JP2014218655A - Heat resistance improver - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition which can improve heat resistance.SOLUTION: A fluorene compound represented by the following formula (1) is added to or mixed with a polyester resin to prepare a resin composition. In the formula (1), a ring Z represents an aromatic hydrocarbon ring, Rand Rrepresent substituents, X represents a group-[(OR)n-Y], where Y represents a hydroxyl group, a mercapto group, a glycidyloxy group or a (meth)acryloyloxy group, Rrepresents an alkylene group and n represents an integer of 0 or more, or an amino group, k represents an integer of 0 to 4, m represents an integer of 0 or more and p represents an integer of 1 or more.

Description

  The present invention relates to an additive (or modifier) for improving the heat resistance of a polyester resin.

  As a resin for toner, a polyester resin is widely used. Such a polyester resin is required to be melted rapidly (sharply) to reduce the viscosity when heated, since the toner is heated and melted at a relatively low temperature for fixing.

  As the polyester resin, a low molecular weight polyester resin is usually used from the viewpoint of reducing the viscosity of the resin. However, when the molecular weight is lowered, the heat resistance (glass transition temperature) is lowered, and the toner is likely to aggregate (block). Therefore, it is necessary to improve heat resistance (glass transition temperature) while maintaining low viscosity.

  Generally, low viscosity and heat resistance are ensured by combining a low molecular weight polyester resin and a high molecular weight polyester resin. However, in recent years, for the purpose of energy saving and the like, there is a demand for a technology that can efficiently achieve both high fixability (such as low viscosity) and heat resistance.

  On the other hand, compounds having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) are known to have excellent functions such as 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.), such as 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.

  Attempts have also been made to add the fluorene compound directly to the 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 was 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 reduced without impairing the mechanical properties and heat resistance of the transparent resin. In a specific example, a fluorene-containing polyester 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 bismuth and 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) Japanese Patent Laying-Open No. 2005-162785 (Claims and Examples) JP2011-8017 A (Claims, Examples) JP 2011-21083 A (Claims, Examples) [0058])

  Accordingly, an object of the present invention is to provide an additive (or modifier) that can improve (or improve or increase) the heat resistance (eg, glass transition temperature) of the polyester resin.

  Another object of the present invention is to provide an additive capable of improving (or improving or increasing) heat resistance while maintaining a low viscosity (or melt viscosity) of a polyester resin.

  Still another object of the present invention is to provide an additive effective for rapidly (sharply) melting a polyester 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. In addition, although Tg is improved in Patent Document 5, it is only disclosed that Tg has increased with the change of polylactic acid from α-crystal to β-crystal, and the heat resistance of the resin itself has been improved. It is not disclosed.

  Under such circumstances, as a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that 9,9--with respect to polyester resins (especially low molecular weight and / or low viscosity polyester resins) among resins. Surprisingly, when a compound having a bisarylfluorene skeleton is added, only a decrease in heat resistance [for example, glass transition temperature (Tg)], which is a general phenomenon when a low molecular weight compound is used as an additive, is not observed. Rather, the heat resistance of the polyester resin is improved, the viscosity (melt viscosity) of the resin can be maintained without extremely increasing the viscosity, and the resin is melted sharply (rapidly). The present invention has been completed.

  That is, the additive of the present invention has a heat resistance [for example, a glass transition temperature (for example, a glass transition temperature by DSC (differential scanning calorimetry))] of a polyester resin (for example, a polyester resin having a number average molecular weight of 10,000 or less). An additive for improving (or increasing or improving) a heat resistance improver (heat resistance 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.

  In particular, compounds having a 9,9-bisarylfluorene skeleton include 9,9-bis (hydroxyalkoxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyalkoxyphenyl) fluorene, and 9,9-bis (aryl-hydroxy). It may be at least one selected from alkoxyphenyl) fluorene and 9,9-bis (hydroxyalkoxynaphthyl) fluorene.

  The melt viscosity at 180 ° C. of the polyester resin may be, for example, 5000 mPa · s or less. Moreover, about 35-75 degreeC may be sufficient as the glass transition temperature of a polyester resin. A typical polyester resin may be a polyester resin having a number average molecular weight of 8000 or less, a melt viscosity at 180 ° C. of 3000 mPa · s or less, and a glass transition temperature of 40 to 70 ° C.

