JP5297030B2 - Urethane (meth) acrylate with fluorene skeleton - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel urethane (meth)acrylate having a fluorene skeleton which can be used as a diluent or a raw material monomer. <P>SOLUTION: The monofunctional urethane (meth)acrylate having one (meth)acryloyl group can be obtained by reacting a compound having a specific fluorene skeleton äsuch as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene or 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene} with a monofunctional (meth)acrylate base compound having an isocyanate group [including a mono(meth)acryloyloxy 2-6C alkyl-isocyanate, such as 2-(meth)acryloyloxyethylisocyanate or 2-(meth)acryloxyethylisocyanate]. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a novel urethane (meth) acrylate having a fluorene skeleton, a method for producing the same, and a polymer of 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 2000-7741 A (Patent Document 3) 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 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.

  JP-A-2000-53628 (Patent Document 4) discloses urethane (meth) acrylate obtained by reacting a diol, diisocyanate and ester residue having a hydroxyl group with a (meth) acrylate represented by the following formula: Is 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.

The urethane (meth) acrylate described in these documents is a urethane (meth) acrylate having two or more (meth) acryloyl groups in the molecule, and is used as a photocurable (or thermosetting) resin.
JP 2002-284864 A (Claims) JP 2004-339499 A (claims, paragraph number [0032]) JP 2000-7741 A (claims, paragraph numbers [0007] [0010]) JP 2000-53628 A (claims, paragraph number [0018])

  Accordingly, an object of the present invention is to provide a novel urethane (meth) acrylate having a fluorene skeleton that can be used as a diluent (polymerizable diluent) or a raw material monomer, a method for producing the same, and the urethane (meth) acrylate as a monomer. It is to provide a polymer.

  Another object of the present invention is to provide a urethane (meth) acrylate capable of easily and efficiently introducing a fluorene skeleton into a resin, a production method thereof, and a polymer of the urethane (meth) acrylate.

  Still another object of the present invention is to provide a urethane (meth) acrylate that can easily and efficiently improve properties such as refractive index and heat resistance of a resin, a method for producing the same, and a polymer of the urethane (meth) acrylate. There is.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a novel urethane (meth) acrylate in which one (meth) acryloyl group is introduced into a polyol having a specific fluorene skeleton is a monomer, diluted It has been found that a fluorene skeleton can be easily and efficiently introduced into a resin, and can be used as an agent (polymerizing diluent, reactive diluent).

  That is, the urethane (meth) acrylate of the present invention is a urethane (meth) acrylate having a compound having a fluorene skeleton represented by the following formula (1) as a reaction component, and one (meth) acryloyl in the molecule. It is a monofunctional urethane (meth) acrylate having a group.

(In the formula, ring Z represents an aromatic hydrocarbon ring, 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, and m is 0 or (An integer of 1 or more, n is 0 or an integer of 1 or more, and r is an integer of 1 or more.)
In the formula (1), for example, the ring Z is a benzene ring or a naphthalene ring, R ² is an alkyl group or an aryl group, m is 0 to 2, and R ³ is a C _2-4 alkylene group. , N may be 1 to 10, and r may be 1 to 3. In particular, the compound represented by the formula (1) includes 9,9-bis (hydroxy (poly) C _2-4 alkoxyphenyl) fluorene, 9,9-bis (mono or di C _1-4 alkyl-hydroxy ( Poly) C _2-4 alkoxyphenyl) fluorene, 9,9-bis (mono or di C _6-8 aryl-hydroxy (poly) C _2-4 alkoxyphenyl) fluorene, 9,9-bis (hydroxy (poly) C _2-4 alkoxy naphthyl) fluorene, 9,9-bis [di (hydroxy _{(poly) C 2-4} alkoxy) phenyl] fluorene, and 9,9-bis [tri (hydroxy _{(poly) C 2-4} alkoxy) phenyl It may be a compound selected from fluorene.

  The urethane (meth) acrylate of the present invention includes, for example, (i) a urethane in which a compound having a fluorene skeleton represented by the formula (1) is reacted with a monofunctional (meth) acrylic compound having an isocyanate group ( (Meth) acrylate, or (ii) a monofunctional (meth) acrylic compound having a fluorene skeleton represented by the formula (1), a polyisocyanate compound, and an active hydrogen atom reactive with an isocyanate group Urethane (meth) acrylate reacted with a compound may be used.

The urethane (meth) acrylate is particularly preferably urethane (meth) acrylate (i). In such urethane (meth) acrylate, since it is not necessary to use polyisocyanate, monofunctional urethane (meth) acrylate can be easily prepared, and the content ratio of the fluorene skeleton in the entire urethane (meth) acrylate can be adjusted. Can be enlarged efficiently. In the typical urethane (meth) acrylate, a monofunctional (meth) acrylic compound having an isocyanate group is mono (meth) acryloyloxyalkyl isocyanate (in particular, mono (meth) acryloyloxy C _2-6 alkyl-). Urethane (meth) acrylate (i) which is an isocyanate) and the like are included.

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

[Wherein J represents the following formula (3)

Wherein R ^4a represents a hydrogen atom or a methyl group, X ¹ represents a direct bond or an ether group, E ¹ represents a hydrocarbon group, and p1 is 0 or 1, or Following formula (4)

(Wherein R ^4b represents a hydrogen atom or a methyl group, A represents a residue of a polyisocyanate compound, X ² and Y represent an ether group, E ² represents a hydrocarbon group, and p2 is 0 or 1) Is a group represented by: Rings Z, R ¹ , R ² , R ³ , k, m, n, and r are the same as described above. ]
In the formula (2), typically, J is a group represented by the formula (3), X ¹ is an ether group, p ¹ is 1, and E ¹ is an alkylene group or a cycloalkylene group. Good.

  In the formula (2), the urethane (meth) acrylate may typically be a urethane (meth) acrylate that satisfies the following combination (a) or (b).

(A) Z is a benzene ring or 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 is 1, and J is A combination represented by formula (3), wherein X ¹ is an ether group, p1 is 1, and E ¹ is an alkylene group (b) Z is 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 is 2 or 3, J is a group represented by the formula (3), X ¹ is an ether group, p1 combinations 1, ^{E 1} is an alkylene group.

In the combinations (a) and (b), the alkylene group E ¹ may in particular be a C _2-6 alkylene group.

  The method for producing a urethane (meth) acrylate of the present invention includes at least a step of reacting a compound having a fluorene skeleton represented by the following formula (1) with a compound having an isocyanate group.

(In the formula, rings Z, R ¹ , R ² , R ³ , k, m, n, and r are the same as described above.)
In such a production method, typically, a compound having a fluorene skeleton represented by the formula (1) and a monofunctional (meth) acrylic compound having an isocyanate group may be reacted.

  The present invention includes a polymer of the urethane (meth) acrylate (specifically, a polymer having the urethane (meth) acrylate as a monomer). Moreover, the resin composition containing the said urethane (meth) acrylate is also contained in this invention. Such a resin composition (curable resin composition) may be composed of a curable resin and the urethane (meth) acrylate. Moreover, the hardened | cured material which the said resin composition hardened | cured is also contained in this invention.

  Since the novel urethane (meth) acrylate of the present invention has a fluorene skeleton and is monofunctional, it can be used as a diluent (polymerizable diluent) or a raw material monomer. When such a urethane (meth) acrylate is used as a raw material monomer (thermoplastic resin raw material), it is possible to obtain a novel polymer having urethane bonds and excellent properties (such as a high refractive index) derived from a fluorene skeleton. . Moreover, such urethane (meth) acrylate has high reactivity, and a fluorene skeleton can be easily and efficiently introduced into the resin. And by using such urethane (meth) acrylate of this invention as a diluent etc., the characteristic (refractive index, heat resistance, etc.) of resin can be improved simply and efficiently. 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 is a urethane (meth) acrylate having a compound (polyol) having a specific fluorene skeleton as a reaction component, and a monofunctional urethane having one (meth) acryloyl group in the molecule. (Meth) acrylate. That is, in such a urethane (meth) acrylate of the present invention, one hydroxyl group and (meth) acryloyl group among a plurality of hydroxyl groups constituting the polyol are a urethane bond (or a group containing a urethane bond). ).

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

(In the formula, ring Z represents an aromatic hydrocarbon ring, 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, and m is 0 or (An integer of 1 or more, n is 0 or an integer of 1 or more, and r is an integer of 1 or more.)
In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z include a benzene ring and a condensed polycyclic hydrocarbon ring (specifically, a condensed polycyclic hydrocarbon ring containing at least a benzene ring). Is mentioned. 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. The two rings Z substituted at the 9-position of fluorene may be the same or different rings, and may usually be the same ring.

