JP2017115055A - Phenoxy resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenoxy resin having excellent heat resistance and excellent solubility in a general-purpose organic solvent.SOLUTION: The present invention provides a phenoxy resin comprising structural units represented by formula (1) and formula (2) [R-Rindependently represent H, a C1-10 alkyl group, a C3-10 cycloalkyl group, a C6-18 aryl group or a halogen atom, and * is a bond].SELECTED DRAWING: None

Description

  The present invention relates to a phenoxy resin.

  Phenoxy resin is generally excellent in transparency, flexibility, impact resistance, insulation, and mechanical properties. Therefore, for example, it is an important material as a thermoplastic resin or a curable resin used in combination with a curing agent. It is widely used as a material for parts constituting IT equipment such as semiconductors, liquid crystal displays, and electronic substrates.

  For example, Patent Documents 1 and 2 include reactions of dihydric phenols containing 9,9-bis (4-hydroxyphenyl) fluorene with epichlorohydrin, or diglycidyl ethers and dihydric phenols of the above dihydric phenols. Phenoxy resins produced by reaction with are described.

JP-A-11-269264 JP 11-302373 A

  With the recent evolution of IT equipment, demands for high performance such as miniaturization, weight reduction, and large capacity have become stricter year by year, and a phenoxy resin excellent in heat resistance is required as a material constituting these. Further, from the viewpoint of handleability when mixed with other materials, the phenoxy resin is required to have excellent solubility in a general-purpose organic solvent.

  However, in the conventional phenoxy resin, it is difficult to achieve both excellent heat resistance and excellent solubility in general-purpose organic solvents.

  This invention is made | formed in view of said situation, and it aims at providing the phenoxy resin which is excellent in heat resistance and excellent in the solubility to a general purpose organic solvent.

  As a result of intensive studies to achieve the above object, the present inventors have at least one selected from the group consisting of a structural unit represented by formula (1) and a structural unit represented by formula (2). The phenoxy resin has been found to be compatible with both high heat resistance and good solubility in general-purpose organic solvents, and has completed the present invention.

  That is, the present invention provides a phenoxy resin having at least one selected from the group consisting of a structural unit represented by formula (1) and a structural unit represented by formula (2).

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom, and * represents a bond.

  In the phenoxy resin, the total mass of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) may be 10% by mass or more based on the total mass of the phenoxy resin.

  The phenoxy resin may have at least one selected from the group consisting of a structural unit derived from the diol compound represented by formula (3) and a structural unit derived from the diol compound represented by formula (4). .

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ Is as defined above.

  The phenoxy resin may have at least one selected from the group consisting of a structural unit derived from the diepoxy compound represented by formula (5) and a structural unit derived from the diepoxy compound represented by formula (6). .

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ Is as defined above, and R represents a glycidyl group.

  The phenoxy resin may have a weight average molecular weight of 10,000 or more.

  The epoxy equivalent of the phenoxy resin may be 5000 g / eq or more.

One embodiment of the present invention is a phenoxy in which R ¹ , R ² , R ^3, and R ⁴ are methyl groups and R ⁵ , R ⁶ , R ^7, and R ⁸ are hydrogen atoms in the above formula (1). Resin may be used.

One embodiment of the present invention is a phenoxy in which R ¹ , R ² , R ^3, and R ⁴ are methyl groups and R ⁵ , R ⁶ , R ^7, and R ⁸ are hydrogen atoms in the above formula (3). Resin may be used.

One embodiment of the present invention is a phenoxy in which R ¹ , R ² , R ^3, and R ⁴ are methyl groups and R ⁵ , R ⁶ , R ^7, and R ⁸ are hydrogen atoms in the above formula (5). Resin may be used.