  In addition, the polyester resin includes, for example, a dicarboxylic acid component including at least one selected from an alicyclic dicarboxylic acid component and an aromatic dicarboxylic acid component, and at least one selected from an alicyclic diol and an aromatic diol. The polyester resin which uses the diol component to contain as a polymerization component may be sufficient.

  The present invention also includes a resin composition containing the polyester resin (for example, a polyester resin having a number average molecular weight of 10,000 or less) and the heat resistance improver (or a compound having a 9,9-bisarylfluorene skeleton). It is. In such a resin composition, the ratio of the heat resistance improver may be about 0.5 to 50 parts by weight with respect to 100 parts by weight of the polyester resin.

  In particular, the resin composition may be a resin composition for toner [or a binder (resin) for toner].

  Furthermore, in the present invention, the heat resistance improver is added to a polyester resin (for example, a polyester resin having a number average molecular weight of 10,000 or less), and the heat resistance of the polyester resin (for example, a polyester resin having a number average molecular weight of 10,000 or less) is improved. Also included are ways to improve.

  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 increase) the heat resistance (eg, glass transition temperature) of the polyester resin. Moreover, such an additive can sharply melt the resin and can maintain the viscosity (or melt viscosity) of the resin without increasing the viscosity. Therefore, according to the additive of the present invention, it is usually very difficult to achieve both low viscosity and improved heat resistance, which are very useful. The polyester resin (or resin composition) modified by the additive of the present invention has heat resistance (blocking (aggregation) resistance) as well as sharp melting characteristics (low viscosity, fixing properties). It can be suitably used as a resin (or resin composition or binder) for toner.

  The additive of the present invention is an additive (heat resistance improver, heat resistance improver) for improving (or improving or increasing) the heat resistance (for example, glass transition temperature) of the polyester 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 the same or 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, and may usually be the same.

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

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 5-position, 6-position, etc.

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.

  In terms of the effect of improving heat resistance, compounds in which n is 0 in Formula (1) (or (1A)) such as 9,9-bis (hydroxyaryl) fluorenes are preferable. On the other hand, from the viewpoint of improving heat resistance while maintaining low viscosity at a high level, the above formula (1) (or (1A)) such as 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes. In which n is 1 or more.

  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.

[Heat resistance improver and resin composition]
As described above, the additive (fluorene compound) of the present invention can be used as an additive (heat resistance improver, heat resistance improver) for improving (or increasing or improving) the heat resistance of the polyester resin. That is, the heat resistance of the resin composition containing the polyester resin is increased by adding or mixing the fluorene compound to the polyester resin.

  In the present invention, the effect of promoting (or improving) heat resistance is not particularly limited, but can be confirmed by, for example, an increase in glass transition temperature. The glass transition temperature can be measured by DSC (differential scanning calorimetry), DMA (dynamic viscoelasticity measurement) or the like.

(Polyester resin)
Although it does not specifically limit as a polyester resin, For example, the polyester resin which uses a dicarboxylic acid component and a diol component as a polymerization component is mentioned.

Examples of the dicarboxylic acid component include dicarboxylic acid and ester-forming derivatives of dicarboxylic acid. Examples of the ester-forming derivative include esters {for example, alkyl esters [for example, lower alkyl esters such as methyl esters and ethyl esters (for example, C _1-4 alkyl esters, particularly C _1-2 alkyl esters], etc.}}. , Acid halides (acid chlorides, etc.), acid anhydrides, etc. The ester-forming derivative may be a monoester (half ester) or a diester, and the dicarboxylic acid component depends on the method for producing the polyester resin as appropriate. Can be selected.

  Specific examples of the dicarboxylic acid component include an aliphatic dicarboxylic acid component, an alicyclic dicarboxylic acid component, and an aromatic dicarboxylic acid component. The dicarboxylic acid components may be used alone or in combination of two or more.

Examples of the aliphatic dicarboxylic acid component include alkane dicarboxylic acid components [for example, C _2-12 alkane dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid, and ester-forming derivatives thereof (such derivatives). Ingredients etc.]. The aliphatic dicarboxylic acid components may be used alone or in combination of two or more.

Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acid (for example, C _3-10 cycloalkane-dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, preferably C _4-8 cycloalkane-dicarboxylic acid), Bi or tricycloalkane dicarboxylic acids (eg, decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.), cycloalkene dicarboxylic acids (eg, C _4-8 cycloalkene-dicarboxylic acids such as cyclohexene dicarboxylic acid) Acid), bi- or tricycloalkene dicarboxylic acid (for example, norbornene dicarboxylic acid), and ester-forming derivatives thereof (such as the aforementioned derivatives). The alicyclic dicarboxylic acid components may be used alone or in combination of two or more.

