JP5513640B2 - Urethane (meth) acrylate having fluorene skeleton and cured product thereof - Google Patents

Description

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

  A compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton) is known to have an excellent function in terms of refractive index, heat resistance, and the like. As a method for expressing such an excellent function of the fluorene skeleton in a resin, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), for example, bisphenol fluorene (BPF), biscresol fluorene (BCF), bis In general, aminophenylfluorene (BAFL), bisphenoxyethanol fluorene (BPEF) or the like is used as a constituent component of the resin, and a fluorene skeleton is introduced into a part of the skeleton structure of the resin. For example, as a polyester resin having such a fluorene skeleton, JP 2002-284864 A (Patent Document 1) discloses a molding material composed of a polyester resin having a 9,9-bisphenylfluorene skeleton. Yes. JP-A-2004-339499 (Patent Document 2) discloses a resin (polyester resin, polycarbonate resin, urethane resin, acrylic resin having bisphenol fluorene, bisaminophenyl fluorene, bisphenoxyethanol fluorene, or the like as a polymerization component. 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. In addition, this document describes diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane diisocyanate as specific examples of the polyisocyanate compound (b). .

  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. Further, in this document, as diisocyanate, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate and the like are described.

As described above, in these documents, 9,9-bisphenyl such as bisphenoxyethanol fluorene (a compound where a = 1, R ¹ = hydrogen atom in the above formula) is used as a polyol used in the production of urethane (meth) acrylate. A specific diol component having a fluorene skeleton is used.

  However, in the urethane (meth) acrylates of these documents, since a fluorene skeleton is introduced, a high refractive index and the like can be imparted, but the flexibility of the cured product is not sufficient. Moreover, the viscosity of urethane (meth) acrylate is high and handling property is not enough only by introduce | transducing a 9,9-bisphenyl fluorene skeleton.

JP 2002-284864 A (Claims) JP 2004-339499 A (claims, paragraph number [0032]) JP 2000-7741 A (claims, paragraph numbers [0007] [0009] [0010]) JP 2000-53628 A (claims, paragraph numbers [0018] [0019])

  Therefore, the objective of this invention is providing the novel urethane (meth) acrylate excellent in a softness | flexibility, its manufacturing method, and the hardened | cured material of the said urethane (meth) acrylate.

  Another object of the present invention is to provide urethane (meth) acrylate capable of achieving both excellent properties such as high heat resistance and high refractive index and excellent flexibility, a production method thereof, and a cured product of the urethane (meth) acrylate. It is to provide.

  Still another object of the present invention is to provide a fluorene skeleton-containing urethane (meth) acrylate having excellent handling properties, a production method thereof, and a cured product of the urethane (meth) acrylate.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a diol having a specific fluorene skeleton, a specific polyisocyanate compound having a polyol skeleton and a terminal isocyanate group, and a reactive group for the isocyanate group (for example, When a (meth) acrylic compound having a hydroxyl group) is reacted, a novel urethane (meth) acrylate is obtained, and such a novel urethane (meth) acrylate has a fluorene skeleton and a polyol skeleton. For this reason, the present invention has been completed by finding that it is excellent in heat resistance and has excellent flexibility even if it has a fluorene skeleton.

  That is, the urethane (meth) acrylate of the present invention comprises a compound having a fluorene skeleton represented by the following formula (1), a polyisocyanate compound (A) having a polyol skeleton and a terminal isocyanate group (simply simply a polyisocyanate compound (A )) And a (meth) acrylic compound having an active hydrogen atom reactive with an isocyanate group is a urethane (meth) acrylate.

(In the formula, ring Z ¹ and ring Z ² represent aromatic hydrocarbon rings, R ¹ and R ² are the same or different and represent a substituent, R ³ represents an alkylene group, k is an integer of 0 to 4; , M is 0 or an integer of 1 or more, and n is 0 or an integer of 1 or more.)
The urethane (meth) acrylate is usually a urethane (meth) acrylate having two or more (meth) acryloyl groups (or bifunctional or more), and in particular, a urethane (meth) having two (meth) acryloyl groups. An acrylate (particularly, a urethane (meth) acrylate having (meth) acryloyl groups at both ends) may be used.

The compound represented by the formula (1) is, for example, (i) in the formula (1), the ring Z ¹ and the ring Z ² are benzene rings, m is 0, and the group R ³ is C _2-4. A compound which is an alkylene group (especially an ethylene group) and n is 1 to 10 (preferably 1 to 4, particularly 1), (ii) in formula (1), ring Z ¹ and ring Z ² are benzene rings , R ² is an alkyl group (C _1-4 alkyl group such as a methyl group) or an aryl group (C _6-10 aryl group such as a phenyl group), m is 1 to 2, and R ³ is C ³ _A compound having _2-4 alkylene group (especially ethylene group) and n being 1 to 10 (preferably 1 to 4, particularly 1), or (iii) in formula (1), ring Z ¹ and ring Z ² are a naphthalene ring, ^{R 3} is _{C 2-4} alkylene group (particularly an ethylene group), n is 1 10 (preferably 1 to 4, in particular 1) may be a compound that is.

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, and 9,9-bis (hydroxy (poly) C _2-4 alkoxy naphthyl) may be a compound selected from fluorene.