  ADVANTAGE OF THE INVENTION According to this invention, the phenoxy resin which is excellent in heat resistance and excellent in the solubility to a general purpose organic solvent can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  The phenoxy resin of this embodiment has at least one selected from the group consisting of a structural unit represented by the formula (1) and a structural unit represented by the formula (2). Such a phenoxy resin has excellent heat resistance and excellent solubility in a general-purpose organic solvent. The phenoxy resin of this embodiment is excellent in handleability by having excellent solubility in a general-purpose organic solvent. Moreover, the phenoxy resin of this embodiment can meet the required specifications of materials for various applications by being able to achieve both excellent heat resistance and solubility in general-purpose organic solvents. The phenoxy resin of this embodiment contains a polyhydroxy polyether structure, for example.

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom, and * represents a bond.

  The present inventors presume the reason why the phenoxy resin of this embodiment is excellent in heat resistance and excellent in solubility in a general-purpose organic solvent as follows.

  As a technique for obtaining a resin having excellent heat resistance, a technique for introducing a rigid structure such as an aromatic ring to make the resin structure rigid can be considered. As for the phenoxy resin, it is considered that the heat resistance of the phenoxy resin is improved by introducing a rigid skeleton such as a fluorene skeleton or a hydroquinone skeleton.

  On the other hand, when a rigid structure such as an aromatic ring is introduced, a rigid and highly heat-resistant resin can be obtained, but compatibility with other materials and solubility in general-purpose organic solvents tend to decrease. .

On the other hand, the phenoxy resin of this embodiment has not only excellent heat resistance but also excellent solubility in general-purpose organic solvents by having a sulfone skeleton (—SO ₂ —) in addition to the aromatic ring. It is thought to have.

Examples of the alkyl group having 1 to 10 carbon atoms as R ^{1 to} R ¹⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a pentyl group. Hexyl group, heptyl group, octyl group, nonyl group and decyl group.

Examples of the cycloalkyl group having 3 to 10 carbon atoms as R ^{1 to} R ¹⁶ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentadienyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group. , Cyclodecyl group and dicyclopentadienyl group.

Examples of the aryl group having 6 to 18 carbon atoms as R ^{1 to} R ¹⁶ include a phenyl group, a naphthyl group, an antonyl group, a fluorenyl group, a biphenyl group, a benzyl group, a tolyl group, an o-xylyl group, and an m-xylyl group. And p-xylyl group.

Examples of the halogen atom as R ¹ to R ^16, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The phenoxy resin of the present embodiment is represented by R ¹ , R ² , R ^3, and R in the formula (1) from the viewpoint of easy availability and a high degree of compatibility between excellent heat resistance and solvent solubility. ^An embodiment in which ⁴ is a methyl group and R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms may be employed.

  In the phenoxy resin, the total mass of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) is 10% by mass based on the total mass of the phenoxy resin from the viewpoint of further improving heat resistance. The above may be sufficient, 15 mass% or more may be sufficient, and 20 mass% or more may be sufficient. The total mass of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) in the phenoxy resin is based on the total mass of the phenoxy resin from the viewpoint of further improving the solubility in a general-purpose organic solvent. 90 mass% or less may be sufficient, 80 mass% or less may be sufficient, and 70 mass% or less may be sufficient.

<Weight average molecular weight (Mw)>
From the viewpoint of further improving the heat resistance, the weight average molecular weight of the phenoxy resin may be, for example, 10,000 or more, 20000 or more, or 30000 or more. The weight average molecular weight of the phenoxy resin may be, for example, 200000 or less, 150,000 or less, or 100000 or less from the viewpoint of further improving the solubility in a general-purpose organic solvent. From these viewpoints, the weight average molecular weight of the phenoxy resin may be, for example, 10,000 to 200,000, 20,000 to 150,000, or 30,000 to 100,000.

  In the present specification, the weight average molecular weight is 0.03 for tetrahydrofuran (2,6-di-tert-butyl-4-methylphenol (dibutylhydroxytoluene) as a stabilizer) in gel permeation chromatography (GPC). It is a polystyrene equivalent value using a calibration curve with standard polystyrene measured using a developing solvent as a developing solvent.

