JP2009235147A - Resin molded product and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin molded product with high transparency and controlled discoloration in spite of being formed by a cured product of a curable resin. <P>SOLUTION: This resin molded product is prepared by curing a curable resin having an aromatic ring or its resin composition in a fluid state while applying a magnetic field and/or an electric field. The aromatic ring may be a fluorene ring. A typical curable resin includes a fluorene backbone-containing epoxy resin, etc. Such a molded product is useful for a lens and an optical material, etc., as discoloration is controlled and high transparency is given. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin molded body that is suitable for various optical materials and lenses, and is formed of a cured product of a curable resin, a manufacturing method thereof, and a coloring suppression method of the resin molded body.

  A material made of an organic resin (for example, an optical material) has many advantages such as light weight and easy molding, and its industrial use has been increasing in recent years. However, a material made of an organic resin has many advantages, but has a problem inherent to the material that it is more easily colored than glass. In particular, among organic resins, a resin composition using a thermosetting or photocurable resin material having an aromatic ring exhibits industrial utility such as a large refractive index as a characteristic derived from an aromatic ring. Because of the presence of an aromatic ring, there is a major material problem that it is easily colored by heat and light in the atmosphere. In general, for such coloring, a method in which an additive such as an antioxidant or an ultraviolet absorber is added to the resin composition to reduce the rate of chemical reaction causing coloring, or a method in which a protective film is used is used. ing.

  For example, JP-A-2005-248125 (Patent Document 1) discloses a light-resistant transparent resin composition comprising a specific transparent rubber-reinforced styrene resin (A) and an ultraviolet absorber masterbatch (B), The ultraviolet absorber master batch (B) comprises 50 to 75% by weight of acrylic monomer and 25 to 50% by weight of aromatic vinyl monomer, has a weight average molecular weight of 3 to 200,000 and a molecular weight distribution of 2. It is a pellet masterbatch composed of 50 to 99% by weight of acrylic copolymer (b-1) in the range of 0 to 3.0 and 1 to 50% by weight of ultraviolet absorber (b-2). A light-resistant transparent resin composition is disclosed. According to this document, some rubber-reinforced styrene resins used for vehicle parts and electrical products are required to have the same transparency as PMMA and polycarbonate, and in applications requiring such transparency, they are exposed to light for a long time. In order to prevent discoloration, it is described that an ultraviolet absorber or a light stabilizer is added to prevent discoloration. However, these additives cause coloring due to a heat history during resin production. This document describes that the light-resistant transparent resin composition is excellent in initial colorability, and has good transparency and light resistance.

  However, the additive effect of these additives is not dramatic, and is a life-long prescription of material quality, and a practical effect cannot be expected depending on the use.

  Japanese Patent Laid-Open No. 2006-287133 (Patent Document 2) discloses an optical semiconductor device sealed with a transparent resin (such as a cured product of a resin composition mainly composed of an alicyclic epoxy resin). An optical semiconductor device is disclosed in which the surface of the transparent resin is covered with a transparent glass protective film. In this document, a transparent resin such as a thermoset of a composition comprising a bisphenol A type epoxy resin and an acid anhydride is frequently used as an LED (light emitting diode) sealing resin, and an aromatic ring is included in the bisphenol structure. And the presence of unsaturated double bonds in the molecular structure of the acid anhydride, the transparent resin may be colored by ultraviolet rays, resulting in a decrease in transparency. It is described that when a latent catalyst is used, the degree of coloring due to ultraviolet rays can be suppressed by not using an acid anhydride, but deterioration due to heat is remarkable. This document describes that deterioration such as coloring can be suppressed by producing a translucent protective film on the surface of the transparent resin.

However, in the method using such a protective film, the coloring of the resin itself cannot be suppressed, and the manufacturing process is complicated, and the cost effectiveness is small industrially.
JP 2005-248125 A (Claim 1, paragraph numbers [0002] to [0006]) JP 2006-287133 A (Claim 1, paragraph numbers [0004] to [0007], paragraph number [0016])

  Accordingly, an object of the present invention is to provide a resin molded body in which coloring is suppressed or reduced even when formed with a cured product of a curable resin having an aromatic ring (or a resin composition thereof) and a method for producing the same. is there.

  Another object of the present invention is to provide a method for efficiently suppressing coloring of a resin molded body formed of a cured product of a curable resin having an aromatic ring (or a resin composition thereof).

  As a result of intensive investigations to achieve the above-mentioned problems, the inventors of the present invention applied the magnetic field and / or electric field to form the aromatic ring into the magnetic field and / or electric field when molding a curable resin containing an aromatic ring. In response to the orientation, the inventors found that coloring was suppressed in a molded body formed of a cured product of the curable resin, thereby completing the present invention.

  That is, the molded body of the present invention is a molded resin body formed from a cured product of a curable resin containing an aromatic ring, in which the aromatic ring is oriented. The aromatic ring may be a fluorene ring.

  In the molded body, the curable resin may be a curable resin obtained using a compound represented by the following formula (1).

(In the formula, ring Z represents an aromatic hydrocarbon ring, X represents a hydroxyl group, a hydroxymethyl group, a mercapto group, a mercaptomethyl group or an amino group, and R ¹ represents a halogen atom, a cyano group or an alkyl group. R ² is a hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, A cyano group or a substituted amino group, k is an integer of 0 to 4, m is an integer of 0 or 1 or more, n is an integer of 1 or more, and k, m, or n is 2 or more, R ¹ , R ² or X may be the same or different groups.
The curable resin may typically be an epoxy compound (or epoxy resin) having a fluorene ring (or fluorene skeleton), for example, a compound represented by the following formula (1A).

(In the formula, R ^3a and R ^3b are the same or different and are an alkylene group, R ^4a and R ^4b are the same or different and represent a hydrogen atom or a methyl group, and p1 and p2 are the same or different and represent 0 or an integer of 1 or more. Z, R ¹ , R ² , k, m and n are the same as above.)
The molded article of the present invention is excellent in transparency. For example, when molded into a film, the transmittance may be 80% or more at all wavelengths in the wavelength region of 400 nm or more and less than 500 nm.

The present invention also includes a method for producing the molded body by curing the curable resin or a resin composition thereof while applying a magnetic field and / or an electric field to the curable resin in a fluid state. In such a method, the magnetic field may be applied in a magnetic field having a residual magnetic flux density of 0.01 to 10T. In such a method, an electric field may be applied in an electric field having an electric field strength of 500 V · cm ⁻¹ .

  The present invention relates to a method for suppressing the coloring of a resin molded body formed of a cured product of a curable resin containing an aromatic ring, and a method for suppressing the coloring of the molded body by orienting the aromatic ring. Is also included.

  In the present specification, the “curable resin” may be used to mean not only a curable resin component but also a curable resin composition containing a curing agent, a polymerization initiator, and the like.

  The molded product of the present invention has suppressed or reduced coloring even if it is formed of a cured product of a curable resin (or a resin composition thereof) having an aromatic ring, because the orientation of the aromatic ring can be used. Moreover, in the method of this invention, the coloring of the resin molding formed with the hardened | cured material of curable resin (or its resin composition) which has an aromatic ring can be suppressed efficiently.

  The resin molded body of the present invention (sometimes simply referred to as a molded body) is formed of a cured product of a curable resin (or a resin composition thereof) containing an aromatic ring, and the aromatic ring (or curable resin) is oriented. ing. In such a molded body, the aromatic ring is usually oriented by a magnetic field and / or an electric field. That is, the aromatic ring can be oriented by applying a magnetic field to the aromatic ring by utilizing the characteristic that the aromatic ring has a response to a magnetic field or an electric field.