The polyisocyanate compound (A) is a diisocyanate compound (or a urethane prepolymer having two isocyanate groups), for example, a urethane prepolymer having isocyanate groups at both ends where the diol compound and the diisocyanate compound (a) have reacted. May be. In such a urethane prepolymer, the diol compound is, for example, a diol compound selected from a low molecular weight diol (such as alkane diol) and a high molecular weight diol (polymer diol compound) (particularly, polyoxy C _2-6 alkylene glycol). Polyether-based diol). The diisocyanate compound (a) may be a diisocyanate compound selected from aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, and aromatic diisocyanate.

The diol compound is typically an alkanediol (for example, C _2-10 alkanediol) or a polyether-based diol compound having a number average molecular weight of 200 to 5000 (for example, a polyoxy C ₂₋ having a number average molecular weight of 250 to 2000). ₆ alkylene glycol). The polyisocyanate compound (A) may be a polyisocyanate compound having an isocyanate group (—NCO) content of about 1 to 20% by weight based on the total amount of the polyisocyanate compound (A).

The (meth) acrylic compound is a hydroxyl group-containing mono (meta) compound such as a hydroxyl group-containing (meth) acrylic compound [particularly, hydroxyalkyl (meth) acrylate (eg, hydroxy C _2-6 alkyl (meth) acrylate)). ) Acrylate etc.].

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

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

(Wherein R ⁴ represents a hydrogen atom or a methyl group, A represents a residue of the polyisocyanate compound (A), X and Y represent an ether group, E represents a linking group, and p represents 0 or 1) , Q is an integer of 1 or more). However, the two groups J have at least two groups [CH ₂ ═CR ⁴ —CO—X] —. Ring Z ¹ , Ring Z ² , R ¹ , R ² , R ³ , k, m, and n are the same as described above. ]
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 ¹ and Z ² are benzene rings, R ² is an alkyl group (C _1-4 alkyl group such as a methyl group) or an aryl group (C _6-10 aryl group such as a phenyl group), and m is 0 to 0 2, R ³ is a C _2-4 alkylene group (especially ethylene group), n is 1 to 4 (preferably 1 to 2, particularly 1), and two Js are groups represented by the formula (3) Wherein p is 1, A is a residue of a urethane prepolymer having an isocyanate group at both ends where a diol compound selected from an alkanediol and a polymer diol compound and a diisocyanate compound (a) are reacted, and q is 1-2. (Especially 1) (b) Z ¹ and Z ² are naphthalene rings, R ³ is a C _2-4 alkylene group (especially ethylene group), n is 1-4 (preferably 1-2, especially 1) Yes, two J This is also a group represented by the formula (3), p is 1, urethane is an isocyanate group at both ends where a diol compound selected from an alkanediol and a polymer diol compound and a diisocyanate compound (a) are reacted. Prepolymer residue, a combination wherein q is 1-2 (especially 1).

In the combination (a) or (b), the (1) diol compound may be, for example, a C _2-10 alkanediol, or a polyether-based diol having a number average molecular weight of about 200 to 5000, and (2) a diisocyanate compound. (A) may be a diisocyanate compound selected from aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate and aromatic diisocyanate, and (3) content ratio of isocyanate group (—NCO) of urethane prepolymer May be about 1 to 20% by weight relative to the entire urethane prepolymer.

In the formula (3), E may be a hydrocarbon group such as an alkylene group (such as a C _2-10 alkylene group).

  The urethane (meth) acrylate of the present invention is reactive to a compound having a fluorene skeleton represented by the following formula (1), a polyisocyanate compound (A) having a polyol skeleton and a terminal isocyanate group, and an isocyanate group. It can be produced by reacting with a (meth) acrylic compound having an active hydrogen atom.

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

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

  Since the novel urethane (meth) acrylate of the present invention combines a diol having a specific fluorene skeleton and a specific polyisocyanate compound having a polyol skeleton, it is flexible even though it has a fluorene skeleton. Excellent in properties. For this reason, the urethane (meth) acrylate of the present invention can achieve both excellent properties such as high heat resistance and a high refractive index, and excellent flexibility. In addition, the fluorene skeleton-containing urethane (meth) acrylate of the present invention may be used with a relatively low viscosity despite having a fluorene skeleton, because of having a polyol skeleton, and handling properties. Excellent (handleability). 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.

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.

  The urethane (meth) acrylate of the present invention has a specific diol having a fluorene skeleton, a specific polyisocyanate compound, and a (meth) acrylic compound having a reactive group for the isocyanate group (simply referred to as a (meth) acrylic compound). It may be a urethane (meth) acrylate that has reacted. In the urethane (meth) acrylate of the present invention, the diol and the polyisocyanate compound are usually bonded via a urethane bond, and the polyisocyanate compound and the (meth) acrylic compound are bonded (for example, And bonded through a urethane bond). That is, the diol and the (meth) acrylic compound are bonded via the polyisocyanate compound (or the isocyanate group of the polyisocyanate compound).

(Diol having a fluorene skeleton)
The diol having a fluorene skeleton may usually be a compound having a fluorene skeleton represented by the following formula (1).

