JP5249570B2 - Urethane (meth) acrylate having fluorene skeleton and cured product thereof - Google Patents

Description

  The present invention relates to a novel urethane (meth) acrylate having a fluorene skeleton, a method for producing the same, and a cured product obtained by curing the urethane (meth) acrylate.

  A compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton) is known to have an excellent function in terms of refractive index, heat resistance, and the like. As a method for expressing such an excellent function of the fluorene skeleton in a resin, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), for example, bisphenol fluorene (BPF), biscresol fluorene (BCF), bis In general, aminophenylfluorene (BAFL), bisphenoxyethanol fluorene (BPEF) or the like is used as a constituent component of the resin, and a fluorene skeleton is introduced into a part of the skeleton structure of the resin. For example, as a polyester resin having such a fluorene skeleton, JP 2002-284864 A (Patent Document 1) discloses a molding material composed of a polyester resin having a 9,9-bisphenylfluorene skeleton. Yes. JP-A-2004-339499 (Patent Document 2) discloses resins containing bisphenol fluorene, bisaminophenyl fluorene, bisphenoxyethanol fluorene, or the like as polymerization components (polyester resin, polycarbonate resin, urethane resin, acrylic resin). A resin, a polyamide resin, a polyimide resin, an epoxy resin, a vinyl ester resin, a phenol resin, an aniline resin, and the like) and an additive are disclosed.

  A urethane (meth) acrylate having such a fluorene skeleton is also known. JP 2000-53628 A (Patent Document 3) discloses a bifunctional urethane (meta) obtained by reacting a diol, a diisocyanate and an ester residue having a hydroxyl group with a (meth) acrylate represented by the following formula: ) Acrylates are disclosed.

(Wherein, a represents an integer of 1 to 5, and R ¹ represents a hydrogen atom or a methyl group)
In this document, as an example of the diol represented by the above formula, an average of 2 to 10 mol of ethylene oxide or propylene oxide was added to 1 mol of 9,9-bis (4- (2-hydroxy) phenyl) fluorene. It is described that 9,9-bis (4- (hydroxyethoxy) phenyl) fluorene is available as a commercial product.

  However, since the urethane (meth) acrylate described in this document is difunctional, the crosslinking density cannot be sufficiently increased in the cured product, and there is a limit to improvement in hardness, heat resistance, and the like.

  JP 2000-7741 A (Patent Document 4) discloses a resin composition containing a specific (meth) acrylate compound having a fluorene skeleton, a specific urethane (meth) acrylate compound, and a polymerization initiator. Yes. In this document, the urethane (meth) acrylate compound contains at least four hydroxyl groups-containing (meth) acrylate compound (a), polyisocyanate compound (b), and polyol compound (c) in a molecule. It is described that urethane (meth) acrylate having a (meth) acryloyl group is included. In addition, in this document, as specific examples of the hydroxyl group-containing (meth) acrylate compound (a), glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane It is described that tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like can be mentioned. In addition, in this document, as specific examples of the polyol compound (c), aliphatic polyhydrides such as ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolpropane, and carboxylic acid-containing polyol are used. Aromatic polyhydric alcohols such as polyhydric alcohols, ethylene oxide reactants of various bisphenols, ethylene oxide and propylene oxide reactants of bisphenolfluorene, and the like. Particularly preferred polyol compounds (c) include dimethylolpropionic acid and dimethylol. It is described that butanoic acid, bisphenoxyethanol fluorene and the like can be mentioned.

However, although the urethane (meth) acrylate of this document has four or more (meth) acryloyl groups, it is fast-curing, and polymerization of only the acrylate occurs before the desired acrylation. It is difficult to obtain a pure product.
JP 2002-284864 A (Claims) JP 2004-339499 A (claims, paragraph number [0032]) JP 2000-53628 A (claims, paragraph number [0018]) JP 2000-7741 A (claims, paragraph numbers [0007] [0008] [0010])

  Accordingly, an object of the present invention is to provide a novel urethane (meth) acrylate having a fluorene skeleton excellent in hardness and heat resistance, a production method thereof and a cured product obtained by curing the urethane (meth) acrylate.

  Another object of the present invention is to provide a urethane (meth) acrylate having a fluorene skeleton that can be efficiently improved in crosslink density and capable of being produced with high purity, a method for producing the same, and a cured product obtained by curing the urethane (meth) acrylate. There is to do.

  Still another object of the present invention is to provide a urethane (meth) acrylate excellent in flexibility and handling properties despite having a fluorene skeleton, a method for producing the same, and a cured product obtained by curing the urethane (meth) acrylate. It is in.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have obtained a compound having a specific fluorene skeleton having three or more hydroxyl groups, a polyisocyanate compound, and a reactive group (for example, a hydroxyl group) with respect to the isocyanate group. ) Having a (meth) acrylic compound, a novel urethane (meth) acrylate (particularly a tetrafunctional or higher functional urethane (meth) acrylate) is obtained, and such a novel urethane (meth) acrylate is obtained. Found that the crosslink density can be improved efficiently and that the cured product can be imparted with excellent hardness and heat resistance, and the present invention has been completed.

  That is, the urethane (meth) acrylate of the present invention is a (meth) acrylic compound having a fluorene skeleton represented by the following formula (1), a polyisocyanate compound, and an active hydrogen atom reactive with an isocyanate group. It is a urethane (meth) acrylate reacted with a system compound.

(In the formula, ring Z ¹ and ring Z ² represent aromatic hydrocarbon rings, R ¹ and R ² are the same or different and represent a substituent, R ³ represents an alkylene group, k is an integer of 0 to 4; , M is 0 or an integer of 1 or more, n is 0 or an integer of 1 or more, r1 and r2 are each an integer of 1 or more, and (r1 + r2) ≧ 3 is satisfied.)
The urethane (meth) acrylate is usually a urethane (meth) acrylate having 3 or more (meth) acryloyl groups (or trifunctional or more), particularly a urethane having 4 or more (meth) acryloyl groups (meth) ) Acrylate (urethane (meth) acrylate having 4 or more (meth) acryloyl groups at its end) may be used.

In the compound represented by the formula (1), for example, in the formula (1), the ring Z ¹ and the ring Z ² are a benzene ring or a naphthalene ring, and R ² is an alkyl group (C _1-4 such as a methyl group). An alkyl group or the like) or an aryl group (such as a C _6-10 aryl group such as a phenyl group), m is 0 to 2, R ³ is a C _2-4 alkylene group (particularly an ethylene group), and n is The compound may be 1 to 10 (preferably 1 to 4, particularly 1), and r1 and r2 may be 2 or 3, respectively.

In particular, the compound represented by the formula (1) includes 9,9-bis [di (hydroxy (poly) C _2-4 alkoxy) phenyl] fluorene, and 9,9-bis [tri (hydroxy (poly) C _It may be a compound selected from _2-4 alkoxy) phenyl] fluorene.

The polyisocyanate compound may be a diisocyanate compound. In addition, the (meth) acrylic compound is a hydroxyl group-containing compound such as a hydroxyl group-containing (meth) acrylic compound [particularly, hydroxyalkyl (meth) acrylate (for example, hydroxy C _2-6 alkyl (meth) acrylate)). (Meth) acrylate etc.].

  Typically, the polyisocyanate compound has an isocyanate group (—NCO) content of 20 to 60% by weight with respect to the whole polyisocyanate compound, and an aliphatic diisocyanate, alicyclic diisocyanate, and araliphatic diisocyanate. And a diisocyanate compound selected from aromatic diisocyanates.

The polyisocyanate compound may be a polyisocyanate compound having a polyol skeleton (sometimes referred to as polyisocyanate compound (A)). When such a polyisocyanate compound is used, a urethane (meth) acrylate excellent in flexibility and handling properties can be obtained despite having a fluorene skeleton. The polyisocyanate compound (A) having such a polyol skeleton may be, for example, a urethane prepolymer having isocyanate groups at both ends where the diol compound and the diisocyanate compound (a) are reacted. In such a urethane prepolymer, the diol compound is, for example, a diol compound selected from a low molecular weight diol (such as alkane diol) and a high molecular weight diol (polymer diol compound) (particularly, polyoxy C _2-6 alkylene glycol). Polyether-based diol). The diisocyanate compound (a) may be a diisocyanate compound selected from aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, and aromatic diisocyanate.

The diol compound is typically an alkanediol (for example, C _2-10 alkanediol) or a polyether-based diol compound having a number average molecular weight of 200 to 5000 (for example, a polyoxy C ₂₋ having a number average molecular weight of 250 to 2000). ₆ alkylene glycol).

  The urethane (meth) acrylate may typically be a compound represented by the following formula (2).

[Wherein J is a hydrogen atom or the following formula (3)

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, A represents a residue of a polyisocyanate compound, X and Y represent an ether group, E represents a linking group, p is 0 or 1, and q is A group represented by an integer of 1 or more. However, (r1 + r2) groups J have at least two groups [CH ₂ ═CR ⁴ —CO—X] —. Ring Z ¹ , Ring Z ² , R ¹ , R ² , R ³ , k, m, n, r1 and r2 are the same as described above. ]
In the urethane (meth) acrylate, preferably, in the formula (2), Z ¹ and Z ² are benzene rings or naphthalene rings (particularly benzene rings), and R ² is an alkyl group (C _1-4 such as a methyl group). Alkyl group etc.) or aryl group (C _6-10 aryl group such as phenyl group etc.), m is 0-2, R ³ is C _2-4 alkylene group, n is 1-4 (preferably 1-2, especially 1), r1 and r2 are each 2 or 3, each of (r1 + r2) J is a group represented by the formula (3), p is 1, A is a residue of a diisocyanate compound, and q is 1 The urethane (meth) acrylate which is -2 may be sufficient. In particular, in the formula (2), the diisocyanate compound is a diisocyanate compound selected from aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, and aromatic diisocyanate, and E is a C _2-10 alkylene group. May be.

Moreover, in Formula (2), the said diisocyanate compound is a urethane prepolymer which has an isocyanate group in the both terminal with which the diol compound and the diisocyanate compound (a) reacted, Comprising: (1) Diol compound is _C2-10. A diisocyanate compound having an alkanediol or a number average molecular weight of 200 to 5000 polyether diol, wherein (2) the diisocyanate compound (a) is selected from an aliphatic diisocyanate, an alicyclic diisocyanate, an araliphatic diisocyanate and an aromatic diisocyanate (3) The content ratio of the isocyanate group (—NCO) of the urethane prepolymer is a diisocyanate compound of 1 to 20% by weight with respect to the entire urethane prepolymer, and E is a C _2-10 alkylene group. May be .

  The urethane (meth) acrylate of the present invention is a (meth) acrylic compound having a fluorene skeleton represented by the following formula (1), a polyisocyanate compound, and an active hydrogen atom reactive with an isocyanate group. It can manufacture by making these react.

(In the formula, ring Z ¹ , ring Z ² , R ¹ , R ² , R ³ , k, m, n, r 1 and r 2 are the same as above.)
In the production method, the reaction may be performed in multiple stages. For example, a reaction product of a polyisocyanate compound and a (meth) acrylic compound is reacted with a compound having a fluorene skeleton represented by the formula (1). Also good.

  The cured product of the urethane (meth) acrylate (or the cured product obtained by curing the urethane (meth) acrylate) is also included in the present invention.

  Since the novel urethane (meth) acrylate of the present invention has a fluorene skeleton and three or more (meth) acryloyl groups, it is excellent in hardness and heat resistance. Moreover, the urethane (meth) acrylate of the present invention can efficiently improve the crosslinking density and can be produced with high purity. Furthermore, in the present invention, by using a specific polyisocyanate compound having a polyol skeleton, it is possible to obtain a urethane (meth) acrylate having excellent flexibility and handling properties despite having a fluorene skeleton. Such urethane (meth) acrylates of the present invention are excellent in the ability to disperse additives such as pigments, and are extremely useful in various applications.

