JP6334236B2 - Strength improver - Google Patents

Description

  The present invention relates to an additive (or modifier) for improving or improving the mechanical strength (such as tensile strength) of a resin.

  Compounds having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) are known to have excellent functions such as a high refractive index and high heat resistance. As a method for expressing the excellent function of such a fluorene skeleton in a resin and making it moldable, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), for example, bisphenol fluorene (BPF), biscresol fluorene, etc. In general, a method in which (BCF), bisphenoxyethanol fluorene (BPEF), or the like is used as a constituent component of a resin and a fluorene skeleton is introduced into a part of the skeleton structure of the resin.

  For example, JP-A-2002-284864 (Patent Document 1) discloses a molding material composed of a polyester-based resin having a 9,9-bisphenylfluorene skeleton. JP 2002-284834 A (Patent Document 2) discloses a polyurethane resin having a 9,9-bisphenylfluorene skeleton and crosslinked with a crosslinking agent. In these documents, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (bisphenoxyethanol) are used as part of the diol component constituting the resin. Fluorene skeleton is introduced into the resin.

  However, in such a method, since the resin skeleton is replaced with a fluorene skeleton, a complicated polymerization reaction is required, and the method cannot be applied to a wide range of resins.

  On the other hand, attempts have been made to add a fluorene compound directly to a resin without polymerizing it.

  For example, Japanese Unexamined Patent Application Publication No. 2005-162785 (Patent Document 3) discloses a resin composition composed of a compound having a 9,9-bisphenylfluorene skeleton and a thermoplastic resin. This document describes that a compound having a 9,9-bisphenylfluorene skeleton can be added to a thermoplastic resin to impart a high refractive index to the thermoplastic resin. In the example, a transparent resin film is prepared by mixing 30 to 40 parts by weight of a specific compound (bisphenol fluorenediglycidyl ether, bisphenoxyethanol fluorene or bisphenoxyethanol fluoredenyl acrylate) with 100 parts by weight of polycarbonate resin. And that the refractive index has increased.

  JP 2011-8017 A (Patent Document 4) discloses an optical resin composition comprising a transparent resin and a fluorene compound having a 9,9-bisarylfluorene skeleton. And in this document, it is described that the birefringence can be lowered without impairing the mechanical properties and heat resistance of the transparent resin. In a specific example, the fluorene-containing polyester resin and the polycarbonate resin 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis (4-glycidyloxyphenyl) fluorene, or 9,9-bis (4-hydroxy-3-methylphenyl) fluorene It is described that a stretched film was prepared from a resin composition containing and the birefringence was lowered.

  Furthermore, JP 2011-21083 A (Patent Document 5) discloses that a phenol compound functions as a nucleating agent (β crystal nucleating agent) for forming a β crystal structure in a crystalline resin such as polylactic acid. Have been described. In the examples of this document, 1 to 5% by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is added to the α-crystal (melting point: 168 ° C.) poly-L lactic acid and melted. Kneaded to obtain poly L-lactic acid in which β crystals (melting point: 163 ° C.) were formed, and Tg was changed from 56.5 ° C. to 60.9-62.1 ° C. as the crystal structure was changed. It is described that changed.

JP 2002-284864 A (Claims, Examples) JP 2002-284834 A (Claims, Examples) JP-A-2005-162785 (Claims, Examples) Examples) JP2011-8017 A (Claims, Examples) JP 2011-21083 A (Claims, Examples)

  An object of the present invention is to provide an additive (or modifier) that can improve or improve (or modify) the mechanical strength (or mechanical properties) of a resin.

  Another object of the present invention is to provide an additive capable of improving or improving the mechanical strength without impairing various properties (for example, heat resistance) of the resin.

  As described above, although several techniques for adding a compound having a fluorene skeleton to a resin have been reported, the addition of a specific resin improves the refractive index, reduces birefringence, and reduces the crystal structure. The change from the α crystal to the β crystal has been observed, and the present situation is that the development has not been made yet.

  Under these circumstances, the present inventors have intensively studied to solve the above problems. As a result, when a compound having a 9,9-bisarylfluorene skeleton is added to the resin, a low molecular compound is surprisingly obtained. Not only does the mechanical property decrease, which is a general phenomenon when used as an additive, not be seen, but rather, the mechanical properties of the resin are improved or improved, and in addition to such mechanical properties, The present inventors completed the present invention by finding that there is a case where the resin characteristics of the resin may be further improved or improved depending on the resin characteristics.

  That is, the additive of the present invention is obtained from the mechanical strength of the resin [for example, the tensile strength, bending strength, and storage elastic modulus E ′ (for example, storage elastic modulus E ′ at room temperature or normal temperature (about 15 to 30 ° C.)). It is an additive for improving (or increasing or improving) at least one selected, and is a strength improver (strength improver) composed of a compound having a 9,9-bisarylfluorene skeleton.

  The compound having a 9,9-bisarylfluorene skeleton may be, for example, a compound represented by the following formula (1).

[Wherein ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is a group — [(OR ³ ) nY] (wherein Y is a hydroxyl group, a mercapto group, glycidyl An oxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is an integer of 0 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is 1 or more. Indicates an integer. ]

  In particular, the compound having a 9,9-bisarylfluorene skeleton may be a compound represented by the following formula (1A).

(In the formula, Z, R ¹ , R ² , k, m, R ³ , n, and p are the same as those in the formula (1).)
In the above formula (1) or (1A), the ring Z may be a benzene ring or a naphthalene ring, R ¹ may be an alkyl group, k may be 0 to 1, and R ² May be an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group, m may be 0 to 2, R ³ may be a C _2-4 alkylene group, and n is 0-2 may be sufficient and p may be 1-3.

  The compounds having a 9,9-bisarylfluorene skeleton typically include 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl- Hydroxyphenyl) fluorene, 9,9-bis (di or trihydroxyphenyl) fluorene, 9,9-bis (hydroxynaphthyl) fluorene, 9,9-bis (hydroxyalkoxyphenyl) fluorene, 9,9-bis (alkyl-) It may be at least one selected from hydroxyalkoxyphenyl) fluorene, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene, and 9,9-bis (hydroxyalkoxynaphthyl) fluorene.

  The resin may be a thermoplastic resin, in particular, an alicyclic thermoplastic resin or a thermoplastic resin having an alicyclic skeleton (for example, a cyclic olefin resin), an aromatic thermoplastic resin, or an aromatic ring skeleton. It may be at least one selected from thermoplastic resins (for example, aromatic polycarbonate resins, aromatic polyester resins, polyphenylene ether resins, etc.) and polymer alloys thereof.