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

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

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

Group substituted on the ring ^{Z 1} and ring ^{Z 2 -} substitution position of _[(OR 3) n -OH] is not particularly limited, for example, when ring ^{Z 1} and the ring ^{Z 2} is a benzene ring, a fluorene 9 2-6 position (especially 4 position) of the phenyl group substituted by position may be sufficient. In addition, when ring Z ¹ and ring Z ² are naphthalene rings, one of 5 to 8 positions (for example, 5 position) depending on the substitution position of a naphthyl group (1 or 2-naphthyl group) substituted with fluorene, etc. ) May be substituted at least. In particular, when a 2-naphthyl group (β-naphthyl group) is substituted at the 9th position of fluorene, the group — [(OR ³ ) _n —OH] may be substituted at the 6th position of the naphthyl group. In many cases, when the 1-naphthyl group (α-naphthyl group) is substituted at the 9th position of fluorene, the group-[(( OR ³ ) _n —OH] is often substituted.

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

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

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

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

The number (addition mole number) n of oxyalkylene groups (OR ³ ) can be selected from a range of about 0 to 15, for example, 0 to 12 (for example, 1 to 12), preferably 0 to 8 (for example, 1 to 1). 8), more preferably 0 to 6 (for example, 1 to 6), particularly 1 or more (for example, about 1 to 4). The number of substitutions n may be the same or different depending on the ring Z ¹ and the ring Z ² . In ring Z ¹ and ring Z ² , the total (n × 2) of oxyalkylene groups can be selected from the range of about 0 to 30, for example, 0 to 24 (for example, 2 to 20), preferably 0 to 16 (for example, 2 to 14), more preferably 0 to 12 (for example, 2 to 10), particularly 2 or more (for example, about 2 to 8) may be used. 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.

  Representative diols having a fluorene skeleton include 9,9-bis (hydroxyphenyl) fluorenes, 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, and 9,9-bis (hydroxynaphthyl) fluorenes. 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes and the like.

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.}.

  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 (hydroxynaphthyl) fluorenes are produced by using hydroxynaphthalenes (for example, naphthol (1-naphthol) instead of phenols in the 9,9-bis (monohydroxyphenyl) fluorene production method. , 2-naphthol) and other naphthols).

Furthermore, 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes or 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes are 9,9-bis (hydroxyphenyl) fluorenes or 9,9 It can be obtained by reacting bis (hydroxynaphthyl) fluorenes with a compound (alkylene oxide, haloalkanol, etc.) corresponding to the group R ³ O. 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.

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

Preferred diols having a fluorene skeleton include 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorene {for example, 9,9-bis such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene. (Hydroxy (poly) C _2-4 alkoxyphenyl) fluorene and the like}, 9,9-bis (alkyl-hydroxy (poly) alkoxyphenyl) fluorene [eg, 9,9-bis [4- (2-hydroxyethoxy)- 9,9-bis (mono- or di-C _1-4 alkyl-hydroxy (poly) such as 3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene ) _{C 2-4} alkoxyphenyl) fluorene, etc.], 9,9-bis (aryl - hydroxy (poly) Al Kishifeniru) fluorene [e.g., 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene such as 9,9-bis (mono- or _{di-C 6-8} aryl - hydroxy (poly) _{C 2 -4} alkoxy - phenyl) fluorene, etc.], 9,9-bis (hydroxy (poly) alkoxy naphthyl) fluorene [e.g., 9,9-bis [1- (6- (2-hydroxyethoxy) naphthyl)], such as fluorene 9,9-bis (hydroxy (poly) C _2-4 alkoxynaphthyl) fluorene etc.] and the like.

In particular, ring Z ¹ and ring Z ² such as 9,9-bis (alkyl-hydroxy (poly) alkoxyphenyl) fluorene, 9,9-bis (aryl-hydroxy (poly) alkoxyphenyl) fluorene have a hydrocarbon group. A specific diol uses a diol [ie, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (bisphenoxyethanol fluorene)] having an unsubstituted fluorene skeleton in ring Z ¹ and ring Z ^2. Compared with the case, the heat resistance of urethane (meth) acrylate can be further improved. In addition to the improvement in heat resistance, the diol 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.

[Polyisocyanate Compound (A)]
In the present invention, a polyisocyanate compound (A) having a polyol skeleton is used as a polyisocyanate compound that is a raw material of urethane (meth) acrylate. By combining such a specific polyisocyanate compound (A) and the specific diol having the fluorene skeleton, urethane (meth) acrylate has excellent characteristics derived from the fluorene skeleton (high heat resistance, high refractive index, etc.) And excellent flexibility and handling properties can be achieved. Moreover, since the ratio of the urethane bond with respect to the whole urethane (meth) acrylate can be made small, it is advantageous also for heat resistance improvement.

  The polyisocyanate compound (A) having a polyol skeleton (sometimes simply referred to as a polyisocyanate compound) 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. As long as the structure is not particularly limited, a polyisocyanate compound (A) 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) is usually used. Reacted product (or urethane prepolymer)]. That is, the polyisocyanate compound (A) is usually a reaction product obtained by reacting a diol compound and a diisocyanate compound, and may be a compound having an isocyanate group at both ends (or a urethane prepolymer).

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

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

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

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

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

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

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

  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.

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

  In the reaction product (urethane prepolymer), as long as 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), Without limitation, for example, polyisocyanate (aliphatic polyisocyanate, alicyclic polyisocyanate, araliphatic polyisocyanate, aromatic polyisocyanate, etc.), modified polyisocyanate [or derivatives such as multimers (dimers) , Trimers, etc.), allophanates, etc.]. These polyisocyanates may have a group containing a hetero atom (for example, ester group, halogen atom, etc.) in the molecule and / or as a substituent.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The linking group E is a polyvalent group (divalent group, trivalent group, tetravalent group, etc.) determined by the number of q. For example, in the formula (B), when q is 1, the linking group E is a divalent group corresponding to an exemplary compound described later.