The aromatic dicarboxylic acid component can be roughly classified into a monocyclic aromatic dicarboxylic acid component and a polycyclic aromatic dicarboxylic acid component. Examples of the monocyclic aromatic dicarboxylic acid component include monocyclic arene dicarboxylic acids [for example, C _1-4 alkyl terephthalic acid such as terephthalic acid, isophthalic acid, phthalic acid, alkyl isophthalic acid (for example, 4-methylisophthalic acid). C _6-10 arene dicarboxylic acid such as acid)], and ester-forming derivatives thereof.

Examples of the polycyclic aromatic dicarboxylic acid component include polycyclic aromatic dicarboxylic acids and ester-forming derivatives thereof. Examples of the polycyclic aromatic dicarboxylic acid include condensed polycyclic aromatic dicarboxylic acid [for example, naphthalenedicarboxylic acid (for example, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalene). Naphthalene dicarboxylic acid having two carboxyl groups in different rings such as dicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid; 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, etc. Naphthalenedicarboxylic acid having two carboxyl groups in the same ring), condensed polycyclic C _10-24 arene-dicarboxylic acid such as anthracene dicarboxylic acid and phenanthrene dicarboxylic acid], arylarene dicarboxylic acid [for example, biphenyldicarboxylic acid (2 , 2'-biphenyldicarbo Acid, _{C 6-10} aryl _{C 6-10} arene such as 4,4'-biphenyl dicarboxylic acid) - dicarboxylic acid, diaryl alkane dicarboxylic acid [for example, diphenyl alkane dicarboxylic acids (e.g., 4,4'-diphenylmethane dicarboxylic Di-C _6-10 aryl C _1-6 alkane-dicarboxylic acid] such as diphenyl C _1-4 alkane-dicarboxylic acid such as acid], diaryl ketone dicarboxylic acid [for example, diphenyl ketone dicarboxylic acid (4,4′-diphenyl) DiC _6-10 aryl ketone-dicarboxylic acid] such as ketone dicarboxylic acid] and the like.

The aromatic dicarboxylic acid component also includes an araliphatic dicarboxylic acid component. Such an araliphatic dicarboxylic acid component includes an aromatic skeleton and a carboxyl group in the aromatic dicarboxylic acid exemplified above as an aliphatic hydrocarbon group [for example, an alkylene group (for example, a C such as a methylene group, an ethylene group, etc.). _1-10 alkylene group, preferably a dicarboxylic acid bound via a _{C 1-4} alkylene group), etc.], for example, di (carboxyalkyl) arene [e.g., 1,4-phenylene diacetic acid (1,4-di ( Carboxymethyl) benzene), di (carboxyC _1-4 alkyl) benzene such as 1,3-phenylenediacetic acid, 1,4-phenylenedipropionic acid], ester-forming derivatives thereof, and the like.

  The aromatic dicarboxylic acid components may be used alone or in combination of two or more. The dicarboxylic acid component may be typically composed of at least one selected from an alicyclic dicarboxylic acid component and an aromatic dicarboxylic acid component, and in particular, may be composed of at least an aromatic dicarboxylic acid component. . In addition, the ratio of at least one selected from the alicyclic dicarboxylic acid component and the aromatic dicarboxylic acid component to the entire dicarboxylic acid component is, for example, 10 mol% or more, preferably 30 mol% or more, more preferably It may be 50 mol% or more, particularly 70 mol% or more.

  Examples of the diol component include aliphatic diol (or aliphatic diol component), alicyclic diol (or alicyclic diol component), aromatic diol (or aromatic diol component), and the like. The diol component may be used alone or in combination of two or more.

Examples of the aliphatic diol (chain aliphatic diol) include alkane diols (for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol). , 1,3-butanediol, 1,4-pentanediol, 1,5-pentanediol, 1,3-pentanediol, C _2-10 alkanediol such as neopentyl glycol, preferably C _2-6 alkanediol, Further preferred are saturated aliphatic diols such as C _2-4 alkane diols) and polyalkane diols (for example, di or tri C _2-4 alkane diols such as diethylene glycol, dipropylene glycol and triethylene glycol). Aliphatic diols may be used alone or in combination of two or more.