Examples of the aromatic ring include a monocyclic aromatic ring such as a benzene ring and a condensed polycyclic aromatic ring (for example, indene ring, naphthalene ring, anthracene ring, fluorene ring, phenanthrene ring, pyrene ring, coronene ring, pentacene). C _10-30 condensed 2 to 7 ring aromatic rings such as a ring). In addition, these aromatic rings are condensed polycyclic hetero rings in which a part of carbon atoms constituting the aromatic ring is substituted with a hetero atom such as nitrogen, oxygen, or sulfur, such as a carbazole ring, a phenoxazine ring, a phenothiazine ring. It may be. Further, these aromatic rings may be derivatives having a substituent such as an alkyl group. These aromatic rings can be used alone or in combination of two or more. Among these aromatic rings, a C _10-20 condensed 2- to 4-cyclic aromatic ring, particularly a fluorene ring is preferable from the viewpoint of excellent optical characteristics, heat resistance, dimensional stability, and the like.

  Typically, the curable resin may be a compound having a skeleton (9,9-bisarylfluorene skeleton) represented by the following formula (A).

(In the formula, ring Z represents an aromatic hydrocarbon ring, R ¹ and R ² represent the same or different substituents, k represents an integer of 0 to 4, m represents an integer of 0 or 1, and k or When m is 2 or more, each of R ^{1 and} R ² may be the same or different group.)
In the above formula (A), examples of the aromatic hydrocarbon ring represented by ring Z include a benzene ring and a condensed polycyclic aromatic hydrocarbon ring (specifically, a condensed polycyclic hydrocarbon ring containing at least a benzene ring). ) And the like. Examples of the condensed polycyclic aromatic hydrocarbon corresponding to the condensed polycyclic aromatic hydrocarbon ring include condensed bicyclic hydrocarbons (for example, C _8-20 condensed bicyclic hydrocarbons such as indene and naphthalene, preferably C _10-16 condensed bicyclic hydrocarbons) and condensed tricyclic hydrocarbons (for example, anthracene, phenanthrene, etc.) and the like, and the like. Preferable condensed polycyclic aromatic hydrocarbons include naphthalene and anthracene, and naphthalene is particularly preferable. The two rings Z may be the same or different rings, and may usually be the same ring.

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

In the formula (A), examples of the substituent represented by the group R ¹ include a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [eg, alkyl group, aryl Non-reactive substituents such as a group (C _6-10 aryl group such as a phenyl group) and the like, and the like, especially a halogen atom, a cyano group or an alkyl group (particularly 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 addition, when k is plural (two or more), the groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number k is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

In the formula (A), the substituent represented by the group R ² is usually a non-reactive substituent such as an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, C _1-20 alkyl group such as s-butyl group and t-butyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group, etc., cycloalkyl group (cyclopentyl group, cyclohexyl group) C _5-10 cycloalkyl group, such as C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group, etc., aryl group [eg, phenyl group, alkylphenyl group (or methylphenyl group (or tolyl, 2-methylphenyl group, and 3-methylphenyl group), a dimethylphenyl group (xylyl)), _{C 6-10} ant naphthyl group Alkoxy group; group, preferably a _{C 6-8} aryl group, especially a phenyl group, a hydrocarbon group such as an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group) (C _1-20 alkoxy group such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy group, preferably C _1-8 alkoxy group, more preferably C _1-6 alkoxy group, etc. ), Cycloalkoxy groups (C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups), aryloxy groups (C _6-10 aryloxy groups such as phenoxy groups), aralkyloxy groups (for example, benzyloxy groups, etc.) _{C 6-10} aryl _{-C 1-4} alkyloxy group) ether groups such as (substituted hydroxyl group); Alkylthio group (methylthio group, ethylthio group, propylthio group, n- butylthio group, _{C 1-20} alkylthio group such as t- butylthio group, preferably a _{C 1-8} alkylthio group, more preferably a _{C 1-6} alkylthio group) (such as _{C 5-10} cycloalkylthio groups such as cyclohexylthio group to cycloalkyl) cycloalkylthio group, _{(C 6-10} arylthio group such as thiophenoxy group) an arylthio group, aralkylthio group (eg, _C, such as benzylthio _6- Thioether groups (substituted mercapto groups) such as ₁₀ aryl-C _1-4 alkylthio groups); acyl groups (such as C _1-6 acyl groups such as acetyl groups); alkoxycarbonyl groups (C _1-4 alkoxy such as methoxycarbonyl groups) Ester groups such as carbonyl groups (substituted carboxyl groups) ); Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom and the like); nitro group; cyano group; substituted amino group (dialkylamino group and the like) and the like.

Among these, the group R ² is a hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, acyl group, alkoxycarbonyl group, halogen. An atom, a nitro group, a cyano group, and a substituted amino group are preferred. Particularly preferred groups R ² include an alkyl group (eg, a C _1-6 alkyl group), an alkoxy group (eg, a C _1-4 alkoxy group), Examples thereof include an alkylthio group (such as a C _1-4 alkylthio group) and a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).

In the same ring Z, when m is plural (two or more), the groups R ² may be different from each other or the same. In the two rings Z, the groups R ² may be the same or different. The preferred substitution number m may be 0 to 8, preferably 0 to 6 (for example, 1 to 5), more preferably 0 to 4, particularly 0 to 2 (for example, 0 to 1). In the two rings Z, the number of substitutions m may be the same or different from each other.

The curable resin has a curable (thermal or photo-curable) functional group in addition to the aromatic ring. Examples of such functional groups include unsaturated bond-containing groups [for example, (meth) acryloyl groups, alkenyl groups (C _2-6 alkenyl groups such as vinyl groups and allyl groups), vinylidene groups, etc.], epoxy group-containing Groups (such as glycidyl groups), phenolic hydroxyl groups (hydroxyl groups substituted on aromatic rings), thiophenolic mercapto groups (mercapto groups substituted on aromatic rings), and the like. The curable resin may have these groups alone or in combination of two or more. Moreover, curable resin may have the same functional group individually or in combination of 2 or more types.

As typical curable resin, for example, phenol resin, unsaturated polyester resin, epoxy resin, thermosetting polyurethane resin, thermosetting polyimide resin, vinyl ester resin (epoxy resin and (meth) acrylic acid or Resin obtained by reaction with the derivative, resin obtained by reaction of polyhydric phenols and glycidyl (meth) acrylate, etc.), polyfunctional (meth) acrylate [polyol poly (meth) acrylate, (poly) urethane ( Meth) acrylate, (poly) ester (meth) acrylate, epoxy (meth) acrylate, etc.], vinyl ether (divinyl ether obtained by reaction of diol component with acetylene, etc.)
Etc. are also included. The curable resins may be used alone or in combination of two or more.

  A preferable curable resin is a curable resin having a skeleton (9,9-bisarylfluorene skeleton) represented by the formula (A) as described above. As such a curable resin, for example, a curable resin obtained by using a compound represented by the following formula (1) (sometimes referred to as a fluorene derivative) (a compound represented by the following formula (1)): Curable resin as a raw material).

(In the formula, X represents a hydroxyl group, a hydroxymethyl group, a mercapto group, a mercaptomethyl group or an amino group, n represents an integer of 1 or more, and Z, R ¹ , R ² , k and m are the same as above. When n is 2 or more, X may be the same or different groups.)
In the above formula (1), X is a hydroxyl group, a hydroxymethyl group, a mercapto group, a mercaptomethyl group, or an amino group as described above. Among these, X is preferably a hydroxyl group, a mercapto group or an amino group, and particularly preferably a hydroxyl group.

  The number n of the groups X substituted on the ring Z may be 1 or more, and may be, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1. When n is 2 or more, X may be the same or different groups.