<Epoxy equivalent>
The epoxy equivalent of the phenoxy resin is, for example, 5000 g / eq or more, 7500 g / eq or more, or 10000 g / eq or more from the viewpoint of having better heat resistance. The epoxy equivalent of the phenoxy resin may be 40000 g / eq or less, 30000 g / eq or less, or 20000 g / eq or less from the viewpoint of improving compatibility with other materials such as an epoxy resin. May be. The epoxy equivalent is measured according to JIS K7236.

<Manufacturing method>
There is no restriction | limiting in particular in the manufacturing method of the phenoxy resin of this embodiment. The phenoxy resin of this embodiment is, for example, a method of reacting at least one selected from the group consisting of a diol compound represented by the formula (3) and a diol compound represented by the formula (4) (hereinafter, “method” A ”), and a method of reacting at least one selected from the group consisting of the diepoxy compound represented by formula (5) and the diepoxy compound represented by formula (6) (hereinafter referred to as“ method B ”in some cases) ). That is, the phenoxy resin of this embodiment has at least one selected from the group consisting of a structural unit derived from the diol compound represented by formula (3) and a structural unit derived from the diol compound represented by formula (4). And may have at least one selected from the group consisting of a structural unit derived from the diepoxy compound represented by formula (5) and a structural unit derived from the diepoxy compound represented by formula (6). Good.

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ Is as defined above, and R represents a glycidyl group.

  Examples of the diol compound represented by the formula (3) include 4,4′-dihydroxydiphenylsulfone, 3,3′-dimethyl-4,4′-dihydroxyphenylsulfone, 3,3 ′, 5,5′-tetra. Methyl-4,4′-dihydroxydiphenylsulfone, 2,2 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylsulfone, and 3,3′-dichloro-4,4′-dihydroxydiphenylsulfone Can be mentioned.

  Examples of the diol compound represented by the formula (4) include 2,4′-dihydroxydiphenyl sulfone.

From the viewpoint of being able to achieve both high availability and excellent heat resistance and solvent solubility at a high level, in formula (3), R ¹ , R ² , R ³ and R ⁴ are methyl groups, and R ⁵ , R ⁶ , R ⁷ and R ⁸ may be a hydrogen atom.

  Examples of the diepoxy compound represented by the formula (5) include 4,4′-diglycidyloxydiphenylsulfone, 3,3′-dimethyl-4,4′-diglycidyloxydiphenylsulfone, 3,3 ′, 5, Examples include 5'-tetramethyl-4,4'-diglycidyloxydiphenylsulfone and 2,2 ', 5,5'-tetramethyl-4,4'-diglycidyloxydiphenylsulfone.

  Examples of the diepoxy compound represented by the formula (6) include 2,4′-diglycidyloxydiphenyl sulfone.

From the viewpoint of achieving both high availability and excellent heat resistance and solvent solubility, R ¹ , R ² , R ³ and R ⁴ are methyl groups in formula (5), and R ⁵ , R ⁶ , R ⁷ and R ⁸ may be a hydrogen atom.

  The method A and the method B will be described in more detail with specific examples.

[Method A]
Specific examples of the method of reacting at least one selected from the group consisting of the diol compound represented by the formula (3) and the diol compound represented by the formula (4) include the diol compound represented by the formula (3) and the formula (4). And a method of reacting an epoxy compound with a diol compound containing at least one selected from the group consisting of diol compounds.

(Diol compound)
In Method A, the diol compound may be an embodiment composed of at least one selected from the group consisting of a diol compound represented by the formula (3) and a diol compound represented by the formula (4). Other diol compounds May be included. The diol compound other than the diol compound represented by the formula (3) and the diol compound represented by the formula (4) is not particularly limited as long as it is a compound having two hydroxyl groups in one molecule. A, bisphenol F, bisphenol AF, bisphenol C, bisphenol Z, brominated bisphenol A, chlorinated bisphenol A, aromatic diols such as 9,9′-bis (4-hydroxyphenyl) fluorene; and ethylene glycol, propylene glycol And aliphatic ether diols such as diethylene glycol, polyethylene glycol, and polypropylene glycol. The said diol compound may be used individually by 1 type, and may be used in combination of 2 or more type.