Examples of the alicyclic diol include cycloalkane diol (for example, C _4-10 cycloalkane diol such as 1,4-cyclohexane diol, preferably C _5-8 cycloalkane diol), polycycloalkane diol (for example, norbornane). diols, di- or tri-Sik alkanediol such as adamantane diol), di (hydroxyalkyl) cycloalkanes [e.g., such as 1,4-cyclohexane dimethanol di (hydroxyalkyl _{C 1-4 alkyl) C 4-10} cycloalkane, preferably Di (hydroxyC _1-3 alkyl) C _5-8 cycloalkane, more preferably di (hydroxyC _1-2 alkyl) C _5-6 cycloalkane etc.], di (hydroxyalkyl) polycycloalkane [eg tri Cyclodecanedimeta Lumpur (tricyclo [5.2.1.0 (2,6)] decane dimethanol), adamantane dimethanol, di (hydroxyalkyl _{C 1-4} alkyl) such as norbornanedimethanol bi- or tri _{C 4-10} cycloalkane , Preferably di (hydroxy C _1-3 alkyl) bi or tri C _5-8 cycloalkane, more preferably di (hydroxy C _1-2 alkyl) bi or tri C _5-6 cycloalkane], heterocycloalkane skeleton Diols having an oxamono or polycycloalkanediol (such as isosorbide), diols having an oxaspiro ring skeleton [for example, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10 -Di (hydroxyalkyl) tetraoxas such as tetraoxaspiro [5.5] undecane Pyroalkanes (for example, di (hydroxyC _1-10 alkyl) tetraoxaspiroalkane)], hydrogenated products of alkylene oxide adducts of bisphenols (such as compounds described below) [for example, water of alkylene oxide adducts of bisphenol A] Additives] and the like. The alicyclic diols may be used alone or in combination of two or more.

Examples of the aromatic diol include dihydroxyarene (hydroquinone, resorcinol, etc.), bisphenols, araliphatic diol {eg, di (hydroxyalkyl) arene [eg, benzenedimethanol (1,4-benzenedimethanol, 1, Di (hydroxy C _1-4 alkyl) C _6-10 arene etc.], alkylene oxide adducts of bisphenols, 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.

In addition, in the alkylene oxide adduct of bisphenols, examples of the alkylene oxide include C _2-6 alkylene oxide (preferably C _2-3 alkylene oxide) such as ethylene oxide, propylene oxide, and butylene oxide. Moreover, in the adduct of alkylene oxide, the addition ratio of alkylene oxide is, for example, 1 mol or more (for example, 1 to 10 mol), preferably 1 to 6 mol (for example, 1 mol of hydroxyl group of bisphenol). For example, it may be about 1 to 5 mol), more preferably about 1 to 4 mol, particularly about 1 to 3 mol (for example, 1 to 2 mol).

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

  The diol component may typically be composed of at least one selected from alicyclic diols and aromatic diols, and particularly at least araliphatic diols (for example, alkylene oxide adducts of bisphenols). It may be configured. The ratio of at least one selected from alicyclic diols and aromatic diols relative to the entire diol component is, for example, 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, In particular, it may be 70 mol% or more.

  Moreover, when combining at least 1 sort (s) selected from alicyclic diol and aromatic diol, and aliphatic diol, these ratios are former / latter (molar ratio) = 99.5 / 0.5-10 / 90 (for example, 99/1 to 15/85), preferably 98/2 to 20/80 (for example, 97/3 to 25/75), more preferably 95/5 to 30/70 (for example, 95/5) ~ 35/65), especially 93/7 to 40/60 (eg 90/10 to 45/55), usually 99/1 to 50/50 (eg 95/5 to 60/40). , Preferably about 90/10 to 70/30).

  In the polyester resin, a dicarboxylic acid component and a diol component may be combined with a trifunctional or higher functional component as long as desired characteristics are obtained. Examples of such tri- or higher functional components include polycarboxylic acid components having three or more carboxyl groups (for example, aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid, and ester-forming derivatives thereof). Polyol components having 3 or more hydroxyl groups [e.g., alkane polyol (e.g., glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, etc.), etc.] and the like.

  In addition, when using a trifunctional or higher component, the proportion of the trifunctional or higher component is 20 mol% or less with respect to the whole monomer (that is, the total amount of the diol component, the dicarboxylic acid component and the trifunctional or higher component), Preferably it may be 10 mol% or less, more preferably 5 mol% or less.