  The additive of the present invention can not only improve the mechanical strength but also improve or improve various properties. For example, the additive of the present invention may be an additive for improving (or increasing or improving) heat resistance (for example, glass transition temperature). Further, the additive of the present invention may be an additive for improving (or increasing) the Abbe number (particularly, Abbe number and refractive index). Furthermore, the additive of the present invention further promotes crystallization (for example, an increase (or improvement) in heat of fusion, a decrease in crystallization start temperature (Tc) at the time of temperature rise, a crystallization start temperature at the time of temperature drop ( And an additive for producing at least one selected from the rise (or improvement) of Tc) and the reduction (or reduction) of crystallization half time in isothermal crystallization.

  The present invention includes a resin composition containing a resin and the strength improver. Moreover, the molded object formed with the said resin composition is also contained in this invention. Such a molded body may be an optical molded body (such as an optical film). Further, the molded body of the present invention may be a film (film-shaped molded body), and such a molded body may be a stretched film.

  Furthermore, the present invention also includes a method of adding (or mixing) the strength improver to the resin to improve (or improve or modify) the strength of the resin.

  In the present specification, “9,9-bis (hydroxyaryl) fluorenes” and “9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes” mean “9,9-bis (hydroxyaryl)”. As long as it has “) fluorene skeleton” or “9,9-bis (hydroxy (poly) alkoxyaryl) fluorene skeleton”, it includes compounds having substituents on aryl groups and fluorene skeletons (specifically, positions 2 to 7 of fluorene) Use for meaning. Furthermore, in this specification, “9,9-bis (hydroxy (poly) alkoxyaryl) fluorene” means 9,9-bis (hydroxyalkoxyaryl) fluorene and 9,9-bis (hydroxypolyalkoxyaryl) fluorene. Used to mean including

  The additive of the present invention can improve or improve (or modify) the mechanical strength (or mechanical properties) of the resin. Although such an additive is a low-molecular compound that is not resinous (that is, a compound having a 9,9-bisarylfluorene skeleton), it does not impair various resin properties, and thus has very usefulness. high.

  In particular, the additive of the present invention can further improve (or improve) or modify the resin properties depending on the resin properties. For example, the additive of the present invention surprisingly improves heat resistance or increases the Abbe number while increasing the refractive index. Note that the heat resistance with the glass transition temperature (Tg) as an index usually decreases with the addition of a low molecular compound, and the Abbe number generally decreases as the refractive index increases. Effect. Furthermore, according to the additive of the present invention, birefringence (for example, orientation birefringence) of the resin can be reduced.

  For this reason, the additive of the present invention is not limited to mechanical strength, and further has an additive (or modifier) for improving or modifying other resin properties [for example, thermal properties (heat resistance, etc.) and optical properties]. ) Can also be used.

  The additive of the present invention is an additive (strength improver, strength improver) for improving (or increasing or improving) the mechanical strength of the resin. The additive is composed of a compound having a 9,9-bisarylfluorene skeleton (hereinafter sometimes referred to as a fluorene compound).

[Fluorene compound]
The fluorene compound only needs to have a 9,9-bisarylfluorene skeleton, and has no reactive group [for example, 9,9-bisarylfluorene (for example, 9,9-bisphenylfluorene). A compound in which p is 0 in formula (1) described later] may be used, but usually has a reactive group.

  Examples of the reactive group include a hydroxyl group, mercapto group, carboxyl group, amino group, (meth) acryloyloxy group, epoxy group (for example, glycidyloxy group) and the like. The fluorene compound may have these reactive groups singly or in combination of two or more.

  The reactive group may be directly bonded to 9,9-bisarylfluorene, or may be bonded via an appropriate linking group (for example, a (poly) oxyalkylene group).

  Specific examples of the fluorene compound include a compound represented by the following formula (1).

[Wherein ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is a group — [(OR ³ ) nY] (wherein Y is a hydroxyl group, a mercapto group, glycidyl An oxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is an integer of 0 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is 1 or more. Indicates an integer. ]

In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon (for example, indene, naphthalene, etc. C _8-20 condensed bicyclic hydrocarbons, preferably C _10-16 condensed bicyclic hydrocarbons), condensed tricyclic hydrocarbons (eg, anthracene, phenanthrene, etc.), etc. ], A ring assembly hydrocarbon ring (bi or tel C _6-10 arene ring such as biphenyl ring, terphenyl ring, binaphthyl ring). The two rings Z may be different rings, and may usually be the same ring. Preferred rings Z include a benzene ring, a naphthalene ring, and a biphenyl ring, and may be a benzene ring.

In the formula (1), examples of the group R ¹ include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [eg, an alkyl group, an aryl group (C ₆ such as a phenyl group). _-10 aryl group) and the like] and acyl groups (for example, alkylcarbonyl groups such as methylcarbonyl, ethylcarbonyl, pentylcarbonyl, etc.) and the like, and in particular, alkyl groups are often used. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, such as _{C 1-12} alkyl group _{(e.g., C 1-8} alkyl groups, especially methyl groups, such as t- butyl group _{C 1- 4} alkyl group) and the like. In addition, when k is plural (2 to 4), the types of the plural groups R ¹ may be the same or different from each other. The types of the groups R ¹ substituted on different benzene rings may be the same or different from each other. Further, the bonding position (substitution position) of the group R ¹ is not particularly limited, and examples thereof include the 2nd, 7th, 2nd and 7th positions of the fluorene ring. The preferred substitution number k is 0 to 1, in particular 0. The two substitution numbers k may be the same or different.

The substituent R ² substituted on the ring Z is usually a non-reactive substituent, for example, an alkyl group (eg, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, C _1-8 alkyl group etc.), cycloalkyl group (C _5-8 cycloalkyl group such as cyclohexyl group), aryl group (eg, phenyl group, tolyl group, xylyl group, naphthyl group etc.) _6-10 an aryl group), a hydrocarbon group such as an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group); an alkoxy group (methoxy group, _{C 1} such as ethoxy groups _-8 an alkoxy group), such as C _5-10 cycloalkyl group such as a cycloalkoxy group (hexyloxy group cyclohexylene), an aryloxy group (Fe _{C 6-10} aryloxy groups such as alkoxy groups), the radical -OR [expression such aralkyloxy groups _{(C 6-10} aryl _{-C 1-4} alkyl group such as a benzyl group), R is a hydrocarbon radical (Such as the hydrocarbon groups exemplified above). A group such as an alkylthio group (such as a C _1-8 alkylthio group such as a methylthio group) —SR (wherein R is as defined above); an acyl group (such as a C _1-6 acyl group such as an acetyl group); Alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); nitro group; cyano group; substituted amino group (for example, dimethyl) And a dialkylamino group such as an amino group).

Preferred group R ² includes a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _6-10 Aryl group), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group and the like), alkoxy group (C _1-4 alkoxy group and the like) and the like. Further preferred groups R ² include an alkyl group [C _1-4 alkyl group (particularly methyl group) and the like], an aryl group [eg C _6-10 aryl group (particularly phenyl group) and the like] and the like. Incidentally, when the group R ² is an aryl group, a group R ^2, together with the ring Z, it may form the ring assembly hydrocarbon ring.

