to 15000 mPa · s, preferably 500 to 13000 mPa · s, more preferably about 600 to 12000 mPa · s at 25 ° C. The viscosity can be measured with a TV-22 viscometer (cone plate type) or the like (hereinafter the same).

The hue (APHA) of the polyfunctional (meth) acrylate (or curable composition) of the present invention may be, for example, 100 or less, preferably 70 or less, and more preferably 50 or less.

The glass transition temperature of the cured product of the polyfunctional (meth) acrylate (or curable composition) of the present invention is, for example, 0 to 40 ° C., preferably 10 to 35 ° C., more preferably 15 to 30 ° C. There may be.

Since such a polyfunctional (meth) acrylate of the present invention is composed of a curable polyfunctional (meth) acrylate, it is useful as a component for forming a curable composition for obtaining a cured product. It is. Below, a curable composition is explained in full detail.

[Curable composition containing polyfunctional (meth) acrylate]
The curable composition (polymerizable composition, radical polymerizable composition) of the present invention includes a curable component (polymerizable component, radical polymerizable component) composed of the polyfunctional (meth) acrylate.

The curable component may be composed only of (i) a polyfunctional (meth) acrylate, or (ii) a monomer that does not belong to the category of the polyfunctional (meth) acrylate (non-fluorene monomer). Good. In this invention, even if a sclerosing | hardenable component is only polyfunctionality (meth) acrylate, it can form hardened | cured material of scratch resistance and high refractive index with high handling property. On the other hand, even when combined with a non-fluorene monomer, scratch resistance and high refractive index derived from polyfunctional (meth) acrylate can be maintained. Therefore, depending on the type of non-fluorene monomer (for example, non-fluorene monofunctional monomer such as monofunctional (meth) acrylate), the handling property is further improved (lowering the viscosity), A cured product having a high refractive index can be obtained efficiently.

(Non-fluorene monomer)
In the curable composition of the above embodiment (ii), the non-fluorene monomer has a polymerizable unsaturated bond or a polymerizable group [for example, an alkenyl group (vinyl group, allyl group, etc.), (meth) acryloyl group]. Monomer. Such a non-fluorene-based monomer includes a monofunctional monomer (or a monofunctional polymerizable monomer, a monomer having one polymerizable unsaturated bond), a polyfunctional monomer [or a polyfunctional polymerizable monomer, Monomers having 2 or more polymerizable unsaturated bonds (for example, 2 to 8, preferably 2 to 6, more preferably 2 to 4)]. In the polyfunctional monomer, the polymerizable groups may be the same or different groups. Such non-fluorene monomers can be used for the purpose of adjusting curability, hardness, viscosity, and the like, and monofunctional monomers are mainly used for adjusting viscosity and curability. The non-fluorene-based monomer may be composed of at least a monofunctional monomer.

(Monofunctional monomer)
Monofunctional monomers (non-fluorene-based monofunctional monomers) include (meth) acrylic monomers, non- (meth) acrylic monomers [for example, styrene-based monomers (for example, styrene, α-methylstyrene, vinyltoluene, etc.), vinyl esters Type monomers (for example, vinyl acetate), N-vinylpyrrolidone, etc.]. The monofunctional monomer may usually contain at least a (meth) acrylic monomer.

When a (meth) acrylic monomer and a non (meth) acrylic monomer are used as the monofunctional monomer, the ratio of the non (meth) acrylic monomer to the whole monofunctional monomer is preferably 30% by weight or less, preferably May be 20% by weight or less, more preferably 10% by weight or less, especially 5% by weight or less.

Monofunctional (meth) acrylic monomers include (meth) acrylic acid, (meth) acrylamide, N-substituted (meth) acrylamide (N, N-diC _1-4 such as N, N-dimethyl (meth) acrylamide) (Meth) acrylic acid ester (or (meth) acrylate) and the like are included in addition to alkyl (meth) acrylamide and the like. Monofunctional (meth) acrylates include aliphatic (meth) acrylates ((meth) acrylates having an aliphatic skeleton), aromatic (meth) acrylates ((meth) acrylates having an aromatic skeleton), sulfur-containing (meta) ) Acrylate and the like.

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

Examples of monofunctional aromatic (meth) acrylates include aryl (meth) acrylates (eg, C _6-10 aryl (meth) acrylates such as phenyl (meth) acrylate), aralkyl (meth) acrylates (eg, benzyl) C _6-10 aryl C _1-4 alkyl (meth) acrylate such as (meth) acrylate), aryloxyalkyl (meth) acrylate (eg C _6-10 aryloxy C _1-10 such as phenoxyethyl (meth) acrylate) Alkyl (meth) acrylate), arylaryloxyalkyl (meth) acrylate (for example, C _6-10 aryl C _6-10 aryloxy C _1-10 alkyl such as 2- (o-phenylphenoxy) ethyl (meth) acrylate ( Meta) Acrelay ), Aryloxy (poly) alkoxyalkyl (meth) acrylates [for example, phenoxy _{C 6-10} aryloxy, such as ethoxyethyl (meth) acrylate _{(poly) C 2-4} alkoxy _{C 2-4} alkyl (meth) acrylate, Alkylaryloxy (poly) alkoxyalkyl (meth) acrylates [eg C _4-20 alkyl C _6-10 aryloxy (poly) C _2-4 alkoxy C _2- such as nonylphenoxy (poly) ethoxyethyl (meth) acrylate _4- alkyl (meth) acrylate], arylaryloxy (poly) alkoxyalkyl (meth) acrylate [for example, C _6-10 aryl C _6-10 aryloxy (poly) such as phenylphenoxy (poly) ethoxyethyl (meth) acrylate) C _2-4 alkoxy C _2-4 alkyl (meth) acrylate], bisphenols or alkylene oxide adducts thereof (for example, C _2-4 alkylene oxide adducts such as ethylene oxide adduct, propylene oxide adduct, etc. Adducts of about 10 alkylene oxides), the same applies hereinafter) mono (meth) acrylates, aromatic epoxy (meth) acrylates {eg 2-hydroxy-3-aryloxypropyl (meth) acrylates [eg 2 -Hydroxy-3-C _6-10 aryloxypropyl (meth) acrylate such as hydroxy-3-phenoxypropyl (meth) acrylate]}, arylthio (meth) acrylate, aralkylthio (meth) acrylate, arylthioa described later Examples include rualkyl (meth) acrylate.

The aromatic (meth) acrylate (monofunctional (meth) acrylate) usually does not contain phenoxybenzyl (meth) acrylate.

Examples of the sulfur-containing (meth) acrylate include alkylthio (meth) acrylate (for example, C _1-10 alkylthio (meth) acrylate such as methylthio (meth) acrylate), arylthio (meth) acrylate (for example, phenylthio (meth) acrylate) , Tolylthio (meth) acrylate, 2-naphthylthio (meth) acrylate, C _6-10 arylthio (meth) acrylate such as chlorophenylthio (meth) acrylate), aralkylthio (meth) acrylate (eg benzylthio (meth) acrylate, etc.) _{C 6-10} and aryl _{C 1-4} alkylthio (meth) acrylate), arylthioalkyl (meth) acrylate (e.g., phenyl thio (meth) _{C 6-10,} such as acrylate Riruchio such _{C 2-10} alkyl (meth) acrylate), and the like. In addition, arylthio (meth) acrylate, aralkylthio (meth) acrylate, and arylthioalkyl (meth) acrylate can also be classified as aromatic (meth) acrylate.

Monofunctional monomers may be used alone or in combination of two or more.

Among these monofunctional monomers, monofunctional (meth) acrylates are preferable, and among monofunctional (meth) acrylates, they may be used properly depending on the application. For example, among monofunctional monomers, from the viewpoint of improving handling properties, aliphatic (meth) acrylate [particularly branched alkyl (meth) acrylate (particularly branched C _3-10 alkyl such as isoamyl (meth) acrylate) ( (Meth) acrylates, preferably branched C _3-6 alkyl (meth) acrylates, alicyclic (meth) acrylates, etc.] can be suitably used. In addition, aromatic (meth) acrylates, sulfur-containing (meth) acrylates, and the like can be suitably used from the viewpoint of achieving a balance between high refractive index and excellent handling properties.

Furthermore, among monofunctional (meth) acrylates, monofunctional (meth) acrylates (monofunctional) that can efficiently maintain scratch resistance in combination with the polyfunctional (meth) acrylate (or composition thereof). (Meth) acrylate (sometimes referred to as (A)) may be suitably used. As monofunctional (meth) acrylate (A), for example, aryl (meth) acrylate, aralkyl (meth) acrylate, aryloxyalkyl (meth) acrylate, aryloxy (poly) alkoxyalkyl (meth) acrylate, alkylaryloxy (Poly) alkoxyalkyl (meth) acrylate, sulfur-containing (meth) acrylate [for example, arylthio (meth) acrylate, aralkylthio (meth) acrylate, arylthioalkyl (meth) acrylate, etc.] etc. are mentioned. The monofunctional (meth) acrylate (A) may be used alone or in combination of two or more.

Such a monofunctional (meth) acrylate (A) has a relatively high refractive index, and even when combined with the polyfunctional (meth) acrylate, the scratch resistance is often not impaired. Low viscosity), high refractive index, and scratch resistance are easily realized in a balanced manner. Among these, sulfur-containing (meth) acrylates such as arylthioalkyl (meth) acrylates are preferable because they have a high effect of maintaining or improving scratch resistance despite having a high refractive index.