  The polyester resin may have a linear structure or a branched structure. The polyester resin may be crystalline or amorphous (non-crystalline).

  The molecular weight of the polyester resin depends on the type of constituent monomer (dicarboxylic acid component, diol component), but is preferably relatively small when used for toners, for example, a number average molecular weight of 30000 or less ( For example, it can be selected from a range of about 500 to 25000), 20000 or less (for example, 800 to 15000), preferably 10,000 or less (for example, 1000 to 9000), more preferably 8000 or less (for example, 1200 to 7000), particularly 6000. (For example, 1500-5500) may be sufficient, and 5000 or less (for example, 1000-5000, preferably 2000-5000, more preferably 2500-4500) may be used.

  The polyester resin only needs to contain at least a low molecular weight (relatively low molecular weight) polyester resin, and a low molecular weight polyester resin and a high molecular weight (relatively high molecular weight) polyester resin may be appropriately combined. . In such a case, a polyester resin having a low molecular weight (for example, a number average molecular weight of 10,000 or less) and a polyester having a high molecular weight [for example, a number average molecular weight exceeding 10,000 (for example, a number average molecular weight of about 12,000 to 30000)] within the above molecular weight range. A resin may be combined, and a polyester resin having the above molecular weight range may be combined with a polyester resin having a high molecular weight [for example, a number average molecular weight exceeding 30000 (for example, a number average molecular weight of about 32000 to 50000)]. The number average molecular weight may be a value measured by GPC (gel permeation chromatography) in terms of polystyrene, for example.

  Polyester resins are usually solid at room temperature, but for toners and the like, they melt sharply (rapidly) under heating to lower the viscosity from the viewpoint of toner fixing properties and energy saving. Is preferred.

  The melting temperature (Tm) of the polyester resin can be selected from the range of about 40 ° C. to 200 ° C., for example, 50 ° C. to 170 ° C., preferably 50 ° C. to 130 ° C., more preferably 60 ° C. to 100 ° C. (eg 70 (Degree C-90 degree C) grade may be sufficient. Melting temperature can be measured by the method of the Example mentioned later.

  Moreover, the viscosity (melt viscosity) of the polyester resin at 180 ° C. can be selected from a range of, for example, 10000 mPa · s or less (eg, 10 to 8000 mPa · s), and is 7000 mPa · s or less (eg, 50 to 6000 mPa · s) Preferably it is 5000 mPa · s or less (for example, 100 to 4000 mPa · s), more preferably 3000 mPa · s or less (for example, 150 to 2500 mPa · s), particularly 2000 mPa · s or less (for example, 200 to 1800 mPa · s). It may be 1500 mPa · s or less (for example, 100 to 1200 mPa · s, preferably 150 to 1000 mPa · s, more preferably 200 to 800 mPa · s).

  The glass transition temperature of the polyester resin is, for example, 20 ° C or higher (for example, 25 to 150 ° C), preferably 30 ° C or higher (for example, 35 to 120 ° C), and more preferably 40 ° C or higher (for example, 40 to 100 ° C). In particular, it may be 45 ° C. or higher (for example, 45 to 80 ° C.), usually 30 to 80 ° C. (for example, 35 to 75 ° C., preferably 40 to 70 ° C., more preferably 45 to 60 ° C.) Also good. In the present invention, since the glass transition temperature can be improved by adding a heat resistance improver, even a polyester resin having a relatively low glass transition temperature can be used. The glass transition temperature may be a glass transition temperature measured by differential scanning calorimetry (measurement).

  Whether the resin is melted rapidly or rapidly depends on the difference between the melting temperature (Tm) and the glass transition temperature (Tg), Tm−Tg (° C.), and the melting temperature (Tm) with respect to the glass transition temperature (Tg). The ratio of Tg / Tm (° C./° C.) is often used for evaluation. The smaller Tm−Tg (° C.) and the larger Tg / Tm (° C./° C.), the sharper the resin is melted. The The Tm-Tg (° C.) of the polyester resin may be, for example, about 20 to 80 ° C., preferably 30 to 70 ° C., more preferably about 35 to 50 ° C. (for example, 40 to 45 ° C.), and Tg / Tm. (C / C) is, for example, 0.2 to 0.7 (C / C), preferably 0.3 to 0.65 (C / C), and more preferably 0.4 to 0.6 (C / C). (Degree C) (for example, 0.5-0.55 (degree C / degree C)) may be sufficient.