In the same ring Z, when m is plural (two or more), the types of the groups R ² may be the same or different from each other. In the two rings Z, the type of the group R ² may be the same or different. The number of substitutions m can be selected according to the type of ring Z, and may be, for example, 0 to 8, preferably 0 to 4 (for example, 0 to 3), and more preferably 0 to 2. In different rings Z, the number of substitutions m may be the same or different from each other.

In the group X of the formula (1), examples of the alkylene group represented by the group R ³ include C _2-6 alkylene such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group. Group, preferably a _C2-4 alkylene group, more preferably a _C2-3 alkylene group. When n is 2 or more, the type of alkylene group may be composed of different alkylene groups, and may be generally composed of the same alkylene group. In the two aromatic hydrocarbon rings Z, the type of the group R ³ may be the same or different.

The number (additional number of moles) n of the oxyalkylene groups (OR ³⁾ may be any of 0 or more (e.g., 0-20), for example, 0 to 15 (e.g., 1-12), preferably 0-10 ( For example, 1 to 6), more preferably 0 to 4 (for example, 1 to 4), particularly 0 to 2 (for example, 0 to 1) may be used. Further, depending on the type of resin, there may be a case where a remarkable improvement effect is obtained when n is 0 or when n is 1 or more. Therefore, either a compound in which n is 0 or a compound in which n is 1 or more may be selected depending on the type of resin. The number of substitutions n may be the same or different for different rings Z.

Preferred X is a group-[(OR ³ ) nY], and particularly Y is preferably a hydroxyl group. In addition, in Formula (1), the compound whose Y is a hydroxyl group is represented by following formula (1A).

(In the formula, Z, R ¹ , R ² , k, m, R ³ , n, and p are the same as those in the formula (1).)
The substitution number p of the group X may be 1 or more (for example, 1 to 6), and may be, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1. In addition, the substitution number p may be the same or different in each ring Z, and is usually the same in many cases.

  In the formula (1) [or (1A)], the substitution position of the group X is not particularly limited as long as it is substituted at an appropriate substitution position of the ring Z. For example, when the ring Z is a benzene ring, the group X may be substituted at the 2- to 6-position of the phenyl group, and preferably at the 4-position. In addition, when the ring Z is a condensed polycyclic hydrocarbon ring, the group X is a hydrocarbon ring different from the hydrocarbon ring bonded to the 9-position of fluorene in the condensed polycyclic hydrocarbon ring (for example, naphthalene In many cases, the ring is substituted at least on the 5th and 6th positions of the ring.

Specific fluorene compounds (or the compounds represented by the formula (1) or (1A)) include 9,9-bis (hydroxyaryl) fluorenes [or 9,9-bis (hydroxyaryl) fluorene skeletons. Compounds having, for example, 9,9-bis (hydroxyphenyl) fluorenes, 9,9-bis (hydroxynaphthyl) fluorenes], 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes [or 9,9 -Compounds having a bis (hydroxy (poly) alkoxyaryl) fluorene skeleton, such as 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes] X is a group in the formula (1), such as ^{- [(OR 3) n-} OH] , compound; this In al compounds, hydroxyl group, mercapto group, and the like glycidyloxy group or a (meth) acrylate compound substituted acryloyloxy group.

The 9,9-bis (hydroxyphenyl) fluorenes include, for example, 9,9-bis (hydroxyphenyl) fluorene [for example, 9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis (alkyl -Hydroxyphenyl) fluorene [e.g., 9,9-bis such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene (Mono- or di-C _1-4 alkyl-hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxyphenyl) fluorene [eg, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, etc. , 9-bis (mono- or _{di-C 6-10} aryl - hydroxyphenyl) fluorene], 9,9-bis ( Rehydroxyphenyl) fluorene [for example, 9,9-bis (di- or trihydroxyphenyl) such as 9,9-bis (3,4-dihydroxyphenyl) fluorene, 9,9-bis (2,4-dihydroxyphenyl) fluorene ) Fluorene].

  In addition, as 9,9-bis (hydroxynaphthyl) fluorenes, compounds corresponding to the 9,9-bis (hydroxyphenyl) fluorenes in which a phenyl group is substituted with a naphthyl group, for example, 9,9-bis ( Hydroxynaphthyl) fluorene [eg, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9,9-bis (5-hydroxy-1-naphthyl) fluorene] and the like.

9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes include, for example, 9,9-bis (hydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) phenyl] 9,9-bis (hydroxyC _2-4 alkoxyphenyl) fluorene} such as fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene}, 9,9-bis (alkyl-hydroxyalkoxyphenyl) Fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, 9, Such as 9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene 9,9-bis (mono or di C _1-4 alkyl-hydroxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- 9,9-bis (mono or di C _6-10 ) such as (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-phenylphenyl] fluorene 9,9-bis (hydroxyalkoxyphenyl) fluorenes such as aryl- _{hydroxyC 2-4} alkoxyphenyl) fluorene} (a compound in which n is 1 in the formula (1)); 9,9-bis (hydroxydi) Alkoxyphenyl) fluorene {eg, 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] phenyl Eniru} 9,9-bis (hydroxy polyalkoxy phenyl) fluorene such as 9,9-bis fluorene _{(hydroxy-di-C 2-4} alkoxyphenyl) fluorene} (In Formula (1), with n is 2 or more A certain compound) and the like.

Further, as 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes, compounds corresponding to the 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, wherein a phenyl group is substituted with a naphthyl group, For example, 9,9-bis (hydroxyalkoxynaphthyl) fluorene {eg, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2-hydroxypropoxy) ), and the like-2-naphthyl] fluorene such as 9,9-bis (hydroxy _{C 2-4} alkoxy naphthyl) fluorene} etc. 9,9-bis (hydroxyalkoxy naphthyl) fluorenes.

Among these fluorene compounds, in particular, 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene [for example, 9,9-bis (mono or diC _1-4 alkyl- Hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxyphenyl) fluorene [e.g., 9,9-bis (mono or di _C6-10 aryl-hydroxyphenyl) fluorene], 9,9-bis (di or A compound in which n is 0 in the formula (1A) such as trihydroxyphenyl) fluorene and 9,9-bis (hydroxynaphthyl) fluorene; 9,9-bis (hydroxyalkoxyphenyl) fluorene {for example, 9,9-bis (hydroxy _{C 2-4} alkoxyphenyl) fluorene}, 9,9-bis (alkyl - hydroxy alkoxyphenyl) fluorene {e.g., 9,9-bis (mono- or _{di-C 1-4} alkyl - hydroxy _{C 2-4} alkoxyphenyl) fluorene}, 9,9-bis (aryl - hydroxyalkoxy phenyl) fluorene {e.g. 9,9-bis (mono or di C _6-10 aryl-hydroxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (hydroxyalkoxynaphthyl) fluorene {eg, 9,9-bis (hydroxy C _{2 In the} formula (1A) such as -4alkoxynaphthyl) fluorene}, a compound in which n is 1 or more (for example, 1 to 4, preferably 1 to 2, more preferably 1) is preferable.