Furthermore, a monofunctional (meth) acrylate (A) and a monofunctional (meth) acrylate (sometimes referred to as a monofunctional (meth) acrylate (B)) that is particularly excellent in terms of increasing the refractive index. You may combine. Examples of the monofunctional (meth) acrylate (B) include, for example, arylaryloxyalkyl (meth) acrylate, arylaryloxy (poly) alkoxyalkyl (meth) acrylate, bisphenols, or mono (meth) of alkylene oxide adducts thereof. An acrylate etc. are mentioned. The monofunctional (meth) acrylate (B) may be used alone or in combination of two or more.

Such a monofunctional (meth) acrylate (B) has a high refractive index among monofunctional monomers, but when combined with a polyfunctional (meth) acrylate at a very high concentration, scratch resistance and handling properties are improved. Although it may be damaged, by combining with the monofunctional (meth) acrylate (A), a high refractive index can be realized while preventing or suppressing a decrease in scratch resistance and handling properties.

When the monofunctional (meth) acrylate (A) and the monofunctional (meth) acrylate (B) are combined, these ratios are the former / the latter (weight ratio) = 99.9 / 0.1 to 5/95 (For example, 99.5 / 0.5 to 8/92), and can be selected from, for example, 99/1 to 10/90 (for example, 98/2 to 20/80), preferably 97/3 to 30 / 70 (eg 96/4 to 35/65), more preferably 95/5 to 40/60 (eg 93/7 to 40/60), in particular 90/10 to 45/55 (eg 85/15). About 45/55).

The viscosity of the monofunctional monomer is not particularly limited, and may be selected from a range of about 200 mPa · s or less at 25 ° C., for example, 100 mPa · s or less (eg, 0.01 to 100 mPa · s), preferably May be 50 mPa · s or less (eg, 0.1 to 50 mPa · s), more preferably 30 mPa · s or less (eg, 0.3 to 30 mPa · s), particularly 20 mPa · s or less [eg, 0 0.01 to 20 mPa · s, preferably 0.05 to 10 mPa · s, more preferably 0.1 to 5 mPa · s (for example, 0.5 to 3 mPa · s).

Of the monofunctional monomers, the viscosity of the monofunctional (meth) acrylate (A) is 100 mPa · s or less (for example, 0.1 to 70 mPa · s), preferably 50 mPa · s at 25 ° C. Or less (for example, 0.3 to 40 mPa · s), more preferably 30 mPa · s or less (for example, 0.5 to 25 mPa · s), particularly about 20 mPa · s or less (for example, 0.5 to 15 mPa · s). There may be.

The viscosity of the monofunctional (meth) acrylate (B) is 30 mPa · s or higher (for example, 40 to 300 mPa · s), preferably 50 mPa · s or higher (for example, 70 to 250 mPa · s) at 25 ° C. More preferably, it may be 100 mPa · s or more (for example, 110 to 200 mPa · s), particularly 120 mPa · s or more (for example, 130 to 180 mPa · s).

The refractive index of the monofunctional monomer may be, for example, 1.4 or more at 25 ° C. and 589 nm, for example, 1.4 to 1.65, preferably 1.41 to 1.62, Preferably, it may be about 1.42 to 1.6. In particular, the refractive index of the monofunctional monomer may be 1.5 or more, for example, 1.5 to 1.65, preferably 1.51 to 1.62, and more preferably 1.515 to 1. It may be about 6, particularly 1.53 or more (for example, about 1.54 to 1.6, preferably about 1.55 to 1.59).

Of the monofunctional monomers, the refractive index of the monofunctional (meth) acrylate (A) is, for example, 1.4 to 1.57, preferably 1.45 to 1. 565, more preferably 1.5 to 1.56, especially 1.51 to 1.56 (eg 1.53 to 1.56), usually 1.5 to 1.565 (eg It may be about 1.515 to 1.56).

The refractive index of the monofunctional (meth) acrylate (B) is, for example, 1.57 to 1.65, preferably 1.571 to 1.62, more preferably 1.573 to 1.5 at 25 ° C. and 589 nm. It may be about 1.6, particularly about 1.575 to 1.59.

The ratio (weight ratio) between the polyfunctional (meth) acrylate and the monofunctional monomer is the former / the latter = 99.9 / 0.1 to 10/90 (for example, 99.5 / 0.5 to 12). For example, 99/1 to 15/85 (for example, 98/2 to 20/80), preferably 97/3 to 25/75 (for example, 96/4 to 30/70). ), More preferably 95/5 to 35/65 (for example, 94/6 to 40/60), particularly about 93/7 to 45/55 (for example, 92/8 to 45/55). In particular, in the present invention, since the excellent scratch resistance and curability derived from the polyfunctional (meth) acrylate can be maintained even when combined with the monofunctional monomer, the proportion of the monofunctional monomer is relatively high [for example, The ratio (weight ratio) between the polyfunctional (meth) acrylate and the monofunctional monomer is the former / the latter = 85/15 to 5/95, preferably 80/20 to 15/85 (for example, 80 / 20 to 20/80), preferably about 75/25 to 20/80 (for example, 70/30 to 25/75), more preferably about 65/35 to 30/70 (for example, 60/40 to 35/65) ].

(Multifunctional monomer)
For the purpose of improving hard coat properties, a polyfunctional monomer may be used as long as the effects of the present invention (improvement of scratch resistance) are not impaired. Examples of the multifunctional monomer (non-fluorene-based multifunctional monomer) include a multifunctional (meth) acrylic monomer {for example, a bifunctional (meth) acrylate {for example, an alkylene glycol di (meth) acrylate [ethylene glycol di C _2-10 alkylene glycol di (meth) acrylate such as (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc.], ( Poly) oxyalkylene glycol di (meth) acrylate [for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) ) Acrylates, (poly) oxy C _2-6 alkylene glycol di (meth) acrylates such as polytetramethylene glycol di (meth) acrylate, etc.], di (meta) of bisphenol A (or its C _2-3 alkylene oxide adduct) ) Acrylate, bridged cyclic (meth) acrylate (eg, tricyclodecane dimethanol di (meth) acrylate, etc.), alkanetri to hexaol di (meth) acrylate [eg, glycerin di (meth) acrylate, trimethylolethane ( meth) acrylates, C _3-10 alkane tri to Hekisaoruji (meth) acrylates such as trimethylolpropane di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, etc.], etc.}, the three officials More polyfunctional (meth) acrylate {e.g., polyhydric alcohols (or its C _2-3 alkylene oxide adducts) (meth) acrylate, for example, glycerin tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, polyoltri to hexa (meth) acrylate} such as dipentaerythritol hexa (meth) acrylate}, multifunctional non- (meth) acrylic monomers (for example, divinyli Benzene and the like) and the like.

Also, the polyfunctional (meth) acrylic monomer includes, for example, a polyfunctional oligomer having a (meth) acryloyl group such as urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate. The number (average number) of (meth) acryloyl groups in the polyfunctional oligomer may be 2 or more (for example, 2 to 8), for example, 2 to 6, preferably 2 to 4, and more preferably 2 to 3 In particular, it may be 2.

Usually, the polyfunctional monomer may be composed of at least polyfunctional (meth) acrylate. The number of functional groups of the polyfunctional monomer (for example, the number of (meth) acryloyl groups) is, for example, 2 to 10 (for example, 2 to 8), preferably 2 to 6, more preferably 2 to 4, particularly 2 It may be. Polyfunctional monomers may be used alone or in combination of two or more.

Preferred polyfunctional monomers (non-fluorene-based polyfunctional monomers) include polyfunctional (meth) acrylates having an aromatic skeleton [for example, bisphenol A or its C _2-3 alkylene oxide adduct (for example, 1 mol of bisphenol A). 1 to 20 mol, preferably 2 to 18 mol, more preferably 3 to 15 mol of an adduct obtained by adding 3 to 15 mol of C _2-3 alkylene oxide)) and a non-fluorene-based aromatic skeleton such as di (meth) acrylate Non-fluorene-based polyfunctionality (such as urethane (meth) acrylate having urethane (meth) acrylate, particularly urethane (meth) acrylate having two (meth) acryloyloxy groups)) Includes meth) acrylates (especially non-fluorene bifunctional (meth) acrylates) That. Even if these polyfunctional monomers are combined with the polyfunctional (meth) acrylate, the scratch resistance can be maintained or further improved, and the scratch resistance, handling properties, refractive index and curability are balanced. It can be suitably used from the viewpoint of imparting.

When using a polyfunctional monomer (for example, a non-fluorene bifunctional (meth) acrylate), the ratio of the polyfunctional (meth) acrylate represented by the formula (1) and the polyfunctional monomer is as follows: For example, the former / the latter (weight ratio) = 99.9 / 0.1 to 30/70 (for example, 99.9 / 0.1 to 50/50) can be selected, and 99.9 / 0.1 to 60/40 (for example, 99.7 / 0.3 to 65/35), preferably 99.5 / 0.5 to 70/30 (for example, 99.3 / 0.7 to 75/25), more preferably May be about 99/1 to 80/20 (for example, 98/2 to 85/15), and usually 99/1 to 50/50 (for example, 95/5 to 60/40, preferably 90/10). ~ 70/30).

When a monofunctional monomer and a polyfunctional monomer are used in combination, the ratio of the former / the latter (weight ratio) = 99/1 to 5/95, preferably 97/3 to 10/90, more preferably Is about 95/5 to 20/80 (for example, 93/7 to 30/70), particularly 90/10 to 40/60 (for example, 88/12 to 50/50, preferably 85/15 to 55/45). It may be.

The ratio of the polyfunctional monomer to the entire curable component can be selected from the range of about 60% by weight or less (for example, 50% by weight or less), for example, 30% by weight or less, preferably 20% by weight or less, more preferably May be 10% by weight or less, and usually 40% by weight or less (for example, 25% by weight or less).