In the formula (1), Z, R ¹ , R ² , k, and m are the same as those described above, and preferred embodiments are also the same as described above.

  Specific examples of the compound represented by the formula (1) include 9,9-bis (hydroxyaryl) fluorenes, 9,9-bis (mercaptoaryl) fluorenes, and 9,9-bis (aminoaryl). ) Fluorenes.

  The 9,9-bis (hydroxyaryl) fluorenes include, for example, (1) 9,9-bis (hydroxyphenyl) fluorenes, (2) 9,9-bis (hydroxynaphthyl) fluorenes, and the like.

(1) 9,9-bis (hydroxyphenyl) fluorenes 9,9-bis (hydroxyphenyl) fluorenes include 9,9-bis (monohydroxyphenyl) fluorenes, 9,9-bis (dihydroxyphenyl) Fluorenes, 9,9-bis (trihydroxyphenyl) fluorenes [for example, 9,9-bis (2,3,4-trihydroxyphenyl) fluorene, 9,9-bis (2,4,6-trihydroxy 9,9-bis (trihydroxyphenyl) such as phenyl) fluorene, 9,9-bis (2,4,5-trihydroxyphenyl) fluorene, 9,9-bis (3,4,5-trihydroxyphenyl) fluorene ) Fluorene, etc.], usually 9,9-bis (monohydroxyphenyl) fluorenes or 9,9-bis (dihydroxy) Cyphenyl) fluorenes, particularly 9,9-bis (monohydroxyphenyl) fluorenes, can be preferably used.

As 9,9-bis (monohydroxyphenyl) fluorenes, for example, 9,9-bis (hydroxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene (bisphenolfluorene) and the like], substituents 9,9-bis (hydroxyphenyl) fluorene {e.g., 9,9-bis (alkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-methylphenyl) fluorene (biscresol fluorene), 9 , 9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-butylphenyl) fluorene, 9,9-bis (3-hydroxy-2-methylphenyl) fluorene, etc. 9,9-bis (C _1-4 alkyl-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene such as 9,9-bis _{(di-C 1-4} alkyl - hydroxyphenyl) fluorene, etc.], 9,9-bis (cycloalkyl - hydroxy Phenyl) fluorene [9,9-bis (C _5-8 cycloalkyl-monohydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene], 9,9-bis (aryl -Hydroxyphenyl) fluorene [eg, 9,9-bis (C _6-8 aryl-hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene], 9,9-bis (Aralkyl-hydroxyphenyl) fluorene [e.g., 9,9-bis (4-hydroxy-3-benzene) Jirufeniru) 9,9-bis _{(C 6-8} aryl _{C 1-2} alkyl, such as fluorene - hydroxyphenyl) fluorene, etc.], etc.} and the like.

As 9,9-bis (dihydroxyphenyl) fluorenes, fluorenes corresponding to the 9,9-bis (monohydroxyphenyl) fluorenes, for example, 9,9-bis (dihydroxyphenyl) fluorene [9,9- Bis (3,4-dihydroxyphenyl) fluorene (biscatecholfluorene), 9,9-bis (3,5-dihydroxyphenyl) fluorene, etc.], substituted 9,9-bis (dihydroxyphenyl) fluorene {e.g. 9,9-bis (alkyl-dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxy-5-methylphenyl) fluorene, 9,9-bis (3,4-dihydroxy-6-methylphenyl) fluorene 9,9-bis (C _1-4 alkyl-dihydroxyphenyl) fluoro Ren, 9,9-bis (2,4-dihydroxy-3,6-dimethylphenyl) fluorene such as 9,9-bis _{(di-C 1-4} alkyl - dihydroxyphenyl) fluorene, etc.], 9,9-bis ( Aryl-dihydroxyphenyl) fluorene [for example, 9,9-bis (C _6-8 aryl-dihydroxyphenyl) fluorene such as 9,9-bis (3,4-dihydroxy-5-phenylphenyl) fluorene, etc.] etc. Can be illustrated.

  Note that bis (monohydroxyphenyl) fluorenes can be prepared 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 (see literature [J. Appl. Poly. Sci., 27 (9), 3289, 1982], JP-A-6-145087, JP-A-8-217713), (b) 9-fluorenone in the presence of an acid catalyst (and alkyl mercaptan) A method of reacting alkylphenols (JP 2000-26349 A), (c) a method of reacting fluorenones and phenols in the presence of hydrochloric acid and thiols (such as mercaptocarboxylic acid) (JP 2002-47227 A). No.), (d) Presence of sulfuric acid and thiols (such as mercaptocarboxylic acid) A method of producing bisphenolfluorene by reacting a fluorenone with a phenol and crystallization with a crystallization solvent composed of a hydrocarbon and a polar solvent (Japanese Patent Laid-Open No. 2003-221352). Can be manufactured.

  In addition, 9,9-bis (di- or trihydroxyphenyl) fluorenes can be obtained by using the corresponding polyhydric alcohols (dihydroxy) instead of phenols in the above-mentioned 9,9-bis (monohydroxyphenyl) fluorenes production method. Phenols and trihydroxyphenols).

(2) 9,9-bis (hydroxynaphthyl) fluorenes As 9,9-bis (hydroxynaphthyl) fluorenes, for example, 9,9-bis (hydroxynaphthyl) fluorenes {for example, 9,9-bis ( Hydroxynaphthyl) fluorene [e.g., 9,9-bis [6- (2-hydroxynaphthyl)] fluorene (or 6,6- (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))] and the like, which may have a substituent such as }, 9,9-bis (polyhydroxynaphthyl) fluorenes corresponding to these 9,9-bis (monohydroxynaphthyl) fluorenes (for example, 9,9-bis (di- or trihydroxynaphthyl) fluorenes) Etc.

  In addition, 9,9-bis (hydroxynaphthyl) fluorenes are hydroxynaphthalenes (for example, naphthols such as naphthol) instead of phenols in the method for producing 9,9-bis (monohydroxyphenyl) fluorenes. , Polyhydroxynaphthalenes such as dihydroxynaphthalene).

9,9-bis (mercaptoaryl) fluorenes include compounds corresponding to the 9,9-bis (hydroxyaryl) fluorenes [that is, in the 9,9-bis (hydroxyaryl) fluorenes, the hydroxy group is Compound substituted with mercapto group], for example, 9,9-bis (mercaptophenyl) fluorenes {for example, 9,9-bis (monomercaptophenyl) fluorenes [9,9-bis (4-mercaptophenyl) fluorene, etc. 9,9-bis (mercaptophenyl) fluorene; 9,9-bis (mono- or di-C _1-4 alkyl-mercaptophenyl) fluorene such as 9,9-bis (4-mercapto-3-methylphenyl) fluorene ], 9,9-bis (dimercaptophenyl) fluorenes}, 9,9- Bis (mercaptonaphthyl) fluorenes are included.

9,9-bis (aminoaryl) fluorenes include compounds corresponding to the 9,9-bis (hydroxyaryl) fluorenes [that is, in the 9,9-bis (hydroxyaryl) fluorenes, Compound substituted with amino group], for example, 9,9-bis (aminophenyl) fluorenes {for example, 9,9-bis (monoaminophenyl) fluorenes [9,9-bis (4-aminophenyl) fluorene, etc. 9,9-bis (aminophenyl) fluorene; 9,9-bis (mono- or di-C _1-4 alkyl-aminophenyl) fluorene such as 9,9-bis (4-amino-3-methylphenyl) fluorene ], 9,9-bis (diaminophenyl) fluorenes, etc.}.