  Fluorene compounds may be used alone or in combination of two or more. The fluorene compound may be a commercially available product or may be synthesized by a conventional method.

[Strength improver and resin composition]
As described above, the additive (fluorene compound) of the present invention can be used as an additive (strength improver or strength improver) for improving (or increasing or improving) the mechanical strength of the resin. That is, by adding or mixing the fluorene compound to the resin, the mechanical strength of the resin composition containing the resin and the fluorene compound becomes higher than the mechanical strength of the resin (resin not added or mixed with the fluorene compound). .

  The effect of improving the mechanical strength is not particularly limited. For example, the tensile strength is improved (or increased), the bending strength is increased (or increased), and the storage elastic modulus (E ′) (hardness). This can be confirmed by improving (or increasing) the value. The tensile strength and the storage elastic modulus can be measured by the methods of the examples described later.

  As the resin, a wide range of resins can be used (or applied), and any of a thermoplastic resin and a curable resin (thermal or photo-curable resin) may be used.

  Examples of the thermoplastic resin include olefin resin {eg, chain olefin resin [ethylene resin (eg, polyethylene), propylene resin (eg, polypropylene (PP)), polymethylpentene, etc.], cyclic olefin resin, etc.] }, Halogen-containing vinyl resins (polyvinyl chloride, fluororesins, etc.), acrylic resins (polymethyl methacrylate (PMMA), etc.), styrene resins (polystyrene (PS); styrene-methyl methacrylate copolymer (MS) Resin), copolymers such as styrene-acrylonitrile copolymer (AS resin); rubber-grafted styrene copolymers such as impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin), MBS resin Coalescence), polycarbonate resin (PC) For example, aromatic polycarbonate resin), polythiocarbonate resin, polyester resin [for example, aliphatic polyester resin (polylactic acid, etc.), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) described later , Aromatic polyester resins including polyarylate resin (PAR), etc.], polyacetal resin (POM), polyamide resin (PA) (for example, polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide 612, polyamide) Aliphatic polyamide resins such as 6/66; aromatic polyamide resins such as polyamide MXD), polyphenylene ether resin (PPE), polysulfone resin (PSF) (polyethersulfone (PE) ), Polyphenylene sulfide resin (PPS), polyimide resin (including polyetherimide (PEI)), polyetherketone resin (PEK) (including polyetheretherketone resin (PEEK)), liquid crystalline polymer (LCP), thermoplastic elastomer and the like.

  The molecular weight of the thermoplastic resin can be selected according to the type of the resin. For example, the number average molecular weight can be selected from a range of 2000 or more (for example, 3000 or more), 5000 or more (for example, 8000 to 1000000), preferably May be 10,000 or more (for example, 12,000 to 800,000), more preferably 15,000 or more (for example, 20,000 to 500,000). The molecular weight can be measured using a conventional method such as gel permeation chromatography (GPC), and may be evaluated as a molecular weight in terms of polystyrene.

  The thermoplastic resins may be used alone or in combination of two or more. For example, a plurality of thermoplastic resins may form a polymer alloy. Examples of polymer alloys include styrene (PS) alloys (styrene resins that may be rubber-grafted styrene copolymers such as ABS resins, and aromatic polyester resins (PET, PBT, PEN, PAR, etc.). , PC, PA, PPE, etc.), polyester alloys (polyester resins such as aromatic polyester resins (PET, PBT, PEN, PAR, etc.), styrene resins such as ABS resin, PC, PPE, etc. Alloys), PA alloys (PA and polyester resins such as aromatic polyester resins (PET, PBT, PEN, PAR, etc.), alloys with PPE), PC alloys (PC and styrene resins such as ABS resins) , PA, aromatic polyester resin and other polyester resins (PET, PBT, PEN PAR), alloys with LCP, etc.), PPE alloys (alloys with PPE and PS, HIPS, ABS, PA, PES, PPS, etc.), PSF or PES alloys (PSF / ABS alloys, etc.), PPS Examples include alloys (such as PPS / PA alloys), PEK or PEEK alloys (such as PEEK / PEI alloys), and LCP alloys (alloys between LCP and PC, PA, PEEK, etc.). These polymer alloys may contain a compatibilizing agent.

  Examples of the curable resin (heat or photo-curable resin) include acrylic resin (heat or photo-curable acrylic resin), phenol resin, amino resin (urea resin, melamine resin, etc.), furan resin, and unsaturated polyester. Resin, epoxy resin, thermosetting urethane resin, silicone resin, thermosetting polyimide resin, diallyl phthalate resin, vinyl ester resin and the like. The curable resins may be used alone or in combination of two or more. The curable resin may contain a curing agent, a curing accelerator, or the like depending on the type.

  The resin may be either a crystalline resin or an amorphous resin. The resins (thermoplastic resin and curable resin) may be used alone or in combination of two or more.

  You may use the additive of this invention suitably for a thermoplastic resin. In particular, the additive of the present invention includes a thermoplastic resin or aliphatic thermoplastic resin having an alicyclic skeleton (for example, a cyclic olefin resin), a thermoplastic resin having an aromatic ring skeleton or an aromatic thermoplastic resin (for example, Aromatic polycarbonate resin, aromatic polyester resin, polyphenylene ether resin (PPE), polysulfone resin (PSF) (including PES), polyphenylene sulfide resin (PPS), polyimide resin (including PEI), polyether ketone resin (PEEK) ), Liquid crystalline polymers (LCP), etc.), polyamide resins (PA) optionally having an aromatic ring skeleton, polymer alloys thereof (for example, polymer alloys containing these thermoplastic resins), etc. May be.

  Hereinafter, the cyclic olefin resin, the aromatic polycarbonate resin, and the aromatic polyester resin will be described in detail.

(Cyclic olefin resin)
Cyclic olefin resin is resin which uses cyclic olefin as a polymerization component at least.