(Other fluorene monomers)
The curable component may further contain another fluorene-based monomer (a fluorene-based monomer that does not belong to the category of the polyfunctional (meth) acrylate represented by the formula (1) or the composition thereof). By combining such other fluorene-based monomer and the polyfunctional (meth) acrylate, there are cases where the refractive index can be further increased, and handling properties and curability can be improved.

The other fluorene-based monomer is usually a fluorene compound having a polymerizable unsaturated bond, in other words, a polymerizable unsaturated compound having a fluorene skeleton. In such a fluorene-based monomer, as the polymerizable unsaturated bond (polymerizable unsaturated group), a carbon-carbon unsaturated bond (carbon-carbon) such as alkenylene group (for example, vinyl group), (meth) acryloyl group, etc. Unsaturated group). A typical fluorene-based monomer is a fluorene compound having a (meth) acryloyl group (or (meth) acryloyloxy group).

In other fluorene monomers (or fluorene compounds), the number of polymerizable unsaturated bonds is, for example, 1 or more (eg, 1 to 8, preferably 1 to 6, more preferably 1 to 4, particularly preferably 1 or 2).

Such other fluorene monomers include (i) a fluorene monomer having one polymerizable unsaturated bond (especially a (meth) acryloyl group) and (ii) a polymerizable unsaturated bond (especially (meta And fluorene-based monomers having two or more acryloyl groups). When the fluorene monomer (i) is used, the refractive index and handling properties may be further improved without impairing scratch resistance. On the other hand, when the fluorene monomer (ii) is used, the curability and the refractive index may be further improved. The fluorene monomer (i) or the fluorene monomer (ii) may be used alone or in combination of two or more, or the fluorene monomer (i) and the fluorene monomer (ii) may be combined.

The fluorene monomer (i) is not particularly limited as long as it is a monofunctional compound having a fluorene skeleton (that is, having one polymerizable unsaturated group). For example, the fluorene monomer (i) is represented by the following formula (3). Examples thereof include monofunctional (meth) acrylates having a fluorene skeleton such as compounds.

(In the formula, R ⁶ is a direct bond or a divalent hydrocarbon group, R ⁷ is a substituent, m 3 is an integer of 0 or more, q is 0 or 1, R ^1a , R ^1b , R ^2a , R ^3a , k1 and k2 are the same as above.)
In the above formula (3), the number (number of added moles) m3 of the oxyalkylene group (OR ^2a ) can be selected, for example, from the range of about 0 to 15 (for example, 0 to 10), for example, 0 to 8 (for example, 1 to 8), preferably 0 to 6 (eg 1 to 6), more preferably 0 to 4 (eg 1 to 4). In particular, from the viewpoint of a high refractive index, m3 may be about 0-2.

In the formula (3), the divalent hydrocarbon group may be an aromatic hydrocarbon group (for example, a C _6-10 arylene group such as a phenylene group or a naphthylene group). It may be a hydrocarbon group. Non-aromatic hydrocarbon groups include, for example, alkylidene groups (eg, C _1-10 alkylidene groups such as methylene group, ethylidene group, propylidene group, propane-2,2-diyl group, preferably C _1-6 alkyl). A lidene group, more preferably a C _1-4 alkylidene group), an alkylene group (for example, a C _2-10 alkylene group such as an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, preferably a C _2-6 alkylene group, Preferably a C _2-4 alkylene group), a cycloalkylene group (for example, a C _5-10 cycloalkylene group such as a cyclohexylene group, preferably a C _5-8 cycloalkylene group), a cycloalkanedimethylene group (for example, 1, 4-cyclohexanedimethylene group and the like. Representative divalent non-aromatic hydrocarbon groups include alkylidene groups and alkylene groups. Preferred groups R ⁶ are a direct bond, an alkylidene group (eg, a C _1-4 alkylidene group, particularly a methylene group), and an alkylene group (eg, a C _2-4 alkylene group such as an ethylene group).

Further, in the formula (3), the substituent R ⁷ is the same as the above R ^4a or R ^4b , for example, a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl] Group (for example, C _5-8 cycloalkyl group), aryl group (for example, C _6-10 aryl group), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group), etc.], alkoxy group ( C _1-4 alkoxy group, etc.).

In Formula (3), R ^1a , R ^1b , R ^2a , R ^3a , k1, and k2 are the same as in Formula (1), including the preferred embodiment.

Representative fluorene-based monomer (i) (or a compound represented by formula (3)) includes a compound in which R ⁶ is a direct bond in formula (3) [for example, 9- (meth) acryloyloxyfluorene, 9- (meth) acryloyloxy-9-alkylfluorene, 9- (meth) acryloyloxy-9-arylfluorene, etc.], a compound in which R ⁶ is a methylene group in formula (3) [eg 9- (meth) Acryloyloxymethyl fluorene (9-fluorenylmethyl (meth) acrylate, etc.)] and the like.

As the fluorene monomer (ii), a polyfunctional (meth) acrylate having a fluorene skeleton, for example, two or more (especially two) (meth) acryloyl groups such as a compound represented by the following formula (4) are used. 9,9-bisarylfluorenes are included.

(In the formula, ring Z represents an aromatic hydrocarbon ring, m4 and m5 each represent a number of less than 8.5, and R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , R ^4a , R ^4b , K1, k2, n1, n2, p1, and p2 are the same as above.)
In the above formula (4), examples of the aromatic hydrocarbon ring represented by ring Z include a benzene ring and a condensed polycyclic arene (or condensed polycyclic aromatic hydrocarbon) ring. As the condensed polycyclic arene (or condensed polycyclic aromatic hydrocarbon) ring, for example, a condensed bicyclic arene ring (for example, a C _8-20 condensed bicyclic arene ring such as an indene ring or a naphthalene ring, preferably And C _10-16 condensed bicyclic arene rings), condensed tricyclic arene rings (eg, anthracene ring, phenanthrene ring, etc.) and the like. The two rings Z may be the same or different rings, and may usually be the same ring. A typical ring Z is a benzene ring or a naphthalene ring.

In the above formula (4), the number of oxyalkylene groups (OR ^2a and OR ^2b ) (addition moles) m4 and m5 may be less than 8.5, for example, 0 to 8 (for example, 0 to 6), preferably 0 to 4 (eg 0 to 3), more preferably 0 to 2 (eg 0 to 1), especially 1.

In the formula (4), R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , R ^4a , R ^4b , k1, k2, n1, n2, p1, and p2 are those in the formula (1). It is the same including a case and a preferable aspect.

Representative fluorene monomers (ii) (or compounds represented by the formula (4)) include 9,9-bis ((meth) acryloyloxyaryl) fluorenes, 9,9-bis ((meth) acryloyl) Oxy (poly) alkoxyaryl) fluorenes are included.

As 9,9-bis ((meth) acryloyloxyaryl) fluorenes, for example, 9,9-bis ((meth) acryloyloxyphenyl) fluorene [for example, 9,9-bis (4- (meth) acryloyloxy) Phenyl) fluorene and the like], 9,9-bis (alkyl- (meth) acryloyloxyphenyl) fluorene [9,9-bis (4- (meth) acryloyloxy-3-methylphenyl) fluorene, 9,9-bis ( 9,9-bis (mono or diC _1-4 alkyl- (meth) acryloyloxyphenyl) fluorene, etc.] such as 4- (meth) acryloyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis ( Aryl (meth) acryloyloxyphenyl) fluorene [9,9-bis (4- (meth) acryloylo 9,9-bis (mono- or di-C _6-8 aryl- (meth) acryloyloxyphenyl) fluorene etc.] such as xyl-3-phenylphenyl) fluorene, 9,9-bis (poly (meth) acryloyloxyphenyl) 9,9 such as fluorene {eg, 9,9-bis (di or tri (meth) acryloyloxyphenyl) fluorene} such as 9,9-bis [3,4-di ((meth) acryloyloxy) phenyl] fluorene} -Bis ((meth) acryloyloxyphenyl) fluorenes (compound in which the ring Z is a benzene ring and m4 and m5 are 0 in the formula (4)); 9,9-bis ((meth) acryloyloxynaphthyl) fluorene [ For example, 9,9-bis [6- (2- (meth) acryloyloxynaphthyl)] fluorene, 9,9-bis [ 9,9-bis ((meth) acryloyloxynaphthyl) fluorenes such as 1- (5- (meth) acryloyloxynaphthyl)] fluorene etc.] (in the formula (4), ring Z is a naphthalene ring, m4 and m5 are Compound that is 0).

The 9,9-bis ((meth) acryloyloxy (poly) alkoxyaryl) fluorenes correspond to the 9,9-bis ((meth) acryloyloxyaryl) fluorenes, and in formula (4), m4 and m5 Is one or more (eg, about 1 to 4), for example, 9,9-bis ((meth) acryloyloxyalkoxyphenyl) fluorene [eg, 9,9-bis (4- (2- (meth) acryloyl) 9,9-bis ((meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene and the like], 9,9-bis ((meth) acryloyloxydialkoxyphenyl) fluorene (for example, 9 , 9-bis {4- [2- (2- (meth) acryloyloxyethoxy) ethoxy] phenyl } Fluorene] 9,9-bis such {[2- (2- (meth) acryloyloxy _{C 2-4} _{alkoxy) C 2-4} alkoxy] phenyl} fluorene), 9,9-bis (alkyl - (meth ) Acryloyloxyalkoxyphenyl) fluorene [eg 9,9-bis (4- (2- (meth) acryloyloxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2- (meth)) 9,9-bis (mono- or di-C _1-4 alkyl (meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene, etc.] such as acryloyloxyethoxy) -3,5-dimethylphenyl) fluorene], 9,9-bis (Aryl- (meth) acryloyloxyalkoxyphenyl) fluorene [9,9-bis (4- (2- (meth) acryloyl) 9,9-bis (mono- or di-C _6-8 aryl (meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene, etc.] such as (Luoxyethoxy) -3-phenylphenyl) fluorene], 9,9-bis [di Or 9,9-bis [di or di ((meth) acryloyloxyalkoxy) phenyl] fluorene [eg 9,9-bis [3,4-di (2- (meth) acryloyloxyethoxy) phenyl] fluorene 9,9-bis ((meth) acryloyloxy (poly) alkoxyphenyl) fluorenes such as tri ((meth) acryloyloxy C _2-4 alkoxy) phenyl] fluorene] (in the formula (4), ring Z is a benzene ring) , M4 and m5 are 1 or more); 9,9-bis ((meth) acryloyloxyalkoxy) Fuchiru) fluorene [e.g., 9,9-bis ((meth) acryloyloxy _{C 2-4} alkoxy naphthyl) fluorene] 9,9-bis ((meth) acryloyloxy (poly) alkoxy naphthyl) fluorene such as (the And a compound in which ring Z is a naphthalene ring and m4 and m5 are 1 or more in formula (4).