A curable resin (heat or photocurable resin) obtained using a typical fluorene derivative can be selected according to the type of X in the formula (1). In addition, such curable resin should just use the compound represented by said Formula (1) as a raw material, and the derivative | guide_body of the compound represented by said Formula (1) [For example, in said Formula (1) In a compound where X is a hydroxyl group, the hydroxyl group may be used as a hydroxyalkyl etherified compound (such as 9,9-bis (hydroxyC _2-4 alkoxyaryl) fluorene). The curable resin may be a resin obtained by using the fluorene derivative, and the compound itself may be used as the curable resin depending on the type of X.

  For example, a curable resin obtained using a compound in which X is a hydroxyl group in the formula (1) [for example, 9,9-bis (hydroxyaryl) fluorenes] includes unsaturated polyester resins, thermosetting And a polyurethane resin, epoxy resin, vinyl ester resin, phenol resin, (meth) acrylic resin [eg, polyol poly (meth) acrylate, urethane (meth) acrylate, etc.]. Such a curable resin is a resin having a polyol component as a polymerization component (or a resin raw material), and a part or all of such a polyol component is a compound in which X is a hydroxyl group in the formula (1) or a compound thereof. It is a curable resin obtained by using a derivative (such as a hydroxyalkyl etherified product).

  In addition, a curable resin obtained using a compound [for example, 9,9-bis (mercaptoaryl) fluorenes, etc.] in which X is a mercapto group in the formula (1) includes a thermosetting resin (for example, heat Curable polythiourethane resin, thioepoxy resin, polythiol poly (meth) acrylate, etc.] Such a curable resin is a resin having a polythiol component as a polymerization component (or resin raw material). It is a curable resin obtained by using a compound or derivative thereof in which X is a mercapto group in the above formula (1) for a part or all of the polythiol component.

  Further, a curable resin obtained using a compound [for example, 9,9-bis (aminoaryl) fluorenes, etc.] wherein X is an amino group in the formula (1) includes a thermosetting resin (polyimide resin). Aniline resin, etc.). Such a curable resin is a resin having a polyamine component as a polymerization component (or resin raw material), and a part or all of such a polyamine component is a compound in which X is an amino group in the formula (1) or a compound thereof. It is a curable resin obtained by using a derivative.

  As examples of typical curable resins, an epoxy resin (epoxy compound) having a fluorene skeleton and a polyol poly (meth) acrylate will be described in detail below.

(Epoxy resin)
Examples of the epoxy resin (epoxy compound having a fluorene skeleton) include a compound represented by the following formula (1A).

(In the formula, R ^3a and R ^3b are the same or different and are an alkylene group, R ^4a and R ^4b are the same or different and represent a hydrogen atom or a methyl group, and p1 and p2 are the same or different and represent 0 or an integer of 1 or more. Z, R ¹ , R ² , k, m and n are the same as above.)
In the above formula (1A), the alkylene group represented by R ^3a and R ^3b is not limited, and examples thereof include a C _2-4 alkylene group (ethylene group, trimethylene group, propylene group, butane-1,2-diyl). Group etc.) etc. can be illustrated and a _C2-3 alkylene group (especially ethylene group, propylene group) is preferable. R ^3a and R ^3b may be the same or different alkylene groups, but are usually the same alkylene group. Moreover, although p1 and p2 are not specifically limited, it is the same or different, and can be selected from the range of about 0-15, for example, 0-12 (for example, 1-12), Preferably it is 0-8, More preferably, it is 0. It may be about -6, especially about 0-4. When p1 (or p2) is 2 or more, the polyalkyleneoxy group may be composed of a mixture of the same or different alkoxy groups (for example, ethoxy group and propyleneoxy group).

In the formula (1A), Z, R ¹ , R ² , k, m, and n are the same as those described above, and preferred embodiments are also the same as described above.

Typical examples of the epoxy compound (epoxy resin) represented by the formula (1A) include 9,9-bis (glycidyloxyaryl) fluorenes {for example, 9,9-bis (glycidyloxyphenyl) fluorene [ For example, 9,9-bis (4-glycidyloxyphenyl) fluorene and the like], 9,9-bis (alkyl-glycidyloxyphenyl) fluorene [9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, 9,9-bis (mono- or di-C _1-4 alkyl-glycidyloxyphenyl) fluorene such as 9,9-bis (4-glycidyloxy-3,5-dimethylphenyl) fluorene], 9,9-bis ( Arylglycidyloxyphenyl) fluorene [9,9-bis (4-glycidyloxy-3-phenyl) 9,9-bis (glycidyloxyphenyl) fluorenes such as 9,9-bis (mono- or di-C _6-8 aryl-glycidyloxyphenyl) fluorene etc.] such as phenyl) fluorene; 9,9-bis (glycidyloxy) Naphthyl) fluorene [e.g., 9,9-bis [6- (2-glycidyloxynaphthyl)] fluorene, 9,9-bis [1- (6-glycidyloxynaphthyl)] fluorene, 9,9-bis [1- 9,9-bis (glycidyloxynaphthyl) fluorenes such as (5-glycidyloxynaphthyl)] fluorene], 9,9-bis (polyglycidyloxyaryl) fluorenes {for example, 9,9-bis [3 , 4-Di (glycidyloxy) phenyl] fluorene, 9,9-bis [3,4,5-tri (glycidyloxy) Ii) 9,9-bis (di or triglycidyloxyaryl) fluorene} such as phenyl] fluorene}, compounds corresponding to these compounds, wherein p1 and p2 are 1 or more in the formula (1A) {for example, 9, 9,9-bis (glycidyloxy C _2-4 alkoxy such as 9,9-bis (glycidyloxyalkoxyphenyl) fluorene [for example, 9,9-bis (4-glycidyloxyethoxyphenyl) fluorene (bisphenoxyethanol fluorenediglycidyl ether) Phenyl) fluorene and the like], 9,9-bis (alkyl-glycidyloxyalkoxyphenyl) fluorene [eg, 9,9-bis (4-glycidyloxyethoxy-3-methylphenyl) fluorene, 9,9-bis (4- Glycidyloxyethoxy-3,5-di 9,9-bis (mono or di C _1-4 alkylglycidyloxy C _2-4 alkoxyphenyl) fluorene etc.] such as methylphenyl) fluorene, 9,9-bis (arylglycidyloxyalkoxyphenyl) fluorene [9,9 9,9-bis (mono- or di-C _6-8 arylglycidyloxy C _2-4 alkoxyphenyl) fluorene such as bis (4-glycidyloxyethoxy-3-phenylphenyl) fluorene], 9,9-bis ( Glycidyloxyalkoxynaphthyl) fluorene [eg, 9,9-bis (glycidyloxy C _2-4 alkoxynaphthyl) fluorene, etc.], 9,9-bis [di or tri (glycidyloxyalkoxy) phenyl] fluorene [eg, 9, 9-bis [3,4-di (2-glycidyloxy) Ethoxy) phenyl] fluorene, 9,9-bis [3,4,5-tri (2-glycidyloxyethoxy) phenyl] fluorene such as 9,9-bis [di or tri (glycidyloxy _{C 2-4} alkoxy) phenyl A compound in which p1 and p2 are 1 in the above formula (1A), such as fluorene]; a compound corresponding to these compounds, in which p1 and p2 are 2 or more in the above formula (1A) [for example, 9,9-bis 9,9-bis {[2- (2-glycidyloxy C _2-4 alkoxy) C _2-4 alkoxy] phenyl} fluorene, such as {4- [2- (2-glycidyloxyethoxy) ethoxy] phenyl} fluorene ] Etc.}. These compounds may be used alone or in combination of two or more.