  The urethane (meth) acrylate of the present invention comprises a compound having a specific fluorene skeleton having three or more hydroxyl groups, a polyisocyanate compound, and a (meth) acrylic compound having a reactive group for the isocyanate group (simply (meth ) Urethane (meth) acrylate reacted with an acrylic compound). In such a urethane (meth) acrylate of the present invention, the compound having a fluorene skeleton and the polyisocyanate compound are usually bonded via a urethane bond, and the polyisocyanate compound and the (meth) acrylic compound are Are bonded (for example, bonded via a urethane bond). That is, the compound having a fluorene skeleton and the (meth) acrylic compound are bonded via the polyisocyanate compound (or the isocyanate group of the polyisocyanate compound).

[Compound having a fluorene skeleton]
The compound having a fluorene skeleton may be a compound having a fluorene skeleton represented by the following formula (1).

(In the formula, ring Z ¹ and ring Z ² represent aromatic hydrocarbon rings, R ¹ and R ² are the same or different and represent a substituent, R ³ represents an alkylene group, k is an integer of 0 to 4; , M is 0 or an integer of 1 or more, n is 0 or an integer of 1 or more, r1 and r2 are each an integer of 1 or more, and (r1 + r2) ≧ 3 is satisfied.)
In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z ¹ and the ring Z ² include a benzene ring and a condensed polycyclic hydrocarbon ring (specifically, a condensed polycyclic ring containing at least a benzene ring). Hydrocarbon ring). Examples of the condensed polycyclic hydrocarbon corresponding to the condensed polycyclic hydrocarbon ring include condensed bicyclic hydrocarbons (for example, C _8-20 condensed bicyclic hydrocarbons such as indene and naphthalene, preferably C _10-16. Condensed bicyclic hydrocarbons) and condensed tricyclic hydrocarbons (for example, anthracene, phenanthrene, etc.) and the like. Preferable condensed polycyclic hydrocarbons include condensed polycyclic aromatic hydrocarbons (naphthalene, anthracene, etc.), and naphthalene is particularly preferable. Ring Z ¹ and ring Z ² may be the same or different rings, and may usually be the same ring.

Preferred rings Z ¹ and Z ² include a benzene ring and a naphthalene ring, and a benzene ring is particularly preferred. In addition, when the ring Z ¹ and the ring Z ² are condensed polycyclic hydrocarbon rings, the substitution positions of the ring Z ¹ and the ring Z ^{2 that} are substituted at the 9-position of fluorene are not particularly limited. ^The naphthyl group substituted on ¹ and ring Z ² may be a 1-naphthyl group, a 2-naphthyl group, or the like.

In addition, the substituent represented by the group R ¹ is not particularly limited, and examples thereof include a cyano group, a hydrocarbon group (for example, an alkyl group, an aryl group (C _6-10 aryl group such as a phenyl group)), and the like. In particular, it is often an alkyl group. Examples of the alkyl group include C _1-6 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 _1-4 alkyl group, particularly a methyl group). . In the same benzene ring, the groups R ¹ may be different from each other or the same. The groups R ¹ substituted on different benzene rings may be the same or different. In addition, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene skeleton is not particularly limited. The preferred substitution number k is 0 or 1, in particular 0. In different benzene rings, the number of substitutions k may be different but is usually the same.

The numbers r1 and r2 of the group-[(OR ³ ) _n —OH] substituted on the ring Z ¹ and the ring Z ^{2 only} have to satisfy (r1 + r2) ≧ 3, and are each 1 to 8, preferably 2 -5, more preferably 2-4, especially 2-3. In particular, when ring Z ¹ and ring Z ² are benzene rings, each of r 1 and r 2 may be 2 to 4, preferably 2 to 3, and more preferably 2. The substitution position of the group — [(OR ³ ) _n —OH] substituted on the ring Z ¹ and the ring Z ² is not particularly limited, and can be selected according to the number of r1 or r2. For example, (1) when ring Z ¹ and ring Z ² are benzene rings and both r 1 and r 2 are 2, two substitution positions among the 2 to 6 positions of the phenyl group that substitutes at the 9 position of fluorene (e.g., 3 and 4 positions; 2 and 4 positions; and 2-position and 5-position) is a well also, (2) the ring ^{Z 1} and the ring ^{Z 2} is a benzene ring, both r1 and r2 are 3, the substitution positions of 3 to 6 positions of the phenyl group substituted at the 9-position of fluorene (for example, the 2-position, the 3-position and the 4-position; the 2-position, the 4-position and the 5-position; the 3-position, 4th and 5th positions; 2nd, 4th and 6th positions).

Examples of the substituent R ² for substituting the ring Z ¹ and the ring Z ² (hereinafter, collectively referred to as ring Z) include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, C _1-20 alkyl group such as butyl group, s-butyl group, t-butyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group, etc., cycloalkyl group (cyclopentyl group, cyclo A C _5-10 cycloalkyl group such as a hexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _5-6 cycloalkyl group, etc., an aryl group [eg, a phenyl group, an alkylphenyl group (methylphenyl) Group (or tolyl group, 2-methylphenyl group, 3-methylphenyl group, etc.), dimethylphenyl group (xylyl group, etc.), naphthyl group, etc. Carbon atoms such as any C _6-10 aryl group, preferably C _6-8 aryl group, especially phenyl group], aralkyl group (C _6-10 aryl-C _1-4 alkyl group such as benzyl group, phenethyl group, etc.) Hydrogen group; alkoxy group (C _1-4 alkoxy group such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group and t-butoxy group); acyl group (C _1-6 acyl such as acetyl group) Group); alkoxycarbonyl group (C _1-4 alkoxycarbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, etc.); nitro group; cyano group; substituted amino group (dialkylamino group etc.), etc. Is mentioned.

Preferred substituents R ² are an alkyl group (eg, C _1-6 alkyl group), a cycloalkyl group (eg, C _5-8 cycloalkyl group), an aryl group (eg, C _6-10 aryl group), an aralkyl group. Hydrocarbon groups such as (for example, C _6-8 aryl-C _1-2 alkyl group), C _1-4 alkoxy groups, C _6-8 aryl groups, etc., in particular, C _1-4 alkyl groups (particularly methyl Group) or a C _6-10 aryl group (particularly a phenyl group). The substituent R ² may be substituted alone or in combination of two or more in the same ring (ring Z ¹ or ring Z ² ). Further, the substituents R ² substituted on the different rings Z ¹ and Z ² may be the same or different from each other, and may usually be the same.

The substitution number m of the substituent R ² can be appropriately selected according to the type of the ring Z ¹ and the ring Z ² and is not particularly limited. For example, 0 or 1 to 8, preferably 0 or 1 to 6 (for example, 1-5), more preferably 0 or about 1-4 may be sufficient. In particular, when ring Z ¹ and ring Z ² are benzene rings, the substitution number m is, for example, 0 or 1 to 3, preferably 0 or 1 to 2, more preferably 0 or 1 (particularly 0). It is. When ring Z ¹ and ring Z ² are condensed hydrocarbon rings such as a naphthalene ring, the preferred substitution number m is 0 or 1 to 8, preferably 0 or 1 to 4, more preferably 0 or 1. In particular, it may be zero. The number of substitutions m may be the same or different in each ring Z ¹ and ring Z ² , and is usually the same in many cases. In addition, the substitution position of the substituent R ² is not particularly limited. For example, when the ring Z is a phenyl group (or a benzene ring), the phenyl group has 2 to 6 positions (for example, 3 position, 3, 5 position). Etc.) can be substituted at an appropriate position.

The alkylene group represented by R ^3, are not particularly limited, for _{example, C 2-10} alkylene group (ethylene group, trimethylene group, a propylene group, butane-1,2-diyl groups, _C such as hexylene _{2- 6} alkylene groups) and the like, and C _2-4 alkylene groups (particularly, C _2-3 alkylene groups such as ethylene group and propylene group) are preferable. R ³ may be the same or different alkylene group depending on the ring Z ¹ and the ring Z ² , but may usually be the same alkylene group.

The number (addition mole number) n of oxyalkylene groups (OR ³ ) can be selected from a range of about 0 to 15, for example, 0 to 12 (for example, 1 to 12), preferably 0 to 8 (for example, 1 to 1). 8), more preferably 0 to 6 (for example, 1 to 6), particularly 1 or more (for example, about 1 to 4). The number of substitutions n may be the same or different depending on the ring Z ¹ and the ring Z ² . When n is 2 or more, the polyalkoxy (polyoxyalkylene) group may be composed of the same oxyalkylene group, and different oxyalkylene groups (for example, an oxyethylene group and an oxypropylene group). Although they may be mixed, they are usually composed of the same oxyalkylene group.

Typical compounds having a fluorene skeleton include 9,9-bis (polyhydroxyphenyl) fluorenes, 9,9-bis [poly (hydroxy (poly) alkoxy) phenyl] fluorenes, 9,9-bis (poly Hydroxynaphthyl) fluorenes [eg, 9,9-bis (di or trihydroxynaphthyl) fluorene, etc. [, 9,9-bis [poly (hydroxy (poly) alkoxy) naphthyl] fluorenes {eg, 9,9-bis [di- or tri (hydroxy _{C 2-4} alkoxy) naphthyl] fluorene such as 9,9-bis [di or tri (hydroxy (poly) alkoxy) naphthyl] fluorenes} and the like.

The 9,9-bis (polyhydroxyphenyl) fluorenes include 9,9-bis (dihydroxyphenyl) fluorenes, 9,9-bis (trihydroxyphenyl) fluorenes, and the like. As 9,9-bis (dihydroxyphenyl) fluorenes, for example, 9,9-bis (dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxyphenyl) fluorene (biscatecholfluorene), 9,9 -Bis (3,5-dihydroxyphenyl) fluorene and the like], 9,9-bis (dihydroxyphenyl) fluorene having a substituent {for example, 9,9-bis (alkyl-dihydroxyphenyl) fluorene [9,9-bis ( 3,4-dihydroxy-5-methylphenyl) fluorene, 9,9-bis (3,4-dihydroxy-6-methylphenyl) fluorene, 9,9-bis (2,4-dihydroxy-3,6-dimethylphenyl) ) 9,9-bis (mono- or di-C _1-4 alkyl-dihydroxyphenyl) such as fluorene Fluorene, 9,9-bis (aryl - dihydroxyphenyl) fluorene [e.g., 9,9-bis (3,4-dihydroxy-5-phenylphenyl) fluorene such as 9,9-bis (mono- or _{di-C 6 -8} aryl-dihydroxyphenyl) fluorene and the like], 9,9-bis (alkoxy-dihydroxyphenyl) fluorene [for example, 9,9- such as 9,9-bis (3,4-dihydroxy-5-methoxyphenyl) fluorene. Bis (mono- or di-C _1-4 alkoxy-dihydroxyphenyl) fluorene] and the like}.

  As 9,9-bis (trihydroxyphenyl) fluorenes, 9,9-bis (trihydroxyphenyl) fluorene [for example, 9,9-bis (2,4,6-trihydroxyphenyl) fluorene, 9,9 -Bis (2,4,5-trihydroxyphenyl) fluorene, 9,9-bis (3,4,5-trihydroxyphenyl) fluorene and the like].

  As 9,9-bis [poly (hydroxy (poly) alkoxy) phenyl] fluorenes, 9,9-bis [di (hydroxy (poly) alkoxy) phenyl] fluorenes, 9,9-bis [tri (hydroxy ( Poly) alkoxy) phenyl] fluorenes and the like.