  The polyester resin can be produced by a conventional method. For example, a polyester resin can be produced by reacting (polymerizing or condensing) a dicarboxylic acid component and a diol component. Examples of the polymerization method (manufacturing method) include conventional methods such as a melt polymerization method (a method in which a dicarboxylic acid component and a diol component are polymerized under melt mixing), a solution polymerization method, and an interfacial polymerization method. A preferred method is a melt polymerization method.

  In the reaction, the amount of dicarboxylic acid component or diol component used (ratio of use) can be selected from the same range as described above. However, when the molecular weight is reduced as described above, for example, as necessary (for example, In the case of lowering the molecular weight of the polyester resin), one component (for example, dicarboxylic acid component) may be used in an excessive amount for reaction. In such a case, the use ratio (preparation ratio) of one component (for example, dicarboxylic acid component) is, for example, 1.01 mol or more (for example, 1) with respect to 1 mol of the other component (for example, diol component). 0.02 to 5 mol), preferably 1.03 mol or more (for example, 1.04 to 3 mol), more preferably 1.05 mol or more (for example, 1.07 to 2.5 mol), particularly 1.09. It may be about mol or more (for example, 1.1 to 2 mol).

  The reaction may be performed in the presence of a catalyst. As a catalyst, the various catalyst utilized for manufacture of a polyester resin can be used. Examples of the catalyst include alkali metals (sodium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (manganese, zinc, cadmium, lead, cobalt, etc.), periodic table group 13 metals (aluminum, etc.) ), Periodic table group 14 metals (germanium, tin, etc.), periodic table group 15 metals (phosphorus, antimony, etc.) and the like are used. Examples of the compound include alkoxide, organic acid salt (acetate, propionate, 2-ethylhexanoic acid, etc.), inorganic acid salt (borate, carbonate, etc.), metal oxide and the like. These catalysts can be used alone or in combination of two or more. The amount of the catalyst used is, for example, 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, more preferably 0.01 to 100 parts by weight with respect to the total amount of the dicarboxylic acid component and the diol component. It may be about 1 part by weight.

  Moreover, you may perform reaction in presence of additives, such as stabilizers (an antioxidant, a heat stabilizer, etc.) as needed. The reaction may be performed in an inert gas (nitrogen, helium, etc.) atmosphere. The reaction can also be performed under reduced pressure (for example, about 100 to 20000 Pa, preferably about 200 to 15000 Pa). The reaction temperature can be selected according to the polymerization method. For example, the reaction temperature in the melt polymerization method may be 150 to 300 ° C, preferably 160 to 280 ° C, and more preferably about 180 to 270 ° C.

  The use ratio of the heat resistance improver (fluorene compound) can be selected, for example, 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 polyester resin. 3 to 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, it may be about 0.7 to 30 parts by weight, and more preferably about 1 to 20 parts by weight.

  Since the heat resistance improver of the present invention can obtain the effect of improving the heat resistance efficiently even in a small amount, for example, the use ratio of the heat resistance improver is 10 parts by weight or less (for example, 100 parts by weight of the polyester resin) 0.1-9 parts by weight), preferably 8 parts by weight or less (eg, 0.2-7 parts by weight), more preferably 6 parts by weight or less (eg, 0.3-5.5 parts by weight), especially It may be 5 parts by weight or less (for example, 0.5 to 3 parts by weight).

  In addition, the heat resistance improver of the present invention is excellent in affinity for the polyester resin, and even when added in a relatively large proportion, the resin properties can often be maintained or improved at a high level. 10 parts by weight or more (for example, 10 to 80 parts by weight), preferably 12 parts by weight or more (for example, 12 to 50 parts by weight), more preferably 15 parts by weight or more (for example, 100 parts by weight of polyester resin) 15 to 30 parts by weight).

  Thus, a polyester resin (resin composition) with improved (or improved) heat resistance is obtained by the heat resistance improver of the present invention. The present invention also includes such a resin composition, that is, a resin composition containing a polyester resin and a heat resistance improver. In addition, in such a resin composition, the kind of the polyester resin and the heat resistance improver, and the mixing ratio (use ratio) are as described above. In the resin composition, the molecular weight (number average molecular weight) and the melting temperature (Tm) can also be selected from the same ranges as described above.