  Representative linking group E includes 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.). In the formula (B), q may be 1 to 6, preferably 1 to 4, more preferably 1 to 3 (for example, 1 to 2), particularly 1.

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

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

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

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

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

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

[Urethane (meth) acrylate]
The urethane (meth) acrylate of the present invention may be a urethane (meth) acrylate having two or more (meth) acryloyl groups (or bifunctional or more), for example, 2 to 10, preferably 2 to 6, and further Preferably, it may be a urethane (meth) acrylate having 2 to 4 (for example, 2 to 3), particularly having two (meth) acryloyl groups (for example, having (meth) acryloyl groups at both ends). The urethane (meth) acrylate of the present invention may be a mixture of urethane (meth) acrylates having different numbers of (meth) acryloyl groups. The number of (meth) acryloyl groups of such urethane (meth) acrylate is the reaction ratio between the diol having the fluorene skeleton, the polyisocyanate compound (A), and the (meth) acrylic compound, It can be selected by selecting the type of the (meth) acrylic compound.

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

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

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

In the formula (2), the group J may be a hydrogen atom or a group represented by the formula (3), and preferably two groups J may be groups represented by the formula (3). Note that the two groups J (or the compound represented by the formula (2)) have at least two groups [CH ₂ = CR ⁴ —CO—X] — ((meth) acryloyl group), that is, at least 2 The urethane (meth) acrylate having the above (meth) acryloyl group (that is, when one of the two Js is a hydrogen atom, q is 2 or more in the other J). For example, when two groups J are both groups represented by the formula (3), the number of (meth) acryloyl groups in the compound represented by the formula (2) is q × 2, and q × 2 ≧ 2 is satisfied (for example, when any q is 1 or more, when one q is 2 or more and the other q is 0).

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

(A) Z ¹ and Z ² are benzene rings, 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), m Is 0 to 2 (especially 1 or 2), R ³ is a C _2-4 alkylene group (especially ethylene group), and n is 1 or more (eg 1 to 4, preferably 1 to 2, more preferably 1). Two Js are groups represented by the formula (3), X and Y are ether groups (that is, (meth) acryloyloxy groups), p is 1, and A is an alkanediol and a polymer diol compound. Residue of urethane prepolymer having isocyanate groups at both ends where the selected diol compound and diisocyanate compound (a) have reacted, a combination wherein q is 1 to 2 (particularly 1).

(B) Z ¹ and Z ² are naphthalene rings, 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), m Is 0 to 2 (for example, 0), R ³ is a C _2-4 alkylene group (particularly an ethylene group), n is 1 or more (for example, 1 to 4, preferably 1 to 2, more preferably 1), Two J are groups represented by the formula (3), X and Y are ether groups (that is, (meth) acryloyloxy groups), p is 1, A is selected from alkanediol and polymer diol compound Residues of urethane prepolymers having isocyanate groups at both ends where the diol compound and diisocyanate compound (a) have reacted, a combination wherein q is 1 to 2 (particularly 1).

In the combination (a) or (b), the alkanediol compound may be the above-described alkanediol (for example, C _2-10 alkanediol). In the combination (a) or (b), the polymer diol compound is the diol compound exemplified above, for example, a polyether diol (for example, polyoxy C _2-4 alkylene glycol such as polytetramethylene ether glycol). May be. The number-average molecular weight of such a polymer diol compound may be in the range exemplified above (for example, about a number-average molecular weight of about 200 to 5,000).

  In the above combination (a) or (b), the diisocyanate compound (a) is a diisocyanate selected from the above exemplified compounds, for example, aliphatic diisocyanates, alicyclic diisocyanates, araliphatic diisocyanates and aromatic diisocyanates. Compound etc. are mentioned.

  Furthermore, in the combination (a) or (b), the content ratio of the isocyanate group (—NCO) of the urethane prepolymer (or polyisocyanate compound (A)) is within the above-described range (for example, the entire urethane prepolymer). 1 to 20% by weight).

Furthermore, in the combination (a) or (b), E represents a group represented by the formula (E1) [for example, an alkylene group (for example, C such as ethylene group, propylene group, trimethylene group, tetramethylene group, etc.) _{A 2-10} alkylene group, preferably a C _2-6 alkylene group, etc.].

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

  The reaction may be carried out by reacting these components in the same reaction system. However, in order to obtain a urethane (meth) acrylate efficiently, usually, the polyisocyanate compound (A), the diol and the (meta) are used. ) After reacting one component of the acrylic compound, the resulting reaction product (precursor) is reacted with the other component [ie, reacting in multiple steps (two steps)] in many cases. . In particular, a reaction product (urethane prepolymer or urethane (meth) acrylate precursor) of the diol (particularly a compound having a fluorene skeleton represented by the formula (1)) and the polyisocyanate compound (A) is added to (meta ) An acrylic compound may be reacted. That is, in such a multi-stage reaction, the polyisocyanate compound (A) and the one component are reacted to each other (when one component is a diol compound, particularly two ends or both ends). A compound having an isocyanate group (a precursor of urethane (meth) acrylate, prepolymer) is prepared, and such a precursor is reacted with the other component to prepare urethane (meth) acrylate.