Among these compounds (epoxy compounds having a fluorene skeleton), in particular, 9,9-bis (glycidyloxyaryl) fluorenes [for example, 9,9-bis (glycidyloxyphenyl) fluorene, 9,9-bis (alkyl -Glycidyloxyphenyl) fluorene, 9,9-bis (glycidyloxynaphthyl) fluorene, etc.], 9,9-bis (glycidyloxy (poly) alkoxyaryl) fluorenes [for example, 9,9-bis (glycidyloxy C _{2) -4} alkoxyphenyl) fluorene such as 9,9-bis (glycidyloxy _{C 2-4} alkoxyphenyl) fluorenes; 9,9-bis (glycidyloxy di _{C 2-4} alkoxyphenyl) fluorene such as 9,9-bis (Glycidyloxypoly C _2-4 alkoxyphenyl ) Fluorenes and the like] are preferred.

  As the epoxy compound having a fluorene skeleton, a commercially available product may be used, and a conventional method (for example, a compound represented by the formula (1) or a derivative thereof and an oxirane compound [for example, epihalohydrin [epichlorohydride] Phosphorous (chloromethyloxirane), epibromohydrin (bromomethyloxirane, etc.), 1-halomethyl-2-methyloxirane (1-chloromethyl-2-methyloxirane, etc.), etc.] You may use what you did.

(Polyol poly (meth) acrylate)
Examples of the polyol poly (meth) acrylate (polyfunctional (meth) acrylate having a fluorene skeleton) include a compound represented by the following formula (1B).

(Wherein R ^5a and R ^5b are the same or different and are an alkylene group, R ^6a and R ^6b are a hydrogen atom or a methyl group, q1 and q2 are the same or different and represent 0 or an integer of 1 or more, Z, R ¹ , R ² , k, m and n are the same as above.)
In the above formula (1B), the alkylene group represented by R ^5a and R ^5b is not limited, and examples thereof include a C _2-4 alkylene group (ethylene group, trimethylene group, propylene group, butane-1,2-diyl). Group etc.) etc. can be illustrated and a _C2-3 alkylene group (especially ethylene group, propylene group) is preferable. R ^5a and R ^5b may be the same or different alkylene groups, but are usually the same alkylene group. Moreover, although q1 and q2 are not specifically limited, they are the same or different and can be selected from the range of about 0-15, for example, 0-12 (for example, 1-12), preferably 0-8, more preferably 0. It may be about -6, especially about 0-4. When q1 (or q2) is 2 or more, the polyalkyleneoxy group may be composed of a mixture of the same or different alkoxy groups (for example, an ethoxy group and a propyleneoxy group).

In the formula (1B), Z, R ¹ , R ² , k, m, and n are the same as described above, and preferred embodiments are also the same as described above.

As a typical compound represented by the formula (1B) (polyol (poly) methacrylate), for example, 9,9-bis ((meth) acryloyloxyaryl) fluorenes {for example, 9,9-bis ( (Meth) acryloyloxyphenyl) fluorene [eg, 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene, etc.], 9,9-bis (alkyl- (meth) acryloyloxyphenyl) fluorene [9,9 9,9-bis (mono or) such as -bis (4- (meth) acryloyloxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy-3,5-dimethylphenyl) fluorene Di-C _1-4 alkyl- (meth) acryloyloxyphenyl) fluorene and the like], 9,9-bis (aryl ( 9,9-bis (mono or di-C _6-8 aryl- (meth) acryloyloxy such as (meth) acryloyloxyphenyl) fluorene [9,9-bis (4- (meth) acryloyloxy-3-phenylphenyl) fluorene 9,9-bis ((meth) acryloyloxyphenyl) fluorenes such as phenyl) fluorene etc .; 9,9-bis ((meth) acryloyloxynaphthyl) fluorene [eg 9,9-bis [6- (2 -(Meth) acryloyloxynaphthyl)] fluorene, 9,9-bis [1- (6- (meth) acryloyloxynaphthyl)] fluorene, 9,9-bis [1- (5- (meth) acryloyloxynaphthyl) ] 9,9-bis ((meth) acryloyloxynaphthyl) fluorenes such as] 9-bis (poly (meth) acryloyloxyaryl) fluorenes {eg, 9,9-bis [3,4-di ((meth) acryloyloxy) phenyl] fluorene, 9,9-bis [3,4,5 -9,9-bis (di- or tri (meth) acryloyloxyaryl) fluorene} such as tri ((meth) acryloyloxy) phenyl] fluorene}, corresponding to these compounds, and q1 and q2 in the formula (1B) are A compound that is one or more {eg, 9,9-bis ((meth) acryloyloxyalkoxyphenyl) fluorene [eg, 9,9-bis such as 9,9-bis (4- (meth) acryloyloxyethoxyphenyl) fluorene) ((Meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene and the like], 9,9-bis (alkyl- (Meth) acryloyloxyalkoxyphenyl) fluorene [e.g., 9,9-bis (4- (meth) acryloyloxyethoxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxyethoxy-3) 9,9-bis (mono- or di-C _1-4 alkyl (meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene, etc.] such as, 5-dimethylphenyl) fluorene], 9,9-bis (aryl (meth) acryloyl) 9,9-bis (mono- or di-C _6-8 aryl (meth) acryloyloxy C ₂ such as oxyalkoxyphenyl) fluorene [9,9-bis (4- (meth) acryloyloxyethoxy-3-phenylphenyl) fluorene _-4 alkoxyphenyl) fluorene, etc.], 9,9-bis ((meta ) Acryloyloxyalkoxynaphthyl) fluorene [eg, 9,9-bis ((meth) acryloyloxy C _2-4 alkoxynaphthyl) fluorene], 9,9-bis [di or tri ((meth) acryloyloxyalkoxy) phenyl ] Fluorene [e.g., 9,9-bis [3,4-di (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [3,4,5-tri (2- (meth) acryloyl) compound q1 and q2 are 1 in such oxy) phenyl] fluorene 9,9-bis [di or tri ((meth) acryloyloxy _{C 2-4} alkoxy) phenyl] fluorene] the expression, such as (1B); Corresponding to these compounds, compounds wherein q1 and q2 are 2 or more in the formula (1B) [Example If, 9,9-bis {4- [2- (2- (meth) acryloyloxy) ethoxy] phenyl} fluorene such as 9,9-bis {[2- (2- (meth) acryloyloxy _{C 2- 4 alkoxy) C 2-4} alkoxy] phenyl} fluorene, etc.], etc.} and the like. These compounds may be used alone or in combination of two or more.

Among these compounds (polyfunctional (meth) acrylate having a fluorene skeleton), in particular, 9,9-bis ((meth) acryloyloxyaryl) fluorenes [for example, 9,9-bis ((meth) acryloyloxy) Phenyl) fluorene, 9,9-bis (alkyl- (meth) acryloyloxyphenyl) fluorene, 9,9-bis ((meth) acryloyloxynaphthyl) fluorene, etc.], 9,9-bis ((meth) acryloyloxy ( poly) alkoxyaryl) fluorenes [e.g., 9,9-bis ((meth) acryloyloxy _{C 2-4} alkoxyphenyl) fluorene such as 9,9-bis ((meth) acryloyloxy _{C 2-4} alkoxyphenyl) fluorene s; 9,9-bis ((meth) acryloyloxy-di _{C 2-4} A Kokishifeniru) including 9,9-bis ((meth) acryloyloxy poly _{C 2-4} alkoxyphenyl) fluorenes such as fluorene], etc. is preferable.