  Preferred ring Z includes a benzene ring and a naphthalene ring, and a benzene ring is particularly preferred. In addition, when the ring Z is a condensed polycyclic hydrocarbon ring, the substitution position of the ring Z substituted at the 9-position of fluorene is not particularly limited. For example, the naphthyl group includes a 1-naphthyl group and a 2-naphthyl group. It may be a group or the like.

Further, the substituent represented by the group R ¹ is not particularly limited, and is non-reactive with respect to an isocyanate group, for example, a cyano group, a hydrocarbon group (for example, an alkyl group, an aryl group (such as a phenyl group). _Or a C _6-10 aryl group), and the like. 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 number r of the group — [(OR ³ ) _n —OH] substituted on the ring Z may be 1 or more, for example, 1 to 8, preferably 1 to 5, more preferably 1 to 4, particularly 1 to 4. 3 may be sufficient. In particular, when ring Z is a benzene ring, r may be 1 to 4, preferably 1 to 3, and more preferably 1 to 2. In addition, r may differ according to the ring Z, and may be the same normally. The substitution position of the group — [(OR ³ ) _n —OH] substituted for ring Z is not particularly limited, and can be selected according to the number of r. For example, (1) when ring Z is a benzene ring and r is 1, it may be the 2-6 position (for example, the 4 position) of the phenyl group substituted at the 9 position of fluorene, (2) When ring Z is a naphthalene ring and r is 1, any one of positions 5 to 8 (depending on the substitution position of a naphthyl group (1- or 2-naphthyl group or the like) substituted at the 9-position of fluorene ( (3) when the ring Z is a benzene ring and r is 2, the 2-6 position of the phenyl group substituted at the 9 position of fluorene. Two of the substitution positions (for example, the 3rd and 4th positions; the 2nd and 4th positions; the 2nd and 5th positions, etc.) may be used. (4) Ring Z is a benzene ring, The three substitution positions among the 2-6 positions of the phenyl group substituted at the 9 position of fluorene (example: If, position 2, 3 and 4 positions; 2-position, 4-position and 5-position; 3-position, 4-position and 5-position; 2-position, may be a 4-position and 6-position, etc.).

As the substituent R ² substituted on the ring Z, a non-reactive group with respect to an isocyanate group, for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, _{C 1-20} alkyl groups such as t- butyl group, preferably a _{C 1-8} alkyl group, more preferably a _{C 1-6} alkyl group), a cycloalkyl group (cyclopentyl group, cyclohexylene, such as cyclohexyl group _{C 5- 10} cycloalkyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group, etc., aryl group [for example, phenyl group, alkylphenyl group (methylphenyl group (or tolyl group, 2- methylphenyl group, 3-methylphenyl group), a dimethylphenyl group (xylyl)), _{C 6-10} aryl such as naphthyl Group, preferably a _{C 6-8} aryl group, especially phenyl group, a hydrocarbon group such as an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group); an alkoxy group ( Methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, C _1-4 alkoxy group such as t-butoxy group); acyl group (C _1-6 acyl group such as acetyl 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.) and the like.

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 in the same ring Z may be substituted alone or in combination of two or more. In addition, the substituents R ² substituted on different rings Z 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 depending on the type of the ring Z and the like, and is not particularly limited. For example, 0 or 1 to 8, preferably 0 or 1 to 6 (for example, 1 to 5), More preferably, it may be 0 or about 1-4. In particular, when the ring Z is a benzene ring, the substitution number m is, for example, 0 or 1-3, preferably 0 or 1-2. When ring Z is a condensed hydrocarbon ring 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, and particularly 0. Also good. The number of substitutions m may be the same or different in each ring Z 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 groups depending on the ring Z, 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. 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.

  As a compound having a typical fluorene skeleton, a fluorene skeleton-containing compound having two hydroxyl groups [for example, 9,9-bis (hydroxyphenyl) fluorenes, 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorene , 9,9-bis (hydroxynaphthyl) fluorenes, 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes, etc.] a fluorene skeleton-containing compound having three or more hydroxyl groups {eg, 9,9 -Bis (polyhydroxyphenyl) fluorenes, 9,9-bis [poly (hydroxy (poly) alkoxy) phenyl] fluorenes, 9,9-bis (polyhydroxynaphthyl) fluorenes, 9,9-bis [poly ( Hydroxy (poly) alkoxy) naphthyl] fluorenes, etc.} Murrell.

Examples of 9,9-bis (hydroxyphenyl) fluorenes include 9,9-bis (hydroxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene (bisphenolfluorene) and the like] and a substituent. 9,9-bis (hydroxyphenyl) fluorene {eg, 9,9-bis (alkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-methylphenyl) fluorene (biscresol fluorene), 9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-butylphenyl) fluorene, 9,9-bis (3-hydroxy-2-methylphenyl) fluorene, 9 , 9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9, - bis (4-hydroxy-2,6-dimethylphenyl) 9,9-bis fluorene (mono- or _{di-C 1-4} alkyl - hydroxyphenyl) fluorene, etc.], 9,9-bis (cycloalkyl - hydroxyphenyl ) Fluorene [9,9-bis (mono or di C _5-8 cycloalkyl-hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene], 9,9-bis ( Aryl-hydroxyphenyl) fluorene [e.g., 9,9-bis (mono or di _C6-8 aryl-hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene], 9 , 9-bis (aralkyl-hydroxyphenyl) fluorene [for example, 9,9-bis (4 Hydroxy-3-benzyl-phenyl) 9,9-bis _{(C 6-8} aryl _{C 1-2} alkyl, such as fluorene - hydroxyphenyl) fluorene, etc.], etc.} and the like.

Examples of 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes include 9,9-bis (hydroxyalkoxyphenyl) fluorene {for example, 9,9-bis [4- (2-hydroxyethoxy) phenyl]. Fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [4- (3-hydroxypropoxy) phenyl] fluorene, 9,9-bis [4- (4-hydroxy) butoxy) phenyl] fluorene such as 9,9-bis (hydroxy _{C 2-4} alkoxyphenyl) fluorene}, 9,9-bis (hydroxyalkoxy - alkylphenyl) fluorene {e.g., 9,9-bis [4- ( 2-hydroxyethoxy) -3-methylphenyl] fluorene [or 2,2′-dimethyl-4 4 '-(9-fluorenylidene) -bisphenoxyethanol], 9,9-bis [2- (2-hydroxyethoxy) -5-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy)- 3-ethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-propylphenyl] fluorene, 9,9-bis [4- (3-hydroxypropoxy) -3-methylphenyl] fluorene 9,9-bis [4- (4-hydroxybutoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene [or 2, 2 ′, 6,6′-tetramethyl-4,4 ′-(9-fluorenylidene) -bisphenoxyethanol], 9,9-bis [4- (2-hydro Ciethoxy) -3,5-diethylphenyl] fluorene, 9,9-bis [4- (3-hydroxypropoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (4-hydroxybutoxy) 9,9-bis (hydroxy C _2-4 alkoxy-mono or diC _1-6 alkylphenyl) fluorene etc., such as 3,5-dimethylphenyl] fluorene}, 9,9-bis (hydroxyalkoxy-cycloalkylphenyl) ) fluorene {e.g., 9,9-bis [4- (2-hydroxyethoxy) -3-cyclohexyl phenyl] fluorene such as 9,9-bis (hydroxy _{C 2-4} alkoxy - mono- or _{di-C 5-8} cycloalkyl Phenyl) fluorene, etc.}, 9,9-bis (hydroxyalkoxy-arylphenyl) fluorene For example, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene [or 2,2′-diphenyl-4,4 ′-(9-fluorenylidene) -bisphenoxyethanol], 9,9 9,9-bis (hydroxyC _2-4 alkoxy-mono or diC _6-8 arylphenyl) fluorene, such as bis [4- (2-hydroxyethoxy) -3,5-diphenylphenyl] fluorene}, 9 , 9-bis (hydroxyalkoxy-aralkylphenyl) fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) -3-benzylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) ) -3,5-dibenzyl phenyl] fluorene such as 9,9-bis [hydroxy _{C 2-4} alkoxy - mono- or di C _6-8 corresponding to aryl _{C 1-4} alkyl) phenyl] fluorene}, and their 9,9-bis (hydroxyalkoxy phenyl) fluorenes, is by the formula (1) n is 2 or more at 9,9 Bis (hydroxypolyalkoxyphenyl) fluorenes {for example, 9,9-bis {(hydroxyC _2-4 alkoxy) such as 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] phenyl} fluorene C _2-4 alkoxyphenyl] fluorene (compound with n = 2) and the like}.