The cyclic olefin may be a monocyclic olefin or a polycyclic olefin. The cyclic olefin may be substituted with, for example, a hydrocarbon group [for example, an alkyl group (for example, a C _1-10 alkyl group such as a methyl group, preferably a C _1-5 alkyl group), a cycloalkyl group (for example, cyclohexyl). A C _5-10 cycloalkyl group such as a group), an aryl group (eg, a C _6-10 aryl group such as a phenyl group), an alkenyl group (eg, a C _2-10 alkenyl group such as a propenyl group), a cycloalkenyl group (For example, C _5-10 cycloalkenyl group such as cyclopentenyl group and cyclohexenyl group), alkylidene group (for example, C _2-10 alkylidene group such as ethylidene group, preferably C _2-5 alkylidene group, etc.) , polar group [e.g., alkoxy groups (e.g., _{C 1-10} alkoxy group such as methoxy group, preferred Ku is C _1-6 alkoxy group), an acyl group (e.g., a C _2-5 alkanoyl group such as acetyl group), an acyloxy group [e.g., an alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group C _1-10 alkoxy-carbonyl group), cycloalkoxycarbonyl group (for example, C _5-10 cycloalkyl-carbonyl group such as cyclohexyloxycarbonyl group, etc.), hydroxyl group, carboxyl group, amino group, substituted amino group , A halogen atom, a haloalkyl group, a nitro group, a cyano group, an oxo group (═O), a heterocyclic group (such as a nitrogen atom-containing heterocyclic group such as a pyridyl group). The cyclic olefin may have a substituent alone or in combination of two or more.

Specific cyclic olefins include monocyclic olefins [eg, cycloalkenes (eg, cycloC _3-10 alkenes such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, etc.), cycloalkadienes (eg, cyclopentadiene, etc. A cyclo C _3-10 alkadiene, etc.]], bicyclic olefins {eg norbornenes [eg norbornene (eg 2-norbornene), alkyl norbornene (eg 5-methyl-2-norbornene, 5, 5 or 5,6-dimethyl-2-norbornene, 5-ethylidene-2-norbornene), aryl norbornene (for example, 5-phenyl-2-norbornene), norbornene having a polar group (for example, 5-cyano-2-norbornene, etc.) Cyanonorbornene Acyloxynorbornene such as 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5,6-dimethoxycarbonyl-2-norbornene, 5-methyl-5-cyclohexyloxycarbonyl-2-norbornene (Alkoxycarbonyl norbornene, cycloalkoxycarbonyl norbornene, etc.); haloalkylnorbornene such as 5,6-di (trifluoromethyl) -2-norbornene; oxonorbornene such as 7-oxo-2-norbornene), etc.], norbornadienes [eg, , Norbornadiene (for example, 2,5-norbornadiene), alkylnorbornadiene (for example, 5-methyl-2,5-norbornadiene, 5,6-dimethyl-2,5-norbornadiene, etc.) Arylnorbornadiene (such as 5-phenyl-2,5-norbornadiene), norbornadiene having a polar group (for example, cyanonorbornadiene such as 5-cyano-2,5-norbornadiene; 5-methoxycarbonyl-2,5-norbornadiene, etc. Acyloxynorbornadiene (such as alkoxycarbonylnorbornadiene); haloalkylnorbornadiene such as 5,6-di (trifluoromethyl) -2,5-norbornadiene; oxonorbornadiene such as 7-oxo-2-norbornadiene)]], tricyclic olefin { For example, tricycloalkenes [eg, C _6-25 tricycloalkenes such as dihydrodicyclopentadienes (such as dihydrodicyclopentadiene)], tricycloalkadienes [eg, Dicyclopentadiene (dicyclopentadiene, methyldicyclopentadiene, etc.), tricyclo [4.4.0.1 ^2,5 ] undeca-3,7-diene, tricyclo [4.4.0.1 ^2,5 ] C _6-25 tricycloalkadiene, such as undeca-3,8-diene, etc.]}, polycyclic olefins having four or more rings {eg, tetracyclic olefins [eg, tetracycloalkenes (eg, tetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-dimethyltetracyclo [4.4.0.1 ^2,5 . _C7-30 tetracycloalkene such as 1 ^{7, 10} ] -3-dodecene)], pentacyclic olefin [eg C _10-35 pentacycloalkadiene such as pentacycloalkadiene (eg tricyclopentadiene) ), etc.], six cyclic olefins [e.g., hexa cycloalkenes (e.g., hexacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- heptadecene _C such as _12-40 Hexacycloalkene) and the like} and the like.

  The cyclic olefin resin may be a cyclic olefin homopolymer or a copolymer (for example, a copolymer of a monocyclic olefin and a polycyclic olefin, a copolymer of a plurality of polycyclic olefins, etc.), or cyclic. A copolymer of an olefin and a copolymerizable monomer may be used.

Examples of the copolymerizable monomer include a chain olefin [alkene (for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 2-methyl-1-pentene). 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1 -Hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, _C2-20 alkene such as 1-eicocene), alkadienes (for example, , 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-nonconjugated _{C 5-20} a such octadiene Cadien etc.), polymerizable nitrile compounds (eg (meth) acrylonitrile etc.), (meth) acrylic monomers (eg (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate) Esters, (meth) acrylic acid and the like), unsaturated dicarboxylic acids or derivatives thereof (maleic anhydride and the like), and the like. The copolymerizable monomers may be used alone or in combination of two or more.

  In the copolymer of cyclic olefin and copolymerizable monomer, the ratio of cyclic olefin is, for example, 10 mol% or more (for example, 20 mol) with respect to the total amount of cyclic olefin and copolymerizable monomer. % Or more), preferably 30 mol% or more, more preferably 40 mol% or more.

Preferred cyclic olefin resins include cyclic olefin copolymers [eg, cyclic olefins (eg, cyclic olefins containing at least norbornenes) and copolymerizable monomers [eg, chain olefins (eg, C ₂₋ Copolymer) with a copolymerizable monomer containing at least ₆ alkene).

In particular, among cyclic olefin copolymers, a cyclic olefin copolymer having a polar group, for example, a cyclic olefin having a polar group {for example, norbornene having a polar group [for example, acyloxynorbornene (for example, 5-methoxycarbonyl-2 An alkoxycarbonyl group such as norbornene and 5-methyl-5-methoxycarbonyl-2-norbornene (for example, norbornene substituted with a C _1-10 alkoxycarbonyl group, preferably a C _1-4 alkoxycarbonyl group), etc.] } And a copolymer of a cyclic olefin and a copolymerizable monomer [for example, a copolymerizable monomer including at least a chain olefin (for example, a C _2-6 alkene such as ethylene)] is preferable. .

  In the cyclic olefin copolymer having a polar group, the ratio of the cyclic olefin having a polar group to the whole cyclic olefin is, for example, 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more. May be.

  Cyclic olefin resins may be used alone or in combination of two or more.

(Aromatic polycarbonate resin)
Examples of the aromatic polycarbonate resin include resins having an aromatic diol and a carbonate-forming compound as polymerization components.