As 9,9-bis [di (hydroxy (poly) alkoxy) phenyl] fluorenes, 9,9-bis [di (hydroxyalkoxy) phenyl] fluorene {for example, 9,9-bis [3,4-di ( 2-hydroxyethoxy) phenyl] fluorene [or 2,2′-bishydroxyethoxy-4,4 ′-(9-fluorenylidene) -bisphenoxyethanol], 9,9-bis [3,5-di (2-hydroxyethoxy) ) Phenyl] fluorene [or 3,3′-bishydroxyethoxy-5,5 ′-(9-fluorenylidene) -bisphenoxyethanol], 9,9-bis [3,4-di (3-hydroxypropoxy) phenyl] fluorene 9,9-bis [3,5-di (3-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3,4-di ( 2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3,5-di (2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3,4-di (4-hydroxybutoxy) phenyl] fluorene 9,9-bis [di (hydroxyC _2-4 alkoxy) phenyl] fluorene}, such as 9,9-bis [3,5-di (4-hydroxybutoxy) phenyl] fluorene}, 9,9 having a substituent -Bis [di (hydroxyalkoxy) phenyl] fluorene {eg 9,9-bis [alkyl-di (hydroxyalkoxy) phenyl] fluorene [eg 9,9-bis [3,4-di (2-hydroxyethoxy) -5-methylphenyl] fluorene, 9,9-bis [3,4-di (2-hydroxyethoxy) -6-methylphenyl] fluor 9,9-bis [mono or di C _1-4 alkyl-di (hydroxy C ₂ ) such as olene, 9,9-bis [2,4-di (2-hydroxyethoxy) -3,6-dimethylphenyl] fluorene _-4 alkoxy) phenyl] fluorene, etc.], 9,9-bis [aryl - di (hydroxyalkoxy) phenyl] fluorene [e.g., 9,9-bis [3,4-di (2-hydroxyethoxy) -5- aryl 9,9-bis [mono or di C _6-8 aryl-di (hydroxyC _2-4 alkoxy) phenyl] fluorene, etc.] such as phenyl] fluorene, 9,9-bis [alkoxy-di (hydroxyalkoxy) phenyl] 9,9-bis such as fluorene [e.g., 9,9-bis [3,4-di (2-hydroxyethoxy) -5-methoxyphenyl] fluorene [Mono- or _{di-C 1-4} alkoxy - di (hydroxy _{C 2-4} alkoxy) phenyl] fluorene, etc.], etc.}, etc. 9,9-bis [di (hydroxyalkoxy) phenyl] fluorenes; of 9,9 Corresponding to bis [di (hydroxyalkoxy) phenyl] fluorenes, 9,9-bis [di (hydroxypolyalkoxy) phenyl] fluorenes {for example, 9,9- 9 such as bis {3,4-di [2- (2-hydroxyethoxy) ethoxy] phenyl} fluorene, 9,9-bis {3,5-di [2- (2-hydroxyethoxy) ethoxy] phenyl} fluorene , 9-bis [di (hydroxy _{C 2-4} alkoxy _{C 2-4} alkoxy] phenyl] compounds of fluorene (n = 2) include etc.} The

As 9,9-bis [tri (hydroxy (poly) alkoxy) phenyl] fluorenes, compounds corresponding to the 9,9-bis [di (hydroxy (poly) alkoxy) phenyl] fluorenes, for example, 9,9 -Bis [tri (hydroxyalkoxy) phenyl] fluorene {eg 9,9-bis [2,3,4-tri (2-hydroxyethoxy) phenyl] fluorene [or 2,2 ', 6,6'-tetrahydroxy Ethoxy-5,5 ′-(9-fluorenylidene) -bisphenoxyethanol], 9,9-bis [2,4,6-tri (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [2,4, 5-tri (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [3,4,5-tri (2-hydroxyethoxy) phenyl] phenyl 9,9-bis such Oren [tri (hydroxy _{C 2-4} alkoxy) phenyl] fluorene}, corresponding to these 9,9-bis [tri (hydroxyalkoxy) phenyl] fluorenes, in the formula (1) 9,9-bis [tri (hydroxypolyalkoxy) phenyl] fluorenes where n is 2 or more {eg, 9,9-bis {2,4,6-tri [2- (2-hydroxyethoxy) ethoxy] phenyl } Fluorene, 9,9-bis {2,4,5-tri [2- (2-hydroxyethoxy) ethoxy] phenyl} fluorene, 9,9-bis {3,4,5-tri [2- (2- hydroxyethoxy) ethoxy] phenyl} fluorene 9,9-bis [tri (hydroxy _{C 2-4} alkoxy _{C 2-4} alkoxy] phenyl] fluorene (n = Compounds), etc.} and the like.

  In addition, 9,9-bis (polyhydroxyphenyl) fluorenes and 9,9-bis (polyhydroxynaphthyl) fluorenes are the conventional methods for producing 9,9-bis (polyhydroxyphenyl) fluorenes [(a) A method of reacting fluorenones with phenols in the presence of hydrogen chloride gas and mercaptocarboxylic acid (reference [J. Appl. Polym. Sci., 27 (9), 3289, 1982], Japanese Patent Laid-Open No. 6-145087) JP-A-8-217713), (b) a method of reacting 9-fluorenone with alkylphenols in the presence of an acid catalyst (and alkyl mercaptan) (JP-A 2000-26349), (c) hydrochloric acid, and Method of reacting fluorenones with phenols in the presence of thiols (such as mercaptocarboxylic acid) (Japanese Patent Laid-Open No. 2002-47227), (d) A method for producing bisphenolfluorene by reacting fluorenones with phenols in the presence of sulfuric acid and thiols (such as mercaptocarboxylic acid), and crystallizing with a crystallization solvent composed of hydrocarbons and polar solvent ( In Japanese Patent Application Laid-Open No. 2003-221352), the corresponding polyhydroxy compound [eg, polyhydroxybenzenes (for example, dihydroxybenzenes such as catechol, resorcinol, dihydroxytoluene, trihydroxy such as pyrogallol) Benzenes, etc.), polyhydroxynaphthalenes (eg 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc.) It can be prepared by the use of mud alkoxy benzenes, etc.).

Also, 9,9-bis [poly (hydroxy (poly) alkoxy) phenyl] fluorenes or 9,9-bis [poly (hydroxy (poly) alkoxy) naphthyl] fluorenes are 9,9-bis (polyhydroxyphenyl). ) Fluorenes or 9,9-bis (polyhydroxynaphthyl) fluorenes and a compound corresponding to the group OR ³ [eg alkylene oxide (such as C _2-4 alkylene oxide such as ethylene oxide), haloalkanol (3-chloropropanol) Etc.)] and the like].

  In addition, refer to Unexamined-Japanese-Patent No. 2005-104935 for the detail of the manufacturing method of 9,9-bis (polyhydroxyphenyl) fluorenes and 9,9-bis [poly (hydroxy (poly) alkoxy) phenyl] fluorenes. You can also.

  These compounds having a fluorene skeleton may be used alone or in combination of two or more.

Preferred compounds having a fluorene skeleton include 9,9-bis [di (hydroxy (poly) alkoxy) phenyl] fluorene {eg, 9,9-bis [3,4-di (2-hydroxyethoxy) phenyl] fluorene, 9,9- such as 9,9-bis [di (hydroxy (poly) C _2-4 alkoxy) phenyl] fluorene} such as 9,9-bis [3,5-di (2-hydroxyethoxy) phenyl] fluorene Bis [di (hydroxy (poly) alkoxy) phenyl] fluorenes (especially 9,9-bis [di (hydroxyalkoxy) phenyl] fluorenes); 9,9-bis [tri (hydroxy (poly) alkoxy) phenyl] Fluorene {for example, 9,9- such as 9,9-bis [3,4,5-tri (2-hydroxyethoxy) phenyl] fluorene 9,9-bis [tri (hydroxy (poly) alkoxy) phenyl] fluorenes such as bis [tri (hydroxy (poly) C _2-4 alkoxy) phenyl] fluorene} (especially 9,9-bis [tri (hydroxy Alkoxy) phenyl] fluorenes) and the like.

[Polyisocyanate compound]
The polyisocyanate compound is not particularly limited as long as it is a compound that can react with the hydroxyl group of the compound having a fluorene skeleton to form a bond (particularly a urethane bond). For example, polyisocyanate (aliphatic polyisocyanate, alicyclic ring) Aromatic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, etc.), modified polyisocyanates and the like. In addition, these polyisocyanate compounds may have a group (for example, ester group, halogen atom, etc.) containing a hetero atom in the molecule and / or as a substituent.

Examples of the aliphatic polyisocyanate include aliphatic diisocyanate {eg, alkane diisocyanate [eg, hexamethylene diisocyanate (HDI) (1,6-hexane diisocyanate, etc.), 2,2,4, or 2,4,4-trimethylhexa C _2-20 alkane-diisocyanate such as methylene diisocyanate, lysine diisocyanate, etc., preferably C _4-12 alkane-diisocyanate, etc.] etc.} Aliphatic polyisocyanate having 3 or more isocyanate groups (for example, 1, 3, 6 -Hexamethylene triisocyanate, triisocyanates such as 1,4,8-triisocyanatooctane) and the like.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanate {cycloalkane diisocyanate (for example, C _5-8 cycloalkane-diisocyanate such as methyl-2,4- or 2,6-cyclohexanediisocyanate), isocyanatoalkyl, and the like. cycloalkanes isocyanate [e.g., 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI) isocyanato _{C 1-6} alkyl _{-C 5-10} cycloalkane such as - isocyanates, preferably isocyanato _{C 1 -4} alkyl _{-C 5-8} cycloalkane - isocyanate, di (isocyanatomethyl) cycloalkanes [e.g., di and hydrogenated xylylene diisocyanate (isocyanato _{C 1-6} a _{Kill) C 5-10} cycloalkane, di (isocyanatomethyl cycloalkyl) alkanes [e.g., hydrogenated diphenylmethane-4,4'-diisocyanate (4,4'-methylene-bis-cyclohexyl isocyanate) bis (such as isocyanato _{C 5- 10} cycloalkyl) C _1-10 alkane etc.], polycycloalkane diisocyanate (eg norbornane diisocyanate etc.)}, alicyclic polyisocyanate having 3 or more isocyanate groups (eg 1,3,5-triisocyanatocyclohexane etc.) And the like.).

Examples of the araliphatic polyisocyanate include di (isocyanatoalkyl) arene [for example, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) (1,3- or 1,4-bis (1-isocyanato). Bis (isocyanato C _1-6 alkyl) C _6-12 arene, preferably bis (isocyanato C _1-4 alkyl) C _6-10 arene etc.] and the like] such as -1-methylethyl) benzene) Can be mentioned.

Aromatic polyisocyanates include aromatic diisocyanates {eg, arene diisocyanates [eg, C _6-12 arenes such as o-, m- or p-phenylene diisocyanate, chlorophenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate (NDI)]. Diisocyanate etc.], di (isocyanatoaryl) alkanes [for example, diphenylmethane diisocyanate (MDI) (2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate etc.), bis (isocyanato C _6-10 aryl such as tolidine diisocyanate, etc. ) C _1-10 alkane, preferably bis (isocyanato C _6-8 aryl) C _1-6 alkane etc.], heteroatom (oxygen atom, sulfur atom etc. Etc.] [for example, di (isocyanatophenyl) ether, di (isocyanatophenyl) sulfone, etc.]} aromatic polyisocyanates having three or more isocyanate groups (for example, 4,4′-diphenylmethane) -2,2 ', 5,5'-triisocyanate, etc.) and the like.