  As 9,9-bis (hydroxynaphthyl) fluorenes, for example, 9,9-bis (hydroxynaphthyl) fluorenes {for example, 9,9-bis [6- (2-hydroxynaphthyl)] fluorene (or 6,9 6- (9-fluorenylidene) -di (2-naphthol)), 9,9-bis [1- (6-hydroxynaphthyl)] fluorene (or 5,5- (9-fluorenylidene) -di (2-naphthol) ), 9,9-bis [1- (5-hydroxynaphthyl)] fluorene (or 5,5- (9-fluorenylidene) -di (1-naphthol)). 9-bis (monohydroxynaphthyl) fluorene} and the like.

The 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes include compounds corresponding to the 9,9-bis (hydroxynaphthyl) fluorenes, such as 9,9-bis (hydroxyalkoxynaphthyl) fluorene {for example, 9,9-bis [6- (2- (2-hydroxyethoxy) naphthyl)] fluorene, 9,9-bis [1- (6- (2-hydroxyethoxy) naphthyl)] fluorene [or 5,5 ′ -(9-fluorenylidene) -bis (2-naphthyloxyethanol)], 9,9-bis [1- (5- (2-hydroxyethoxy) naphthyl)] fluorene and the like may have a substituent 9 , 9-bis (hydroxy C _2-4 alkoxynaphthyl) fluorene, etc.}.

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.

The 9,9-bis (polyhydroxynaphthyl) fluorenes include compounds corresponding to the 9,9-bis (hydroxynaphthyl) fluorenes, such as 9,9-bis (di or trihydroxynaphthyl) fluorene. It is. Moreover, as 9,9-bis [poly (hydroxy (poly) alkoxy) naphthyl] fluorenes, compounds corresponding to the 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes, for example, 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.

  Bis (hydroxyphenyl) fluorenes can be synthesized by various synthesis methods, for example, (a) a method of reacting a fluorenone with a phenol in the presence of hydrogen chloride gas and mercaptocarboxylic acid (reference [J. Appl. Polym Sci., 27 (9), 3289, 1982], JP-A-6-145087, JP-A-8-217713), (b) 9-fluorenone and alkylphenol in the presence of an acid catalyst (and alkyl mercaptan). (C) a method of reacting a fluorenone with a phenol in the presence of hydrochloric acid and thiols (such as mercaptocarboxylic acid) (Japanese Patent Laid-Open No. 2002-47227). Gazette), (d) reacting fluorenones with phenols in the presence of sulfuric acid and thiols (such as mercaptocarboxylic acid) It can be produced using a method of producing bisphenolfluorene by crystallization with a crystallization solvent composed of a polar solvent (Japanese Patent Laid-Open No. 2003-221352). In addition, 9,9-bis (polyhydroxyphenyl) fluorenes are obtained by using polyhydroxybenzenes (for example, catechol, resorcinol, etc.) in place of phenols in the method for producing 9,9-bis (hydroxyphenyl) fluorenes. Dihydroxybenzenes such as dihydroxytoluene and trihydroxybenzenes such as pyrogallol). In addition, 9,9-bis (hydroxynaphthyl) fluorenes and 9,9-bis (polyhydroxynaphthyl) fluorenes are used instead of phenols in the method for producing 9,9-bis (hydroxyphenyl) fluorenes. , And corresponding hydroxy naphthalenes (for example, naphthols such as naphthol (1-naphthol, 2-naphthol) and polyhydroxynaphthalenes such as dihydroxynaphthalene).

Furthermore, 9,9-bis ((poly) hydroxy (poly) alkoxyphenyl) fluorenes or 9,9-bis ((poly) hydroxy (poly) alkoxynaphthyl) fluorenes are 9,9-bis ((poly) Hydroxyphenyl) fluorenes or 9,9-bis ((poly) hydroxynaphthyl) fluorenes and compounds corresponding to the group R ³ O [alkylene oxides (such as C _2-4 alkylene oxides such as ethylene oxide), haloalkanols (3 -Chloropropanol etc.) and the like]. For example, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene is obtained by adding ethylene oxide to 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. 9,9-bis [4- (3-hydroxypropoxy) -3-methylphenyl] fluorene may be, for example, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and 3-chloropropanol. May be obtained by reacting these under alkaline conditions.

  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 (hydroxy (poly) alkoxyphenyl) fluorene [eg, 9,9-bis (hydroxy (poly) C _2-4 alkoxyphenyl) fluorene, etc.], 9,9 -Bis (alkyl-hydroxy (poly) alkoxyphenyl) fluorene [for example, 9,9-bis (mono- or di-C _1-4 alkyl-hydroxy (poly) C _2-4 alkoxyphenyl) fluorene, etc.], 9,9- 9,9 such as bis (aryl-hydroxy (poly) alkoxyphenyl) fluorene [eg, 9,9-bis (mono or diC _6-8 aryl-hydroxy (poly) C _2-4 alkoxy-phenyl) fluorene, etc.] -Bis (hydroxy (poly) alkoxyphenyl) fluorenes [especially 9,9-bis (hydride) Alkoxyphenyl) fluorenes]; 9,9-bis (hydroxy (poly) alkoxy naphthyl) fluorene [e.g., 9,9-bis (such as hydroxy _{(poly) C 2-4} alkoxy-naphthyl) fluorene] 9,9 -Bis (hydroxy (poly) alkoxynaphthyl) fluorenes [especially 9,9-bis (hydroxyalkoxynaphthyl) fluorenes], 9,9-bis [di (hydroxy (poly) alkoxy) phenyl] fluorene {for example 9 , 9-bis [di (hydroxy _{(poly) C 2-4} alkoxy) phenyl] fluorene} 9,9-bis [di (hydroxy (poly) alkoxy) phenyl] fluorene such as (in particular, 9,9-bis [ Di (hydroxyalkoxy) phenyl] fluorenes); 9,9-bis [tri (hydroxy ( Li) alkoxy) phenyl] fluorene {e.g., 9,9-bis [tri (hydroxy _{(poly) C 2-4} alkoxy) phenyl] fluorene} etc. 9,9-bis [tri (hydroxy (poly) alkoxy) phenyl] Fluorenes (particularly 9,9-bis [tri (hydroxyalkoxy) phenyl] fluorenes) and the like are included.

In particular, among 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, 9,9-bis (alkyl-hydroxy (poly) alkoxyphenyl) fluorene, 9,9-bis (aryl-hydroxy (poly) alkoxy) Specific polyols having hydrocarbon groups in ring Z ¹ and ring Z ² such as phenyl) fluorene are diols having an unsubstituted fluorene skeleton in ring Z ¹ and ring Z ² [ie, 9,9-bis [4- Compared to the case of using (2-hydroxyethoxy) phenyl] fluorene (bisphenoxyethanol fluorene)], the heat resistance of the urethane (meth) acrylate can be further improved. In addition to the improvement in heat resistance, the polyol in which the ring Z ¹ such as 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorene and the ring Z ² are condensed aromatic hydrocarbon rings such as a naphthalene ring, Reduction of thermal expansibility can be realized, and the dimensional accuracy of urethane (meth) acrylate can also be improved.

[Urethane (meth) acrylate]
As described above, the urethane (meth) acrylate of the present invention is a urethane (meth) acrylate having the compound having the fluorene skeleton as a reaction component (or polymerization component), and has one (meth) acryloyl group. ing. The urethane (meth) acrylate of the present invention is a mixture of different urethane (meth) acrylates (for example, urethane (meth) having different substitution positions of (meth) acryloyl groups and bonding positions of urethane bonds to the compound having the fluorene skeleton. It may be a mixture of acrylates).

  Such urethane (meth) acrylate is typically monofunctional having (i) a compound having the fluorene skeleton (particularly a compound having a fluorene skeleton represented by the formula (1)) and an isocyanate group. A reaction product (urethane (meth) acrylate) with a reactive (meth) acrylic compound, or (ii) a compound having the fluorene skeleton (particularly a compound having a fluorene skeleton represented by the formula (1)) A reaction product (urethane (meth) acrylate) obtained by reacting a polyisocyanate compound with a monofunctional (meth) acrylic compound having an active hydrogen atom reactive with an isocyanate group.

  A preferred urethane (meth) acrylate is urethane (meth) acrylate (i). In urethane (meth) acrylate (i), compared with the case where a polyisocyanate compound is used, the content rate of the fluorene skeleton with respect to the whole urethane (meth) acrylate can be increased. Therefore, when used as a diluent or the like, the content ratio of the fluorene skeleton in the resin to be added can be easily increased, and characteristics (such as a high refractive index) derived from the fluorene skeleton in the resin can be efficiently imparted.