  In the reaction (preparation of the precursor) between the polyisocyanate compound (A) and one component (for example, the diol), the usage ratio of both components can be appropriately selected according to the type of the one component. For example, when one component is the diol compound, the ratio (charge ratio) of the polyisocyanate compound (A) is 0.7 mol or more (for example, about 0.8 to 4 mol) with respect to 1 mol of the diol compound. ), Preferably 1 mol or more (for example, about 1.5 to 3 mol), more preferably 1.8 mol or more (for example, about 1.85 to 2.5 mol). In particular, in the case of producing a compound in which J is a group represented by the formula (3) in the formula (2), the ratio of the polyisocyanate compound (A) is the diol (compound having a fluorene skeleton) 1 The amount is usually 1.9 mol or more (for example, 1.95 to 3 mol) with respect to mol, and 1.98 to 2.5 mol, preferably 1.99 to 2.5 mol in order to obtain a precursor efficiently. It may be about 2.3 mol, more preferably about 2 to 2.1 mol.

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

  The reaction between the polyisocyanate compound (A) and one component 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). Organometallic catalysts such as cobalt acid; tertiary amines [eg, trialkylamines such as triethylamine, chain tertiary amines such as benzyldimethylamine; pyridine, methylpyridine, N, N-dimethylpiperazine, tri Cyclic tertiary amines such as ethylenediamine] and the like. These catalysts may be used alone or in combination of two or more.

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

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

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

  And the 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, but is usually reacted by mixing the other component as it is in the reaction system of the polyisocyanate compound (A) and one component. May be performed.

  In the reaction between the precursor and the other component, the ratio (preparation ratio) of the other component (particularly the (meth) acrylic compound) can also be appropriately selected according to the type of the other component. In particular, when the other component is the (meth) acrylic compound, the proportion of the (meth) acrylic compound is, for example, 0.7 mol or more (for example, with respect to 1 mol of the precursor (or the diol)) 0.8 to 5 mol), preferably 0.9 mol or more (for example, about 0.95 to 3 mol), more preferably 2 to 2.5 mol, particularly 2 to 2.3 mol (for example 2 (About 2.1 mol).

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

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

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

  The polymerization initiator can be selected depending on the application. For example, in the case of constituting a photopolymerizable composition, a photopolymerization initiator such as benzoins (benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether) is used. Benzoin alkyl ethers, etc.), phenyl ketones [for example, acetophenones (eg, acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc.), alkylphenyl ketones such as 2-hydroxy-2-methylpropiophenone; cycloalkylphenylketo such as 1-hydroxycyclohexyl phenyl ketone 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), 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 is 0.1 to 30 parts by weight (for example, 0.5 to 30 parts by weight), preferably 1 to 20 parts by weight (for example, 1) with respect to 100 parts by weight of the urethane (meth) acrylate. 0.5 to 15 parts by weight), more preferably about 2 to 10 parts by weight, and usually about 1 to 10 parts by weight.

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

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

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

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

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

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

  The use amount (addition amount) of the non-reactive diluent varies depending on the coating method and the like, but is, for example, 10 to 400 parts by weight, preferably 20 to 300 parts by weight, and more preferably 100 to 100 parts by weight of urethane (meth) acrylate. Preferably, it may be about 30 to 200 parts by weight.

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

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

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

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

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

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

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

  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. Prepolymerization reaction step 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF, Osaka Gas Chemical Co., Ltd.) was added to a brown 100 mL flask equipped with a condenser and a stirrer shielded with aluminum foil. 4.81 g (0.011 mol) and 1,4-dioxane 24.65 g were added to dissolve BPEF in 1,4-dioxane, and a diisocyanate having a polyol skeleton (manufactured by Sanyo Chemical Industries, Ltd.) , “Samprene P-6090”, 24.1 g (0.022 mol) of a prepolymer having isocyanate groups at both ends reacted with polytetramethylene ether glycol and diphenylmethane diisocyanate, NCO% = 7.6%) Di-n-butyls diluted to 1% by weight with 1,4-dioxane 0.17 g of Zuji laurate (DTD, manufactured by Kishida Chemical Co., Ltd., Lot No. “G00333T”, hereinafter referred to as 1% DTD) was added, the inside of the flask was replaced with argon, and the reaction was carried out at 80 ° C. for 20 hours with stirring. did. In the reaction solution, the NCO% of the obtained prepolymer was 3.1%.

2. Acrylation reaction step To the obtained reaction solution, 2.72 g (0.023 mol) of 2-hydroxyethyl acrylate (HEA, manufactured by Nacalai Tesque, Lot No. “M4P3126”), and 0.55 g of 1% DTD And allowed to react at room temperature for 24 hours. After completion of the reaction, 18.1 mg of hydroquinone (manufactured by Nacalai Tesque) was added. Confirmation that the reaction was completed was performed by confirming that the NCO group had disappeared by FT-IR measurement of the reaction solution.

3. Desolvation step A capillary was attached to the flask, and desolvation was performed at 65 to 70 ° C for 1 hour under reduced pressure with an evaporator in the presence of air. The residual amount of the solvent was calculated from the analysis result of gas chromatography. The product after solvent removal was a colorless and transparent liquid with a very high viscosity, and the solvent recovery rate was 57.3%.