The ratio of the polyfunctional (meth) acrylate (the compound represented by the formula (1) or the composition thereof) and the other fluorene monomer is, for example, the former / the latter (weight ratio) = 99.9 / 0. 1 to 10/90 (eg 99.5 / 0.5 to 20/80), preferably 99/1 to 30/70 (eg 98/2 to 35/65), more preferably 97/3 to It may be about 40/60 (for example, 95/5 to 50/50).

In particular, the ratio between the polyfunctional (meth) acrylate and the fluorene monomer (i) (such as the compound represented by the formula (3)) is the former / the latter (weight ratio) = 99/1 to 10/90 ( For example, 98/2 to 20/80), preferably 95/5 to 30/70 (for example, 93/7 to 35/65), more preferably 90/10 to 40/60 (for example, 88/12 to 50). / 50), particularly about 85/15 to 60/40 (for example, 83/17 to 65/35).

The ratio of the polyfunctional (meth) acrylate and the fluorene monomer (ii) (the compound represented by the formula (4)) is the former / the latter (weight ratio) = 99.9 / 0.1 to 50/50 (for example, 99.7 / 0.3 to 60/40), preferably 99.5 / 0.5 to 70/30 (for example, 99.3 / 0.7 to 75/25), more preferably Is about 99/1 to 80/20 (for example, 98.7 / 1.3 to 85/15), particularly about 98.5 / 1.5 to 90/10 (for example, 98/2 to 93/7). May be.

In addition, the ratio of the other fluorene-type monomer with respect to the whole curable component can be selected from the range of about 70 weight% or less, for example, 60 weight% or less, Preferably it is 50 weight% or less, More preferably, it is 40 weight% or less. It may be. In particular, the ratio of the fluorene-based monomer (ii) to the entire curable component may be, for example, 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, particularly 7% by weight or less.

(Polymerization initiator)
The curable composition of this invention may contain the polymerization initiator further as needed. Such a polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photo radical generator). A preferred polymerization initiator is a photopolymerization initiator.

Examples of the photopolymerization initiator or photo radical generator include benzoins (benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether); acetophenones (acetophenone, p- Dimethylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-phenyl-2-hydroxy-acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc.); propiophenones (p-dimethylaminopropiophenone) 2-hydroxy-2-methyl-propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.); butyrylphenones [1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propane -1-one etc.]; aminoacetophenones [2-methyl-2-morpholino (4-thiomethylphenyl) propane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- Tyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino- 2-methyl-1- (4-methylphenyl) propan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1- (4 -Methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Dimethylaminophenyl) -butan-1-one, etc.]; ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.); thioxanthenes (Thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, etc.); Anthraquinones (2-ethylanthraquinone, 1-chloroanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc.); Thio) xanthones (thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone); acridines (1,3-bis- (9-acridinyl) propane 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, etc.); triazines (2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-Methoxyphenyl) -4,6-bis (trick (Romethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, etc.); sulfides (eg, benzyldiphenyl sulfide); acylphosphine oxides ( 2,4,6-trimethylbenzoyldiphenylphosphine oxide); titanocene photopolymerization initiators; oxime esters and the like. These photopolymerization initiators can be used alone or in combination of two or more.

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

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

The ratio of the polymerization initiator (particularly the photopolymerization initiator) is a curable component (for example, the polyfunctional (meth) acrylate represented by the formula (1) alone, the polyfunctional represented by the formula (1). For example, 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight (total amount of the functional (meth) acrylate and the monofunctional monomer) For example, it may be about 2 to 7 parts by weight.

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

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

(Other additives)
The curable composition of the present invention further contains conventional additives such as resin components, solvents, thermal polymerization inhibitors (hydroquinone, hydroquinone monoethyl ether, etc.), antifoaming agents, coating property improvers, thickeners, lubricants. , Stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), plasticizers, surfactants, dissolution accelerators, colorants, fillers, antistatic agents, silane coupling agents, leveling agents, dispersants, A dispersion aid or the like may be included. The additives may be used alone or in combination of two or more.

The curable composition of the present invention is excellent in curability (particularly photocurability) and has characteristics such as a high refractive index even before curing. For example, the refractive index of the curable composition can be selected from a range of about 1.5 or more (eg, 1.5 to 1.65) at 25 ° C. and 589 nm, and 1.51 or more (eg, 1.515 to 1.62), preferably 1.52 or more (eg 1.525 to 1.61), more preferably 1.53 or more (eg 1.535 to 1.6), especially 1.54 or more (eg 1.545 to 1.58), usually 1.53 to 1.58 (eg, 1.535 to 1.575, preferably 1.54 to 1.57, more preferably 1.545 to 1.545). It may be about 1.565).

Moreover, the curable composition of the present invention has excellent handling properties despite having a high refractive index. Therefore, the curable composition of the present invention may be usually liquid at normal temperature (for example, 15 to 25 ° C.). The viscosity of such a curable composition is, for example, 15000 mPa · s or less (eg, 1 to 13000 mPa · s), preferably 12000 mPa · s or less (eg, 5 to 11000 mPa · s), more preferably at 25 ° C. It may be about 10,000 mPa · s or less (for example, 10 to 8000 mPa · s), usually 50 to 15000 mPa · s (for example, 70 to 12000 mPa · s, preferably 100 to 10000 mPa · s, more preferably 150 to 8000 mPa · s). about s). In many cases, the viscosity can be lowered by using a monofunctional monomer as compared with the case of using a polyfunctional (meth) acrylate alone.

In addition, such a curable composition of this invention can be prepared by mixing each component.

[Cured product]
The curable composition of this invention hardens | cures easily by providing active energy (active energy ray). Therefore, the curable resin composition of the present invention is useful for forming a cured product using thermal energy and / or light energy (particularly, light energy) as active energy. The curable composition of the present invention is often excellent in photocurability and may be cured by applying at least light energy (light irradiation). The cured product may have a three-dimensional structure and is usually a cured film in many cases. The cured film may be a film pattern (particularly a thin film pattern). The cured film can be formed by applying the resin composition to a base material or a substrate and drying it if necessary, and then heating or exposing to an actinic ray. Then, it can be formed by selectively exposing and developing the generated latent image pattern.

The base material or the substrate can be selected according to the use, and may be a porous material such as wood, a metal such as aluminum or copper, a ceramic such as glass or quartz, a plastic such as polymethyl methacrylate or polycarbonate. The curable composition of the present invention is excellent in adhesion to a substrate, and has a high refractive index and high transparency. Therefore, the curable composition of the present invention is suitable for optical applications, and among these substrates, by coating on a transparent film. You may utilize as a laminated body with a transparent base material or a transparent film. As the transparent film, for example, it is excellent in transparency and has excellent adhesion to the curable composition. For example, cyclic olefin resin, styrene resin, (meth) acrylic resin (polymethyl methacrylate, etc.), acrylonitrile type, etc. A transparent film composed of a resin, a polyester-based resin, a polyamide-based resin, a cellulose ester (such as triacetyl cellulose) or the like is preferable. The thickness of the transparent film can be selected depending on the application, and may be, for example, about 1 to 1000 μm, preferably 10 to 500 μm, and more preferably about 30 to 300 μm.

The coating method is not particularly limited. For example, flow coating method, spin coating method, spray coating method, screen printing method, casting method, bar coating method, curtain coating method, roll coating method, gravure coating method, dipping method, slit method. It may be.

The curable composition may be applied and then dried (for example, dried at about 40 to 150 ° C.). The thickness of the coating film varies depending on the application, but can be selected from the range of about 0.01 to 1000 μm, and may be, for example, 1 to 500 μm, preferably 5 to 400 μm, and more preferably about 10 to 300 μm.

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

When the coating film is cured by heating, the heating temperature may be, for example, 60 to 200 ° C. (eg, 80 to 180 ° C.), preferably about 100 to 150 ° C. Since the curable composition of this invention is excellent in photopolymerizability, it can also obtain hardened | cured material by irradiation of actinic light, without heating.

In the exposure step, the entire surface may be exposed depending on the application, or a patterned latent image may be formed by selective exposure using a photomask or the like. For exposure, radiation (gamma rays, X-rays, etc.), ultraviolet rays, visible rays, etc. can be used, and usually ultraviolet rays are often used. As the light source, for example, in the case of ultraviolet rays, a deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, a laser light source (light source such as helium-cadmium laser or excimer laser), etc. Can be used. The amount of irradiation light (irradiation energy) varies depending on the thickness of the coating film, but can be selected from a range of, for example, about 50 to 10,000 mJ / cm ² , 75 to 5000 mJ / cm ² , more preferably 100 to 3000 mJ / cm ² (for example, 100 to 2000 mJ / cm ² ).