(Urethane (meth) acrylate (i))
In the urethane (meth) acrylate (i), the monofunctional (meth) acrylic compound having an isocyanate group (sometimes simply referred to as a (meth) acrylic compound) has an isocyanate group and one (meth) in the molecule. Any compound having an acryloyl group may be used. In such a compound, the number of isocyanate groups may usually be 1.

  Representative (meth) acrylic compounds include compounds represented by the following formula (A).

_{^{CH 2 = CR 4a -CO-X}} 1 - (E 1) p1 -NCO (A)
(In the formula, R ^4a represents a hydrogen atom or a methyl group, X ¹ represents a direct bond, an ether group or an imino group, and E ¹ represents a linking group. P1 is 0 or 1.)
In the above formula (A), preferred X ¹ includes a direct bond or an ether group (particularly an ether group). In the formula (A), examples of the compound corresponding to the linking group E ¹ include alkanes (for example, methane, ethane, propane, butane, isopentane, 2-methylbutane, 2,2-dimethylpropane, 2,2-dimethylbutane). Hydrocarbon compounds (especially aliphatic hydrocarbon compounds) such as C _1-20 alkanes, preferably C _2-10 alkanes), cycloalkanes (eg C _4-10 cycloalkanes such as cyclohexane); dialkyl ethers (diethyl) Examples thereof include compounds having an ether bond such as di-C _2-4 alkyl ethers such as ether) and polyoxyalkylenes (such as polyoxy C _2-4 alkylene). These compounds (or linking group E) are substituted with a substituent [halogen atom (for example, fluorine atom, chlorine atom, bromine atom etc.), alkoxy group (C _1-6 alkoxy group such as methoxy group), aryloxy group (phenoxy Group, etc.)] and the like. The above substituents may be substituted for the substituents alone or in combination of two or more.

Preferred linking groups E ¹ are alkylene groups (or alkanediyl groups such as C _1-20 alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, 2-methylbutane-1,3-diyl group, Is a C _2-12 alkylene group, more preferably a C _2-8 alkylene group, especially a C _2-4 alkylene group), a cycloalkylene group (for example, a C _4-10 cycloalkylene group such as a 1,4-cyclohexylene group, Preferably, a hydrocarbon group such as a C _5-8 cycloalkylene group (hydrocarbon group corresponding to the hydrocarbon compound, divalent hydrocarbon group) is included.

Typical (meth) acrylic compounds include (meth) acryloyl isocyanate, mono (meth) acrylate having an isocyanate group {for example, mono (meth) acryloyloxyalkyl isocyanate [for example, 2- (meth) acryloyloxyethyl isocyanate (Or 2- (meth) acryloxyethyl isocyanate or 2-isocyanatoethyl (meth) acrylate), (meth) acryloyloxy C _1-20 alkyl such as 4- (meth) acryloyloxy-3-methyl-2-isocyanatobutane - isocyanate, preferably (meth) acryloyloxy _{C 2-12} alkyl - isocyanate, more preferably (meth) acryloyloxy _{C 2-6} alkyl - isocyanate, in particular (meth) acryloyloxy _2-4 alkyl - isocyanate, etc.], (meth) acryloyloxy cycloalkyl isocyanate [e.g., 4- (meth) acryloyloxy-cyclohexyl isocyanate such as (meth) acryloyloxy _{C 4-10} cycloalkyl - isocyanate, preferably (meth) Acryloyloxy C _5-8 cycloalkyl-isocyanate and the like] and the like}.

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

Preferable (meth) acrylic compounds include mono (meth) acryloyloxyalkyl isocyanate [for example, (meth) acryloyloxy C _2-6 alkyl-isocyanate such as 2- (meth) acryloyloxyethyl isocyanate] and the like.

  The molecular weight of the (meth) acrylic compound is, for example, 500 or less (for example, about 100 to 400), preferably 350 or less (for example, about 110 to 300), and more preferably 250 or less (for example, about 120 to 220). ), Particularly 200 or less (for example, about 130 to 180).

(Urethane (meth) acrylate (ii))
In the urethane (meth) acrylate (ii), the polyisocyanate compound is not particularly limited as long as it is a compound capable of reacting with a hydroxyl group of the compound having a fluorene skeleton to form a bond (particularly a urethane bond). Examples include polyisocyanates (aliphatic polyisocyanates, alicyclic 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.

Aliphatic polyisocyanates include, for example, aliphatic diisocyanates {eg, alkane diisocyanates [eg, C _2-20 alkanes such as hexamethylene diisocyanate, 2,2,4 or 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, etc. -Diisocyanate etc.) etc.] etc.} etc. are mentioned. Examples of the alicyclic polyisocyanate include alicyclic diisocyanate {cycloalkane diisocyanate (for example, C _5-8 cycloalkane-diisocyanate such as cyclohexane diisocyanate), isocyanatoalkylcycloalkane isocyanate [for example, isocyanato such as isophorone diisocyanate. C _1-6 alkyl-C _5-10 cycloalkane-isocyanate], di (isocyanatoalkyl) cycloalkane [for example, di (isocyanato C _1-6 alkyl) C _5-10 cycloalkane such as hydrogenated xylylene diisocyanate] , di (isocyanatomethyl cycloalkyl) alkanes [e.g., such as 4,4'-methylene-bis-cyclohexyl isocyanate bis (isocyanato _{C 5-10 cycloalkyl) C 1-10} Glucan, etc.], etc.} and the like. Examples of the araliphatic polyisocyanate include di (isocyanatoalkyl) arene [for example, bis (isocyanato C _1-6 alkyl) C _6-12 arene such as xylylene diisocyanate and tetramethyl xylylene diisocyanate] and the like. Aliphatic diisocyanates are mentioned. Aromatic polyisocyanates include aromatic diisocyanates {eg, arene diisocyanates [eg, C _6-12 arene-diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, etc.], di (isocyanatoaryl) alkanes [eg, diphenylmethane. Bis (isocyanato C _6-10 aryl) C _1-10 alkanes such as diisocyanate and tolidine diisocyanate], aromatic diisocyanates having hetero atoms [eg, di (isocyanatophenyl) ether, di (isocyanatophenyl) sulfone, etc.] Etc.}.

  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 often composed of a diisocyanate compound [aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, aromatic diisocyanate, etc.].

  A polyol-modified product (specifically, a polyol-modified product of polyisocyanate) can also be 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. Polyether-based polyols (particularly polyether-based diols) include, for example, 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 such as polyethylene glycol and polytetramethylene ether glycol), preferably polyoxy C _2-4 alkylene glycol etc.]], alkylene oxide adducts of bisphenol A or hydrogenated bisphenol A, and the like.

Polyester polyols (particularly polyester diols) include dicarboxylic acid components [dicarboxylic acids or derivatives thereof (for example, lower alkyl esters, acid halides, etc.)] and diol components, lactones (C _3-10 lactones). Etc.) homopolymers or copolymers (such as poly-ε-caprolactone). In the dicarboxylic acid component, examples of the dicarboxylic acid include aromatic dicarboxylic acids (for example, dicarboxylic acids such as terephthalic acid), aliphatic dicarboxylic acids (for example, linear C _4-10 dicarboxylic acids such as adipic acid), and the like. It is done. Examples of the diol component include alkane diols (eg, C _2-10 alkane diols such as ethylene glycol, propylene glycol, 1,4-butane diol, 1,6-hexane diol, etc.), polyalkane diols (eg, diethylene glycol, etc.) ) And the like. These dicarboxylic acid components and diol components may be used alone or in combination of two or more. Typical polyester-based polyols include, for example, polyethylene adipate, polydiethylene adipate, polypropylene adipate, polytetramethylene adipate, polyhexamethylene adipate, and copolymers obtained by combining these components.

  Examples of polyolefin polyols (particularly polyolefin diols) include, for example, polyalkadienes having hydroxyl groups at both ends (for example, 1,2-polybutadiene, 1,4-polybutadiene, polyisoprene) or hydrogenated products thereof, Examples thereof include polyisobutylene having a hydroxyl group at the terminal. 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, alkane diols, polyether diols, include such polyester diols, in particular, (such as C _2-10 alkanediol) alkane diols, polyether diols (e.g., polyethylene glycol, polypropylene glycol, poly A diol compound (polymer diol compound) such as polyoxy C _2-4 alkylene glycol such as tetramethylene ether glycol) is 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). It is not specifically limited, The modified polyisocyanate of the said illustration, a polyisocyanate, etc. are mentioned. The polyisocyanate compound (a) is usually composed of a diisocyanate compound (aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, aromatic diisocyanate, 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), and A ² represents the residue of the polyol compound)
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.

  In the urethane (meth) acrylate (ii), these polyisocyanate compounds may be used alone or in combination of two or more.