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

¹ H-NMR (ppm): 7.73 (d), 7.4-7.2 (m), 7.07 (brs), 6.75 (d), 6.5-6.4 (m, Acrylate), 6.2-6.1 (m, acrylate), 5.9-5.8 (m, acrylate), 4.44 (brs), 4.40 (s), 4.32 (s), 4.31 (t), 4.29 (s), 4.2-4.1 (m), 3.9-3.8 (m), 3.41 (m).

[Example 2]
1. Prepolymerization reaction step 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF, Osaka Gas Chemical Co., Ltd.) was added to a brown 100 mL flask equipped with a condenser and a stirrer shielded with aluminum foil. 6.18 g (0.014 mol) and 1,4-dioxane 29.67 g were added to dissolve BPEF in 1,4-dioxane, and a diisocyanate having a polyol skeleton (manufactured by Asahi Kasei Chemicals Corporation) "Duranate D-201", a prepolymer having isocyanate groups at both ends reacted with alkanediol and hexamethylene diisocyanate, NCO% = 15.8%) 15.34 g (0.028 mol) was added and dissolved. After that, 0.33 g of 1% DTD was added, the inside of the flask was replaced with argon, and stirring was continued. And reacted at 80 ° C. for 18.5 hours. In the reaction solution, the NCO% of the obtained prepolymer was 5.6%.

2. Acrylation Reaction Step To the obtained reaction solution, 3.44 g (0.029 mol) of 2-hydroxyethyl acrylate (HEA, manufactured by Nacalai Tesque, Lot No. “M4P3126”), and 1% DTD 1.29 g Was added and allowed to react at room temperature for 117 hours. After completion of the reaction, 14.2 mg of hydroquinone (manufactured by Nacalai Tesque) was added. Confirmation that the reaction was completed was performed by confirming that the NCO group had disappeared by FT-IR measurement of the reaction solution.

3. Desolvation step A capillary was attached to the flask, and desolvation was performed at 65 to 70 ° C for 1 hour under reduced pressure with an evaporator in the presence of air. The residual amount of the solvent was calculated from the analysis result of gas chromatography. The product after removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a high viscosity, and the solvent recovery rate was 75.1%.

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

¹ H-NMR (ppm): 7.74 (d), 7.4-7.3 (m), 7.3-7.2 (m), 7.09 (d), 6.74 (d) 6.5-6.4 (m, acrylate), 6.2-6.1 (m, acrylate), 5.9-5.8 (m, acrylate), 4.88 (brs), 4.3 (M), 4.07 (brs9), 3.9-3.8 (m), 3.64 (s), 3.14 (brs), 1.47 (brs), 1.31 (brs), 0.92 (brs).

[Example 3]
4.81 g (0.011 mol) of BPEF and 5.13 g (0.011 mol) of bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene (BCF-EO, Osaka Gas Chemical Co., Ltd.) A prepolymerization reaction step, an acrylation reaction step, and a desolvation step were performed in the same manner as in Example 1 except that the product was changed to (manufactured). The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a very high viscosity, and the solvent recovery rate was 60.4%.

[Example 4]
6.18 g (0.014 mol) of BPEF 6.53 g (0.014 mol) of bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene (BCF-EO, Osaka Gas Chemical Co., Ltd.) A prepolymerization reaction step, an acrylation reaction step, and a desolvation step were performed in the same manner as in Example 2 except that the product was changed to (manufactured). The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a very high viscosity, and the solvent recovery rate was 77.3%.

[Example 5]
4.81 g (0.011 mol) of BPEF, 5.44 g (0.011 mol) of 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene (BXF-EO, A prepolymerization reaction step, an acrylation reaction step, and a desolvation step 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 removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a very high viscosity, and the solvent recovery rate was 56.3%.

[Example 6]
6.18 g (0.014 mol) of BPEF and 6.92 g (0.014 mol) of 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene (BXF-EO, A prepolymerization reaction step, an acrylation reaction step, and a desolvation step were performed in the same manner as in Example 2 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 removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a very high viscosity, and the solvent recovery rate was 72.5%.

[Example 7]
4.81 g (0.011 mol) of BPEF 5.92 g (0.011 mol) of 6,6 ′-(9-fluorenylidene) -bis (2-naphthyloxyethanol) (Osaka Gas Chemical Co., Ltd.) A prepolymerization reaction step, an acrylation reaction step, and a desolvation step 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 removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a very high viscosity, and the solvent recovery rate was 58.0%.

[Example 8]
Example 1 with the exception that 4.81 g (0.011 mol) of BPEF was replaced with 5.92 g (0.011 mol) of 5,5 ′-(9-fluorenylidene) -bis (2-naphthyloxyethanol). The prepolymerization reaction step, the acrylation reaction step, and the desolvation step 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 removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a very high viscosity, and the solvent recovery rate was 57.1%.

[Example 9]
6.18 g (0.014 mol) of BPEF, 7.54 g (0.014 mol) of 6,6 ′-(9-fluorenylidene) -bis (2-naphthyloxyethanol) (BNF-EO, Osaka Gas Chemical ( A prepolymerization reaction step, an acrylation reaction step, and a desolvation step were carried out in the same manner as in Example 2 except that the product was changed to (manufactured). The completion of the reaction was performed by confirming the disappearance of the NCO group by FT-IR measurement. The product after removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a very high viscosity, and the solvent recovery rate was 68.5%.