(Epoxy compound)
In Method A, the epoxy compound may be, for example, a diepoxy compound or epichlorohydrin. From the viewpoint of easily obtaining a uniform and high molecular weight phenoxy resin efficiently, the epoxy compound is preferably a diepoxy compound. In the present specification, a diepoxy compound refers to a compound having two epoxy groups in one molecule.

  The diepoxy compound is not particularly limited as long as it is a compound having two epoxy groups in one molecule. The diepoxy compound may have, for example, a biphenyl skeleton or a fluorene skeleton. Examples of the diepoxy compound include a bisphenol A diepoxy compound, a bisphenol F diepoxy compound, a bisphenol AF diepoxy compound, 9,9-bis (4-glycidyloxyphenyl) fluorene, and a biphenyl diepoxy compound (for example, product name: YX4000, manufactured by Mitsubishi Chemical Corporation, product name: YL6121H, available as Mitsubishi Chemical Corporation), naphthalene diepoxy compound (for example, product name: HP-4032D, available as DIC Corporation), etc. Aromatic diepoxy compounds; and aliphatic ether diepoxy compounds (for example, product names: Denacol EX-211, EX-212, EX-252, EX-810, EX-811, EX-850, EX-821, EX- 830, manufactured by Nagase ChemteX Corporation And available in), and the like. The diepoxy compound is preferably a compound having two glycidyl groups in one molecule from the viewpoint of obtaining better heat resistance and obtaining a high molecular weight phenoxy resin. The said epoxy compound may be used individually by 1 type, and may be used in combination of 2 or more type.

[Method B]
Specific examples of the method of reacting at least one selected from the group consisting of the diepoxy compound represented by formula (5) and the diepoxy compound represented by formula (6) include a diol compound and the diepoxy compound represented by formula (5) And an epoxy compound containing at least one selected from the group consisting of diepoxy compounds represented by formula (6).

(Diol compound)
In Method B, the diol compound is not particularly limited as long as it is a compound having two hydroxyl groups in one molecule. From the viewpoint of easy reactivity with the epoxy compound, the viewpoint of increasing the molecular weight of the phenoxy resin, and the viewpoint of further improving the heat resistance of the phenoxy resin, the diol compound preferably has a phenolic hydroxyl group. Examples of the diol compound include bisphenol A, bisphenol F, bisphenol AF, and 9,9′-bis (4-hydroxyphenyl) fluorene. The said diol compound may be used individually by 1 type, and may be used in combination of 2 or more type.

(Epoxy compound)
In Method B, the epoxy compound may be an embodiment composed of at least one selected from the group consisting of the diepoxy compound represented by the formula (5) and the diepoxy compound represented by the formula (6). Other diepoxy compounds May be included. As a diepoxy compound other than the diepoxy compound represented by the formula (5) and the diepoxy compound represented by the formula (6), for example, a bisphenol A diepoxy compound, a bisphenol F diepoxy compound, a bisphenol AF diepoxy compound, 9,9- Bis (4-glycidyloxyphenyl) fluorene, biphenyl diepoxy compound (for example, product name: YX4000, manufactured by Mitsubishi Chemical Corporation, product name: YL6121H, available as Mitsubishi Chemical Corporation), naphthalene type diepoxy compound ( For example, aromatic diepoxy compounds such as product name: HP-4032D, available from DIC Corporation); and aliphatic ether diepoxy compounds (for example, product names: Denacol EX-211, EX-212, EX- 252, EX-810, EX-8 1, EX-850, EX-821, EX-830, available as Nagase Chemtex Co., Ltd.) and the like. The said epoxy compound may be used individually by 1 type, and may be used in combination of 2 or more type.