  In the polyisocyanate compound (or polyisocyanate, particularly diisocyanate), the content ratio of the isocyanate group (—NCO) is, for example, 10 to 65% by weight (for example, 15 to 62% by weight), preferably based on the whole polyisocyanate compound. May be 20 to 60% by weight (for example, 22 to 58% by weight), more preferably 25 to 57% by weight (for example, 27 to 56% by weight), and particularly about 30 to 55% by weight.

  Examples of modified polyisocyanates (or derivatives) include multimers (dimers, trimers, etc.), carbodiimide bodies, biuret bodies, allophanate bodies, uretdione bodies, polyol modified bodies, polyamine modified bodies, and the like. Can be mentioned.

  The polyisocyanate compound (or polyisocyanate) is usually a diisocyanate compound [aliphatic diisocyanate (eg, HDI), alicyclic diisocyanate (eg, IPDI), araliphatic diisocyanate (eg, XDI, TMXDI), aromatic diisocyanate ( For example, MDI, TDI, NDI) are often used. Diisocyanates such as IPDI can be suitably used because they are non-yellowing and have low toxicity.

  In the present invention, in particular, a polyol-modified product (specifically, a polyol-modified product of polyisocyanate) can be suitably used. Such a polyol modified product is useful for imparting flexibility and handling properties to urethane (meth) acrylate. Moreover, since the ratio of the urethane bond with respect to the whole urethane (meth) acrylate can be made small by using a polyol modified body, it is advantageous also for a heat resistant improvement.

(Polyol modified product)
The polyol-modified product usually has a polyol skeleton in the molecule. A polyisocyanate compound having such a polyol skeleton (sometimes referred to as polyisocyanate compound (A)) is a compound having a polyol skeleton (or a skeleton derived from a polyol compound) in the molecule and having a plurality of isocyanate groups. The structure is not particularly limited as long as it is present, but usually a polyisocyanate compound having a polyol skeleton and a terminal isocyanate group [or a polyol compound (particularly a diol compound) and a polyisocyanate compound (a) (particularly a diisocyanate compound) reacted. Reaction product (or urethane prepolymer)]. That is, the polyisocyanate compound (A) is usually a reaction product obtained by reacting a diol compound and a diisocyanate compound, and may be a compound having an isocyanate group at both ends (or a urethane prepolymer).

  Examples of the polyol compound (or a compound corresponding to the polyol skeleton) include a low molecular weight polyol (polyol) and a high molecular weight polyol (or polymer polyol).

Examples of the low molecular weight polyol (low molecular polyol skeleton) include alkanediol (ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol. C _2-20 alkane diols such as 1,8-octanediol, preferably C _2-12 alkane diols, more preferably C _2-10 alkane diols, especially C _2-6 alkane diols), di to tetraalkylene glycols ( For example, di to tetra C _2-4 alkylene glycol such as diethylene glycol and triethylene glycol).

Examples of the high molecular weight polyol (polymer polyol skeleton, polymer polyol skeleton) include polyether polyol, polyester polyol, polyolefin polyol, and polycarbonate polyol. Examples of polyether polyols (particularly polyether diols) include polyalkylene oxides [or polyalkylene glycols such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran oxide homopolymers or copolymers (for example, Polyoxy C _2-6 alkylene glycol (or poly (oxy C _2-6 alkylene)) such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyethylene oxide-polypropylene oxide block copolymer, preferably polyoxy C _2-4 Alkylene glycol (or poly (oxy C _2-4 alkylene) etc.)], bisphenol A or hydrogenated bisphenol A alkylene oxide adduct (For example, an adduct in which 1 to 5 moles of C _2-4 alkylene oxide is added to a hydroxyl group) can be exemplified.

Examples of polyester polyols (particularly polyester diols) include dicarboxylic acid components [dicarboxylic acids or derivatives thereof (for example, dicarboxylic acid lower alkyl esters (such as C _1-2 alkyl esters such as methyl esters), dicarboxylic acid halides, etc.)] Reaction products with diol components, homopolymers or copolymers (poly-ε-caprolactone, etc.) of lactones (C _3-10 lactones such as ε-caprolactone, δ-valerolactone, etc.) Dicarboxylic acid components As the dicarboxylic acid, aromatic dicarboxylic acid (for example, dicarboxylic acid such as terephthalic acid and isophthalic acid), aliphatic dicarboxylic acid (for example, linear C _4-10 dicarboxylic acid such as adipic acid and sebacic acid) In addition, as the diol component, Le Kanji ol (illustrated above alkanediols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, _{C 2,} such as neopentyl glycol Polyether diols such as _-10 alkane diols, preferably C _2-6 alkane diols), polyalkane diols (eg, polyalkane diols exemplified above such as diethylene glycol), etc. These dicarboxylic acid components and diols Each component may be used alone or in combination of two or more.

  Examples of the reaction product (polyester polyol) of a dicarboxylic acid component and a diol component include, for example, polyethylene adipate, polydiethylene adipate, polypropylene adipate, polytetramethylene adipate, polyhexamethylene adipate, and these Copolymers in which the components are combined are included.

  Examples of polyolefin-based polyols (particularly polyolefin-based diols) include polyalkadienes having hydroxyl groups at both ends (for example, polybutadienes such as 1,2-polybutadiene and 1,4-polybutadiene, polyisoprene) or hydrogenation thereof. And polyisobutylene having hydroxyl groups at both ends. Such polyolefin-based diols include radical polymerization (and hydrogenation) of conjugated diene monomers (butadiene, isoprene, etc.) using hydroxyl group-containing initiators such as hydrogen peroxide, and anionic living conjugated diene monomers. It can be produced by a polymerization method or the like.

  As the polycarbonate-based polyol, for example, a polycarbonate diol (for example, a polysiloxane) obtained by a reaction between a polyol (alkane polyol, polyether polyol, polyester polyol and the like exemplified above) and a dialkyl carbonate (for example, an alkyl carbonate such as dimethyl carbonate) is used. Hexamethylene carbonate) and the like.

Representative polyol compounds include diol compounds. Preferred polyol compounds include alkane diols, polyether diols, polyester diols and the like, and in particular, alkane diols (such as C _2-10 alkane diols), polyether diols (eg, polyethylene glycol, polypropylene glycol, poly Polyoxy _C2-4 alkylene glycols such as tetramethylene ether glycol) are preferred.

  The molecular weight of the high molecular weight polyol (polymer polyol) is a number average molecular weight, for example, 180 or more (for example, about 190 to 6000), preferably 200 or more (for example, about 200 to 5000), more preferably 250 to 2000, particularly It may be 300 to 1500 (for example, 400 to 1300), particularly preferably about 500 to 1200.

  In the reaction product (urethane prepolymer), the polyisocyanate compound (a) is a compound capable of forming a urethane prepolymer by reaction (formation of a urethane bond) with the polyol compound (particularly a diol compound). The polyisocyanate exemplified above (eg, aliphatic polyisocyanate, alicyclic polyisocyanate, araliphatic polyisocyanate, aromatic polyisocyanate, etc.), modified polyisocyanate [or derivative, eg, multimer (Dimer, trimer, etc.), alohanate, etc.].

  The polyisocyanate compound (a) is usually a diisocyanate compound [aliphatic diisocyanate (eg, HDI), alicyclic diisocyanate (eg, IPDI), araliphatic diisocyanate (eg, XDI, TMXDI), aromatic diisocyanate (eg, MDI, TDI, NDI), etc.] in many cases.

  In the polyisocyanate compound (a), the content ratio of the isocyanate group (—NCO) is, for example, 10 to 65% by weight (for example, 15 to 62% by weight), preferably 20 to 20% by weight with respect to the whole polyisocyanate compound. It may be 60% by weight (for example, 22 to 58% by weight), more preferably 25 to 57% by weight (for example, 27 to 56% by weight), and particularly about 30 to 55% by weight.

  The polyisocyanate compound (A) having a polyol skeleton may be a compound having a plurality of isocyanate groups (urethane prepolymer), and preferably a diisocyanate compound [or urethane diisocyanate, in particular, a diisocyanate compound having isocyanate groups at both ends ( Urethane prepolymer)]. A diisocyanate compound having such a polyol skeleton is usually (i) a compound in which a diisocyanate compound is bonded by a urethane bond via a diol compound and has an isocyanate group at both ends (a compound having two urethane bonds in the molecule). (Ii) A compound in which a diol compound and a diisocyanate compound react to have isocyanate groups at both ends (a compound having 4 or more urethane bonds in the molecule) may be used.

  The polyisocyanate compound (A) having a specific polyol skeleton includes a compound (diisocyanate compound) represented by the following formula (A1).

^{OCN-A 1 - (NH-} COO-A 2 -OCO-NH-A 1) r -NCO (A1)
(In the formula, A ¹ represents the residue of the polyisocyanate compound (a), A ² represents the residue of the polyol compound, and r represents an integer of 1 or more)
In the above formula, A ¹ corresponds to the polyisocyanate compound (a), A ² corresponds to the polyol compound, and examples of each compound (polyisocyanate compound (a), polyol compound) are the same as described above. A plurality of A ¹ may be the same or different, and may usually be the same. Moreover, r should just be 1 or more, for example, 1-20, Preferably it is 1-15, More preferably, about 1-10 may be sufficient. In particular, when n is 2 or more, n may be 2 to 8, preferably 2 to 6, and more preferably about 2 to 4.

Preferred combinations of A ¹ , A ² and r include: (i) A ¹ is a diisocyanate compound (eg, a diisocyanate compound selected from aliphatic diisocyanates, alicyclic diisocyanates, araliphatic diisocyanates, and aromatic diisocyanates). A residue, A ² is a residue of a low molecular weight diol (eg, alkane diol such as C _2-10 alkane diol), and r is 2 or more (eg, 2 to 10, preferably 2 to 5). Combination (ii) A ¹ is the residue of a diisocyanate compound (eg, a diisocyanate compound selected from aliphatic diisocyanates, alicyclic diisocyanates, araliphatic diisocyanates, and aromatic diisocyanates), and A ² is a polyether-based Diol (eg, polyethylene glycol) Call, polypropylene glycol, a polyoxy C _2-4 alkyl residue of glycol), such as polytetramethylene ether glycol, r is the like combination is 1.

  The polyisocyanate compound (A) may be a commercially available product, or can be prepared by a conventional method in which a polyol compound and a polyisocyanate compound (a) are reacted.

  In the polyisocyanate compound (A) having a polyol skeleton, the content ratio of the isocyanate group (—NCO) is, for example, 0.5 to 30% by weight (for example, 1 to 27% by weight) with respect to the whole polyisocyanate compound, Preferably 1.5 to 25% by weight (eg 2 to 22% by weight), more preferably 3 to 20% by weight (eg 4 to 18% by weight), in particular 5 to 15% by weight (eg 6 to 12% by weight). %), And usually about 1 to 20% by weight.

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

[(Meth) acrylic compound]
The (meth) acrylic compound has a reactive group with respect to an isocyanate group (or an active hydrogen atom reactive with an isocyanate group). That is, in the urethane (meth) acrylate of the present invention, at least one (particularly one or one) of the isocyanate groups (particularly two) of the polyisocyanate compound (particularly diisocyanate compound) is (meth). It reacts with the acrylic compound (the reactive group of the (meth) acrylic compound) to form a bond.

  Examples of the reactive group (or functional group) include a hydroxyl group and an amino group. A preferred reactive group is a hydroxyl group. The (meth) acrylic compound may have these reactive groups alone or in combination of two or more, and may have a plurality of the same reactive groups (for example, hydroxyl groups). A corresponding bond is formed by the reaction between the (meth) acrylic compound and the polyisocyanate compound. For example, a urethane bond is formed in the reaction between a hydroxyl group as a reactive group and an isocyanate group, and a urea bond is formed in the reaction between an amino group as a reactive group and an isocyanate group.

  Typical (meth) acrylic compounds include compounds represented by the following formula (B).