[Example 10]
Example 2 with the exception that 6.18 g (0.014 mol) of BPEF was replaced with 7.54 g (0.014 mol) of 5,5 ′-(9-fluorenylidene) -bis (2-naphthyloxyethanol). The prepolymerization reaction step, the acrylation reaction step, and the desolvation step 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 removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a very high viscosity, and the solvent recovery rate was 69.3%.

[Example 11]
4.81 g (0.011 mol) of BPEF 6.50 g (0.011 mol) of 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene (BOPPF-EO, Osaka Gas) A prepolymerization reaction step, an acrylation reaction step, and a desolvation step were performed in the same manner as in Example 1 except that the product 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 removal of the solvent (urethane acrylate) was a colorless and transparent liquid with a very high viscosity, and the solvent recovery rate was 55.3%.

[Example 12]
6.18 g (0.014 mol) of BPEF and 7.54 g (0.014 mol) of 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene (BOPPF-EO, Osaka Gas) A prepolymerization reaction step, an acrylation reaction step, and a desolvation step were performed in the same manner as in Example 2 except that the product 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 removal of the solvent (urethane acrylate) was a colorless and transparent liquid having a very high viscosity, and the solvent recovery rate was 71.4%.

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

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

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

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

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

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

[Example 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 to be cured.

  The refractive index (589 nm) of the cured film thus obtained was measured using an Abbe refractometer (manufactured by ATAGO, DR-M2), and the refractive index was 1.557.

  When the pencil hardness of the obtained cured film was measured with a surface property measuring instrument HEIDON-14 (Peeling / Slipping / Scratching TESTER manufactured by HEIDON), the pencil hardness was <6B.

  Moreover, when the glass transition temperature (Tg) of the obtained cured film was measured at a frequency of 10 Hz and a temperature rising rate of 5 ° C./min with a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM), it was 40 ° C. Met. The tensile strength and elastic modulus were measured with a Tensilon universal testing machine RTC-1250A (manufactured by A & D). As a result, the tensile strength was 6.3 MPa and the elastic modulus was 3.0 MPa. It was found to be superior in flexibility as compared with the cured film obtained.

  These characteristics are shown in Table 1.

[Example 14]
A cured film 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. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 15]
A cured film was prepared 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. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 16]
A cured film 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. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 17]
A cured film 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. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 18]
A cured film 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. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 19]
A cured film 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. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 20]
A cured film was prepared 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. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 21]
A cured film 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. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 22]
A cured film 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. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 23]
A cured film was prepared 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. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Example 24]
A cured film was prepared 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. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Comparative Example 3]
A cured film was prepared in the same manner as in Example 13 except that 5 g of the product after desolvation obtained in Comparative Example 1 was used instead of 5 g of the product after desolvation obtained in Example 1. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

[Comparative Example 4]
A cured film was prepared in the same manner as in Example 13, except that 5 g of the product after removal of solvent obtained in Comparative Example 2 was used instead of 5 g of the product after removal of solvent obtained in Example 1. Obtained. Various characteristics were measured by the same method as in Example 13. The results are shown in Table 1.

  As is clear from Table 1, the cured films obtained in the examples had a high refractive index and were excellent in flexibility as compared with the films obtained in the comparative examples. The glass transition temperature was in a practical range, although it was slightly lower. Further, as is clear from the comparison between Example 13 and Comparative Example 3, it can be seen that the urethane (meth) acrylate obtained in the Example is remarkably excellent in flexibility even if it has the same fluorene skeleton. It was.

  The novel urethane (meth) acrylate (and polymerizable composition thereof) of the present invention has a high refractive index, heat resistance, light transmission, hardness, weather resistance, mechanical strength, dimensional stability and processability. In addition to being excellent in flexibility, it is also useful as a plastic raw material (adhesive, paint, etc.) satisfying various required performances. The cured product of the present invention can be particularly suitably used as an optical material, and examples of the shape of such an optical material include a film or sheet shape, a plate shape, a lens shape, and a tubular shape.

Typically, the urethane (meth) acrylate (or a cured product thereof) of the present invention is an ink material, a light emitting material (for example, a light emitting material for organic EL), an organic semiconductor, a graphitization precursor, a gas separation membrane (for example, , CO ₂ gas separation membrane, etc.), coating agent (for example, optical overcoat agent such as coating agent for LED (light emitting diode) element or hard coating agent), lens [pickup lens (eg, DVD (digital versatile) Pickup lens for disk), microlens (for example, microlens for liquid crystal projector), spectacle lens, etc.], polarizing film (for example, polarizing film for liquid crystal display), antireflection film (or antireflection film, for example) , Antireflection films for display devices, etc.), touch panel films, flexible substrates Film, display film [for example, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction electron-emitting device display), FED (field emission display), NED (nano Emissive displays), cathode ray tubes, electronic paper displays (particularly thin displays) films (filters, protective films, etc.)], fuel cell membranes, optical fibers, optical waveguides, holograms, and the like.