In addition, you may heat-process (after cure, post-baking etc.) before exposure with exposure after exposure as needed. The heating temperature may be, for example, about 60 to 200 ° C., preferably about 100 to 150 ° C.

When a patterned latent image is formed, a developed coating film pattern can be formed by developing the latent image pattern. Developers include water, alkaline aqueous solutions (eg, tetramethylammonium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc.), acidic aqueous solutions, hydrophilic solvents (eg, alcohols such as methanol, ethanol, isopropanol, Ketones such as acetone, ethers such as dioxane and tetrahydrofuran, cellosolves, cellosolve acetates, etc.), and mixtures thereof. The development can be performed using immersion, washing, spraying or spray development.

As described above, a cured product (cured film or the like) is obtained. Such a cured product has scratch resistance and is excellent in optical properties such as high transparency and high refractive index. In addition, such scratch resistance is not impaired even when a curable composition is constituted in combination with a monofunctional monomer or the like, and a cured product having excellent scratch resistance and a high refractive index is obtained. For example, the refractive index of the cured product of the present invention can be selected from a range of about 1.5 or more (eg, 1.5 to 1.65) at 25 ° C. and 589 nm, and 1.51 or more (eg, 1.515). 1.62), preferably 1.52 or more (eg 1.525 to 1.61), more preferably 1.53 or more (eg 1.535 to 1.6), especially 1.54 or more (eg 1.545 to 1.58), usually 1.55 or more (eg 1.555 to 1.59), 1.56 or more [eg 1.56 to 1.6, preferably 1 565 or more (for example, 1.565 to 1.59), more preferably 1.57 or more (for example, 1.57 to 1.585)].

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the examples, the various components (and their abbreviations) used are as follows.

[(A) Multifunctional acrylate]
BPEFA: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (in formula (1), bifunctional acrylate with m1 = m2 = n1 = n2 = 1, manufactured by Osaka Gas Chemical Co., Ltd.) )
Urethane acrylate: Nippon Synthetic Chemical Industry Co., Ltd., “UV-3200B”, 2 acryloyl groups in one molecule
Urethane acrylate: manufactured by Daicel Cytec Co., Ltd., “EBECRYL8402”, the number of acryloyl groups in one molecule is 2.

[(B) Monofunctional monomer]
IAA: Isoamyl acrylate, manufactured by NOF Corporation, viscosity (25 ° C.) 1 mPa · s, refractive index (25 ° C., 589 nm) 1.419
POA: Phenoxyethyl acrylate, “Light acrylate PO-A” manufactured by Kyoeisha Chemical Co., Ltd., viscosity (25 ° C.) 8 mPa · s, refractive index (25 ° C., 589 nm) 1.518
BZA: benzyl acrylate, “FA-BZA” manufactured by Hitachi Chemical Co., Ltd., viscosity (25 ° C.) 2 mPa · s, refractive index (25 ° C., 589 nm) 1.515
PTEA: Phenylthioethyl acrylate BIMAX Co., Ltd., viscosity (25 ° C.) 6 mPa · s, refractive index (25 ° C., 589 nm) 1.555
OPPEOA: o-phenylphenol monoethoxy acrylate, manufactured by BIGEN, viscosity (25 ° C.) 145 mPa · s, refractive index (25 ° C., 589 nm) 1.577.

[(C) Non-fluorene bifunctional monomer]
Urethane acrylate: Nippon Synthetic Chemical Industry Co., Ltd., “UV-3200B”, 2 acryloyl groups in one molecule
Urethane acrylate: Daicel Cytec Co., Ltd., “EBECRYL8402”, number of acryloyl groups in one molecule is 2
Diacrylate of ethylene oxide adduct of bisphenol A (addition of 10 mol of ethylene oxide to 1 mol of bisphenol A): “FA-321A” manufactured by Hitachi Chemical Co., Ltd.

[(D) Fluorene monomer]
9-FMA: 9-fluorenylmethyl acrylate, synthesized by the following method: 9-fluorenylmethanol (manufactured by Kanto Chemical Co., Inc.) 196.2 g (1.0 mol) in a four-necked flask and acrylic An acid 93.7 g (1.3 mol), p-toluenesulfonic acid 23.8 g (0.13 mol), toluene 577 g, and methoquinone 2.1 g were charged, and a stirrer, thermometer, condenser, and water separator were attached. Thereafter, dehydration esterification reaction was performed for 3.3 hours while refluxing at 110 to 120 ° C. Subsequently, the reaction solution was neutralized with 10% sodium hydroxide and washed with 20% saline. After drying over magnesium sulfate and filtration, 2.1 g of methoquinone was added, and toluene was removed by concentration under reduced pressure. As a result, 237 g (yield: 95%) of 9-fluorenylmethyl acrylate as a target product was obtained.

BPEFA: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd.).

[Polymerization initiator]
Photopolymerization initiator: “IRGACURE 184” manufactured by Ciba Japan Co., Ltd.
In the following examples and comparative examples, various properties and evaluations were measured as follows.

(Refractive index)
A multi-wavelength Abbe refractometer (manufactured by Atago, DR-M2 <using circulating water bath 60-C3>) was used, and the refractive index at 589 nm (refractive index before and after curing) was measured while maintaining a temperature of 25 ° C.

(viscosity)
At 25 ° C., an optional rotor (01: 1 ° 34 × R24, 07: 3) corresponding to the measured viscosity using a TV-22 viscometer (cone plate type, “TVE-22L” manufactured by Toki Sangyo Co., Ltd.) (° × R7.7) at 0.5 to 20 rpm (selected according to viscosity).

(Glass transition temperature (℃))
The glass transition temperature of the cured product was measured using DSC 6220 manufactured by SII NanoTechnology at a measurement temperature of 30 to 220 ° C. and a heating time of 10 ° C./min.

(Scratch resistance)
A cured product (15 × 50 × 2 mm) prepared using a SUS mold having a thickness of 2 mm was placed on a pencil hardness meter (“HEIDON-14” manufactured by Shinto Kagaku Co., Ltd.). Then, steel wool (# 0000) is attached to the tip of the pencil hardness meter, pressed against the front surface of the cured product with a load of 200 g and 1 kg, moved on the cured product at a speed of 1 mm / second, and scratches generated on the cured product. It was measured by visually confirming the presence or absence.

A: No damage at 200 g load, no damage at 1 kg load, or complete recovery within 5 minutes at room temperature (about 25 ° C.) B: Damage at 200 g load There is no scratch and the wound is immediately after moving with 1 kg load, and the wound does not recover after 5 minutes at room temperature (about 25 ° C). But the wound does not recover after 5 minutes.

(Curable)
The surface of a cured product (15 × 50 × 2 mm) prepared using a SUS mold having a thickness of 2 mm was palpated and the curability was evaluated according to the following criteria.

A: No tack (adhesiveness) B: There is tack.

(Addition number of ethylene oxide (EO))
Based on JIS K0070, the hydroxyl value was measured by the following method to determine the EO addition number (average value of m1 + m2 in the formula (1)).

A sample of 1.5 g was put into a Meyer with 100 ml rubbed, an acetic anhydride-pyridine solution was added, and the mixture was stirred at 95-100 ° C. for 20 minutes to acetylate the sample. After 20 minutes, the mixture was allowed to cool, 1 ml of distilled water was added, and the mixture was further heated at 95-100 ° C. for 10 minutes. Titrated with KOH ethanol solution. For titration, an automatic titration device GT-100 manufactured by Dia Instruments Co., Ltd. was used.

(HPLC measurement)
The measurement was performed with the following apparatus and conditions.

L-2000 made by Hitachi High-Technologies Corporation
Column Imtakt Cadenza 3 μm CD-CL18 3.0 × 250 mm
Guard column Imtakt GCCDOS
Acetonitrile / distilled water = 70/30 (Kanto Chemical, LC grade), flow rate 0.5 ml / min.

(Solid content concentration)
Using a halogen moisture meter HG53 manufactured by METTLER TOLEDO Co., Ltd., the volatile residue at 200 ° C. was measured as a solid content.

(Hue (APHA))
In accordance with JIS K0071, the color difference / turbidity meter COH-300A manufactured by Nippon Denshoku Industries Co., Ltd. was used.

(Example 1)
1 mol of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEF) in the same manner as in Example 1 of JP-A-2001-139651 The product was reacted using 8 mol of ethylene oxide (EO) to obtain 923.9 g of the product (98% yield based on BPEF). From the hydroxyl value of the obtained product, 9. mol of EO was added to 1 mol of BPEF, that is, 9. mol of 9,9- (4-hydroxyphenyl) fluorene (BPF) to 1 mol. It was found to be a compound to which 0 mol of EO was added (a compound having an average value of m1 + m2 of 9.0 in the formula (1)). APHA of the obtained compound (referred to as BPF-9.0EO) was 111.

Into a 4-necked flask, 1.0 mol of BPF-9.0EO obtained above, 187.4 g (2.6 mol) of acrylic acid, 23.8 g (0.13 mol) of p-toluenesulfonic acid, 876 g of toluene, methoquinone 2.1 g was charged and equipped with a stirrer, thermometer, condenser, and water separator. Thereafter, dehydration esterification reaction was performed for 3.3 hours while refluxing at 110 to 120 ° C. Subsequently, the reaction solution was neutralized with 10% sodium hydroxide and washed with 20% saline. After drying over magnesium sulfate and filtration, 2.1 g of methoquinone was added, and toluene was removed by concentration under reduced pressure. 893.2 g (yield 95%) of a liquid target product (polyfunctional acrylate) was obtained.