[catalyst]
In the above method A and method B, for example, a catalyst may be used to promote the reaction between the diol compound and the epoxy compound. The catalyst to be used is not particularly limited, but is preferably a compound having a catalytic ability to promote the etherification reaction between the hydroxyl group of the diol compound and the epoxy group of the epoxy compound.

  Examples of the catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; thirds such as triethylamine, benzyldimethylamine, and 1,8-diazabicyclo (5.4.0) undecene-1 (DBU). Quaternary amines; imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole; quaternary ammonium salts such as tetramethylammonium bromide and benzyltrimethylammonium bromide; phosphine compounds such as triphenylphosphine and tributylphosphine; and Examples thereof include phosphonium salts such as n-butyltriphenylphosphonium bromide. These catalysts may be used alone or in combination of two or more. Among these catalysts, an imidazole compound, a tertiary amine, and a quaternary ammonium salt are preferable from the viewpoint of easy handling, and an imidazole compound is more preferable.

  0.0001-100 mass parts may be sufficient as the quantity of the catalyst to be used with respect to 100 mass parts of total mass of an epoxy compound, and 0.001-10 mass parts may be sufficient as it.

[solvent]
In the above method A and method B, the reaction can be carried out in the absence or presence of a solvent. From the viewpoint of allowing uniform reaction and easy production of a uniform phenoxy resin, it is preferable to use a solvent for the reaction.

  The solvent is not particularly limited as long as it does not inhibit the etherification reaction between the hydroxyl group of the diol compound and the epoxy group of the epoxy compound. Examples of the solvent include water; alcohols such as methanol and ethanol; ether compounds such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. Glycol ether compounds such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether; alkylene glycols such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, 3-methoxybutyl-1-acetate Monoalkyl ether acetate; aromatic hydrocarbon compounds such as toluene and xylene; ketone compounds such as acetone, 2-butanone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; Ethyl hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3-methoxypropionic acid And ester compounds such as methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate; and γ-butyrolactone. These solvents may be used alone or in combination of two or more.

  The mass of the solvent to be used is preferably 0.1 times or more, more preferably 0.5 times or more with respect to the total mass of the diol compound and the epoxy compound, from the viewpoint that the reaction easily proceeds uniformly. More preferred. The mass of the solvent to be used is preferably 20 times or less, more preferably 10 times or less, with respect to the total mass of the diol compound and the epoxy compound, from the viewpoint of a high reaction rate. From these viewpoints, it is preferably 0.1 to 20 times, and more preferably 0.5 to 10 times the total mass of the diol compound and the epoxy compound.

[Reaction temperature]
In Method A and Method B, the reaction temperature is not particularly limited and can be appropriately selected. The reaction temperature is preferably 50 ° C. or higher from the viewpoint of a high reaction rate. The temperature is more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher. The reaction temperature is preferably 300 ° C. or less, more preferably 250 ° C. or less, and still more preferably 200 ° C. or less from the viewpoint that side reactions hardly occur. From these viewpoints, the reaction temperature is preferably 50 to 300 ° C, more preferably 100 to 250 ° C, and still more preferably 120 to 200 ° C.

[Reaction time]
In the above method A and method B, the reaction time can be appropriately selected while confirming the molecular weight of the phenoxy resin and the viscosity of the reaction solution so that a phenoxy resin suitable for the purpose can be obtained. The reaction time may be, for example, 30 minutes to 36 hours, 1 to 24 hours, or 2 to 20 hours.

  The phenoxy resin of the present embodiment is considered to have excellent heat resistance and be soluble in a general solvent (general-purpose organic solvent) used for organic synthesis and polymer synthesis. Examples of such general-purpose organic solvents include water; alcohols such as methanol and ethanol; ether compounds such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, Glycol ether compounds such as diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol monobutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, 3-methoxybutyl-1-acetate and the like Renglycol monoalkyl ether acetate; aromatic hydrocarbon compounds such as toluene and xylene; ketone compounds such as acetone, 2-butanone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; And ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3- Examples thereof include ester compounds such as methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate. Here, acetone, 2-butanone, ethyl acetate, and toluene have good handleability and a relatively low boiling point, and in recent years, they are often used as a dilution solvent or the like when forming a film. Since the phenoxy resin of this embodiment is considered to exhibit particularly good solubility in acetone, 2-butanone, ethyl acetate and toluene, it is considered that the usable range is wide.