  In the urethane (meth) acrylate (ii), the (meth) acrylic compound has a reactive group with respect to the isocyanate group (or an active hydrogen atom reactive with the isocyanate group). That is, in the urethane (meth) acrylate (ii), at least one (especially one or one) of the isocyanate groups (especially 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 4b -CO-X}} 2 - (E 2) p2 -Y-H (B)
(Wherein R ^4b represents a hydrogen atom or a methyl group, X ² and Y are the same or different and represent a direct bond, an ether group or an imino group, and E ² represents a linking group. P2 is 0 or 1) .)
In the above formula (B), preferred X ² and Y include an ether group. X ² and Y are usually not directly bonded at the same time. In the formula (B), typical combinations of X ² , p 2 and Y include (i) a combination in which X ² is an ether group or imino group, p 2 is 1 and Y is an ether group, (ii) ) X ² is an ether group or imino group, p2 is 0, and Y is a direct bond.

In the formula (B), the compound corresponding to the linking group E ² is 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); ether bonds such as dialkyl ethers (such as diC _2-4 alkyl ethers such as diethyl ether), polyoxyalkylenes (such as polyoxy C _2-4 alkylene) Compounds having an ester group such as (poly) hydroxycarboxylic acid (6-hydroxyhexanoic acid, polyε-caprolactone, etc.), and the like.

These compounds (or the linking group E ² ) are substituted with a substituent [halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), hydroxyl group, alkoxy group (methoxy group, ethoxy group, etc. C _1-6 alkoxy group). ), An aryloxy group (such as a phenoxy group)] and the like. The above substituents may be substituted for the substituents alone or in combination of two or more.

Representative linking groups E ^2, include a group represented by the following formula (E1).

-[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.).

A preferred linking group E ² is a hydrocarbon group such as an alkylene group (in the formula (E1), ^Ra is a hydrocarbon group, t = u = 0).

  Typical (meth) acrylic compounds include hydroxyl group-containing monofunctional (meth) acrylic compounds, amino group-containing monofunctional (meth) acrylic compounds [for example, (meth) acrylamide, N-methyl (meta ) Acrylamide, N-isopropyl (meth) acrylamide, N-mono-substituted (meth) acrylamide such as N-butoxymethyl (meth) acrylamide] and the like.

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.

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

  In the urethane (meth) acrylate (ii), preferable (meth) acrylic compounds include hydroxyl group-containing monofunctional (meth) acrylic compounds [for example, hydroxyalkyl (meth) acrylates and the like].

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

[Wherein J represents the following formula (3)

In the formula, R ^4a represents a hydrogen atom or a methyl group, X ¹ represents a direct bond, an ether group or an imino group, E ¹ represents a linking group, and p1 is 0 or 1. Or the following formula (4)

(Wherein R ^4b represents a hydrogen atom or a methyl group, A represents a residue of a polyisocyanate compound, X ² and Y are the same or different and represent a direct bond, an ether group or an imino group, and E ² represents a linkage. And p2 is 0 or 1). Rings Z, R ¹ , R ² , R ³ , k, m, n, and r are the same as described above. ]
The above formula (3) corresponds to the compound represented by the formula (A). That is, in the formula (3), X ¹ , E ¹ and p1 are the same as described above. Preferred X ¹ is a direct bond or an ether group (particularly an ether group).

In the formula (4), the residue A corresponds to the polyisocyanate compound exemplified above. That is, the residue A is usually a divalent group corresponding to the polyisocyanate compound. The formula (4) corresponds to the compound represented by the formula (B). In the formula (4), X ² , Y, E ² and p2 are the same as described above. Preferred linking groups E ² is a hydrocarbon group such as an alkylene group. Preferred X ² and Y are ether groups. In the above formula (4), preferable residues A include residues of diisocyanate compounds (for example, diisocyanate compounds selected from aliphatic diisocyanates, alicyclic diisocyanates, araliphatic diisocyanates, and aromatic diisocyanates). .

  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 formula (2), preferable J is a group represented by the formula (3).

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

(A) Z is a benzene ring or naphthalene 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 aryl group such as a phenyl group), and m is 0 to 2 (in particular 1 or 2 when Z is a benzene ring), R ³ is a C _2-4 alkylene group (particularly an ethylene group), and n is 1 or more (for example, 1 to 4, preferably 1 to 2, More preferably, 1), r is 1, J is a group represented by the formula (3), X ¹ is an ether group (that is, (meth) acryloyloxy group), p1 is 1, and E ¹ is alkylene. A combination that is a divalent hydrocarbon group such as a group (for example, a C _2-6 alkylene group such as an ethylene group) (b) Z is a benzene ring or a naphthalene ring (particularly a benzene ring), and R ² is an alkyl group (particularly, _{C 1-4} alkyl group such as methyl group) Aryl group (particularly, _{C 6-8} aryl group such as phenyl group), m is 0-2 (e.g., 0), ^{R 3} is _{C 2-4} alkylene group (particularly an ethylene group), n is 1 or more (e.g. 1 to 4, preferably 1 to 2, more preferably 1), r is 2 or 3, J is a group represented by the formula (3), and X ¹ is an ether group (ie, (meth) acryloyloxy group), p1 combinations 1, E ¹ is a divalent hydrocarbon group such as an alkylene group (e.g., C _2-6 alkylene group such as ethylene group).

[Production method]
The urethane (meth) acrylate (such as the compound represented by the formula (2)) of the present invention is a reaction component of the compound having the fluorene skeleton (particularly, the compound having the fluorene skeleton represented by the formula (1)). It can manufacture by making it react. That is, the urethane (meth) acrylate of the present invention comprises a compound having the fluorene skeleton and a compound having an isocyanate group (for example, a monofunctional (meth) acrylic compound having an isocyanate group; a polyisocyanate compound; a polyisocyanate compound; At least a step of reacting with a reaction product (specifically, a reaction product having an isocyanate group or a prepolymer) with a monofunctional (meth) acrylic compound having an active hydrogen atom reactive with an isocyanate group. Can be manufactured. Such a manufacturing method can be normally selected according to the kind (for example, the said urethane (meth) acrylate) of urethane (meth) acrylate.

(Method for producing urethane (meth) acrylate (i))
The urethane (meth) acrylate (i) can be produced by reacting the compound having the fluorene skeleton with the monofunctional (meth) acrylic compound having the isocyanate group.

  In the reaction, the ratio (preparation ratio) of the (meth) acrylic compound is, for example, 0.7 to 1.5 mol, preferably 0.85 to 1.2 mol, with respect to 1 mol of the compound having a fluorene skeleton. More preferably, it may be about 0.9 to 1.1 mol, particularly about 0.95 to 1.05 mol.

  The reaction may be performed in a solvent. The solvent is not particularly limited as long as it is an inert or non-reactive solvent with respect to the (meth) acrylic compound (and the compound having a fluorene skeleton). For example, ethers (for example, diethyl ether, diether) Dialkyl ethers such as propyl ether, cyclic ethers such as 1,4-dioxane, dioxolane and tetrahydrofuran), ketones (eg, dialkyl ketones such as acetone, methyl ethyl ketone, diisopropyl ketone, isobutyl methyl ketone), esters (eg, acetic acid) Methyl acetate, ethyl acetate, acetate esters such as butyl acetate), hydrocarbons (for example, aromatic hydrocarbons such as toluene, xylene, ethylbenzene), halogenated solvents (methylene chloride, chloroform, carbon tetrachloride, tetra Chloroethane, G Halogenated hydrocarbons such as chloroethane), and the like nitriles (such as acetonitrile). These solvents may be used alone or in combination of two or more.

  The reaction may be performed in the 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). Organic metal catalysts such as cobalt acid; tertiary amines [for example, trialkylamines such as triethylamine, chain tertiary amines such as benzyldimethylamine, N, N, N ′, N′-tetraalkylethylenediamine, etc. Pyridine, methylpyridine, N, N-dimethylpiperazine, cyclic tertiary amines such as triethylenediamine, etc.]. 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 with respect to 100 parts by weight of the total amount of the compound having a fluorene skeleton and the (meth) acrylic compound. Preferably, it may be about 0.01 to 1 part by weight (for example, 0.02 to 0.5 part by weight).

  The reaction may be carried out in the 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 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.). Note that the reaction may be performed in an inert atmosphere (an atmosphere of nitrogen, helium, argon, or the like).

(Method for producing urethane (meth) acrylate (ii))
Urethane (meth) acrylate (ii) reacts the compound having the fluorene skeleton, the polyisocyanate compound, and a monofunctional (meth) acrylic compound having an active hydrogen atom reactive with the isocyanate group. Can be manufactured.