The polyfunctional acrylate (composition) is a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-9.0EO (ie, a compound in which n1 = n2 = 1 in the formula (1), In addition to BPF-9.0EO-2A), a compound obtained by reacting 1 mol of acrylic acid with 1 mol of BPF-9.0EO (that is, a compound in which n1 = n2 = 1 in the formula (2), (Hereinafter referred to as BPF-9.0EO-1A). The ratio (HPLC purity) of BPF-9.0EO-1A to the total amount of BPF-9.0EO-2A and BPF-9.0EO-1A was 11.5%, and the polyfunctionality determined from this ratio The reaction rate of the functional acrylate (acrylation reaction rate) was 94.2%.

The solid content concentration of the polyfunctional acrylate was 99.9% by weight, the refractive index (25 ° C., 589 nm) was 1.563, and the viscosity (25 ° C.) was 10500 mPa · s.

Further, 3 parts by weight of a photopolymerization initiator was added to 100 parts by weight of the obtained polyfunctional acrylate, and the mixture was melt-mixed and then irradiated with ultraviolet light (UV) (2000 mJ / cm ² , 20 seconds). The evaluation of scratch resistance of the cured product was B.

In addition, 3 parts by weight of a photopolymerization initiator was added to 100 parts by weight of the obtained polyfunctional acrylate and melt-mixed, followed by ultraviolet light (UV) irradiation (500 mJ / cm ² , 20 seconds). The cured product had a refractive index (25 ° C., 589 nm) of 1.583 and a glass transition temperature of 30 ° C.

(Example 2)
A compound in which 10.5 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1 except that the amount of EO used was changed to 9.5 mol in Example 1. APHA of the obtained compound (referred to as BPF-10.5EO) was 76.

Then, a polyfunctional acrylate was obtained in a yield of 96% in the same manner as in Example 1 except that 1 mol of BPF-10.5EO was used and the reaction time was changed to 3.0 hours.

The polyfunctional acrylate (composition) includes a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-10.5EO (referred to as BPF-10.5EO-2A), and 1 mol of BPF-10.5EO. Also included was a compound (referred to as BPF-10.5EO-1A) in which 1 mol of acrylic acid had reacted. The ratio (HPLC purity) of BPF-10.5EO-1A to the total amount of BPF-10.5EO-2A and BPF-10.5EO-1A is 14.9%, and the polyfunctionality determined from this ratio The reaction rate of the functional acrylate (acrylation reaction rate) was 92.5%.

The solid content concentration of the polyfunctional acrylate was 99.7% by weight, the refractive index (25 ° C., 589 nm) was 1.556, and the viscosity (25 ° C.) was 7900 mPa · s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.575, the scratch resistance was evaluated as A, and the glass transition temperature was 24 ° C.

(Example 3)
In Example 1, except that the amount of EO used was changed to 9.9 mol, a compound in which 10.9 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1. APHA of the obtained compound (referred to as BPF-10.9EO) was 59.

Then, a polyfunctional acrylate was obtained in a yield of 95% in the same manner as in Example 1 except that 1 mol of BPF-10.9EO was used and the reaction time was changed to 3.2 hours.

The polyfunctional acrylate (composition) includes a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-10.9EO (referred to as BPF-10.9EO-2A), and 1 mol of BPF-10.9EO. Also included was a compound (referred to as BPF-10.9EO-1A) in which 1 mol of acrylic acid had reacted. The ratio (HPLC purity) of BPF-10.9EO-1A to the total amount of BPF-10.9EO-2A and BPF-10.9EO-1A was 9.9%, and the polyfunctionality determined from this ratio The reaction rate of the functional acrylate (acrylation reaction rate) was 95.1%.

The solid content concentration of the polyfunctional acrylate was 99.7% by weight, the refractive index (25 ° C., 589 nm) was 1.554, and the viscosity (25 ° C.) was 6600 mPa · s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.574, the scratch resistance was evaluated as A, and the glass transition temperature was 18 ° C.

(Example 4)
In Example 1, except that the amount of EO used was changed to 10 mol, a compound in which 11.0 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1. APHA of the obtained compound (referred to as BPF-11.0EO) was 30.

Then, a polyfunctional acrylate was obtained in a yield of 97% in the same manner as in Example 1 except that 1 mol of BPF-11.0EO was used and the reaction time was changed to 3.8 hours.

In addition to the compound (referred to as BPF-11.0EO-2A) obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-11.0EO, the polyfunctional acrylate (composition) contains 1 mol of BPF-11.0EO. Also included was a compound (referred to as BPF-11.0EO-1A) in which 1 mol of acrylic acid had reacted. The ratio (HPLC purity) of BPF-11.0EO-1A to the total amount of BPF-11.0EO-2A and BPF-11.0EO-1A was 10.1%, and the polyfunctionality determined from this ratio The reaction rate of the functional acrylate (acrylation reaction rate) was 94.9%.

The solid content concentration of the polyfunctional acrylate was 99.6% by weight, the refractive index (25 ° C., 589 nm) was 1.552, and the viscosity (25 ° C.) was 5000 mPa · s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.572, the scratch resistance was evaluated as B, and the glass transition temperature was 16 ° C.

(Example 5)
In Example 1, except that the amount of EO used was changed to 11 mol, a compound in which 12.0 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1. APHA of the obtained compound (referred to as BPF-12.0EO) was 25.

Then, a polyfunctional acrylate was obtained in a yield of 95% in the same manner as in Example 1 except that 1 mol of BPF-12.0EO was used and the reaction time was changed to 3.3 hours.

In addition to the compound (referred to as BPF-12.0EO-2A) obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-12.0EO, the polyfunctional acrylate (composition) contains 1 mol of BPF-12.0EO. Also included was a compound (referred to as BPF-12.0EO-1A) in which 1 mol of acrylic acid had reacted. The ratio (HPLC purity) of BPF-12.0EO-1A to the total amount of BPF-12.0EO-2A and BPF-12.0EO-1A is 10.5%, and the polyfunctionality determined from this ratio The reaction rate of the functional acrylate (acrylation reaction rate) was 94.7%.

The solid content concentration of the polyfunctional acrylate was 99.7% by weight, the refractive index (25 ° C., 589 nm) was 1.547, and the viscosity (25 ° C.) was 2100 mPa · s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.567, the scratch resistance was evaluated as B, and the glass transition temperature was 14 ° C.

(Example 6)
In Example 1, except that the amount of EO used was changed to 13 mol, a compound in which 14.2 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1. APHA of the obtained compound (referred to as BPF-14.2EO) was 40.

Then, a polyfunctional acrylate was obtained in a yield of 96% in the same manner as in Example 1 except that 1 mol of BPF-14.2EO was used and the reaction time was changed to 2.8 hours.

The polyfunctional acrylate (composition) includes a compound obtained by reacting 2 moles of acrylic acid with 1 mole of BPF-14.2EO (referred to as BPF-14.2EO-2A), and 1 mole of BPF-14.2EO. Also included was a compound (referred to as BPF-14.2EO-1A) in which 1 mol of acrylic acid had reacted. The ratio of BPF-14.2EO-1A to the total amount of BPF-14.2EO-2A and BPF-14.2EO-1A (HPLC purity) was 12.0%, and the polyfunctionality determined from this ratio The reaction rate of the functional acrylate (acrylation reaction rate) was 94.0%.

The solid content concentration of the polyfunctional acrylate was 99.8% by weight, the refractive index (25 ° C., 589 nm) was 1.539, and the viscosity (25 ° C.) was 900 mPa · s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.559, the scratch resistance was evaluated as B, and the glass transition temperature was 13 ° C.

(Example 7)
In Example 1, except that the amount of EO used was changed to 15 mol, a compound in which 16.0 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1. APHA of the obtained compound (referred to as BPF-16.0EO) was 58.

A polyfunctional acrylate was obtained in a yield of 97% in the same manner as in Example 1, except that 1 mol of BPF-16.0EO was used and the reaction time was changed to 2.7 hours.

The polyfunctional acrylate (composition) includes a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-16.0EO (referred to as BPF-16.0EO-2A), and 1 mol of BPF-16.0EO. Also included was a compound (referred to as BPF-16.0EO-1A) in which 1 mol of acrylic acid had reacted. The ratio (HPLC purity) of BPF-16.0EO-1A to the total amount of BPF-16.0EO-2A and BPF-16.0EO-1A was 16.0%, and the polyfunctionality determined from this ratio The reaction rate of the functional acrylate (acrylation reaction rate) was 92.0%.

The solid content concentration of the polyfunctional acrylate was 99.7% by weight, the refractive index (25 ° C., 589 nm) was 1.530, and the viscosity (25 ° C.) was 400 mPa · s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.548, the scratch resistance was evaluated as B, and the glass transition temperature was 11 ° C.

(Reference Example 1)
A compound in which 6.6 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1 except that the amount of EO used was changed to 5.6 mol in Example 1. APHA of the obtained compound (referred to as BPF-6.6EO) was 43.

A polyfunctional acrylate was obtained in a yield of 96% in the same manner as in Example 1 except that 1 mol of BPF-6.6EO was used and the reaction time was changed to 2.4 hours.

In addition to a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-6.6EO (referred to as BPF-6.6EO-2A), the polyfunctional acrylate (composition) contains 1 mol of BPF-6.6EO. Also included was a compound (referred to as BPF-6.6EO-1A) in which 1 mol of acrylic acid had reacted. The ratio of BPF-6.6EO-1A to the total amount of BPF-6.6EO-2A and BPF-6.6EO-1A (HPLC purity) was 18.1%, and the polyfunctionality determined from this ratio The reaction rate of the functional acrylate (acrylation reaction rate) was 91.0%.

The solid content concentration of the polyfunctional acrylate was 99.95% by weight, the refractive index (25 ° C., 589 nm) was 1.588, and the viscosity (25 ° C.) was 134,000 mPa · s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.596, the scratch resistance was evaluated as C, and the glass transition temperature was 62 ° C.