  The phenoxy resin of this embodiment is also considered to be excellent in transparency, flexibility, impact resistance, adhesion to various substrates, and mechanical properties.

  Therefore, the phenoxy resin of the present embodiment can be suitably used as a material in the electrical and electronic fields such as an electrical laminate and an insulating varnish. These materials may be in the form of molded bodies, adhesives and films, for example. The phenoxy resin of this embodiment can also be mixed with other compounds and used in the form of a resin composition, for example. The phenoxy resin of this embodiment can be used also as a binder component of an anisotropic conductive film, for example.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

<Synthesis of phenoxy resin>
(Example 1) Phenoxy resin (P-1)
To a 300 mL separable flask equipped with a reflux condenser, a thermometer and a stirrer, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylsulfone (Tokyo Chemical Industry Co., Ltd.) was used as a diol compound. 9.2 g as a diepoxy compound, 5.7 g of YX4000 (Mitsubishi Chemical Corporation, epoxy equivalent 185 g / eq), 9,9-bis (4-glycidyloxyphenyl) fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 7.8 g as a catalyst and 0.01 g of 2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as “2E4MZ”) as a solvent and γ-butyrolactone (Wako Pure Chemical Industries, Ltd.) 25.5 g) (hereinafter referred to as “GBL”), and stirred at 25 ° C. for 10 minutes. Thereafter, the obtained solution was heated to 160 ° C. and reacted for 20 hours to obtain a GBL solution of phenoxy resin (P-1).

  The PBL GBL solution was poured into water, and the precipitate was collected. This precipitate was pulverized and dried to obtain solid P-1. As a result of measurement by GPC, the weight average molecular weight of the obtained P-1 was 64000 in terms of standard polystyrene.

(Comparative Example 1) Phenoxy resin (P-2)
The diol compound was changed to 11.4 g of 2,2-bis (4-hydroxyphenyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the diepoxy compound was changed to 2,2-bis (4-glycidyloxyphenyl) propane ( Tokyo Chemical Industry Co., Ltd.) 17.0 g, except that 2E4MZ as a catalyst was changed to 0.02 g, and GBL as a solvent was changed to 19.0 g. A solid phenoxy resin (P-2) was obtained. As a result of measurement by GPC, the weight average molecular weight of the obtained P-2 was 45000 in terms of standard polyester.

(Comparative Example 2) Phenoxy resin (P-3)
Diol compound was changed to 7.5 g of 2,2-bis (4-hydroxyphenyl) propane (Tokyo Chemical Industry Co., Ltd.), YX4000 as diepoxy compound was changed to 6.2 g, 9,9-bis (4 -Glycidyloxyphenyl) fluorene was changed to 8.6 g, 2E4MZ as a catalyst was changed to 0.02 g, and GBL as a solvent was changed to 25.4 g. Thus, a solid phenoxy resin (P-3) was obtained. As a result of measurement by GPC, the weight average molecular weight of the obtained P-3 was 55000 in terms of standard polyester.

(Comparative Example 3) Phenoxy resin (P-4)
Diol compound was changed to 9.6 g of 9,9-bis (4-hydroxyphenyl) fluorene, YX4000 as diepoxy compound was changed to 5.4 g, 9,9-bis (4-glycidyloxyphenyl) fluorene was changed to 7 .4 g, respectively, except that 2E4MZ as a catalyst was changed to 0.02 g, and GBL as a solvent was changed to 25.0 g. -4) was obtained. As a result of measurement by GPC, the weight average molecular weight of the obtained P-4 was 60000 in terms of standard polyester.