Examples of the aromatic diol include bisphenols and dihydroxyarene (hydroquinone, resorcinol, etc.). Examples of the bisphenol include dihydroxyarene [eg, di ( _{hydroxyC 6-10} arene) such as 4,4′-dihydroxybiphenyl], bis (hydroxyphenyl) alkane [eg, bis (4-hydroxyphenyl) methane, etc. 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis ( 4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2 -Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2 Bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane Bis (hydroxy) such as 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) diphenylmethane Phenyl) C _1-10 alkanes, preferably bis (hydroxyphenyl) C _1-8 alkanes], bis (hydroxyphenylaryl) alkanes [eg 2,2-bis (4-hydroxy-3,3′- biphenyl) propane and bis (hydroxy _{biphenylyl) C 1-10} alkanes, preferably bis (arsenate B carboxymethyl _{biphenylyl) C 1-8} alkanes, bis (hydroxyphenyl) cycloalkane [e.g., 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis ( Bis (hydroxyphenyl) C _4-10 cycloalkanes such as 3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane , Preferably bis (hydroxyphenyl) C _5-8 cycloalkane], bis (hydroxyphenyl) ethers (for example, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyl) Diphenyl ether), bis (hydroxyphenyl) sulfones ( For example, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone, 4,4′-dihydroxy-3,3′-diphenyldiphenylsulfone, etc.), bis (hydroxyphenyl) Sulfoxides (for example, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfoxide, etc.), bis ( Hydroxyphenyl) sulfides (eg, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, etc.) Bis (hydroxyphenyl-alkyl) array [For example, bis (hydroxyphenyl-C _1-4 alkyl) C _6-10 arenes such as 4,4 ′-(o, m or p-phenylenediisopropylidene) diphenol, preferably bis (hydroxyphenyl- C _1-4 alkyl) benzene] and the like.

Among these aromatic diols, in particular, bis (hydroxyphenyl) alkanes [especially bis (hydroxyphenyl) C _1-4 alkanes such as 2,2-bis (4-hydroxyphenyl) propane], bis (hydroxyphenyl) - bisphenols such as an alkyl) arenes [bis (hydroxyphenyl _{-C 1-4} alkyl) benzene, etc.] is preferable. Aromatic diols may be used alone or in combination of two or more.

  Examples of the carbonate-forming compound include carbonates such as phosgene (phosgene, diphosgene, triphosgene, etc.), carbonates [eg, dialkyl carbonate (dimethyl carbonate, diethyl carbonate, etc.), diaryl carbonate (diphenyl carbonate, dinaphthyl carbonate, etc.). Diesters] and the like. Among these, phosgene, diphenyl carbonate and the like may be preferably used. The carbonate-forming compounds may be used alone or in combination of two or more.

  Aromatic polycarbonate resins may be used alone or in combination of two or more.

(Aromatic polyester resin)
Examples of aromatic polyester resins include polyalkylene arylate resins, polyarylate resins [for example, aromatic dicarboxylic acids (such as terephthalic acid) and aromatic diols (biphenol, bisphenol A, xylylene glycol, alkylene oxide adducts thereof, etc.) And the like)], and liquid crystalline polyester resins.

Examples of the polyalkylene arylate resin include polyalkylene terephthalate resin [eg, polyalkylene terephthalate (for example, poly C _2-4 alkylene terephthalate such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate), alkylene terephthalate unit (polyalkylene terephthalate unit) ), Polyalkylene naphthalate resin [for example, polyalkylene naphthalate (for example, poly C _2-4 alkylene naphthalate such as polyethylene naphthalate), alkylene naphthalate unit (polyalkylene naphthalate unit) Having a copolyester], polycycloalkane dialkylene terephthalate resin [for example, polycycloalkanedia Sharp emission terephthalate (e.g., poly cyclohexane dimethylene terephthalate), such as a copolyester having cycloalkandienyl alkylene terephthalate units (poly cycloalkane alkylene terephthalate unit), and the like.

In the copolyester, examples of the copolymer component include a diol component [eg, alkane diol (eg, C _2-6 alkane diol such as ethylene glycol, propylene glycol, butane diol, hexane diol), polyalkane diol (eg, diethylene glycol). Di-hexaC _2-4 alkanediols such as polytetramethylene glycol), alicyclic diols (eg 1,4-cyclohexanedimethanol etc.), aromatic diols (eg C _2-4 alkylenes of bisphenols) Oxide adducts etc.)], dicarboxylic acid components {eg, aliphatic dicarboxylic acids (eg, C _4-12 alkane dicarboxylic acids such as glutaric acid, adipic acid, sebacic acid), aromatic dicarboxylic acids [eg, asymmetric aromatics] Zika Rubonic acid (eg phthalic acid, isophthalic acid etc.), diphenyldicarboxylic acid etc.]}, hydroxycarboxylic acid component (eg hydroxybenzoic acid etc.) and the like. The copolymerization components may be used alone or in combination of two or more.

  In the copolyester, the proportion of alkylene arylate units (alkylene terephthalate units, alkylene naphthalate units, etc.) may be, for example, 40% by weight or more, preferably 50% by weight or more.

  The aromatic polyester resin may be crystalline or non-crystalline. The aromatic polyester resin may have a linear structure or a branched structure. Aromatic polyester resins may be used alone or in combination of two or more.

  The use ratio of the strength improver (fluorene compound) can be selected from a range of about 0.1 parts by weight or more (for example, 0.2 to 200 parts by weight) with respect to 100 parts by weight of the resin. 100 parts by weight, preferably 0.5 to 80 parts by weight, more preferably about 1 to 50 parts by weight, and usually 0.5 to 50 parts by weight (for example, 0.5 to 40 parts by weight, preferably 0.7 to 30 parts by weight, more preferably 1 to 20 parts by weight).

  Since the strength improver of the present invention can efficiently obtain a strength improving effect even in a small amount, for example, the use ratio of the strength improver is 20 parts by weight or less (for example, 0.1% with respect to 100 parts by weight of the resin). To 18 parts by weight), preferably 15 parts by weight or less (for example, 0.2 to 12 parts by weight), more preferably 10 parts by weight or less (for example, 0.3 to 7 parts by weight), particularly 5 parts by weight or less (for example, 0.5-5 parts by weight).

  In addition, the strength improver of the present invention is excellent in affinity for the resin, and even when added in a relatively large proportion, the resin properties can often be maintained or improved at a high level. 20 parts by weight or more (for example, 20 to 100 parts by weight) with respect to 100 parts by weight, preferably 25 parts by weight or more (for example, 25 to 80 parts by weight), more preferably 30 parts by weight or more (for example, 30 to 70 parts). Part by weight).

  As described above, a resin (resin composition) having improved or improved strength (mechanical strength) can be obtained by the strength improver of the present invention. The present invention also includes such a resin composition, that is, a resin composition containing a resin and a strength improver.

  The resin composition may contain various additives [for example, fillers or reinforcing agents, colorants (dye pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, ultraviolet rays). Absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress agents, carbon materials, etc.] Good. These additives may be used alone or in combination of two or more.