(Reference Example 2)
In Example 1, except that the amount of EO used was changed to 7 mol, a compound in which 8.0 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1. APHA of the obtained compound (referred to as BPF-8.0EO) was 106.

Then, a polyfunctional acrylate was obtained in a yield of 97% in the same manner as in Example 1 except that 1 mol of BPF-8.0EO was used and the reaction time was changed to 2.8 hours.

The polyfunctional acrylate (composition) includes a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-8.0EO (referred to as BPF-8.0EO-2A), and 1 mol of BPF-8.0EO. Also included was a compound (referred to as BPF-8.0EO-1A) in which 1 mol of acrylic acid had reacted. The ratio of BPF-8.0EO-1A to the total amount of BPF-8.0EO-2A and BPF-8.0EO-1A (HPLC purity) was 18.4%, and the polyfunctionality determined from this ratio The reaction rate of the functional acrylate (acrylation reaction rate) was 90.8%.

The solid content concentration of the polyfunctional acrylate was 99.7% by weight, the refractive index (25 ° C., 589 nm) was 1.573, and the viscosity (25 ° C.) was 62000 mPa · s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.591, the scratch resistance was evaluated as C, and the glass transition temperature was 55 ° C.

(Comparative Example 1)
When the refractive index and viscosity of BPEFA were measured, the refractive index (25 ° C., 589 nm) was 1.616, and the viscosity (25 ° C.) was over 100,000 mPa · s. Moreover, the refractive index (25 degreeC, 589 nm) of the hardened | cured material produced like Example 1 was 1.626, evaluation of scratch resistance was C, and the glass transition temperature was 211 degreeC.

(Comparative Example 2)
When the refractive index and viscosity of the urethane acrylate (UV-3200B) were measured, the refractive index (25 ° C., 589 nm) was 1.507, and the viscosity (25 ° C.) exceeded 100,000 mPa · s. Moreover, although preparation of the hardened | cured material was tried like Example 1, it has a tack | tuck and scratch resistance was not able to be evaluated. The glass transition temperature was −8 ° C.

(Comparative Example 3)
When the refractive index and viscosity of the urethane acrylate (EBECRYL8402) were measured, the refractive index (25 ° C., 589 nm) was 1.490, and the viscosity (25 ° C.) was 12500 mPa · s. Moreover, the refractive index (25 degreeC, 589 nm) of the hardened | cured material produced like Example 1 was 1.508, evaluation of scratch resistance was C, and the glass transition temperature was 14 degreeC.

The results are shown in Table 1.

As is clear from Table 1, the polyfunctional acrylates of the Examples could form a cured product having a high refractive index and excellent scratch resistance despite having a low viscosity. On the other hand, the polyfunctional acrylates of Reference Example 1, Reference Example 2 and Comparative Example 1 have a high refractive index, but are poor in handling properties with high viscosity, and are also poor in scratch resistance of the obtained cured product. It was a thing. Further, in Comparative Examples 2 and 3, urethane acrylate having flexibility was used, but the refractive index was low, and a cured product sufficient in scratch resistance could not be obtained. Specifically, Comparative Example 2 had tack and poor handling properties, and the refractive index was smaller than that of the Examples. On the other hand, Comparative Example 3 had a lower viscosity than Comparative Example 2, but the refractive index was remarkably reduced as the viscosity was lowered, and scratch resistance was not obtained.

(Example 8)
90 parts by weight of the polyfunctional acrylate obtained in Example 3, 10 parts by weight of isoamyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.541, and the viscosity (25 degreeC) was 2100 mPa * s.

The refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.563, the scratch resistance evaluation was A, and the curability evaluation was A.

Example 9
90 parts by weight of the polyfunctional acrylate obtained in Example 3, 10 parts by weight of phenoxyethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.551, and the viscosity (25 degreeC) was 3000 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.574, the scratch resistance evaluation was A, and the curability evaluation was A.

(Example 10)
70 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of phenoxyethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.543, and the viscosity (25 degreeC) was 1800 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.568, the scratch resistance evaluation was A, and the curability evaluation was A.

(Example 11)
50 parts by weight of the polyfunctional acrylate obtained in Example 3, 50 parts by weight of phenoxyethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.536, and the viscosity (25 degreeC) was 600 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.561, the scratch resistance evaluation was B, and the curability evaluation was A.

Example 12
90 parts by weight of the polyfunctional acrylate obtained in Example 3, 10 parts by weight of benzyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.550, and the viscosity (25 degreeC) was 1500 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.572, the scratch resistance evaluation was A, and the curability evaluation was A.

(Example 13)
70 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of benzyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.542, and the viscosity (25 degreeC) was 500 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.565, the scratch resistance evaluation was A, and the curability evaluation was A.

(Example 14)
50 parts by weight of the polyfunctional acrylate obtained in Example 3, 50 parts by weight of benzyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.534, and the viscosity (25 degreeC) was 100 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.559, the scratch resistance evaluation was B, and the curability evaluation was A.

(Example 15)
90 parts by weight of the polyfunctional acrylate obtained in Example 3, 10 parts by weight of phenylthioethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.554, and the viscosity (25 degreeC) was 3000 mPa * s.

(Example 16)
70 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of phenylthioethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.555, and the viscosity (25 degreeC) was 800 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.577, the scratch resistance evaluation was A, and the curability evaluation was A.

(Example 17)
50 parts by weight of the polyfunctional acrylate obtained in Example 3, 50 parts by weight of phenylthioethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.555, and the viscosity (25 degreeC) was 200 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.578, the scratch resistance evaluation was A, and the curability evaluation was A.

(Example 18)
90 parts by weight of the polyfunctional acrylate obtained in Example 3, 10 parts by weight of o-phenylphenol monoethoxy acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.557, and the viscosity (25 degreeC) was 4500 mPa * s.

(Example 19)
70 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of o-phenylphenol monoethoxy acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.561, and the viscosity (25 degreeC) was 2500 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.586, the scratch resistance evaluation was B, and the curability evaluation was A.

(Example 20)
70 parts by weight of the polyfunctional acrylate obtained in Example 2, 30 parts by weight of benzyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.544, and the viscosity (25 degreeC) was 1000 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.566, the scratch resistance evaluation was A, and the curability evaluation was A.

(Example 21)
60 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of phenoxyethyl acrylate, 10 parts by weight of o-phenylphenol monoethoxy acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition. Obtained.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.544, and the viscosity (25 degreeC) was 600 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.567, the scratch resistance evaluation was A, and the curability evaluation was A.

(Example 22)
40 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of phenoxyethyl acrylate, 30 parts by weight of o-phenylphenol monoethoxy acrylate, and 3 parts by weight of a photopolymerization initiator are melt-mixed to obtain a curable composition. Obtained.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.548, and the viscosity (25 degreeC) was 500 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.575, the scratch resistance evaluation was B, and the curability evaluation was A.

(Example 23)
60 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of phenylthioethyl acrylate, 10 parts by weight of o-phenylphenol monoethoxy acrylate, and 3 parts by weight of a photopolymerization initiator are melt-mixed to obtain a curable composition. Got.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.557, and the viscosity (25 degreeC) was 600 mPa * s.

(Example 24)
40 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of phenylthioethyl acrylate, 30 parts by weight of o-phenylphenol monoethoxy acrylate, and 3 parts by weight of a photopolymerization initiator are melt-mixed to obtain a curable composition. Got.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.561, and the viscosity (25 degreeC) was 500 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.579, the scratch resistance was evaluated as B, and the curability was evaluated as A.

(Comparative Example 4)
70 parts by weight of BPEFA, 30 parts by weight of phenoxyethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.586, and the viscosity (25 degreeC) was 7000 mPa * s.

Furthermore, the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.608, the scratch resistance evaluation was C, and the curability evaluation was A.

The results are shown in Table 2.

As is apparent from the results in Table 2, in the examples, excellent scratch resistance and further curability derived from the polyfunctional acrylate could be maintained while the viscosity was further reduced by the monofunctional monomer. In addition, the refractive index is maintained at a high level, and it should be noted that the refractive index is equivalent to that of a polyfunctional acrylate without diminishing scratch resistance and curability even when diluted at a high concentration of 30 to 60%. Or more.

In addition, among the monofunctional monomers, a cured product having a good balance of excellent scratch resistance, high refractive index and handling property while maintaining or improving scratch resistance by combining POA, PTEA and OPPEOA. Could get.

(Example 25)
80 parts by weight of the polyfunctional acrylate obtained in Example 3, 20 parts by weight of urethane acrylate (UV-3200B), and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.545, and the viscosity (25 degreeC) was 11100 mPa * s.

And the refractive index (25 degreeC, 589 nm) of the hardened | cured material created like Example 1 from the curable composition was 1.565, evaluation of scratch resistance was B, and evaluation of curability was A.

(Example 26)
80 parts by weight of the polyfunctional acrylate obtained in Example 3, 20 parts by weight of urethane acrylate (EBECRYL8402), and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.542, and the viscosity (25 degreeC) was 11100 mPa * s.

And the refractive index (25 degreeC, 589 nm) of the hardened | cured material created like Example 1 from the curable composition was 1.561, evaluation of scratch resistance was B, and evaluation of curability was A.

(Example 27)
80 parts by weight of the polyfunctional acrylate obtained in Example 3, 20 parts by weight of diacrylate (FA-321A) of an ethylene oxide adduct of bisphenol A, and 3 parts by weight of a photopolymerization initiator are melt-mixed to obtain a curable composition. Got.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.546, and the viscosity (25 degreeC) was 4500 mPa * s.

And the refractive index (25 degreeC, 589 nm) of the hardened | cured material created like Example 1 from the curable composition was 1.566, evaluation of scratch resistance was A, and evaluation of curability was A.