^{_{[CH 2 = CR 4 -CO-}} X] q - (E) p -Y-H (B)
(Wherein R ⁴ represents a hydrogen atom or a methyl group, X and Y are the same or different and represent a direct bond, an ether group or an imino group, E represents a linking group, p is 0 or 1, and q is 1) (It is an integer above.)
In the above formula (B), preferred X and Y include an ether group. X and Y are not usually direct bonds at the same time. In the formula (B), typical combinations of X, p and Y include (i) a combination in which X is an ether group or imino group, p is 1 and Y is an ether group, (ii) X Includes an ether group or imino group, p is 0, and Y is a direct bond.

In the formula (B), as a compound corresponding to the linking group E, alkane (C _1-20 alkane such as methane, ethane, propane, butane, isopentane, 2,2-dimethylpropane, 2,2-dimethylbutane), Hydrocarbon compounds such as bridged cyclic hydrocarbons (such as norbornane); having ether bonds such as dialkyl ethers (such as di-C _2-4 alkyl ethers such as diethyl ether) and polyoxyalkylenes (such as polyoxy-C _2-4 alkylene) Compound: Examples include compounds having an ester group such as (poly) hydroxycarboxylic acid (6-hydroxyhexanoic acid, polyε-caprolactone, etc.).

These compounds (or linking group E) are substituted with a substituent [halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, alkoxy group (C _1-6 alkoxy group such as methoxy group, ethoxy group, etc.). And an aryloxy group (such as a phenoxy group)]. The above substituents may be substituted for the substituents alone or in combination of two or more.

  The linking group E is a polyvalent group (divalent group, trivalent group, tetravalent group, etc.) determined by the number of q. For example, in the formula (B), when q is 1, the linking group E is a divalent group corresponding to the exemplified compounds described below. A typical linking group E is represented by the following formula (E1). And the like.

-[R ^a- (OR ^b ) _t- (OCOR ^c ) _u ]-(E1)
(Wherein R ^a , R ^b , and R ^c are hydrocarbon groups that may have a substituent, and t and u each represent 0 or an integer of 1 or more)
In the groups R ^a , R ^b , and R ^c , the hydrocarbon group may be a hydrocarbon group corresponding to the hydrocarbon compound exemplified above [for example, an alkylene group (or an alkylidene group such as a methylene group, an ethylene group, a propylene group, C _1-20 such as trimethylene group, tetramethylene group, pentamethylene group, 2,2-dimethylpropane-1,3-diyl group, 2-methyl-2-ethylpropane-1,3-diyl group, hexamethylene group, etc. Alkylene group, preferably C _2-10 alkylene group, more preferably C _2-6 alkylene group, etc.].

Preferred groups R ^a include C _2-10 alkylene groups (particularly C _2-6 alkylene groups such as ethylene groups). Preferred groups R ^b include alkylene groups (eg, C _2-4 alkylene groups such as ethylene groups), and preferred groups R ^c include alkylene groups (eg, tetramethylene group, pentamethylene group, hexamethylene group). C _2-6 alkylene group such as methylene group). T and u may each be 0 to 20 (for example, 0 to 10), preferably 0 to 6, and more preferably about 0 to 4 (for example, 0 to 2). In particular, u may be 0 or 1, preferably 0. In addition, examples of the substituent that substitutes the hydrocarbon group include the substituents exemplified above (halogen atom, hydroxyl group, etc.). In the formula (B), q may be 1 to 6, preferably 1 to 4, more preferably 1 to 3 (for example, 1 to 2), particularly 1.

  Typical (meth) acrylic compounds include hydroxyl group-containing (meth) acrylic compounds, amino group-containing (meth) acrylic compounds [for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl N-monosubstituted (meth) acrylamides such as (meth) acrylamide and N-butoxymethyl (meth) acrylamide], epoxy group-containing (meth) acrylic compounds (such as glycidyl (meth) acrylate), and the like.

  Examples of the hydroxyl group-containing (meth) acrylic compound include a monofunctional (meth) acrylic compound having a hydroxyl group and a polyfunctional (meth) acrylic compound having a hydroxyl group.

Examples of the monofunctional (meth) acrylic compound having a hydroxyl group include a hydroxyl group-containing mono (meth) acrylate {for example, hydroxyalkyl (meth) acrylate [for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxy Hydroxy C _2-20 alkyl- (meth) acrylate such as propyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, preferably hydroxy C _2-12 alkyl- (meth) acrylate, more preferably hydroxy C _2-6 Alkyl- (meth) acrylate], polyalkylene glycol mono (meth) acrylate [for example, poly C _2-4 alkyle such as diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc. Mono (meth) acrylate], mono (meth) acrylate of polyol having 3 or more hydroxyl groups [for example, alkane polyol mono (meth) acrylate such as glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, etc. , Etc.], N-hydroxyalkyl (meth) acrylamide (for example, N-methylol (meth) acrylamide, N- (2- hydroxyethyl) (meth) acrylamide such as N- hydroxy C _1-4 alkyl (meth) acrylamide), these compounds (e.g., a lactone to a hydroxyl group of a hydroxyalkyl (meth) acrylate) (e.g., epsilon C _4-10 lactone) was added adduct such as caprolactone (e.g., a lactone are added about 1-5 moles adduct) and the like.

Examples of the polyfunctional (meth) acrylic compound having a hydroxyl group include alkane polyol poly (meth) acrylate having a hydroxyl group [for example, glycerin di (meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolpropane C _3-20 alkane polyol-di to hexa (meth) acrylate such as (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, preferably C _3-10 alkane polyol-di to tetra ( Meth) acrylate], poly (alkane polyol) poly (meth) acrylate having a hydroxyl group [e.g. diglycerin di or tri (meth) acrylate, ditrimethylolethane or tri (meth) a] Relate, ditrimethylolpropane di or tri (meth) acrylate, dipentaerythritol di to penta (meth) C _3-20 dimer or trimer of di- to hexa (meth) acrylate of an alkane polyol, such as acrylates, preferably C _3-10 And alkane polyol dimer or trimer di to tetra (meth) acrylate].

  These (meth) acrylic compounds may be used alone or in combination of two or more.

  Preferred (meth) acrylic compounds include hydroxyl group-containing (meth) acrylic compounds [for example, monofunctional (meth) acrylic compounds having a hydroxyl group such as hydroxyalkyl (meth) acrylate (particularly hydroxyl group-containing mono (Meth) acrylate)].

[Urethane (meth) acrylate]
The urethane (meth) acrylate of the present invention may be a urethane (meth) acrylate having 2 or more (meth) acryloyl groups (or bifunctional or more), and usually 3 or more (for example, 3 to 12, preferably May be a urethane (meth) acrylate having a (meth) acryloyl group of 3 to 8, more preferably 4 to 6). The urethane (meth) acrylate of the present invention may be a mixture of urethane (meth) acrylates having different numbers of (meth) acryloyl groups. The number of (meth) acryloyl groups of such urethane (meth) acrylates depends on the reaction ratio between the compound having the fluorene skeleton, the polyisocyanate compound, and the (meth) acrylic compound, and the (meth) acrylic compound. It can select by selecting the kind of system compound.

  Representative urethane (meth) acrylates of the present invention include compounds represented by the following formula (2).

[Wherein J is a hydrogen atom or the following formula (3)

(Wherein R ⁴ represents a hydrogen atom or a methyl group, A represents a residue of a polyisocyanate compound, X and Y are the same or different and represent a direct bond, an ether group or an imino group, and E represents a linking group. P is 0 or 1, and q is an integer of 1 or more. However, (r1 + r2) groups J have at least two groups [CH ₂ ═CR ⁴ —CO—X] —. Ring Z ¹ , Ring Z ² , R ¹ , R ² , R ³ , k, m, n, r1 and r2 are the same as described above. ]
In the above formula (3), the residue A corresponds to the exemplified polyisocyanate compound. That is, the residue A is usually a divalent group corresponding to the polyisocyanate compound. Moreover, the said Formula (3) respond | corresponds to the compound represented by the said Formula (B). In the formula (3), X, Y, E, p and q are also the same as described above. Preferred X and Y are ether groups. Note that groups or coefficients such as R ⁴ , X, E, Y, p, and q may be the same or different depending on J, and may usually be the same.

In the formula (2), the group J may be a hydrogen atom or a group represented by the formula (3), and may be different depending on the number of r1 or r2. For example, (i) when r1 (or r2) is 2, one J may be a hydrogen atom and the other J may be a group represented by the formula (3). Preferably, all of the (r1 + r2) groups J may be a group represented by the formula (3). (Ii) Of the Js in the ring Z ¹ and the ring Z ² , one J is represented by the formula (3) The other J may be a hydrogen atom, and (iii) J may be configured in a combination of these. Note that (r1 + r2) groups J (or a compound represented by the formula (2)) have at least two groups [CH ₂ = CR ⁴ —CO—X] — ((meth) acryloyl group), that is, And urethane (meth) acrylate having at least two (meth) acryloyl groups.

  In the compound represented by the formula (2), typical combinations include the following combinations.

Z ¹ and Z ² are a benzene ring or a naphthalene ring (particularly a benzene ring), R ² is an alkyl group (particularly a C _1-4 alkyl group such as a methyl group) or an aryl group (particularly a C _6-8 such as a phenyl group). Aryl group), m is 0 to 2 (eg, 0), R ³ is a C _2-4 alkylene group (particularly an ethylene group), and n is 1 or more (eg, 1 to 4, preferably 1 to 2, more preferably). 1), r1 and r2 are each 2 or 3, each of (r1 + r2) J is a group represented by the formula (3), and X and Y are ether groups (that is, (meth) acryloyloxy groups) ), P is 1, A is a residue of a diisocyanate compound, and q is 1 to 2 (particularly 1).

  In the above combinations, preferred diisocyanate compounds include, for example, diisocyanate compounds selected from aliphatic diisocyanates, alicyclic diisocyanates, araliphatic diisocyanates, and aromatic diisocyanates.

In the above combination, preferable diisocyanate compounds also include urethane prepolymers having isocyanate groups at both ends where the diol compound and diisocyanate compound (a) have reacted. In such a urethane prepolymer, the diol compound may be a diol compound exemplified above, such as an alkanediol (for example, C _2-10 alkanediol) and a polymer diol compound [for example, a polyether diol (for example, polytetramethylene). A diol compound selected from polyoxy C _2-4 alkylene glycol such as ether glycol). In such a diol compound, the number average molecular weight of the polymer diol compound may be in the range exemplified above (for example, the number average molecular weight of about 200 to 5000). Examples of the diisocyanate compound (a) include the above-exemplified compounds, for example, diisocyanate compounds selected from aliphatic diisocyanates, alicyclic diisocyanates, araliphatic diisocyanates and aromatic diisocyanates. Moreover, the content rate of the isocyanate group (-NCO) of a urethane prepolymer (or polyisocyanate compound (A)) is the range of the said illustration (for example, about 1 to 20 weight% with respect to the whole urethane prepolymer), Also good.

Further, in the above combination, E represents a group represented by the formula (E1) [for example, 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 C _2-6 alkylene group, etc.)].

[Production method]
The urethane (meth) acrylate (such as the compound represented by the formula (2)) of the present invention includes a compound having the fluorene skeleton (particularly a compound having a fluorene skeleton represented by the formula (1)), It can be produced by reacting a polyisocyanate compound with the (meth) acrylic compound.