  As the polyfunctional (meth) acrylate having a fluorene skeleton, a commercially available product may be used, and a conventional method (for example, a compound represented by the formula (1) or a derivative thereof and (meth) acrylic acid may be used. Alternatively, a derivative produced by a derivative thereof (such as a method of reacting with (meth) acrylic acid halide (such as (meth) acrylic acid chloride), (meth) acrylic anhydride, etc.)) may be used.

  In addition, the curable resin containing the aromatic ring may be used alone, or depending on the type of functional group of the curable resin (heat or photo-curable resin), the curing agent, the curing accelerator, the start An agent, a diluent (non-reactive diluent, reactive diluent), a sensitizer and the like may be contained. That is, the cured product may be a cured product of a resin composition containing a curable resin. For example, when thermal curing is performed in a system that generates a cured product by radical polymerization of an acryl group or a methacryl group, a thermal polymerization initiator (an azo compound such as azobisisobutyronitrile or various peroxides) is used. Can be used. In the case of photocuring, a photopolymerization initiator (benzophenone series, triazine series, etc.) can be used. When photocuring, a photoacid catalyst or the like can be added. In addition, when an epoxy group or an oxetane group is thermally cured, a curing agent (such as an acid anhydride or a polyamine) can be used. In the case of a phenol group, it can be thermally condensed by itself or a curing agent such as hexamethylenetetramine can be used.

  Among the curing agents, examples of the curing agent for the epoxy resin include amine-based curing agents [particularly primary amines such as chain aliphatic amines (for example, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, etc. Cycloaliphatic amines such as mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, 3,9-bis (3-aminopropyl) -2, Monocyclic aliphatic polyamines such as 4,8,10-tetraoxaspiro [5.5] undecane; bridged cyclic polyamines such as norbornanediamine), araliphatic polyamines (eg, xylylenediamine), aromatics Amines (eg, metaphenylenediamine)], polyaminoamides Agent, acid anhydride curing agent (for example, aliphatic acid anhydrides such as dodecenyl succinic anhydride; alicyclic acid anhydrides such as tetrahydrophthalic anhydride; aromatic acid anhydrides such as phthalic anhydride ), Phenol resin-based curing agents (for example, novolak resins) and the like. These curing agents may be used alone or in combination of two or more.

  The ratio of the curing agent is about 0.1 to 600 parts by weight, preferably about 1 to 500 parts by weight, and more preferably about 10 to 400 parts by weight with respect to 100 parts by weight of the curable resin (for example, epoxy resin). Also good. In particular, in the epoxy resin composition, the ratio of the curing agent is 0.1 to 4.0 equivalents, preferably 0.3 to 2.0, of the functional group of the curing agent with respect to 1 equivalent of the epoxy group of the epoxy resin. You may adjust the ratio of both components so that it may become an equivalent, More preferably, it is 0.5-1.5 equivalent.

  Among the curing accelerators, epoxy resin curing accelerators include, for example, amines [eg, tertiary amines (eg, triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylamino)]. Methyl) phenol, 1,8-diazabicyclo [5.4.0] undecene-1), imidazoles (eg, alkylimidazoles such as 2-methylimidazole; arylimidazoles such as 2-phenylimidazole) and derivatives thereof ( For example, phenol salts, phenol novolac salts, carbonates, formate salts, etc.)], alkali metal or alkaline earth metal alkoxides, phosphines, amide compounds (such as dimer acid polyamides), Lewis acid complex compounds (trifluoride trifluoride) Boron Eth Such as an amine complex), sulfur compounds [polysulfide, mercaptan compound (thiol compound), etc.], boron compounds (phenyl dichloroborane, etc.), condensable organic metal compound (an organic titanium compound, an organoaluminum compound) and the like. The curing accelerators may be used alone or in combination of two or more.

  The ratio (addition amount) of the curing accelerator is, for example, 0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 100 parts by weight of the curable resin (for example, epoxy resin). About 0.1-10 weight part may be sufficient.

  Thermal polymerization initiators include dialkyl peroxides (such as dicumyl peroxide), diacyl peroxides (such as lauroyl peroxide, benzoyl peroxide), and peracid esters (such as alkyl percarboxylates such as t-butyl peracetate). Esters), ketone peroxides, peroxycarbonates, peroxyketals, and other organic peroxides; azonitrile compounds [2,2′-azobis (isobutyronitrile), etc.], azoamide compounds {2,2 ′ -Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like}, azoamidine compound {2,2′-azobis (2-amidinopropane) dihydrochloride and the like }, An azoalkane compound [2,2′-azobis (2,4,4-to Methylpentane), etc.], an azo compound having an oxime skeleton [2,2'-azobis (2-methylpropionamide oxime), etc.] and the like azo compounds such as. You may use a thermal-polymerization initiator individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator include various known photopolymerization initiators such as benzoins (benzoin alkyl ethers such as benzoin and benzoin methyl ether), acetophenones (acetophenone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one), aminoacetophenones {2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1 etc., anthraquinones (anthraquinone, 2-methylanthraquinone etc.), thioxanthones (2,4-dimethylthioxanthone etc.), ketals (acetophenone dimethyl ketal, benzyldimethyl ketal etc.), benzophenones (Benzo Enon etc.), etc. xanthones can be exemplified. These photopolymerization initiators may be used alone or in combination of two or more.

  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, and more preferably 1.5 to 100 parts by weight of the curable resin. It may be about -10 parts by weight.

  Examples of the solvent (non-reactive diluent) include conventional solvents such as hydrocarbons (aliphatic hydrocarbons such as pentane and hexane, alicyclic hydrocarbons such as cyclohexane, toluene, xylene and the like. Aromatic hydrocarbons), halogenated solvents (haloalkanes such as dichloromethane, haloarenes such as monochlorobenzene), alcohols (alkyl alcohols such as methanol, ethanol, and propanol), diols (ethylene glycol, propylene glycol, etc.) Alkanediols such as (poly) oxyalkylene glycols such as diethylene glycol and polyoxyethylene glycol), ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran), esters, etc. Methyl acetate, ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy- Methyl 2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate), ketones (acetone, ethyl methyl ketone) , Dialkyl ketones such as methyl isobutyl ketone and methyl amyl ketone, cyclic ketones such as cyclopentanone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone), glycol ethers (ethylene glycol monomethyl) Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, etc.), glycol ether esters (ethylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether acetate, cellosolve acetate, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), carbitols (carbitol, etc.) can be used. These solvents may be used alone or in combination of two or more.

  The use amount (addition amount) of the solvent can be selected from the range of 0 to 500 parts by weight, for example, 10 to 400 parts by weight, preferably 20 to 100 parts by weight of the curable resin (for example, epoxy resin). It may be about -300 parts by weight, more preferably about 30-200 parts by weight.

  In addition to the curable resin, the curable resin composition may further include conventional additives such as stabilizers (antioxidants, thermal stabilizers, ultraviolet absorbers, etc.), mold release agents, depending on the application. , Flame retardants, bluing agents, fluorescent brighteners, colorants, antistatic agents, antibacterial agents, lubricants, fillers, and the like. Furthermore, other transparent resins not having an aromatic ring may be included as long as the transparency and refractive index are not lowered.

[Molded body and manufacturing method thereof]
The resin molded body of the present invention is a cured product of the curable resin (or resin composition thereof), and the aromatic ring (or curable resin or cured product thereof) of the curable resin is oriented. Such a molded article of the present invention can be obtained by curing (or solidifying) (or molding) the curable resin while applying a magnetic field and / or an electric field to the curable resin (note that the curable resin is molded). The solidifying step may be referred to as a solidifying step, an application / solidifying step, or the like).

  By applying a magnetic field and / or an electric field, the orientation of the aromatic ring occurs. And by such orientation, although a reason is not certain, transparency of hardened | cured material improves and coloring can also be suppressed.