  The resin composition can be obtained by mixing a resin, a fluorene compound (strength improver) and [and other components (such as additives) as necessary]. The mixing method is not particularly limited, and may be mixed by, for example, melt kneading, or may be mixed by dissolving each component in a solvent.

  The present invention also includes a molded body formed from such a resin composition. The shape of the molded body is not particularly limited and can be appropriately selected depending on the application. For example, a two-dimensional structure (film shape, sheet shape, plate shape, etc.), a three-dimensional structure (tubular, rod-shaped, tubular shape, hollow) Etc.).

  In particular, the resin composition of the present invention is often excellent in various optical properties, and an optical material or an optical molded body (particularly, an optical film, an optical lens, etc.) may be suitably formed.

  The molded body can be manufactured using, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, a casting molding method, and the like.

  In particular, the resin composition of the present invention is useful for forming a film (particularly an optical film). Therefore, the present invention also includes a film (such as an optical film) formed from the resin composition. A film (such as an optical film) is produced by forming (or molding) the resin composition using a conventional film formation method, for example, a casting method (solvent casting method), a melt extrusion method, a calendar method, or the like. it can.

  The thickness of the film can be selected from the range of about 1 to 1000 μm depending on the application, and may be, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably about 10 to 120 μm.

  The film may be a stretched film (uniaxially stretched film or biaxially stretched film). The stretching ratio may be about 1.05 to 10 times (for example, 1.1 to 5 times) in each direction in uniaxial stretching or biaxial stretching, and is usually 1.1 to 3 times (for example, 1. 2 to 2.5 times). In the case of biaxial stretching, it may be equal stretching or partial stretching. In the case of uniaxial stretching, longitudinal stretching or lateral stretching may be used. The stretching method is not particularly limited. In the case of uniaxial stretching, a wet stretching method or a dry stretching method may be used. In the case of biaxial stretching, a tenter method (also referred to as a flat method), a tube method, or the like may be used. Good.

  The stretched film may have a thickness of, for example, 1 to 150 μm, preferably 3 to 120 μm, and more preferably about 5 to 100 μm.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the examples, various characteristics were measured as follows.

(Tensile strength)
A sample (thickness 0.2 mm, width 5 mm, length 50 mm) is prepared from the stretched film, and a tensile tester (Tensilon RTC-1250 (A & D)) is used in this sample, and the distance between chucks is set to 20 mm. The strength until the sample was cut at a tensile speed of 2 mm / min was measured. Further, in this tensile test, the strength at which the strength became maximum (maximum strength) was also measured.

(Dynamic viscoelasticity)
A sample (thickness 0.2 mm, width 1-2 mm, length 50 mm) was prepared from the stretched film, and a dynamic viscoelasticity tester (Rheogel E4000 (UBM)) was used for this sample, and the uniaxial tension mode was used. At 100 Hz, the storage elastic modulus (E ′) at room temperature (25 ° C.) and the temperature (tan δ _max ) at which tan δ becomes maximum were measured.

Example 1
After melting polyethylene terephthalate resin (A-PET, manufactured by Toyobo Co., Ltd.) with Laboplast mill, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene (biscresol fluorene, Osaka Gas Chemical Co., Ltd.) (Hereinafter referred to as “BCF”) was mixed at 270 ° C. so as to have the ratio shown in Table 1 to obtain a resin composition. In addition, the resin composition was transparent and mixed uniformly in any ratio.

  The obtained resin composition was dried at 120 ° C. and then hot pressed at 260 ° C. to prepare a sheet. Furthermore, after heat-treating the obtained sheet | seat at 150 degreeC, it was heat-stretched by the stretch temperature of 140 degreeC and the draw ratio of 1.2 time in the silicone bath, and the stretched film was obtained.

  Using the obtained stretched film, the tensile strength and dynamic viscoelasticity were measured.

  In addition, using the obtained stretched film, a differential scanning calorimeter (Thermo Plus DSC 8230, manufactured by Rigaku Corporation) was used, and the heat of fusion was performed in a range of room temperature to 300 ° C. in nitrogen at a heating rate of 10 ° C./min. Was measured. In addition, regarding the heat of fusion, two types of heat of fusion of the resin composition and the resin were calculated. That is, the heat of fusion of the resin composition indicates the heat of fusion per weight of the entire resin composition, and the heat of fusion of the resin indicates the heat of fusion per weight of the resin in the resin composition.

  Furthermore, the refractive index and the Abbe number of the stretched film having a thickness of 2 mm were measured with an Abbe refractometer (manufactured by Atago) at the temperature (measurement temperature) shown in Table 1.

  The results are shown in Table 1. In Table 1, for comparison, the result of the BCF ratio of 0% by weight is also shown.

  As is clear from the results in Table 1, the mechanical strength (tensile strength) was improved by adding BCF. Further, the temperature at which tan δ was maximized was increased, and an increase in the glass transition temperature was also confirmed. Furthermore, the heat of fusion, which is an index of ease of crystallization, increased in both the polyethylene terephthalate resin and the resin composition. The Abbe number also increased.

(Example 2)
Example 1 except that 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEF) was used instead of BCF in Example 1. Measured in the same manner as above.

  As is apparent from the results in Table 2, even when BPEF was added, improvement in mechanical strength could be confirmed. Also, the heat of fusion increased.

(Example 3)
In Example 1, it measured like Example 1 except having replaced with polyethylene terephthalate resin and having used polyethylene naphthalate resin (the Kanebo make, H-PEN).

  Further, the birefringence (Δn / λ) increased per unit magnification at the time of stretching was measured for the stretched film using a polarizing microscope (manufactured by NIKON, OPTIPHOT-POL) by a method of canceling polarized light with a compensator.

  The mixing temperature was 280 ° C., the hot press temperature was 270 ° C., the heat treatment temperature was 190 ° C., and the stretching temperature was 180 ° C.

  The results are shown in Table 3.

  As is clear from the results in Table 3, improvement in mechanical strength was confirmed even in the polyethylene naphthalate resin. Further, the temperature at which tan δ was maximized was increased, and an increase in the glass transition temperature was also confirmed. In addition, the Abbe number also increased. Furthermore, birefringence was reduced.

Example 4
In Example 1, it measured like Example 1 except having replaced with the polyethylene terephthalate resin and using polycarbonate resin (Teijin Chemicals Co., Ltd. product, AD5003). The mixing temperature was 250 ° C., the hot pressing temperatures were 240 ° C. (0 wt%) and 200 ° C. (5 wt%), respectively, and the stretching temperature was 180 ° C.

  The results are shown in Table 4.

  As is clear from the results in Table 4, improvement in mechanical strength was also confirmed in the polycarbonate resin.