  The reaction may be carried out by reacting these components in the same reaction system. However, in order to obtain urethane (meth) acrylate efficiently, usually, a polyisocyanate compound, a compound having the fluorene skeleton and the above ( After reacting one component of the (meth) acrylic compound, the obtained reaction product (precursor) is reacted with the other component [ie, reacted in multiple steps (eg, two steps)] There are many cases. In particular, a compound having a fluorene skeleton (particularly a compound having a fluorene skeleton represented by the formula (1)) as a reaction product (urethane (meth) acrylate precursor) of the (meth) acrylic compound and the polyisocyanate compound. ) May be reacted. Since the compound having a fluorene skeleton has three or more hydroxyl groups reactive with an isocyanate group, there is a risk of gelation when reacted with a polyisocyanate compound. By reacting with an acrylic compound, urethane (meth) acrylate can be efficiently produced while suppressing such gelation.

  That is, in such a multistage reaction, a polyisocyanate compound and the one component (especially a (meth) acrylic compound) are reacted, and a compound having an isocyanate group at the terminal (a precursor of urethane (meth) acrylate) ) And reacting such a precursor with the other component to prepare urethane (meth) acrylate.

  In the reaction (preparation of the precursor) between the polyisocyanate compound and one component (for example, (meth) acrylic compound), the usage ratio of both components can be appropriately selected according to the type of the one component. For example, when a (meth) acrylic compound is used as one component, the ratio (preparation ratio) of the polyisocyanate compound (particularly the diisocyanate compound) is 0.5 with respect to 1 mole of the (meth) acrylic compound. To 1.5 mol, preferably 0.7 to 1.2 mol (e.g. 0.8 to 1.1 mol), more preferably 0.9 to 1.05 mol (e.g. 0.95 to 1.04). Mol) degree.

  You may perform reaction with a polyisocyanate compound and one component (for example, (meth) acrylic-type compound) in a solvent. The solvent is not particularly limited as long as it is inert or non-reactive with respect to the polyisocyanate compound (and one component), and examples thereof include ethers (for example, dialkyl such as diethyl ether and dipropyl ether). Ethers, cyclic ethers such as 1,4-dioxane, dioxolane, tetrahydrofuran, etc.), ketones (eg, dialkyl ketones such as acetone, methyl ethyl ketone, diisopropyl ketone, isobutyl methyl ketone), esters (eg, methyl acetate, ethyl acetate, Acetates such as butyl acetate), hydrocarbons (for example, aromatic hydrocarbons such as toluene, xylene, ethylbenzene), halogen solvents (methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, etc.) Halogenated hydrocarbons), and the like nitriles (such as acetonitrile). These solvents may be used alone or in combination of two or more.

  Moreover, you may perform reaction with a polyisocyanate compound and one component in presence of a catalyst. Examples of the catalyst include organic tin compounds (for example, tin carboxylates such as tin octylate, dibutyltin diacetate, dibutyltin dioctoate, and dibutyltin dilaurate), metal naphthenates (copper naphthenate, zinc naphthenate, naphthene). Organometallic catalysts such as cobalt acid; tertiary amines [eg, trialkylamines such as triethylamine, chain tertiary amines such as benzyldimethylamine; pyridine, methylpyridine, N, N-dimethylpiperazine, tri Cyclic tertiary amines such as ethylenediamine] and the like. These catalysts may be used alone or in combination of two or more.

  The amount of the catalyst used is, for example, 0.001 to 3 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 to 100 parts by weight of the total amount of the polyisocyanate compound and one component. It may be about ˜1 part by weight (for example, 0.02 to 0.5 part by weight). In particular, when one component is the diol, the amount of the catalyst used may be 0.005 to 5 parts by weight, preferably about 0.01 to 1 part by weight with respect to 100 parts by weight of the diol.

  In addition, when one component is a (meth) acrylic-type compound, you may react in presence of a polymerization inhibitor (thermal polymerization inhibitor or inhibitor). As polymerization inhibitors, phenol polymerization inhibitors (hydroquinone, hydroquinone monomethyl ether, methoquinone, 2-t-butylhydroquinone, 4-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, etc.), phenothiazine And heavy metal compounds (for example, heavy metal halides such as copper chloride, and heavy metal acid salts such as copper naphthoate and cobalt naphthoate). These polymerization inhibitors may be used alone or in combination of two or more. The polymerization inhibitor may be added to the reaction system in advance or after the reaction.

  The reaction between the polyisocyanate compound and one component may be carried out at room temperature or under heating (for example, 40 to 150 ° C., preferably 50 to 120 ° C., more preferably about 60 to 100 ° C.). Also good. When one component is the diol, the reaction may be carried out particularly under heating. Note that the reaction may be performed in an inert atmosphere (an atmosphere of nitrogen, helium, argon, or the like).

  And the precursor (urethane prepolymer) of the obtained urethane (meth) acrylate and the other component (for example, compound which has a fluorene skeleton) are made to react. The precursor may be separated prior to the reaction with the other component. Usually, the other component is mixed and reacted in the reaction system of the polyisocyanate compound and one component. Also good.

  In the reaction between the precursor and the other component (for example, the compound having the fluorene skeleton), the ratio (charge ratio) of the other component can also be selected according to the type of the other component. For example, when the other component is a compound having the fluorene skeleton, the ratio of the precursor (or the polyisocyanate compound) is 1 mol or more (for example, 1.5 mol) with respect to 1 mol of the compound having a fluorene skeleton. About 2 to 6 mol, for example, 2 to 5 mol, preferably 2.5 to 4.5 mol, and more preferably about 3 to 4.2 mol.

  In the reaction between the precursor and the other component, a solvent or a catalyst may be newly added, and the kind and ratio thereof are the same as described above. The reaction conditions are the same as described above. Furthermore, when the other component is a (meth) acrylic compound, it may be reacted in the presence of a polymerization inhibitor, as described above, or a polymerization inhibitor may be added after the reaction.

  After completion of the reaction, the product urethane (meth) acrylate can be separated and purified by a conventional separation method, for example, separation means such as distillation, concentration, extraction and filtration, or a separation means combining these. Usually, the solvent component may be separated from the product after completion of the reaction using vacuum distillation or the like.

[Polymerizable composition and cured product]
The urethane (meth) acrylate of the present invention may be used as it is as a polymerizable (photopolymerizable) compound, and may constitute a polymerizable composition (thermally polymerizable composition or photopolymerizable composition). The polymerizable composition (heat or photopolymerizable composition) may be composed of, for example, the urethane (meth) acrylate and a polymerization initiator. In the polymerizable composition, urethane (meth) acrylates may be used alone or in combination of two or more.

  The polymerization initiator can be selected depending on the application. For example, in the case of constituting a photopolymerizable composition, a photopolymerization initiator such as benzoins (benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether) is used. Benzoin alkyl ethers, etc.), phenyl ketones [for example, acetophenones (eg, acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc.), alkylphenyl ketones such as 2-hydroxy-2-methylpropiophenone; cycloalkylphenylketo such as 1-hydroxycyclohexyl phenyl ketone ), Aminoacetophenones {2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 etc.}, anthraquinones (anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc.), thioxanthones (2,4-dimethylthioxanthone, 2,4-diethylthioxanthone) , 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.), ketals (acetophenone dimethyl ketal, benzyldimethyl ketal, etc.), benzophenones (benzophenone, etc.), xanthones, phosphine oxides (for example, 2 4,6 etc. trimethyl benzoyl diphenyl phosphine oxide), and others. These photopolymerization initiators may be used alone or in combination of two or more.

  In addition, as the thermal polymerization initiator, dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxide (lauroyl peroxide, etc.), dialoyl peroxide ( Benzoyl peroxide, 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.] ], Peroxides such as ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds [2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyronitrite) ), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile)], azoamide compound {2,2′-azobis { 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like}, azoamidine compounds {2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2 '-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride etc.}, azoalkane compound [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis ( 4-cyanopentanoic acid), etc.], and azo compounds having an oxime skeleton [2,2′-azobis (2-methylpropionamidooxime), etc.] . You may use a thermal-polymerization initiator individually or in combination of 2 or more types.

  The polymerization initiator may be composed of a thermal polymerization initiator and a photopolymerization initiator.

  The amount of the polymerization initiator used is 0.1 to 30 parts by weight (for example, 0.5 to 30 parts by weight), preferably 1 to 20 parts by weight (for example, 1) with respect to 100 parts by weight of the urethane (meth) acrylate. 0.5 to 15 parts by weight), more preferably about 2 to 10 parts by weight, and usually about 1 to 10 parts by weight.

  Moreover, you may combine a photoinitiator with a photosensitizer. As photosensitizers, tertiary amines {eg, trialkylamines, trialkanolamines (such as triethanolamine), ethyl N, N-dimethylaminobenzoate [such as ethyl p- (dimethylamino) benzoate] , N, N-dimethylaminobenzoic acid amyl [p- (dimethylamino) benzoic acid amyl etc.] and other dialkylaminobenzoic acid alkyl esters, 4,4-bis (diethylamino) benzophenone (Michler's ketone) and other bis (dialkylamino) Benzophenone, dialkylaminobenzophenone such as 4- (dimethylamino) benzophenone}, polythiols [for example, 1,4-bis (3-mercaptobutyloxy) butane (manufactured by Showa Denko KK, “Karenz MT”, etc.), Pentaerythritol tetrakis (3- Mercaptoethyloleates butyrate)], and others conventional photosensitizers such. The photosensitizers may be used alone or in combination of two or more.

  The amount of the photosensitizer used is 5 to 200 parts by weight, preferably 10 to 150 parts by weight, and more preferably about 20 to 100 parts by weight with respect to 100 parts by weight of the polymerization initiator (photopolymerization initiator). May be.

  Furthermore, the polymerizable composition can be prepared by using diluents and conventional additives such as colorants, stabilizers (heat stabilizers, antioxidants, UV absorbers, etc.), fillers, antistatic agents as necessary. , Flame retardants, flame retardant aids, leveling agents, thermal polymerization inhibitors and the like may be included. Diluents and additives may be used alone or in combination of two or more.

  Diluents include reactive diluents, non-reactive diluents and the like. As the reactive diluent (polymerizable diluent), a monofunctional monomer [for example, (meth) acrylic compound (for example, (meth) acrylic compound in addition to the above-illustrated (meth) acrylic compound, etc.) (Meth) acrylic acid esters, etc.), aromatic vinyl monomers (such as styrene), etc.], multifunctional monomers {for example, polyfunctional (meth) acrylic compounds [for example, the multifunctional (meta) described above ) Acrylic compounds, (poly) alkylene glycol di (meth) acrylate (ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, hexanediol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, etc.) Acrylic compounds; glycerin tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) Trifunctional or higher functional (meth) acrylic compounds such as acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate], triallyl (iso) cyanurate, etc.} Is mentioned. The reactive diluent may be used alone or in combination of two or more.

  Even if the usage-amount of a reactive diluent is 1-100 weight part with respect to 100 weight part of urethane (meth) acrylates, Preferably it is 1-50 weight part, More preferably, it is about 1-30 weight part. Good.

  Diluents include non-reactive diluents. When a non-reactive diluent is used, the applicability of the polymerizable composition can be improved. Non-reactive diluents (or solvents) include organic solvents such as aliphatic hydrocarbons such as hexane, heptane, octane and decane; ketones such as ethyl methyl ketone and cyclohexanone; toluene, xylene, tetramethylbenzene and the like Aromatic hydrocarbons: glycols such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether Ethers; carboxylate esters (methyl acetate, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbide Ether acetate, propylene glycol monomethyl ether acetate, acetate esters such as dipropylene glycol monomethyl ether acetate, butyl lactate, etc.), esters such as carbonate esters (propylene carbonate, etc.); petroleum solvents such as petroleum ether, petroleum naphtha, solvent naphtha, etc. Can be illustrated. A non-reactive diluent can be used individually or in combination of 2 or more types.

  The use amount (addition amount) of the non-reactive diluent varies depending on the coating method and the like. Preferably, it may be about 30 to 200 parts by weight.