  In the method as described above, in order to generate orientation efficiently, a magnetic field and / or an electric field is usually applied (acted) to a curable resin in a fluid state. Since the aromatic ring is a functional group having a high magnetic susceptibility, it has a property of responding to a magnetic field and / or electric field and orienting regularly (constant direction) along the magnetic field and / or electric field. In the present invention, this property of the aromatic ring is utilized to align the aromatic ring by applying a magnetic field and / or an electric field. However, molecules (compounds such as resins) having an aromatic ring are easily aligned. Therefore, it is necessary to make the fluidity high. That is, the curable resin or the resin composition when applying a magnetic field and / or an electric field is preferably in a fluid state from the viewpoint of securing a degree of freedom for movement of molecules having an aromatic ring.

  The fluid state may be a solution state in which a curable resin or a resin composition thereof is dissolved or dispersed in a solvent, or may be a liquid curable resin state before curing. Further, the liquid curable resin may be in a state of being melted or softened by heating as necessary. The application and solidification step of the magnetic field and / or electric field may be performed on the curable resin that is the raw material before molding depending on the target molded body, but as described above, the magnetic field and / or electric field is used. In order to maintain the orientation of the aromatic ring, it is preferable to carry out as a solidification step in the production process of the molded body (that is, to cure or mold while applying a magnetic field and / or an electric field).

  Examples of the method for applying a magnetic field include a method for applying a magnetic field using a magnet such as a permanent magnet, an electromagnet, or a superconducting magnet. As a method using these magnets, for example, a static magnetic field (a magnetic field in which the magnitude of the magnetic field does not fluctuate over time) may be applied using a permanent magnet, or a dynamic magnetic field ( A method of applying a magnetic field in which the magnitude of the magnetic field periodically varies with time may be used. Among these methods, the method of applying a static magnetic field using a permanent magnet is preferable from the viewpoint of simplicity.

  Examples of permanent magnets include rare earth magnets such as neodymium magnets and samarium cobalt magnets, cast magnets such as alnico magnets, and ferrite magnets. Among these magnets, rare earth magnets such as neodymium magnets and cast magnets such as alnico magnets are preferable from the viewpoint of application efficiency.

  In the present invention, the applied magnetic field strength (residual magnetic flux density) is preferably, for example, 30 T (Tesla) or less from the viewpoint of industrial properties such as equipment. It may be about 01 to 10T, preferably 0.1 to 5T, more preferably about 0.3 to 3T (particularly 0.5 to 2T). The magnetic field strength means a magnetic flux density that remains even after the magnetic field is removed after the magnetic material is magnetized by an external magnetic field.

  A specific application method using a permanent magnet is, for example, that two plate-like permanent magnets are arranged so that the north and south poles face each other, and a curable resin is generated in a magnetic field generated between the two magnets. It may be a method of fixing. The distance between the two magnets can be appropriately selected according to the magnetic field strength of the magnet, the size of the curable resin used for molding, and the like, for example, 1 to 100 mm, preferably 3 to 50 mm, more preferably about 5 to 30 mm. . The application time of the magnetic field is not particularly limited as long as the magnetic field is applied at the time of solidification of the resin. Usually, from the point of simplicity, the application of the magnetic field is started before the start of the flow state, and after the solidification is completed. Stop applying the magnetic field.

  Moreover, as an application method of an electric field, the method of applying an electric field using an electric field application apparatus etc. is mentioned, for example. For example, a curable resin before curing or a resin composition thereof (or a preformed body thereof) may be sandwiched between two electrodes and a predetermined voltage may be applied.

The applied field strength (field strength), from the viewpoint of industrial properties such equipment, for example, 500V · ^{cm -1} or more, preferably 600~5000V · ^{cm -1,} more preferably at about 700~3000V · ^{cm -1} There may be.

  As a method for producing a molded product, a conventional method (resin molding method, wet resin molding method using a solvent) can be selected according to the type of resin. For example, coating or casting method, casting method, casting method A molding method, a compression molding method, an injection molding method, or the like can be used.

  As described above, the application / solidification step can be provided as various steps depending on the type of molding method. For example, a wet resin molding method (for example, a curable resin or a resin composition thereof is dissolved or dispersed in a solvent). In the molding method for applying or casting the solution, the drying step for removing the solvent may be the application / solidification step. In the case of the wet resin molding method, a magnetic field and / or a state in which the solvent and the curable resin or its resin composition are mixed until the solvent is distilled off and the curable resin or its resin composition is completely solidified. It is sufficient that an electric field can be applied.

  In this case, as the usable solvent, the above exemplified solvents can be used according to the kind of the curable resin. The ratio of the solvent can be selected from the same range as described above. Moreover, the ratio of a solvent should just be a range which does not impair a moldability, and solid content concentration of curable resin composition is 1 to 90 weight%, for example, Preferably it is 5 to 80 weight%, More preferably, it is 10 to 10 weight%. The ratio may be about 70% by weight (particularly 20 to 60% by weight).

  Such a solution is used for a coating or casting method, a casting method, or the like among the above-described molding methods, and is usually molded into a sheet by coating or casting on a substrate. As a casting or coating method, a conventional method such as a spin coating method, a dipping method, or a casting method can be used. Examples of the substrate include paper, cloth, plastic film, glass, quartz, ceramics, and metal.

  The applied liquid resin composition may be dried by heating or may be naturally dried. The temperature in the case of heating can be suitably selected according to the kind of solvent to be used, and is usually a temperature not higher than the boiling point of the solvent, for example, about 50 to 120 ° C., preferably about 60 to 100 ° C. The drying time is, for example, about 10 seconds to 30 minutes, preferably about 30 seconds to 20 minutes, and more preferably about 1 to 15 minutes. Thus, a highly transparent sheet | seat is obtained by peeling the solidified transparent resin composition from a base material after drying.

  The application of a magnetic field and / or an electric field can be performed while curing a curable resin (or a resin composition thereof) in a fluid state (particularly liquid). The application is preferably continued with molding (curing) until a sufficiently cured state (experimental index is that the surface pencil hardness is H or higher) in order to maintain a magnetic field or electric field responsive state. And after hardening fully progresses (especially, after a molded object is fully cooled), a magnetic field and / or an electric field can be removed.

  In curing, when heating is performed, the heating temperature (curing temperature) may be, for example, 50 to 250 ° C, preferably 60 to 150 ° C, and more preferably about 70 to 120 ° C. The curing time (heating time) may be, for example, 10 minutes to 10 hours, preferably 20 minutes to 8 hours, and more preferably about 30 minutes to 5 hours.

In addition, when performing light irradiation in curing, as a light irradiation source, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury 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. The light irradiation may be performed in an atmosphere of an inert gas such as nitrogen or argon or in the air, and may be performed under normal pressure, increased pressure, or reduced pressure.

  Note that heating (treatment) and light irradiation (treatment) may be combined.

  In the obtained molded body, the orientation state of the aromatic ring is, for example, in the case of a compound in which the compound having an aromatic ring emits light (usually emitting fluorescence), the fluorescence spectrum of the molded body to which a magnetic field is applied and the magnetic field applied. It can be evaluated by comparing with the fluorescence spectrum of the molded body that is not. This evaluation is possible because the light absorption and emission characteristics of the aromatic ring compound have anisotropy inside the molecule, and macroscopically in a random state where the aromatic ring compound is not oriented. While the anisotropy of individual molecules is offset, when the aromatic ring compound is oriented, it becomes macroscopically anisotropic. As a result, a remarkable difference in fluorescence intensity occurs between the state where the aromatic ring is not oriented and the state where the aromatic ring is oriented.