Claims (14)

A compound having a fluorene skeleton represented by the following formula (1), a polyisocyanate compound (A) having a polyol skeleton and a terminal isocyanate group, and a (meth) acrylic compound having an active hydrogen atom reactive with the isocyanate group A urethane (meth) acrylate reacted with a compound,
The polyisocyanate compound (A) is a urethane prepolymer having isocyanate groups at both ends where the diol compound and the diisocyanate compound (a) have reacted, and the diol compound is selected from alkanediols and polymer diol compounds. Further, urethane (meth) acrylate, which is at least one diol compound, and the diisocyanate compound (a) is a diisocyanate compound composed of an aromatic diisocyanate.

(In the formula, ring Z ¹ and ring Z ² represent aromatic hydrocarbon rings, R ¹ and R ² are the same or different and represent a substituent, R ³ represents an alkylene group, k is an integer of 0 to 4; , M is 0 or an integer of 1 or more, and n is 0 or an integer of 1 or more.)   The urethane (meth) acrylate according to claim 1, which is a urethane (meth) acrylate having a (meth) acryloyl group at both ends. In the compound represented by formula (1), (i) in formula (1), ring Z ¹ and ring Z ² are benzene rings, m is 0, and group R ³ is a C _2-4 alkylene group. A compound in which n is 1 to 10, (ii) in formula (1), ring Z ¹ and ring Z ² are benzene rings, R ² is an alkyl group or an aryl group, and m is 1 to 2 A compound in which R ³ is a C _2-4 alkylene group and n is 1 to 10, or (iii) in formula (1), ring Z ¹ and ring Z ² are naphthalene rings, and R ³ is C ³ The urethane (meth) acrylate according to claim 1 or 2, which is a compound having a _2-4 alkylene group and n is 1 to 10. 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, and 9,9-bis (hydroxy (poly) C _{2− 4} alkoxy naphthyl) urethane (meth) acrylate according to claim 1 is a compound selected from fluorene.   The diol compound is an alkanediol or a polyether diol compound having a number average molecular weight of 200 to 5,000, and the polyisocyanate compound (A) is a content ratio of an isocyanate group (—NCO) to the whole polyisocyanate compound (A). The urethane (meth) acrylate according to any one of claims 1 to 4, wherein the polyisocyanate compound is 1 to 20 wt%. 5. The urethane (meth) acrylate according to claim 1, wherein the diol compound is C _2-10 alkanediol or polyoxy C _2-6 alkylene glycol having a number average molecular weight of 250 to 2,000.   The urethane (meth) acrylate according to any one of claims 1 to 6, wherein the (meth) acrylic compound is a hydroxyl group-containing mono (meth) acrylate. It is a compound represented by following formula (2), Urethane (meth) acrylate in any one of Claims 1-7.

[ Wherein , ring Z ¹ and ring Z ² represent an aromatic hydrocarbon ring, R ¹ and R ² are the same or different and represent a substituent, R ³ represents an alkylene group, and J represents a hydrogen atom or Formula (3)

(Wherein R ⁴ represents a hydrogen atom or a methyl group, A represents a residue of the polyisocyanate compound (A), X and Y represent an ether group, E represents a linking group, and p represents 0 or 1) , Q is an integer of 1 or more). However, the two groups J have at least two groups [CH ₂ ═CR ₄ —CO—X] —. k is an integer of 0 to 4, m is an integer of 0 or 1 or more, and n is an integer of 0 or 1 or more . ] The urethane (meth) acrylate according to claim 8, which satisfies the following combination (a) or (b) in the formula (2).
(A) Z ¹ and Z ² are benzene rings, 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 two Js are Is a group represented by the formula (3), p is 1, urethane is a urethane prepolymer having isocyanate groups at both ends where a diol compound selected from an alkanediol and a polymer diol compound and a diisocyanate compound (a) are reacted. Residue of polymer, combination in which q is 1-2 (b) Z ¹ and Z ² are naphthalene rings, R ³ is a C _2-4 alkylene group, n is 1-4, and both J are formulas (3) is a group represented by p is 1, and A is an isocyanate group at both ends where a diol compound selected from an alkanediol and a polymer diol compound is reacted with a diisocyanate compound (a). Residue of urethane prepolymer having a combination of q and 1-2. In the combination (a) or (b), (1) the diol compound is a C _2-10 alkanediol, or a number average molecular weight 200 to 5000 polyether diol, and (2) an isocyanate group (—NCO) of the urethane prepolymer. The urethane (meth) acrylate of Claim 9 whose content rate of 1) is 20 to 20 weight% with respect to the whole urethane prepolymer. In Formula (3), E is a _C2-10 alkylene group, The urethane (meth) acrylate in any one of Claims 8-10. A compound having a fluorene skeleton represented by the following formula (1), a polyisocyanate compound (A) having a polyol skeleton and a terminal isocyanate group, and a (meth) acrylic compound having an active hydrogen atom reactive with the isocyanate group The method to manufacture the urethane (meth) acrylate in any one of Claims 1-11 by making a compound react.

(In the formula, ring Z ¹ and ring Z ² represent an aromatic hydrocarbon ring , R ¹ and R ² are the same or different and represent a substituent , and R ³ represents an alkylene group. K is an integer of 0 to 4 , M is 0 or an integer of 1 or more, and n is 0 or an integer of 1 or more .)   The manufacturing method of Claim 12 with which a (meth) acrylic-type compound is made to react with the reaction material of the compound and the polyisocyanate compound (A) which have a fluorene skeleton represented by Formula (1).   Hardened | cured material of the urethane (meth) acrylate in any one of Claims 1-11.

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