  The urethane (meth) acrylate or polymerizable composition (particularly, photopolymerizable composition) of the present invention is useful for obtaining a cured product (molded product) that has been polymerized or cured (or crosslinked). Such a cured product obtained by curing the urethane (meth) acrylate (or polymerizable composition) is subjected to a curing treatment (heating treatment or light treatment) in the polymerizable composition in the molding process or after molding depending on the form of the molded body. (Irradiation treatment). For example, a film-like cured product is applied to a substrate with a polymerizable composition (or urethane (meth) acrylate, hereinafter the same) to form a coating film (or thin film), and then subjected to a curing treatment. May be obtained. For the formation of such a coating film (or thin film), conventional methods such as flow coating method, spin coating method, spray coating method, screen printing method, casting method, bar coating method, curtain coating method, roll coating method are used. A dip method or the like can be used. Moreover, after application of the polymerizable composition (after application), a drying process may be performed by a conventional method, and drying may be performed by heating as necessary. The heating temperature in drying can be appropriately selected according to the type of polymerization initiator and diluent (non-reactive diluent), and is usually about 40 to 250 ° C.

  The thickness of the coating film (or thin film) may be, for example, from 0.01 to 100 μm, preferably from 0.05 to 10 μm, more preferably from about 0.1 to 1 μm, depending on the application.

  The curing treatment for the polymerizable composition can be selected according to the type of the polymerization initiator (thermal polymerization initiator and / or photopolymerization initiator), and can be performed by heat treatment and / or light irradiation treatment.

  In the heat treatment, the heating temperature is, for example, about 50 to 250 ° C., preferably 60 to 150 ° C., and more preferably about 70 to 120 ° C., depending on the type of polymerization initiator.

In the light irradiation treatment, examples of the light irradiation source include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a UV lamp, a hydrogen lamp, a deuterium lamp, a fluorescent lamp, a halogen lamp, an excimer laser, a nitrogen laser, Examples thereof include a dye laser and a helium-cadmium laser. Moreover, although the amount of light irradiation energy changes with uses, the film thickness of a coating film, etc., it is about 0.1-10000 mJ / cm < ² > normally, Preferably it is about 0.5-2000 mJ / cm < ² >. The exposure time is, for example, about 1 second to 3 hours, preferably about 5 seconds to 2 hours, and more preferably about 10 seconds to 1 hour.

  Note that heat treatment and light irradiation treatment may be combined. For example, a polymerizable composition containing a photopolymerization initiator may be further heated after light irradiation (or while light irradiation) in order to promote curing or crosslinking.

  The shape of the cured product (molded product) is not particularly limited, and for example, a two-dimensional structure (film shape, sheet shape, plate shape, etc.), a three-dimensional structure (tubular, rod shape, tube shape, hollow shape, etc.) Etc.

  The novel urethane (meth) acrylate (and its polymerizable composition) of the present invention has a high refractive index, heat resistance, light transmission, hardness, weather resistance, flexibility, mechanical strength, dimensional stability. It is excellent as a plastic raw material (adhesive, paint, etc.) satisfying various required performances. The cured product of the present invention is excellent in heat resistance, has a high refractive index and high hardness, and can be suitably used particularly as an optical material. Examples of the shape of such an optical material include a film or a sheet. , Plate shape, lens shape, tubular shape and the like.

Typically, the urethane (meth) acrylate (or a cured product thereof) of the present invention is 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 agent (for example, optical overcoat agent such as coating agent for LED (light emitting diode) element or hard coating agent), lens [pickup lens (eg, DVD (digital versatile) Pickup lens for disk), microlens (for example, microlens for liquid crystal projector), spectacle lens, etc.], polarizing film (for example, polarizing film for liquid crystal display), antireflection film (or antireflection film, for example) , Antireflection films for display devices, etc.), touch panel films, flexible substrates Film, display film [for example, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction electron-emitting device display), FED (field emission display), NED (nano Emissive displays), cathode ray tubes, electronic paper displays (particularly thin displays) films (filters, protective films, etc.)], fuel cell membranes, optical fibers, optical waveguides, holograms, and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Example 1]
1. Prepolymer synthesis step In a brown 100 mL flask equipped with a cooling tube shielded with aluminum foil and a stirrer, 9.05 g of isophorone diisocyanate (IPDI, manufactured by Huls Japan KK, “VESTANAT IPDI” NCO% = 38%) 0.041 mol) and 37.17 g of 1,4-dioxane were added to dissolve IPDI in 1,4-dioxane, and 2-hydroxyethyl acrylate (HEA, manufactured by Nacalai Tesque, Inc., Lot No. 1) was added. “M4P3126”) 4.88 g (0.042 mol) was added and dissolved, and then diluted to 1% by weight with 1,4-dioxane, di-n-butyltin dilaurate (DTD, manufactured by Kishida Chemical Co., Ltd.) , Lot No. “G00333T”) was added, the inside of the flask was replaced with argon, and stirring was not performed. The reaction was carried out at room temperature for 53 hours to obtain a reaction solution containing a prepolymer. In this reaction solution, the NCO% of the prepolymer was 12.4%.

2. Urethane (meth) acrylate synthesis step 9,9-bis [3,4-di (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd.) was added to a 200 mL flask equipped with a condenser and a stirrer shielded with aluminum foil. ), “BCAF-EO”) 5.56 g (0.010 mol) was added, and 50.68 g of 1,4-dioxane was further added and heated to 80 ° C. to dissolve BCAF-EO. It was. To this solution, the reaction solution obtained in the prepolymer synthesis step was added and dissolved, and then di-n-butyltin dilaurate (DTD, Kishida Chemical Co., Ltd.) diluted to 1% by weight with 1,4-dioxane. ), Lot No. “G00333T”) 1.54 g was added, the inside of the flask was replaced with argon, and the mixture was reacted at room temperature for 120 hours with stirring. After completion of the reaction, 10.6 mg of hydroquinone (manufactured by Nacalai Tesque) was added. Confirmation that the reaction was completed was performed by confirming that the NCO group had disappeared by FT-IR measurement of the reaction solution.

3. Desolvation step A capillary was attached to the flask, and desolvation was performed at 65 to 70 ° C for 1 hour under reduced pressure with an evaporator in the presence of air. The residual amount of the solvent was calculated from the analysis result of gas chromatography. The product after desolvation was a highly viscous liquid, and the residual ratio of the solvent was 15.7%.

¹ H-NMR measurement of the obtained product was performed using FT-NMR JNM-GSX270 (manufactured by JEOL Datum). FIG. 1 shows an NMR chart and the NMR spectrum data is shown below.

¹ H-NMR (ppm): 7.75 (d), 7.35 (brs), 6.9-6.6 (m), 6.5-6.4 (m, acrylate), 6.2 6.1 (m, acrylate), 5.9-5.8 (m, acrylate), 4.9-4.8 (m), 4.33 (m), 4.2-3.9 (m) , 2.9 (m), 1.69 (s), 1.05 (s), 0.9-0.8 (m).

[Example 2]
1. Prepolymer synthesis step In a brown 100 mL flask equipped with a cooling tube shielded with aluminum foil and a stirrer, a diisocyanate having a polyol skeleton ("Duranate D-201" manufactured by Asahi Kasei Chemicals Corporation), alkanediol and hexamethylene diisocyanate 21.70 g (0.041 mol) of a prepolymer having isocyanate groups at both ends reacted with N, and 41.04 g of 1,4-dioxane were added, and the diisocyanate was converted to 1,4- After dissolving in dioxane and further adding 4.85 g (0.042 mol) of 2-hydroxyethyl acrylate (HEA, manufactured by Nacalai Tesque, Lot No. “M4P3126”), 1,4 -Di-n-butyltin dilaurate diluted to 1% by weight with dioxane (DTD, manufactured by Kishida Chemical Co., Ltd., Lot No. “G00333T”) was added, the inside of the flask was replaced with argon, and the reaction was allowed to proceed at room temperature for 42 hours with stirring to obtain a reaction solution containing a prepolymer. It was. In this reaction solution, the NCO% of the prepolymer was 6.5%.

2. Urethane (meth) acrylate synthesis step 9,9-bis [3,4-di (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd.) was added to a 200 mL flask equipped with a condenser and a stirrer shielded with aluminum foil. ), “BCAF-EO”) 5.57 g (0.010 mol) was added, and 50.69 g of 1,4-dioxane was further added and heated to 80 ° C. to dissolve BCAF-EO. It was. To this solution, the reaction solution obtained in the prepolymer synthesis step was added and dissolved, and then di-n-butyltin dilaurate (DTD, Kishida Chemical Co., Ltd.) diluted to 1% by weight with 1,4-dioxane. ), Lot No. “G00333T”) 1.40 g was added, the inside of the flask was replaced with argon, and the mixture was reacted at room temperature for 118 hours while stirring. After completion of the reaction, 16.0 mg of hydroquinone (manufactured by Nacalai Tesque) was added. Confirmation that the reaction was completed was performed by confirming that the NCO group had disappeared by FT-IR measurement of the reaction solution.

3. Desolvation step A capillary was attached to the flask, and desolvation was performed at 65 to 70 ° C for 1 hour under reduced pressure with an evaporator in the presence of air. The residual amount of the solvent was calculated from the analysis result of gas chromatography. The product after desolvation was a highly viscous liquid, and the residual ratio of the solvent was 17.8%.

¹ H-NMR measurement of the obtained product was performed using FT-NMR JNM-GSX270 (manufactured by JEOL Datum). FIG. 2 shows an NMR chart and the NMR spectrum data is shown below.

¹ H-NMR (ppm): 7.75 (d), 7.3 (m), 7.27 (d), 6.9-6.7 (m), 6.44 (dd, acrylate), 6 .14 (dd, acrylate), 5.86 (dd, acrylate), 5.1-4.7 (brs), 4.32 (d), 4.20 (brs), 4.11 (brs), 3 .85 (s), 3.65 (s), 3.14 (brs), 1.48 (brs), 1.33 (brs), 0.93 (brs).

[Example 3]
Step 1 was performed in the same manner as in Example 1 except that 9.05 g (0.041 mol) of IPDI was replaced with 10.26 g (0.041 mol) of diphenylmethane diisocyanate (MDI, manufactured by BASF INOAC Polyurethane Co., Ltd.). Step 2 and step 3 were performed. The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a high viscosity, and the residual ratio of the solvent was 10.3%.

[Example 4]
Step 1 was performed in the same manner as in Example 1 except that 9.05 g (0.041 mol) of IPDI was replaced with 7.15 g (0.041 mol) of tolylene diisocyanate (TDI, manufactured by Nippon Polyurethane Industry Co., Ltd.). , Step 2 and Step 3 were performed. The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a high viscosity, and the residual ratio of the solvent was 13.8%.

[Example 5]
Step 1 was performed in the same manner as in Example 1 except that 9.05 g (0.041 mol) of IPDI was replaced with 8.62 g (0.041 mol) of naphthalene diisocyanate (NDI, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.). Step 2 and step 3 were performed. The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a high viscosity, and the residual ratio of the solvent was 14.2%.

[Example 6]
Diisocyanate having 24.9 g (0.041 mol) of P-201 having a polyol skeleton of 44.9 g (0.041 mol) (manufactured by Sanyo Chemical Industries, Ltd., “Samprene P-6090”, polytetramethylene ether glycol) Step 1, Step 2, and Step 3 were carried out in the same manner as in Example 1 except that the prepolymer having an isocyanate group at both ends where N and diphenylmethane diisocyanate were reacted was replaced with NCO% = 7.6%. The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a high viscosity, and the residual ratio of the solvent was 15.7%.