  The molded body of the present invention has superior characteristics compared to a normal molded body because the aromatic rings are oriented. Typically, the molded article of the present invention is excellent in transparency. For example, when the molded article of the present invention is formed into a film shape, the transmittance is 70% or more (for example, 73 to 95%), preferably 75% or more (for example, for all wavelengths in the wavelength range of 400 nm to less than 500 nm). 78 to 93%), more preferably about 80% or more (for example, 81 to 90%). Further, when formed into a film, the transmittance is 75% or more (for example, 78 to 98%), preferably 80% or more (for example, 81 to 95%) at all wavelengths in the wavelength range of 500 nm to 800, More preferably, it is about 83% or more (for example, 85 to 93%). In addition, you may measure the transmittance | permeability using the film-form molded object normally about 100 nm-200 micrometers in thickness. Furthermore, the molded body of the present invention has no coloration (or coloration is suppressed) at a level that can be visually confirmed.

  As described above, in the present invention, the transparency of the resin molded body can be improved. Moreover, in the resin molding of this invention, coloring is suppressed. Therefore, the present invention includes a method for suppressing coloring (or a method for improving or improving transparency) of a resin molded body (transparent resin molded body) formed from a cured product of a curable resin containing the aromatic ring. In addition, a method of suppressing coloring of the molded body (or a method of improving or improving transparency) by orienting the aromatic ring is also included.

  Since the aromatic ring is oriented in a certain direction, the molded article of the present invention has a high refractive index. Although the refractive index of a molded object changes according to the kind of resin, it is 1.56 or more (for example, about 1.56-1.7), Preferably it is 1.57-1.69, More preferably, it is 1. It is about 60 to 1.68 (particularly 1.61 to 1.67). Furthermore, in this invention, a refractive index becomes high by the application of a magnetic field, for example, 0.001 or more compared with before application, Preferably it is 0.005-0.1, More preferably, it is 0.01-0.08 ( In particular, an increase in refractive index of about 0.02 to 0.05) is observed.

  Since the molded article of the present invention has excellent characteristics (in particular, transparent and high optical characteristics such as high refractive index and low birefringence), an optical lens, an optical film, an optical sheet, an optical disk, It can be suitably used for pickup lenses, holograms, liquid crystal films, organic EL (electroluminescence) films, and the like.

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

Example 1
29 parts by weight of an epoxy resin having a fluorene skeleton (bisphenoxyethanol fluorenediglycidyl ether, BPEFG, manufactured by Osaka Gas Chemical Co., Ltd.) was dissolved in 29 parts by weight of cyclohexanone to prepare a 50% by weight solution. After BPEFG was completely dissolved, 10 parts by weight of diethylenetriamine was added to prepare a coating film preparation solution. The coating film preparation solution was applied onto a quartz substrate (25 × 25 mm) by spin coating (2500 rpm × 20 seconds). After coating, the formed coating film together with the quartz substrate is immediately set in a magnetic field generated by opposing two square neodymium magnets (40 mm × 40 mm × 10 mm) having a magnetic field strength of about 1.3 T at intervals of 32 mm, A magnetic field was applied in the film surface direction. And it put into 80 degreeC oven as it was, and it was made to heat and harden for 90 minutes, and the thin film sample with a film thickness of about 1 micrometer was produced. The obtained thin film sample was colorless and transparent. In addition, evaluation of coloring was performed visually.

(Comparative Example 1)
A thin film sample was produced in the same manner as in Example 1 except that the coating film was not held in a magnetic field (no magnetic field was applied). The obtained thin film sample was colored yellow. In addition, evaluation of coloring was performed visually.

(Transmittance)
The transmittance of the samples obtained in Example 1 and Comparative Example 1 was measured. A transmission spectrum chart is shown in FIG. As is clear from FIG. 1, the sample obtained in Example 1 has a higher transmittance in the wavelength range of about 350 nm to 500 nm than the sample obtained in Comparative Example 1.

(Chemical structure evaluation of cured product)
The FT-IR spectrum by the ATR (infrared total reflection absorption spectrum method) of the sample (cured product) obtained in Example 1 and Comparative Example 1 was measured, and the chemical structure of the cured product was evaluated. A chart of the FT-IR spectrum is shown in FIG. As is clear from FIG. 2, it was found that the chemical structures of Example 1 and Comparative Example 1 were the same. Then, from the visual evaluation and FIG. 1, in the sample obtained in Example 1, the coloring is suppressed despite the same chemical structure as that of the sample obtained in Comparative Example 1 (and further transmission) The rate has improved.

(Evaluation of orientation)
The degree of orientation was evaluated based on the intensity of the fluorescence spectrum. That is, when the resin is irradiated with ultraviolet rays, fluorescence derived from a fluorene ring is emitted. The intensity of the fluorescence at this time reflects the degree of orientation of the fluorene ring. When the fluorene ring is oriented, the intensity of the fluorescence changes. FIG. 3 shows fluorescence spectra emitted by the samples prepared in Example 1 and Comparative Example 1 by irradiation with ultraviolet rays. As an excitation spectrum for emitting fluorescence, ultraviolet rays having a wavelength of 275 nm were irradiated. In Comparative Example 1 and Example 1 which are considered not to have molecular orientation in the film, the fluorescence intensity clearly changed, and in Example 1, it was shown that the fluorene ring was oriented.

FIG. 1 is a chart showing transmission spectra of samples obtained in Example 1 and Comparative Example 1. FIG. 2 is a chart showing FT-IR spectra of the samples obtained in Example 1 and Comparative Example 1. FIG. 3 is a chart showing fluorescence spectra in the samples of Example 1 and Comparative Example 1.

Claims (9)

  A molded article formed of a cured product of a curable resin containing an aromatic ring, wherein the aromatic ring is oriented.   The molded article according to claim 1, wherein the aromatic ring is a fluorene ring. The molded body according to claim 1 or 2, wherein the curable resin is a curable resin obtained by using a compound represented by the following formula (1).

(In the formula, ring Z represents an aromatic hydrocarbon ring, X represents a hydroxyl group, a hydroxymethyl group, a mercapto group, a mercaptomethyl group or an amino group, and R ¹ represents a halogen atom, a cyano group or an alkyl group. R ² is a hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, A cyano group or a substituted amino group, k is an integer of 0 to 4, m is an integer of 0 or 1 or more, n is an integer of 1 or more, and k, m, or n is 2 or more, R ¹ , R ² or X may be the same or different groups. The molded body according to any one of claims 1 to 3, wherein the curable resin is a compound represented by the following formula (1A).

(In the formula, R ^3a and R ^3b are the same or different and are an alkylene group, R ^4a and R ^4b are the same or different and represent a hydrogen atom or a methyl group, and p1 and p2 are the same or different and represent 0 or an integer of 1 or more. Z, R ¹ , R ² , k, m and n are the same as above.)   The molded article according to any one of claims 1 to 4, wherein when molded into a film, the transmittance is 80% or more at all wavelengths in a wavelength range of 400 nm or more and less than 500 nm.   The molded body according to any one of claims 1 to 5, wherein the curable resin or a resin composition thereof is cured while applying a magnetic field and / or an electric field to a curable resin containing an aromatic ring in a fluid state. How to manufacture.   The manufacturing method of Claim 6 which applies a magnetic field in the magnetic field which has a residual magnetic flux density of 0.01-10T. The manufacturing method according to claim 6, wherein an electric field is applied in an electric field having an electric field strength of 500 V · cm ⁻¹ .   A method for suppressing coloring of a resin molded body formed of a cured product of a curable resin containing an aromatic ring, wherein the coloring of the molded body is suppressed by orienting the aromatic ring.