  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) and the other component are reacted [that is, they are reacted in multiple steps (two steps)]. Many.

  In the reaction (preparation of the precursor) between the polyisocyanate compound and one component (for example, a compound having a fluorene skeleton), the proportion of both components used can be appropriately selected according to the type of the one component. For example, the ratio (preparation ratio) of the polyisocyanate compound is 0.7 to 1.5 mol, preferably 0.85 to 1. mol with respect to 1 mol of the one component (for example, the compound having the fluorene skeleton). The amount may be 2 mol, more preferably 0.9 to 1.1 mol, particularly 0.95 to 1.05 mol.

  The reaction between the polyisocyanate compound and one component may be performed in a solvent. As the solvent, the same solvents as described above can be used. Moreover, you may perform reaction with a polyisocyanate compound and one component in presence of a catalyst. As the catalyst, the same catalyst as described above can be used.

  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 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 the polymerization inhibitor, the same polymerization inhibitors as described above can be used. 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. Note that the reaction may be performed in an inert atmosphere (an atmosphere of nitrogen, helium, argon, or the like).

  And the obtained urethane prepolymer (or the precursor of urethane (meth) acrylate) and the other component (for example, (meth) acrylic compound) 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, the ratio (charge ratio) of the other component is 0.7 to 1.5 mol, preferably 1 mol relative to 1 mol of the precursor (or the polyisocyanate compound). It may be 0.85 to 1.2 mol, more preferably 0.9 to 1.1 mol, and particularly about 0.95 to 1.05 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.

  In any of the production methods (i) and (ii), after completion of the reaction, the product urethane (meth) acrylate is separated from conventional separation methods such as distillation, concentration, extraction, filtration and the like. , And can be separated and purified by 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.

  In addition, the product obtained by such a method (or the urethane (meth) acrylate of the present invention) may contain a urethane (meth) acrylate having one (meth) acryloyl group as a main component, and a small amount. The reaction double product (for example, urethane (meth) acrylate having a plurality of (meth) acryloyl groups) may be included.

[Usage of urethane (meth) acrylate]
The urethane (meth) acrylate of the present invention is a monofunctional urethane (meth) acrylate having one (meth) acryloyl group in the molecule and has high reactivity (polymerizability). Can be used for applications. For example, the urethane (meth) acrylate of the present invention may be used as a use (additive use) such as a diluent (reactive diluent, polymerizable diluent) or as a monomer. In addition, the urethane (meth) acrylate having two or more (meth) acryloyl groups as described in the background art section has a high viscosity and is not usually used as a diluent.

  The viscosity (25 ° C., rotational viscometer, 900 rpm) of the urethane (meth) acrylate of the present invention is, for example, 1 to 400 Pa · s (eg, 3 to 350 Pa · s), preferably 5 to 300 Pa · s (eg, 8 ˜250 Pa · s), more preferably about 10 to 220 Pa · s (for example, 15 to 200 Pa · s).

  By using for such an application, the fluorene skeleton can be introduced into the resin simply and efficiently, so that the excellent properties (high refractive index, high heat resistance, etc.) of the fluorene skeleton can be imparted to the resin. In addition, when the diluent is used, the properties (refractive index, etc.) of the added resin are usually lowered, but when the urethane (meth) acrylate of the present invention is used, the resin properties such as the refractive index can be improved. . Further, when the urethane (meth) acrylate of the present invention is used as a monomer (thermoplastic resin raw material), a novel polymer (thermoplastic resin) having a fluorene skeleton (9,9-bisarylfluorene skeleton) and a urethane bond is obtained. be able to. Such a polymer (the polymer of the urethane (meth) acrylate) has excellent characteristics derived from a fluorene skeleton (such as a high refractive index), and also has characteristics derived from a urethane bond such as flexibility, A polymer with unprecedented properties.

When used as a monomer, the resin (thermoplastic resin) may be a polymer in which the monomer component is the urethane (meth) acrylate of the present invention alone (the urethane (meth) acrylate alone or a copolymer), It may be a copolymer of the urethane (meth) acrylate and a copolymerizable monomer. The copolymerizable monomer is not particularly limited. For example, a (meth) acrylic monomer [for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester (for example, methyl (meth) acrylate, (meth) acrylic) (Meth) acrylic acid C _1-10 alkyl ester such as ethyl acid, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate), cyclohexyl (meth) acrylate, hydroxyl group-containing (meth) acrylate (for example, 2- (Meth) acrylic acid esters such as hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate), glycidyl (meth) acrylate, dialkylaminoethyl (meth) acrylate, etc. Etc.], styrene monomers (for example, styrene), vinyl cyanide monomers (for example, (meth) acrylonitrile, etc.), vinyl ethers (alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, etc. Cycloalkyl vinyl ethers), vinyl esters (vinyl acetate, vinyl propionate, etc.), nitrogen-containing heterocyclic vinyl compounds (N-vinylpyrrolidone, etc.), maleic anhydride, and the like. These copolymerizable monomers may be used alone or in combination of two or more.

  In the copolymer of urethane (meth) acrylate and copolymerizable monomer, the ratio of urethane (meth) acrylate to the whole copolymer is, for example, 1 to 80 mol%, preferably in terms of raw material monomer. May be about 3 to 60 mol%, more preferably about 5 to 40 mol%.

  The urethane (meth) acrylate polymer (polymer having the urethane (meth) acrylate as a monomer) is obtained by, for example, polymerizing the urethane (meth) acrylate (and a copolymerizable monomer if necessary) (radical). Polymerization). Typically, the polymer can be prepared by polymerizing the urethane (meth) acrylate (and optionally a copolymerizable monomer) in the presence of.

  As the polymerization initiator, the following compounds (heat or photopolymerization initiator) can be used. The amount of the polymerization initiator used is 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 1 with respect to 100 parts by weight of the urethane (meth) acrylate (and copolymerizable monomer). It may be about -10 parts by weight.

  The polymerization may be performed according to a conventional polymerization method, or may be performed by a method similar to the case of curing described later (for example, a method of subjecting the coating film to heat treatment and / or light irradiation treatment, etc.). Moreover, a sensitizer, a solvent, etc. may be used similarly to the case of the below-mentioned case, and the ratio etc. are the same as that of the below-mentioned range.

  Moreover, when using the urethane (meth) acrylate of this invention as a diluent etc., it can comprise a resin composition. That is, such a resin composition (polymerizable resin composition, polymerizable composition) is composed of a curable resin (heat or photocurable resin, particularly photocurable resin) and the urethane (meth) acrylate. Has been.

  The curable resin is not particularly limited as long as the urethane (meth) acrylate acts as a diluent, and a conventional resin can be used. Examples of the curable resin (curable compound) include bifunctional compounds [for example, (poly) alkylene glycol di (meth) acrylate (ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate). , Bifunctional (meth) acrylic compounds such as hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.)], trifunctional or more polyfunctional compounds [for example, Glycerin tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) a Tri- or higher functional (meth) acrylic compounds such as relate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.], photopolymerizable oligomer [eg, epoxy Examples thereof include (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate (urethane (meth) acrylate having two or more (meth) acryloyl groups), silicone (meth) acrylate, and the like.

  Further, as the curable resin (or photo-curable resin), a fluorene skeleton-containing (meth) acrylate having two or more (meth) acryloyl groups [for example, the urethane (meth) acrylate exemplified in the background art section, the above-mentioned Urethane (meth) acrylates having two or more (meth) acryloyl groups, etc., having the compound represented by formula (1) as a polyol component can also be used.

  These curable resins (photocurable resins) may be used alone or in combination of two or more.

  In the resin composition, the proportion of the urethane (meth) acrylate of the present invention is, for example, 0.5 to 300 parts by weight, preferably 1 to 200 parts by weight with respect to 100 parts by weight of the curable resin (photo-curable resin). Part, more preferably about 2 to 100 parts by weight (for example, 3 to 80 parts by weight), and usually about 1 to 50 parts by weight.

  The resin composition may contain a polymerization initiator. 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 Etc.], aminoacetophenones {2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butanone-1}, anthraquinones (anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc.), thioxanthones (2,4-dimethylthioxanthone, 2,4-diethyl) Thioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.), ketals (acetophenone dimethyl ketal, benzyl dimethyl 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 may be about 0.1 to 20% by weight, preferably about 0.5 to 20% by weight, more preferably about 1 to 10% by weight, based on the resin composition.

  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.

  Further, the polymerizable composition may be prepared by adding conventional additives such as colorants, stabilizers (thermal stabilizers, antioxidants, ultraviolet absorbers, etc.), fillers, antistatic agents, flame retardants, as necessary. A flame retardant aid, leveling agent, thermal polymerization inhibitor and the like may be included. Diluents and additives may be used alone or in combination of two or more.