[Comparative Example 1]
1. Prepolymerization reaction process
In a brown 100 mL flask equipped with a condenser and a stirrer shielded with aluminum foil, 4.3 g of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF, manufactured by Osaka Gas Chemical Co., Ltd.) 4.3 g (0.0098 mol) and 17.2 g of 1,4-dioxane were added to dissolve BPEF in 1,4-dioxane, and isophorone diisocyanate (IPDI, manufactured by Huls Japan KK, “VESTANAT”). IPDI "NCO% = 38%) 4.5 g (0.020 mol) was added and dissolved, and then diluted to 1% by weight with 1,4-dioxane (di-n-butyltin dilaurate (DTD, Kishida Chemical) 0.43 g of Lot No. “G00333T” manufactured by Co., Ltd. was added, the inside of the flask was replaced with argon, and the mixture was stirred at 80 ° C. It was reacted for 24 hours. In the reaction solution, the NCO% of the obtained prepolymer was 9.5%.

2. Acrylation reaction step To the resulting reaction solution, 2.45 g (0.021 mol) of 2-hydroxyethyl acrylate (HEA, manufactured by Nacalai Tesque, Lot No. “M4P3126”), and 1,4-dioxane Di-n-butyltin dilaurate (DTD, manufactured by Kishida Chemical Co., Ltd., Lot No. “G00333T”) diluted to 1 wt% was added and reacted at room temperature for 69 hours. After completion of the reaction, 1 mg of hydroquinone (manufactured by Nacalai Tesque) was added. Confirmation that the reaction was completed was performed by confirming that the NCO group had disappeared by FT-IR measurement of the reaction solution.

3. Desolvation step A capillary was attached to the flask, and desolvation was performed at 65 to 70 ° C for 1 hour under reduced pressure with an evaporator in the presence of air. The residual amount of the solvent was calculated from the analysis result of gas chromatography. The product after solvent removal was a colorless and transparent liquid with high viscosity, and the solvent recovery rate was 90.6%.

[Comparative Example 2]
1. Prepolymerization reaction step In a brown 100 mL flask equipped with a condenser tube and a stirrer shielded from light by aluminum foil, 5.25 g (0.023 mol) of bisphenol A (BPA, manufactured by Kishida Chemical Co., Ltd.) and 1,4-dioxane 17. 2 g was added, BPA was dissolved in 1,4-dioxane, and isophorone diisocyanate (IPDI, manufactured by Huls Japan, “VESTANAT IPDI” NCO% = 38%) 10.28 g (0.046 mol) Was added and dissolved, and 0.43 g of di-n-butyltin dilaurate (DTD, manufactured by Kishida Chemical Co., Ltd., Lot No. “G00333T”) diluted to 1% by weight with 1,4-dioxane was added. Then, the inside of the flask was replaced with argon and reacted at 80 ° C. for 24 hours with stirring. In the reaction solution, the NCO% of the obtained prepolymer was 9.5%.

2. Acrylation reaction step To the obtained reaction solution, 2-hydroxyethyl acrylate (HEA, manufactured by Nacalai Tesque, Lot No. “M4P3126”) 5.59 g (0.048 mol) and 1,4-dioxane Then, 0.86 g of di-n-butyltin dilaurate (DTD, manufactured by Kishida Chemical Co., Ltd., Lot No. “G00333T”) diluted to 1 wt% was added and reacted at room temperature for 69 hours. After completion of the reaction, 1 mg of hydroquinone (manufactured by Nacalai Tesque) was added. Confirmation that the reaction was completed was performed by confirming that the NCO group had disappeared by FT-IR measurement of the reaction solution.

3. Desolvation step A capillary was attached to the flask, and desolvation was performed at 65 to 70 ° C for 1 hour under reduced pressure with an evaporator in the presence of air. The residual amount of the solvent was calculated from the analysis result of gas chromatography. The product after solvent removal was a colorless and transparent liquid with high viscosity, and the solvent recovery rate was 93.2%.

[Example 7]
0.15 g of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., “Irgacure 184”) was added to 5 g of the product obtained after the solvent removal step obtained in Example 1, and an applicator (Japanese oak tree ( (Made by Co., Ltd.) and coated (cast) on a polyethylene terephthalate film with a thickness of 250 μm, and then UV light having a wavelength of 354 nm using a metal halide lamp by a conveyor type UV lamp (made by Eye Graphics Co., Ltd., “ECS-151U”). (UV) was irradiated for 30 seconds to be cured.

  When the refractive index (589 nm) of the cured film thus obtained was measured using an Abbe refractometer (manufactured by ATAGO, DR-M2), the refractive index was 1.527.

  When the pencil hardness of the obtained cured film was measured with a surface property measuring instrument HEIDON-14 (Peeling / Slipping / Scratching TESTER manufactured by HEIDON), the pencil hardness was 5H.

  Further, when the glass transition temperature (Tg) of the obtained cured film was measured with a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM) at a frequency of 10 Hz and a temperature rising rate of 5 ° C./min, the glass transition temperature was measured. The temperature was 100 ° C.

  These characteristics are shown in Table 1.

[Example 8]
A cured film was prepared in the same manner as in Example 7 except that 5 g of the product after removal of solvent obtained in Example 2 was used instead of 5 g of the product after removal of solvent obtained in Example 1. Obtained. Various characteristics were measured by the same method as in Example 7.

  Further, the tensile strength and elastic modulus were measured with a Tensilon universal testing machine RTC-1250A (manufactured by A & D). As a result, the tensile strength was 11.2 MPa and the elastic modulus was 11 MPa.

  The results are shown in Table 1.

[Example 9]
A cured film was obtained in the same manner as in Example 7, except that 5 g of the product after removal of solvent obtained in Example 3 was used instead of 5 g of the product after removal of solvent obtained in Example 1. Obtained. Various characteristics were measured by the same method as in Example 7. The results are shown in Table 1.

[Example 10]
A cured film was prepared in the same manner as in Example 7 except that 5 g of the product after removal of solvent obtained in Example 4 was used instead of 5 g of the product after removal of solvent obtained in Example 1. Obtained. Various characteristics were measured by the same method as in Example 7. The results are shown in Table 1.

[Example 11]
A cured film was obtained in the same manner as in Example 7 except that 5 g of the product after removal of solvent obtained in Example 5 was used instead of 5 g of the product after removal of solvent obtained in Example 1. Obtained. Various characteristics were measured by the same method as in Example 7. The results are shown in Table 1.

[Example 12]
A cured film was prepared in the same manner as in Example 7 except that 5 g of the product after removal of solvent obtained in Example 6 was used instead of 5 g of the product after removal of solvent obtained in Example 1. Obtained. Various characteristics were measured by the same method as in Example 7.

  The tensile strength and elastic modulus were measured in the same manner as in Example 8. The results are shown in Table 1.

[Comparative Example 3]
A cured film was obtained in the same manner as in Example 7, except that 5 g of the product after desolvation obtained in Comparative Example 1 was used instead of 5 g of the product after desolvation obtained in Example 1. Obtained. Various characteristics were measured by the same method as in Example 7.

  The tensile strength and elastic modulus were measured in the same manner as in Example 8. The results are shown in Table 1.

[Comparative Example 4]
A cured film was prepared in the same manner as in Example 7 except that 5 g of the product after removal of solvent obtained in Comparative Example 2 was used instead of 5 g of the product after removal of solvent obtained in Example 1. Obtained. Various characteristics were measured by the same method as in Example 7.

  The tensile strength and elastic modulus were measured in the same manner as in Example 8. The results are shown in Table 1.

  As is clear from Table 1, the cured film obtained in Example 7 had a high refractive index and a high hardness. In particular, the cured films obtained in Examples 7 and 9 to 11 had a high refractive index and higher heat resistance than the cured products obtained in the comparative examples. In addition, the cured films obtained in Examples 8 and 12 were excellent in flexibility as compared with the films obtained in Comparative Examples while having a high refractive index.

1 is a ¹ H-NMR spectrum chart of the product obtained in Example 1. FIG. FIG. 2 is a ¹ H-NMR spectrum chart of the product obtained in Example 2.

Claims (12)

A urethane (meth) acrylate obtained by reacting a compound having a fluorene skeleton represented by the following formula (1), a polyisocyanate compound, and a (meth) acrylic compound having an active hydrogen atom reactive with an isocyanate group. There,
A urethane in which the polyisocyanate compound is a diisocyanate compound selected from isophorone diisocyanate, araliphatic diisocyanate and aromatic diisocyanate, and the content of isocyanate groups (—NCO) is 20 to 60% by weight with respect to the whole polyisocyanate compound. (Meth) acrylate.

(In the formula, ring Z ¹ and ring Z ² represent aromatic hydrocarbon rings, R ¹ and R ² are the same or different and represent a substituent, R ³ represents an alkylene group, k is an integer of 0 to 4; , M is 0 or an integer of 1 or more, n is 0 or an integer of 1 or more, r1 and r2 are each an integer of 1 or more, and (r1 + r2) ≧ 3 is satisfied.)   The urethane (meth) acrylate according to claim 1, which is a urethane (meth) acrylate having 3 or more (meth) acryloyl groups. In the compound represented by the formula (1), in the formula (1), the ring Z ¹ and the ring Z ² are a benzene ring or a naphthalene ring, R ² is an alkyl group or an aryl group, and m is 0 to 2. The urethane (meth) acrylate according to claim 1 or 2, wherein R ³ is a C _2-4 alkylene group, n is 1 to 10, and r1 and r2 are 2 or 3, respectively. Compounds represented by the formula (1) are 9,9-bis [di (hydroxy (poly) C _2-4 alkoxy) phenyl] fluorene, and 9,9-bis [tri (hydroxy (poly) C _2-4 The urethane (meth) acrylate according to any one of claims 1 to 3, which is a compound selected from alkoxy) phenyl] fluorene. The urethane (meth) acrylate according to any one of claims 1 to 4, wherein the ( meth) acrylic compound is a hydroxyl group-containing (meth) acrylic compound. The urethane (meth) acrylate according to any one of claims 1 to 5 , wherein the (meth) acrylic compound is a hydroxyl group-containing mono (meth) acrylate. It is a compound represented by following formula (2), Urethane (meth) acrylate in any one of Claims 1-6 .

[Wherein J is a hydrogen atom or the following formula (3)

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, A represents a residue of a polyisocyanate compound, X and Y represent an ether group, E represents a linking group, p is 0 or 1, and q is A group represented by an integer of 1 or more. However, (r1 + r2) groups J have at least two groups [CH ₂ ═CR ⁴ —CO—X] —. Ring Z ¹ , Ring Z ² , R ¹ , R ² , R ³ , k, m, n, r1 and r2 are the same as described above. ] In Formula (2), Z ¹ and Z ² are a benzene ring or a naphthalene ring, R ² is an alkyl group or an aryl group, m is 0 to 2, R ³ is a C _2-4 alkylene group, n is 1 to 4, r 1 and r2 are each 2 or 3, (r1 + r2) number of J is a group both represented by the formula (3), p is 1, q is urethane according to claim 7, wherein the 1-2 (meth ) Acrylate. The urethane (meth) acrylate according to claim 8 , wherein E is a _C2-10 alkylene group. A compound having a fluorene skeleton represented by the following formula (1), a polyisocyanate compound, and a (meth) acrylic compound having an active hydrogen atom reactive with an isocyanate group are reacted, A method for producing the urethane (meth) acrylate according to any one of 9 .

(In the formula, ring Z ¹ , ring Z ² , R ¹ , R ² , R ³ , k, m, n, r 1 and r 2 are the same as above.) The manufacturing method of Claim 10 with which the compound which has a fluorene skeleton represented by Formula (1) is made to react with the reaction material of a polyisocyanate compound and a (meth) acrylic-type compound. Urethane (meth) cured acrylates according to any of claims 1-9.

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