  The glass transition temperature of the resin composition is higher than that of a polyester resin (or a polyester resin not containing a fluorene compound). Specifically, when the glass transition temperature of the polyester resin is A (° C.), the glass transition temperature of the resin composition (resin composition comprising a polyester resin and a fluorene compound) exceeds A (° C.), for example, A + 0. 1 (° C.) to A + 30 (° C.), preferably A + 0.3 (° C.) to A + 25 (° C.), more preferably about A + 0.5 (° C.) to A + 20 (° C.), A + 1 (° C.) or more [For example, A + 1.5 (° C) to A + 25 (° C), preferably A + 2 (° C) to A + 20 (° C), and more preferably A + 3 (° C) to A + 15 (° C)].

  Further, by adding the heat resistance improver of the present invention, Tm-Tg (° C.) decreases and / or Tg / Tm (° C./° C.) increases, and the polyester resin can be melted sharply. When the value of Tm-Tg of the polyester resin is B ° C, the Tm-Tg (° C) of the polyester resin composition after the addition is, for example, B-10 to B-0.1 ° C, preferably B-7 to B -0.5 ° C, more preferably about B-5 to B-1 ° C (for example, B-4 to B-2 ° C). When Tg / Tm is C (° C / ° C), The Tg / Tm (° C./° C.) of the subsequent polyester resin composition is, for example, C + 0.01 to C + 0.3 (° C./° C.), preferably C + 0.01 to C + 0.2 (° C./° C.) (eg, C + 0 0.02 to C + 0.15 (° C./° C.)), more preferably about C + 0.05 to C + 0.1 (° C./° C.).

  Further, 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. In particular, when used for toner, it may contain a colorant, a dispersant, a charge control agent, and the like. These additives may be used alone or in combination of two or more.

  The resin composition can be obtained by mixing a polyester resin and a fluorene compound (heat resistance improver) [and other components (additives and the like 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.

  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.

(Molecular weight)
The weight average molecular weight Mw and the number average molecular weight Mn for calculating the polydispersity were measured by gel permeation chromatography (GPC). A HLC-8320GPC model manufactured by Tosoh Corporation is used as an apparatus, tetrahydrofuran (reagent special grade) is used as an eluent, a differential refractometer is used as a detector, a measurement flow rate is 1.00 mL / min, and a molecular weight standard For this, polystyrene manufactured by Tosoh Corporation was used.

(Glass transition temperature (Tg))
The glass transition temperature was measured with a differential scanning calorimeter (DSC). For DSC, an EXTAR DSC6220 manufactured by Seiko Instruments Inc. was used as an apparatus, a sample was put in an aluminum pan, and the measurement temperature range was 30 to 200 ° C.

(Melt viscosity)
The melt viscosity was measured using a melt viscometer (CAP2000 + manufactured by BROOKFIELD). The measurement conditions were 180 ° C. and 900 rpm, and the average value during three measurements was taken as the value.

(Melt flow rate (MFR))
A melt indexer (Toyo Seiki Seisakusho C-5059D2) was used, and the temperature was set at 100 ° C. and the load was 2.16 kgf in accordance with JIS K7210.

(Melting temperature (Tm))
The melting temperature (Tm) was measured by the same method as in the examples of JP-A-06-110250.

(Examples 1-9, Comparative Examples 1-7)
The table shows 2,2-di [4- (2-hydroxyethoxy) phenyl] propane (an adduct obtained by adding 2 mol of ethylene oxide to 1 mol of bisphenol A) in a 300 ml separable flask equipped with a stirrer. A fixed amount was added and heated and melted at 120 to 150 ° C., and then a catalyst (di (2-ethylhexanoic acid) tin) was further added at a rate shown in the table to dissolve it sufficiently. Further, after adding a predetermined amount of terephthalic acid as shown in the table, the temperature was increased and reduced, and the temperature was increased and reduced to 100 torr at 180 ° C. while confirming the distillation of water. Subsequently, the temperature was increased and the pressure was reduced, and the reaction was performed at 220 ° C. and 10 torr until the appearance changed from white to transparent (reaction time 4 to 5 hours).

  Then, after adding the predetermined amount shown in the table [Fluorene compound, bisphenol A (BisA) or BPA-2EO] shown in the table and confirming that it was uniformly mixed visually, the temperature was lowered to 150 ° C. A resin composition was obtained. The resin composition was discharged on release paper (Teflon (registered trademark) film) and pulverized with a mixer.