<Evaluation of general-purpose organic solvent solubility>
The obtained phenoxy resin was dissolved in 2-butanone (hereinafter referred to as “MEK”) so as to have a solid content of 40% by mass, and the presence or absence of undissolved residue was visually observed. The case where there was no undissolved portion was evaluated as “good”, and the case where there was undissolved portion was evaluated as “bad”. The results are shown in Table 1.

<Tg measurement of phenoxy resin>
Tg (° C.) of the obtained phenoxy resin was measured using a differential scanning calorimetry (DSC) apparatus (manufactured by Rigaku Corporation, ThermoPlus, DSC8230).

<Measurement of elastic modulus of phenoxy resin>
The obtained phenoxy resin was dissolved in tetrahydrofuran (hereinafter referred to as “THF”) to a solid content of 30% by mass to prepare a THF solution of the phenoxy resin. The obtained phenoxy resin in THF was formed into a film having a thickness of 100 μm using an explosion-proof hot air dryer and a bar coater. About the obtained film-form phenoxy resin, using a dynamic viscoelasticity measuring apparatus (Rheogel-E4000, manufactured by UBM Co., Ltd.), at a temperature rising rate of 10 ° C./min and at a measurement temperature of 40 to 200 ° C., the storage elastic modulus (KPa) was measured. Of the measured storage elastic modulus, the value at 150 ° C. was read and used as the storage elastic modulus of the phenoxy resin. The results are shown in Table 1.

<General organic solvent solubility and heat resistance of synthesized phenoxy resin>
From the results in Table 1, it can be seen that the phenoxy resin (P-1) of the example exhibits good solubility in a general-purpose organic solvent. Moreover, Tg and the storage elastic modulus of the phenoxy resin (P-1) of an Example are 134 degreeC and 580 kPa, respectively, and a value higher than the phenoxy resin (P-2, P-3, and P-4) of a comparative example. It can be seen that From this, the phenoxy resin (P-1) of an Example is excellent in the solubility to a general purpose organic solvent, and heat resistance is compared with the phenoxy resin (P-2, P-3, and P-4) of a comparative example. I understand that it is expensive. P-2 shows good solubility in a general-purpose organic solvent, but the values of Tg and storage elastic modulus are small, and it can be seen that the heat resistance is low. Moreover, P-3 and P-4 did not melt | dissolve in a general purpose organic solvent. That is, according to the present invention, it was confirmed that a phenoxy resin having excellent heat resistance and excellent solubility in a general-purpose organic solvent can be provided.

Claims (9)

A phenoxy resin having at least one selected from the group consisting of a structural unit represented by formula (1) and a structural unit represented by formula (2).

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom, and * represents a bond. ]   The phenoxy resin according to claim 1, wherein the total mass of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) is 10% by mass or more based on the total mass of the phenoxy resin. . The phenoxy of Claim 1 or 2 which has at least 1 type selected from the group which consists of the structural unit derived from the diol compound shown by Formula (3), and the diol compound shown by Formula (4). resin.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom. ] The phenoxy of Claim 1 or 2 which has at least 1 type selected from the group which consists of the structural unit derived from the diepoxy compound shown by Formula (5), and the structural unit derived from the diepoxy compound shown by Formula (6). resin.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom, and R represents a glycidyl group. ]   The phenoxy resin according to any one of claims 1 to 4, wherein the weight average molecular weight is 10,000 or more.   The phenoxy resin according to claim 4, wherein the epoxy equivalent is 5000 g / eq or more. ^{3. The} formula (1), wherein R ¹ , R ² , R ³ and R ⁴ are methyl groups, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms. Phenoxy resin. The phenoxy according to claim 3, wherein, in the formula (3), R ¹ , R ² , R ³ and R ⁴ are methyl groups, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms. resin. The phenoxy according to claim 4, wherein R ¹ , R ² , R ³ and R ^{4 in the} formula (5) are methyl groups, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms. resin.