  Moreover, the non-reactive diluent may be included. 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 amount (addition amount) of the non-reactive diluent varies depending on the coating method and the like, but is, for example, 10 to 400 parts by weight, preferably 20 to 300 parts by weight, and more preferably 30 parts per 100 parts by weight of the resin component. About 200 parts by weight may be used.

  The resin composition (particularly the photopolymerizable composition) is useful for obtaining a cured product (molded product) obtained by polymerization or curing (or crosslinking). Such a cured product can be obtained by subjecting the polymerizable composition to a curing treatment (heating treatment or light irradiation treatment) in the molding process or after molding depending on the form of the molded body. For example, a film-like cured product may be obtained by applying a polymerizable composition to a substrate to form a coating film (or thin film) and then performing a curing treatment. 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.

[Diluent]
In addition, the diluent comprised by the said urethane (meth) acrylate is also contained in this invention. Such a diluent may be comprised only with the said urethane (meth) acrylate as a reactive diluent, and may contain the other component. For example, the diluent may be composed of the urethane (meth) acrylate and another diluent. Other diluents include reactive diluents (other reactive diluents, reactive diluents other than the urethane (meth) acrylate) and non-reactive diluents (for example, the non-reactive diluent). included. These other diluents may be used alone or in combination of two or more. Examples of reactive diluents (polymerizable diluents) include monofunctional monomers [eg, (meth) acrylic compounds (eg, (meth) acrylic acid esters such as (meth) acrylic acid alkyl esters), aromatic vinyls, etc. Monomers (such as styrene)], multifunctional monomers {for example, polyfunctional (meth) acrylic compounds [for example, (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 and the like); glycerin tri ( (Meth) acrylate, trimethylolethanetri (meth) Chlorate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate , Trifunctional or higher functional (meth) acrylic compounds such as dipentaerythritol hexa (meth) acrylate], triallyl (iso) cyanurate, etc.}. The reactive diluent may be used alone or in combination of two or more.

  In the diluent of the present invention, the ratio of other diluents can be appropriately selected according to the type of the diluent. For example, the ratio of the reactive diluent is 0.1 to 1000 parts by weight, preferably 0.5 to 700 parts by weight, and more preferably about 1 to 500 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate. It may be. Moreover, although the usage-amount (addition amount) of a non-reactive diluent changes with coating methods etc., it is 10-1000 weight part with respect to 100 weight part of said urethane (meth) acrylate, Preferably it is 20-700 weight. Part, more preferably about 30 to 500 parts by weight.

  The novel urethane (meth) acrylate (and its polymerizable composition) of the present invention has excellent characteristics (high performance) that the fluorene skeleton has easily and efficiently when used as an additive or as a heat or photocurable resin. Heat resistance, high refractive index, etc.) can be imparted to the resin or molded body. Such a urethane (meth) acrylate of the present invention is useful as, for example, a reactive diluent (polymerizable diluent) or a raw material monomer. Specifically, the urethane (meth) acrylate of the present invention is used, for example, as a polymer and oligomer plasticizer, a component of a polymer, and the like, such as a liquid crystal display panel, a clear coating agent, a photosensitive resin, a resin for solder resist ink, and the like. It is suitable for.

  It is also useful as a plastic raw material (adhesive, paint, etc.) that satisfies various required performances. Furthermore, the cured product obtained by curing the resin composition of the present invention is excellent in characteristics such as heat resistance and has a high refractive index, and thus can be suitably used particularly as an optical material. Examples thereof include a film or sheet shape, a plate shape, a lens shape, and a tubular shape.

Typically, the urethane (meth) acrylate (or its polymerizable composition and its cured product) 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. Gas separation membranes (for example, CO ₂ gas separation membranes), coating agents (for example, optical overcoat agents such as coating agents for LED (light emitting diode) elements or hard coating agents), lenses [pickup lenses (for example, , DVD (digital versatile disk) pickup lens, etc.), micro lens (eg, micro lens for liquid crystal projector), spectacle lens, etc.], polarizing film (eg, polarizing film for liquid crystal display), anti-reflection film ( Or an antireflection film (for example, an antireflection film for a display device), a touch panel film. Rum, flexible substrate 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 display), cathode ray tube, electronic paper and other displays (especially thin displays) films (filters, protective films, etc.), fuel cell membranes, optical fibers, optical waveguides, holograms, etc. .

  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. Urethane Acrylate Synthesis Process 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF, manufactured by Osaka Gas Chemical Co., Ltd.) was added to a brown 200 mL flask equipped with a condenser and a stirrer shielded with aluminum foil. ) 19.95 g (0.046 mol) and 1,4-dioxane 80.00 g were added to dissolve BPEF in 1,4-dioxane, and 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK). , “Karenz AOI”) was added and dissolved, and then diluted to 10% by weight with 1,4-dioxane (Di-n-butyltin dilaurate (DTD, Kishida Chemical Co., Ltd.). ), Lot No. “G00333T”) was added, and the inside of the flask was replaced with argon. It stirred and allowed to react for 18 hours at 80 ° C. while in error. After completion of the reaction, 3.6 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.

2. 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 transparent liquid, and the solvent recovery rate was 81.1%.

  The molecular weight of the obtained product was a weight average molecular weight 586 and a number average molecular weight 516. The molecular weight was measured using gel permeation chromatography (GULLIVER SERIES UV = 975, manufactured by JASCO Corporation).

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

¹ H-NMR (ppm): 7.74 (d), 7.7-7.4 (m), 7.3-7.2 (m), 7.1 (dt), 6.75 (dd) 6.40 (dd, acrylate), 6.09 (dd, acrylate), 5.83 (dd, acrylate), 5.04 (brs), 4.38 (t), 4.22 (t), 4 0.08 (t), 4.01 (t), 3.9 (m), 3.67 (s), 3.5-3.4 (m), 2.02 (t).

[Example 2]
1. Urethane acrylate synthesis process 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene (BCFEO, Osaka Gas Chemical) was added to a brown 200 mL flask equipped with a condenser and a stirrer shielded with aluminum foil. 10.74 g (0.023 mol) and 43.98 g of 1,4-dioxane were added to dissolve BCFEO in 1,4-dioxane, and 2-acryloyloxyethyl isocyanate (Showa Denko) Co., Ltd., “Karenz AOI”) 3.32 g (0.023 mol) was added and dissolved, and then diluted with 1,4-dioxane to 5% by weight, di-n-butyltin dilaurate (DTD, 0.12 g of Lot No. “G00333T” manufactured by Kishida Chemical Co., Ltd.) was added, and the inside of the flask was replaced with argon. Ne was stirred and reacted for 21 hours at 80 ° C. while at stirrer. After completion of the reaction, 1.8 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.

2. 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 transparent liquid, and the solvent recovery rate was 80.7%.

  The molecular weight of the obtained product was a weight average molecular weight 615 and a number average molecular weight 551. The molecular weight was measured using gel permeation chromatography (GULLIVER SERIES UV = 975, manufactured by JASCO Corporation).

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

¹ H-NMR (ppm): 7.74 (d), 7.4-7.2 (m), 7.0-6.9 (m), 6.63 (dd), 6.40 (dd, Acrylate), 6.10 (dd, acrylate), 5.83 (dd, acrylate), 4.99 (brs), 4.40 (t), 4.22 (t), 4.08 (t), 4 0.02 (t), 4.0-3.9 (m), 3.5-3.4 (m), 2.12 (s), 2.10 (s), 1.97 (t).

[Example 3]
19.95 g (0.046 mol) of BPEF, 22.45 g (0.046 mol) of 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene (BXF-EO, Step 1 and Step 2 were performed in the same manner as in Example 1 except that the gas was replaced with Osaka Gas Chemical Co., Ltd. The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after solvent removal was a colorless and transparent liquid, and the solvent recovery rate was 82.6%.

[Example 4]
19.95 g (0.046 mol) of BPEF, 27.17 g (0.046 mol) of 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene (BOPPF-EO, Osaka Gas) Step 1 and Step 2 were carried out in the same manner as in Example 1 except that it was changed to Chemical Co., Ltd. The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after solvent removal was a colorless and transparent liquid, and the solvent recovery rate was 84.3%.

[Example 5]
19.95 g (0.046 mol) of BPEF, 24.78 g (0.046 mol) of 6,6 ′-(9-fluorenylidene) -bis (2-naphthyloxyethanol) (Osaka Gas Chemical Co., Ltd., Steps 1 and 2 were carried out in the same manner as in Example 1 except that “BNF-EO”) was used. The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after solvent removal was a colorless and transparent liquid, and the solvent recovery rate was 83.9%.