  Various properties of the obtained resin composition were measured. The results are shown in the table. In the table, various abbreviations are as follows.

BPA-2EO: 2,2-di [4- (2-hydroxyethoxy) phenyl] propane (manufactured by Nippon Emulsifier Co., Ltd., BA2 glycol)
BCF: 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd.)
BPEF: 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd.)
TA: terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
For comparison, the results of Comparative Examples 1 and 2 in which no additive is used and Comparative Examples 3 to 7 in which bisphenol A (BisA) or BPA-2EO is used in place of the fluorene compound are also shown in the table. In the table, “addition ratio” is a ratio with respect to the total amount of monomer and fluorene compound (that is, the total amount of BPA-2EO, TA, and fluorene compound).

  As described above, the smaller the value of Tm−Tg (° C.) and the larger the value of Tg / Tm (° C./° C.), the sharper the resin can be melted.

  As shown in Comparative Examples 1 and 2 and Examples in Table 1, when the additives of the examples are added to the polyester resin, the glass transition temperature (Tg) is improved and the value of Tg / Tm is also increased. And the resin is melted sharply. Moreover, in Examples 5-7, while the value of Tg / Tm increases and the value of Tm-Tg also decreases, it shows that addition of the additive of an Example melt | dissolves a resin sharply. Further, even when the additive is added, the melt viscosity does not increase, but rather is improved in Examples 6 and 7.

  On the other hand, in the comparative example, when the additive of the comparative example is added to the polyester resin, the glass transition temperature is decreased, the value of Tg / Tm is also decreased, and the value of Tm-Tg is increased as the addition amount is increased. That is, even when the additive of the comparative example is added, the heat resistance is not improved and the resin does not melt sharply.

  The additive of the present invention can be used as an additive for improving or increasing the heat resistance of the polyester resin. In addition, such an additive is very useful because it does not impair the various properties of the polyester resin. In particular, the additive of the present invention can improve the heat resistance without increasing the viscosity (while maintaining the viscosity of the polyester resin) and can melt the resin sharply, so it is suitable for the polyester resin for toner. Can be used.

Claims (13)

  A heat resistance improver composed of a compound having a 9,9-bisarylfluorene skeleton, which is an additive for improving the heat resistance of a polyester resin having a number average molecular weight of 10,000 or less. The heat resistance improver according to claim 1, wherein the compound having a 9,9-bisarylfluorene skeleton is 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. ] The heat resistance improver according to claim 1 or 2, wherein the compound having a 9,9-bisarylfluorene skeleton is 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).) 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 The heat resistance improver according to claim 2 or 3, wherein _2-4 alkylene group, n is 0 to 2, and p is 1 to 3.   Compounds having a 9,9-bisarylfluorene skeleton 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-hydroxyalkoxyphenyl) fluorene 5, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene, and 9,9-bis (hydroxyalkoxynaphthyl) fluorene. Agent.   The heat resistance improver according to any one of claims 1 to 5, wherein the polyester resin has a viscosity at 180 ° C of 5000 mPa · s or less and a glass transition temperature of 35 to 75 ° C.   The heat resistance improver according to any one of claims 1 to 6, wherein the polyester resin is a polyester resin having a number average molecular weight of 8000 or less, a viscosity at 180 ° C of 3000 mPa · s or less, and a glass transition temperature of 40 to 70 ° C.   A dicarboxylic acid component containing at least one selected from an alicyclic dicarboxylic acid component and an aromatic dicarboxylic acid component; and a diol component containing at least one selected from an alicyclic diol and an aromatic diol. The heat resistance improver according to any one of claims 1 to 7, which is a polyester resin having a polymerization component.   The heat resistance improver according to any one of claims 1 to 8, which improves the glass transition temperature of the polyester resin.   A resin composition comprising a polyester resin having a number average molecular weight of 10,000 or less and the heat resistance improver according to claim 1.   The resin composition according to claim 10, wherein the ratio of the heat resistance improver is 0.5 to 50 parts by weight with respect to 100 parts by weight of the polyester resin.   The resin composition according to claim 10 or 11, which is a resin composition for toner.   A method for improving the heat resistance of a polyester resin having a number average molecular weight of 10,000 or less by adding the heat resistance improver according to claim 1 to a polyester resin having a number average molecular weight of 10,000 or less.