(Example 5)
In Example 1, a polycarbonate resin (manufactured by Teijin Chemicals Ltd., AD5003) was used in place of the polyethylene terephthalate resin, and measurements were performed in the same manner as in Example 1 except that BPEF was used instead of BCF. The mixing temperature was 250 ° C., the hot press temperature was 240 ° C., and the stretching temperature was 180 ° C.

  The results are shown in Table 5.

  As is clear from the results in Table 5, the improvement in mechanical strength was also confirmed in the polycarbonate resin.

(Example 6)
In Example 1, it measured like Example 1 except having replaced with the polyethylene terephthalate resin and having used cyclic olefin resin (the JSR Co., Ltd. product, cyclic olefin copolymer, Arton4531F). Further, birefringence was measured in the same manner as in Example 3.

  The mixing temperature is 250 ° C. (0 wt% and 1 wt%) or 240 ° C. (5 wt%), and the hot press temperature is 220 ° C. (0 wt% and 1 wt%) or 230 ° C. (5 wt%). The stretching temperature was 180 ° C.

  The results are shown in Table 6.

  As is clear from the results in Table 6, the improvement in mechanical strength was also confirmed in the cyclic olefin resin. Birefringence was also reduced.

(Example 7)
In Example 1, a cyclic olefin resin (manufactured by JSR Co., Ltd., cyclic olefin copolymer, Arton 4531F) was used instead of polyethylene terephthalate resin, and BPEF was used instead of BCF. Measured. Further, birefringence was measured in the same manner as in Example 3.

  The mixing temperature was 250 ° C., the hot press temperature was 220 ° C. (0 wt% and 1 wt%) or 230 ° C. (5 wt%), and the stretching temperature was 180 ° C.

  As is clear from the results in Table 7, improvement in mechanical strength was also confirmed in the cyclic olefin resin. Birefringence was also reduced.

(Example 8)
In Example 1, polyphenylene ether resin (manufactured by Asahi Kasei Chemicals Co., Ltd., Zyron S201A) was used instead of polyethylene terephthalate resin, and measurement was performed in the same manner as in Example 1 except that BCF or BPEF was used. The mixing temperature was 265 to 290 ° C, and the hot press temperature was 265 to 290 ° C.

  Table 8 shows the BCF results and Table 9 shows the BPEF results.

  As is clear from the results in Tables 8 and 9, the improvement in mechanical strength was also confirmed in the polyphenylene ether resin.

Example 9
In Example 1, in place of polyethylene terephthalate resin, polyphenylene ether / polystyrene alloy resin (manufactured by Asahi Kasei Chemicals Co., Ltd., Zylon H1000) was used, and measurement was performed in the same manner as in Example 1 except that BCF or BPEF was used. did. The mixing temperature was 265 ° C., and the hot press temperature was 265 ° C.

  Table 10 shows the BCF results and Table 11 shows the BPEF results.

  As is clear from the results of Tables 10 and 11, improvement in mechanical strength was confirmed even in the alloy resin.

  The additive of the present invention can be used as an additive for improving or improving the mechanical properties of the resin. In addition, such additives can obtain effects other than improvement of mechanical properties such as improved heat resistance, reduced birefringence, improved Abbe number while improving refractive index, and so on. Highly useful.

  Therefore, the resin (or the resin composition containing the resin and the strength improver) modified by the additive of the present invention (or the resin composition containing the resin and the strength improver) depends on the type of resin to be combined. It has excellent properties such as high refractive index, high heat resistance, and high transparency. Such a resin composition can be suitably used particularly for an optical lens, an optical film, an optical sheet, a pickup lens, a hologram, a liquid crystal film, an organic EL film, and the like. Resin compositions include paints, antistatic agents, inks, adhesives, pressure-sensitive adhesives, resin fillers, charging trays, conductive sheets, protective films (protective films for electronic equipment, liquid crystal members, etc.), electrical / electronic materials (Carrier transport agent, luminous body, organic photoreceptor, thermal recording material, hologram recording material), electrical / electronic component or equipment (optical disk, inkjet printer, digital paper, organic semiconductor laser, dye-sensitized solar cell, EMI shield film) Resin for photochromic materials, organic EL elements, color filters, etc.), resin for mechanical parts or equipment (automobiles, aerospace materials, sensors, sliding members, etc.) and the like.

  In particular, since the resin composition is excellent in optical characteristics, it is useful for constituting (or forming) a molded product for optical use (optical molded product). Examples of the optical molded body formed (configured) with such a resin composition include an optical film and an optical lens.

  As an optical film, a polarizing film (and a polarizing element and a polarizing plate protective film constituting it), a retardation film, an alignment film (alignment film), a viewing angle expansion (compensation) film, a diffusion plate (film), a prism sheet, Light guide plate, brightness enhancement film, near infrared absorption film, reflection film, antireflection (AR) film, reflection reduction (LR) film, antiglare (AG) film, transparent conductive (ITO) film, anisotropic conductive film (ACF) ), Electromagnetic wave shielding (EMI) film, film for electrode substrate, film for color filter substrate, barrier film, color filter layer, black matrix layer, adhesive layer or release layer between optical films. In particular, the film of the present invention is useful as an optical film for use in an apparatus display. Specific examples of the display member (or display) including the optical film of the present invention include FPD devices such as personal computer monitors, televisions, mobile phones, car navigation systems, and touch panels (for example, , LCD, PDP, etc.).

Claims (4)

A resin comprising at least one resin selected from cyclic olefin resins, aromatic polycarbonate resins, polyphenylene ether resins, and polymer alloys thereof, and a strength improver composed of a compound represented by the following formula (1A) Composition.

(In the formula, ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, R ³ is an alkylene group, k is an integer of 0 to 4, m is an integer of 0 or more, n is an integer of 0 or more, p represents an integer of 1 or more.) Ring Z is a benzene ring or naphthalene ring, R ¹ is an alkyl group, k is 0 to 1, R ² is an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkoxy group, m is 0 to 2, and R ³ is C _2-4 alkylene radical, n is 0 to 2, p is claim 1 Symbol placement of the resin composition is 1-3. Compound you express by the formula (1A) is 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl - hydroxyphenyl) fluorene, 9,9-bis (aryl - hydroxyphenyl) fluorene, 9, 9-bis (di- or trihydroxyphenyl) fluorene, 9,9-bis (hydroxynaphthyl) fluorene, 9,9-bis (hydroxyalkoxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyalkoxyphenyl) fluorene, 9 , 9-bis (aryl - hydroxyalkoxy phenyl) fluorene, 9,9-bis (hydroxyalkoxy naphthyl) according to claim 1 or 2 resin composition, wherein at least one member selected from fluorene. The resin composition according to any one of claims 1 to 3 , wherein the strength improver is an improver that improves at least one mechanical property selected from tensile strength, bending strength, and storage elastic modulus E '.