(Example 28)
80 parts by weight of the polyfunctional acrylate obtained in Example 3, 20 parts by weight of 9-fluorenylmethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.564, and the viscosity (25 degreeC) was 4000 mPa * s.

And the refractive index (25 degreeC, 589 nm) of the hardened | cured material created like Example 1 from the curable composition was 1.579, evaluation of scratch resistance was A, and evaluation of curability was A.

(Example 29)
70 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of 9-fluorenylmethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.57, and the viscosity (25 degreeC) was 1000 mPa * s.

And the refractive index (25 degreeC, 589 nm) of the hardened | cured material created like Example 1 from the curable composition was 1.590, evaluation of scratch resistance was B, and evaluation of curability was A.

(Example 30)
95 parts by weight of the polyfunctional acrylate obtained in Example 3, 5 parts by weight of BPEFA, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.

In addition, the refractive index (25 degreeC, 589 nm) of the curable composition (composition which does not contain a photoinitiator) was 1.558, and the viscosity (25 degreeC) was 8400 mPa * s.

And the refractive index (25 degreeC, 589 nm) of the hardened | cured material created like Example 1 from the curable composition was 1.578, evaluation of scratch resistance was B, and evaluation of curability was A.

The results are shown in Table 3.

As is apparent from the results in Table 3, a cured product having excellent scratch resistance and a high refractive index could be obtained even when combined with a non-fluorene bifunctional monomer. Moreover, by combining with other fluorene monomers, a cured product having a high refractive index could be obtained without impairing scratch resistance.

The polyfunctional (meth) acrylate or curable composition of the present invention is, for example, an ink material, a light emitting material (for example, a light emitting material for organic EL), an organic semiconductor, a graphitization precursor, a gas separation membrane (for example, CO ₂ gas separation membrane, etc.), coating agents (for example, optical overcoat agents such as coating agents for LED (light emitting diode) elements or hard coating agents), lenses [pickup lenses (eg, DVD (digital versatile tiles) Disc) pick-up lens, etc.), microlens (eg, microlens for liquid crystal projector), spectacle lens, etc.], polarizing film (eg, polarizing film for liquid crystal display), composite sheet, brightness enhancement film, prism sheet, reflection Anti-reflection film (or anti-reflection film such as anti-reflection film for display device) ), Touch panel film, flexible substrate film, display film [eg, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction electron-emitting device display), FED (electric field) Emission display), NED (nano-emissive display), cathode ray tube, film for display (especially thin display) such as electronic paper (protective film, etc.), retardation film, diffusion sheet, light guide plate, reflection sheet diffusion plate, Barrier film, protective film, overcoat, flexible film substrate, anisotropic conductive adhesive film (ACF), color filter [eg, lens filter, color filter for display, etc.], negative photo for liquid crystal display devices Dist [e.g. TFT array etching photoresist, pigment dispersion type photoresist, dye type photoresist, protective film, etc.], interlayer insulation film, solder resist, liquid crystal display photo spacer, fuel cell film, optical fiber, optical waveguide, It can be suitably used for holograms, various optical adhesives [for example, optical lenses, prisms, optical fibers, optical filters, optical waveguides], keypads, keyboards, touch panels, and the like. In particular, the multifunctional (meth) acrylate or curable composition of the present invention can balance a high refractive index and excellent scratch resistance in a well-balanced manner, so that it can be used for optical materials that require scratch resistance [for example, It can be suitably used for a prism sheet (for example, a prism sheet for a display such as a prism sheet for a liquid crystal display), a sheet for a touch panel (or a film for a touch panel, for example, a touch panel sheet for a liquid crystal display) and the like. Examples of the shape of the optical material include a film or sheet shape, a plate shape, a lens shape, and a tubular shape.

Claims

Following formula (1)

(Wherein R 1a and R 1b are non-radically polymerizable substituents, R 2a and R 2b are alkylene groups, R 3a and R 3b are hydrogen atoms or methyl groups, and R 4a and R 4b are non-radical polymerizable substituents. , K1 and k2 are each an integer of 0 to 4, m1 and m2 are each an integer of 0 or more, n1 and n2 are each an integer of 1 to 4, and p1 and p2 are each an integer of 0 to 4. However, n1 + p1 ≦ 5, n2 + p2 ≦ 5.)
A polyfunctional (meth) acrylate represented by the formula (1), wherein the average value of m1 + m2 is 8.5 to 17.
The polyfunctional (meth) acrylate according to claim 1, wherein in formula (1), n1 and n2 are each 1, m1 and m2 are each 1 or more, and an average value of m1 + m2 is 9 to 15.
The polyfunctional (meth) acrylate according to claim 1, wherein in formula (1), the average value of m1 + m2 is 9.5 to 11.
A polyfunctional (meth) acrylate represented by the formula (1) according to any one of claims 1 to 3, and the following formula (2)

(In the formula, R 5a and R 5b represent a hydrogen atom or a (meth) acryloyl group, and R 1a , R 1b , R 2a , R 2b , R 4a , R 4b , k1, k2, m1, m2, n1, n2, p1, p2 are the same. However with the, at least one of R 5a and R 5b is (meth) acryloyl groups, all of R 5a and R 5b are (meth) never becomes acryloyl group.)
The polyfunctional (meth) acrylate composition containing the compound represented by these.
The ratio of the compound represented by the formula (2) is the area by high performance liquid chromatography with respect to the total amount of the polyfunctional (meth) acrylate represented by the formula (1) and the compound represented by the formula (2). The multifunctional (meth) acrylate composition according to claim 4, wherein the ratio is 5 to 30%.
In the formula (1) and the formula (2), n1 and n2 are each 1, m1 and m2 are each 1 or more, and the average value of m1 + m2 is 9 to 15, and the compound represented by the formula (2) Of the polyfunctional (meth) acrylate represented by the formula (1) and the total amount of the compound represented by the formula (2) is 8 to 20% as an area ratio by high performance liquid chromatography. The polyfunctional (meth) acrylate composition according to claim 4 or 5.
The polyfunctional (meth) acrylate or polyfunctional according to any one of claims 1 to 6, which has a refractive index (589 nm) of 1.53 or more and a viscosity (25 ° C) of 20000 mPa · s or less at 25 ° C. (Meth) acrylate composition.
A curable composition comprising a curable component comprising the multifunctional (meth) acrylate or the multifunctional (meth) acrylate composition according to any one of claims 1 to 7.
The curable composition according to claim 8, wherein the curable component further contains a non-fluorene monofunctional monomer.
The curable composition according to claim 9, wherein the non-fluorene monofunctional monomer contains a monofunctional (meth) acrylate.
At least one monofunctional (non-fluorene-based monofunctional monomer selected from branched alkyl (meth) acrylates, alicyclic (meth) acrylates, aromatic (meth) acrylates, and sulfur-containing (meth) acrylates ( The curable composition of Claim 9 or 10 containing a (meth) acrylate.
The non-fluorene-based monofunctional monomer contains at least one monofunctional (meth) acrylate selected from aromatic (meth) acrylates and sulfur-containing (meth) acrylates. Curable composition.
Non-fluorene-based monofunctional monomers are aryl (meth) acrylate, aralkyl (meth) acrylate, aryloxyalkyl (meth) acrylate, aryloxy (poly) alkoxyalkyl (meth) acrylate, alkylaryloxy (poly) alkoxyalkyl ( A monofunctional (meth) acrylate (A) selected from meth) acrylate, arylthio (meth) acrylate, aralkylthio (meth) acrylate, and arylthioalkyl (meth) acrylate, and arylaryloxyalkyl (meth) acrylate, Monofunctional selected from arylaryloxy (poly) alkoxyalkyl (meth) acrylates and mono (meth) acrylates of bisphenols or their alkylene oxide adducts (Meth) acrylate (B) a curable composition according to any one of claims 9-12 including.
The curability according to claim 13, wherein the ratio of the monofunctional (meth) acrylate (A) to the monofunctional (meth) acrylate (B) is the former / the latter (weight ratio) = 97/3 to 30/70. Composition.
The curing according to any one of claims 9 to 14, wherein the ratio of the polyfunctional (meth) acrylate and the non-fluorene-based monofunctional monomer is the former / the latter (weight ratio) = 99/1 to 15/85. Sex composition.
The curing according to any one of claims 9 to 15, wherein the ratio of the polyfunctional (meth) acrylate and the non-fluorene monofunctional monomer is the former / the latter (weight ratio) = 80/20 to 20/80. Sex composition.
The curable composition according to any one of claims 8 to 16, wherein the curable component further contains a non-fluorene bifunctional (meth) acrylate.
18. The curable composition according to claim 17, wherein the ratio of the polyfunctional (meth) acrylate and the non-fluorene bifunctional (meth) acrylate is the former / the latter (weight ratio) = 99/1 to 50/50.
The curable composition according to any one of claims 8 to 18, wherein the curable component further contains another fluorene-based monomer.
The curable composition according to claim 19, wherein the other fluorene-based monomer contains a compound represented by the following formula (3).

(In the formula, R 6 is a direct bond or a divalent hydrocarbon group, R 7 is a substituent, m 3 is an integer of 0 or more, q is 0 or 1, R 1a , R 1b , R 2a , R 3a , k1 and k2 are the same as above.)
21. The curable composition according to claim 20, wherein the ratio between the polyfunctional (meth) acrylate and the compound represented by the formula (3) is the former / the latter (weight ratio) = 95/5 to 30/70.
A cured product obtained by curing the curable composition according to any one of claims 8 to 21.
The cured product according to claim 22, which is a prism sheet.
The cured product according to claim 22, which is a touch panel sheet.
The method for producing a cured product according to any one of claims 22 to 24, wherein the curable composition according to any one of claims 8 to 21 is cured by applying active energy.