[Example 6]
Example 1 with the exception that 19.95 g (0.046 mol) of BPEF was replaced by 24.78 g (0.046 mol) of 5,5 ′-(9-fluorenylidene) -bis (2-naphthyloxyethanol). Steps 1 and 2 were performed in the same manner as described above. The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after solvent removal was a colorless and transparent liquid, and the solvent recovery rate was 83.9%.

[Example 7]
6.62 g (0.046 mol) of 2-acryloyloxyethyl isocyanate was replaced with 7.14 g (0.046 mol) of 2-methacryloyloxyethyl isocyanate (“Karenz MOI” manufactured by Showa Denko KK). Except for the above, Step 1 and Step 2 were performed in the same manner as in Example 1. The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after the solvent removal was a colorless and transparent liquid, and the solvent recovery rate was 85.9%.

[Example 8]
19.95 g (0.046 mol) of BPEF 21.46 g (0.046 mol) of bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene (BCF-EO, Osaka Gas Chemical Co., Ltd.) 6.62 g (0.046 mol) of 2-acryloyloxyethyl isocyanate, 7.14 g (0.046 mol) of 2-methacryloyloxyethyl isocyanate (produced by Showa Denko K.K. Step 1 and Step 2 were performed in the same manner as in Example 1 except that the MOI was changed to “MOI”). 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 methacrylate) was a colorless and transparent liquid, and the solvent recovery rate was 86.0%.

[Example 9]
19.95 g (0.046 mol) of BPEF, 22.75 g (0.046 mol) of 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene (BXF-EO, In addition to 6.62 g (0.046 mol) of 2-acryloyloxyethyl isocyanate, and 7.14 g (0.046 mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko ( Step 1 and Step 2 were carried out in the same manner as in Example 1 except that the product was changed to “Karenz MOI”). The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after solvent removal was a colorless and transparent liquid, and the solvent recovery rate was 86.0%.

[Example 10]
19.95 g (0.046 mol) of BPEF, 27.17 g (0.046 mol) of 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene (BOPPF-EO, Osaka Gas) In addition to 6.62 g (0.046 mol) of 2-acryloyloxyethyl isocyanate, and 7.14 g (0.046 mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko K.K.). Step 1 and Step 2 were performed in the same manner as in Example 1 except that the product was changed to “Karenz MOI”. The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after solvent removal was a colorless and transparent liquid, and the solvent recovery rate was 86.0%.

[Example 11]
19.95 g (0.046 mol) of BPEF, 24.78 g (0.046 mol) of 6,6 ′-(9-fluorenylidene) -bis (2-naphthyloxyethanol) (Osaka Gas Chemical Co., Ltd., In addition to “BNF-EO”), 6.62 g (0.046 mol) of 2-acryloyloxyethyl isocyanate was replaced with 7.14 g (0.046 mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko K.K.). Step 1 and Step 2 were performed in the same manner as in Example 1 except that the product was changed to “Karenz MOI”. 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 methacrylate) was a colorless and transparent liquid, and the solvent recovery rate was 86.1%.

[Example 12]
19.95 g (0.046 mol) of BPEF was replaced with 24.78 g (0.046 mol) of 5,5 ′-(9-fluorenylidene) -bis (2-naphthyloxyethanol) and 6.62 g (0 0.046 mol) of 2-acryloyloxyethyl isocyanate was replaced with 7.14 g (0.046 mol) of 2-methacryloyloxyethyl isocyanate (“Karenz MOI” manufactured by Showa Denko KK). Step 1 and Step 2 were performed in the same manner as in Step 1. 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 methacrylate) was a colorless and transparent liquid, and the solvent recovery rate was 86.0%.

[Example 13]
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 for polymerization.

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

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

  Furthermore, the viscosity of the product after the desolvation step was measured using a viscometer (manufactured by Toki Sangyo Co., Ltd., VISCOMETER TV-22) at 25 ° C. under a rotation speed of 900 rpm. These results are shown in Table 1.

[Example 14]
A membrane was obtained in the same manner as in Example 13, 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. It was. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 15]
A membrane was obtained in the same manner as in Example 13, 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. It was. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 16]
A membrane was obtained in the same manner as in Example 13 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. It was. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 17]
A membrane was obtained in the same manner as in Example 13 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. It was. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 18]
A membrane was obtained in the same manner as in Example 13, 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. It was. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 19]
A membrane was obtained in the same manner as in Example 13, except that 5 g of the product after removal of solvent obtained in Example 7 was used instead of 5 g of the product after removal of solvent obtained in Example 1. It was. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 20]
A membrane was obtained in the same manner as in Example 13, except that 5 g of the product after removal of solvent obtained in Example 8 was used instead of 5 g of the product after removal of solvent obtained in Example 1. It was. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 21]
A membrane was obtained in the same manner as in Example 13 except that 5 g of the product after removal of solvent obtained in Example 9 was used instead of 5 g of the product after removal of solvent obtained in Example 1. It was. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 22]
A membrane was obtained in the same manner as in Example 13, except that 5 g of the product after removal of solvent obtained in Example 10 was used instead of 5 g of the product after removal of solvent obtained in Example 1. It was. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 23]
A membrane was obtained in the same manner as in Example 13, except that 5 g of the product after removal of solvent obtained in Example 11 was used instead of 5 g of the product after removal of solvent obtained in Example 1. It was. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 24]
A membrane was obtained in the same manner as in Example 13, except that 5 g of the product after removal of solvent obtained in Example 12 was used instead of 5 g of the product after removal of solvent obtained in Example 1. It was. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

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 (9)

A urethane (meth) acrylate obtained by reacting a compound having a fluorene skeleton represented by the following formula (1) and a monofunctional (meth) acrylic compound having an isocyanate group, and having a monofunctionality having an isocyanate group ( A monofunctional urethane (meth) acrylate in which the ( meth) acrylic compound is mono (meth) acryloyloxyalkyl isocyanate and / or (meth) acryloyloxycycloalkyl isocyanate and has one (meth) acryloyl group in the molecule .

(In the formula, ring Z represents an aromatic hydrocarbon ring, 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, and m is 0 or (An integer of 1 or more, n is 0 or an integer of 1 or more, and r is an integer of 1 or more.) In formula (1), ring Z is 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, and n is The urethane (meth) acrylate according to claim 1, wherein 1 to 10 and r is 1 to 3. The compound represented by the formula (1) is 9,9-bis (hydroxy (poly) C _2-4 alkoxyphenyl) fluorene, 9,9-bis (mono or di C _1-4 alkyl-hydroxy (poly) C. _2-4 alkoxyphenyl) fluorene, 9,9-bis (mono or di C _6-8 aryl-hydroxy (poly) C _2-4 alkoxyphenyl) fluorene, 9,9-bis (hydroxy (poly) C _2-4 From alkoxy naphthyl) fluorene, 9,9-bis [di (hydroxy (poly) C _2-4alkoxy ) phenyl] fluorene, and 9,9-bis [tri (hydroxy (poly) C _2-4alkoxy ) phenyl] fluorene The urethane (meth) acrylate according to claim 1 or 2, which is a selected compound. The urethane (meth) acrylate according to claim 1, wherein the monofunctional (meth) acrylic compound having an isocyanate group is mono (meth) acryloyloxy C _2-6 alkyl-isocyanate. It is a compound represented by following formula (2), The urethane (meth) acrylate in any one of Claims 1-4 .

[Wherein J represents the following formula (3)

(Wherein, R ^4a represents a hydrogen atom or a methyl group, X ¹ is it shows an error ether group, E ¹ is .p1 showing an alkylene group or a cycloalkylene group in which 1) a group represented by. Rings Z, R ¹ , R ² , R ³ , k, m, n, and r are the same as described above. ] The urethane (meth) acrylate according to claim 5, which satisfies the following combination (a) or (b) in the formula (2).
(A) Z is 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 is 1, and E ¹ (B) Z is a benzene ring or 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, and r is 2 or 3, in combination ^{E 1} is an alkylene group. The urethane (meth) acrylate according to claim 6 , wherein in the combinations (a) and (b), the alkylene group E ¹ is a C _2-6 alkylene group. The urethane according to any one of claims 1 to 7 , comprising at least a step of reacting a compound having a fluorene skeleton represented by the following formula (1) with a monofunctional (meth) acrylic compound having an isocyanate group. Method for producing meth) acrylate.

(In the formula, rings Z, R ¹ , R ² , R ³ , k, m, n, and r are the same as described above.) The urethane (meth) acrylate polymer according to any one of claims 1 to 7 .

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