JP6470593B2 - Phenoxy resin having fluorene skeleton, method for producing the same, and molded article - Google Patents

Description

  The present invention relates to a novel phenoxy resin having a fluorene skeleton, a method for producing the same, and a molded body formed from the phenoxy resin.

  Phenoxy resin, also known as polyhydroxy resin, is excellent in transparency, flexibility, impact resistance, adhesion, mechanical properties, etc., so it is curable as a thermoplastic resin or in combination with a curing agent. It is an important material as a resin.

  On the other hand, in order to improve characteristics such as heat resistance, it is known that a rigid skeleton such as a benzene skeleton may be introduced, and an attempt to introduce a fluorene skeleton or a hydroquinone skeleton has also been made for phenoxy resins. Yes.

  For example, Japanese Patent Application Laid-Open No. 11-279260 (Patent Document 1) discloses a phenoxy resin having a diphenylmethane skeleton or a 9,9-bisphenylfluorene skeleton as a phenoxy resin constituting the epoxy resin composition.

  Japanese Patent Application Laid-Open No. 2008-255308 (Patent Document 2) discloses phenols composed of 9,9-bis (hydroxyphenyl) fluorenes and 9,9-bis (hydroxynaphthyl) fluorenes as polymerization components. A phenoxy resin is disclosed.

  In Patent Documents 1 and 2, as a method for producing a phenoxy resin, (i) a method by a direct reaction of a dihydric phenol and epichlorohydrin, (ii) a diglycidyl ether of a dihydric phenol and a dihydric phenol Addition polymerization methods are known. Also, in the examples of these documents, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, or 6,6 ′-(9-fluorenylidene) An example in which a dihydric phenol such as) -di (2-naphthol) is reacted with an epoxy resin such as a bisphenol A type epoxy resin is disclosed. Further, in Patent Documents 1 and 2, the fluorene skeleton is introduced into the phenoxy resin as a dihydric phenol because it is recognized that the synthesis is easy.

  However, when a phenol having a fluorene skeleton among dihydric phenols is used as the phenol, polymerization does not proceed easily, the molecular weight cannot be sufficiently increased, and a phenoxy resin having poor moldability may be obtained. In particular, such a tendency is remarkable in phenols having a 9,9-bis-fused polycyclic arylfluorene skeleton among phenols having a fluorene skeleton. That is, the phenoxy resin having a 9,9-bis-fused polycyclic arylfluorene skeleton has more excellent characteristics (for example, heat resistance, refractive index, etc.) than the phenoxy resin having a 9,9-bisphenylfluorene skeleton. However, the molecular weight cannot be increased further, and a practical resin cannot be obtained.

JP 11-279260 A (claims, paragraph [0014], examples) JP 2008-255308 A (claims, paragraph [0046], examples)

  Accordingly, an object of the present invention is to provide a method for efficiently producing a phenoxy resin having a 9,9-bis-fused polycyclic arylfluorene skeleton.

  Another object of the present invention is that even if it has a 9,9-bis-fused polycyclic aryl fluorene skeleton, it has a large molecular weight, film retention and mechanical properties (such as tensile strength and elastic modulus), heat resistance, The object is to provide a phenoxy resin excellent in practicality such as electrical insulation.

  Still another object of the present invention is to provide a self-supporting film of a phenoxy resin having a 9,9-bis-fused polycyclic arylfluorene skeleton.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that when a 9,9-bis-fused polycyclic aryl skeleton is used, not a dihydric phenol but a glycidyl etherified compound, When reacted with phenol, a relatively high molecular weight (or high degree of polymerization) phenoxy resin can be obtained efficiently. In particular, such a phenoxy resin alone can form a self-supporting film having high film retention. It has been found that the resin has sufficient moldability and has a high glass transition temperature and excellent heat resistance, thereby completing the present invention.

  That is, in the production method of the present invention, an epoxy compound (A) containing a compound represented by the following formula (A1) is reacted with a phenol compound (B) containing a compound represented by the following formula (B1). This is a method for producing a phenoxy resin.

(In the formula, ring Z represents a condensed polycyclic arene ring, R ¹ represents a substituent, R ² represents an alkylene group, R ³ and R ⁴ represent a substituent, k represents an integer of 0 to 4, m Is an integer of 0 or more, n is an integer of 0 to 3, and p is an integer of 0 or more)

(Wherein, ^{R 5} represents a hydrogen atom or a hydrocarbon group, ^{R 6} and ^{R 7} represents a substituent, q is an integer of 0 to 4, r is an integer of 0 to 5).

In the formula (A1), Z may particularly be a naphthalene ring. In formula (A1), R ¹ may be an alkyl group, k may be about 0 to 1, R ² may be a C _2-4 alkylene group, and m is 0 to 0. it may be about 10, n may be 0, R ⁴ may be an alkyl or aryl group, p is may be about 0-4.

  In particular, in the formula (A1), m may be 0, and the compound represented by the formula (A1) may be typically 9,9-bis (glycidyloxynaphthyl) fluorene. Good.

  The epoxy compound (A) may contain a compound represented by the formula (A1) in a proportion of 30 mol% or more (particularly 50 mol% or more).

In the formula (B1), R ⁵ and R ⁶ may be an alkyl group or an aryl group, q may be about 0 to 2, R ⁷ may be an alkyl group, and r 0 to 1 may be sufficient.

  The phenol compound (B) may further contain bis (hydroxyphenyl) alkanes.

  In this invention, the phenoxy resin (B) obtained by reaction of the epoxy compound (A) containing the compound represented by the said Formula (A1), and the phenol compound (B) containing the compound represented by the said Formula (B1) ( Alternatively, a phenoxy resin obtained by the above method is also included. The weight average molecular weight of such a phenoxy resin may be 15000 or more, for example. Moreover, the phenoxy resin has a high elastic modulus. For example, the temperature at which the storage elastic modulus measured by a dynamic viscoelasticity analysis (DMA) method becomes 10 MPa may be 95 ° C. or higher. Furthermore, the phenoxy resin is excellent in heat resistance, and the glass transition temperature by a differential scanning calorimeter (DSC) may be 100 ° C. or higher.

  The present invention also includes a molded body formed of the phenoxy resin. The phenoxy resin of the present invention (or the phenoxy resin obtained by the above method) can usually form a self-supporting film. Therefore, the present invention includes a phenoxy obtained by a reaction between an epoxy compound (A) containing a compound represented by the formula (A1) and a phenol compound (B) containing a compound represented by the formula (B1). A free-standing film made of resin is also included.

  In the method of the present invention, polymerization can proceed efficiently even if it has a 9,9-bis-fused polycyclic arylfluorene skeleton. Therefore, a phenoxy resin having a 9,9-bis fused polycyclic arylfluorene skeleton can be efficiently produced. In addition, the phenoxy resin of the present invention has sufficient moldability, such as having a relatively high molecular weight and being capable of forming a film, even if it has a 9,9-bis-fused polycyclic arylfluorene skeleton. ing. In particular, the phenoxy resin of the present invention is excellent in film formability or moldability so that a self-supporting film having high film retention can be formed alone. In addition, it has excellent characteristics such as high heat resistance, high elastic modulus, high strength, optical characteristics (high refractive index, etc.), electrical characteristics (electrical insulation, etc.). Thus, the phenoxy resin of the present invention is extremely practical and highly useful.

FIG. 1 is a graph showing measurement results of dynamic viscoelastic properties of the phenoxy resin obtained in Example 1. FIG. 2 is a graph showing measurement results of dynamic viscoelastic properties of the phenoxy resin obtained in Example 2. FIG. 3 is a graph showing measurement results of dynamic viscoelastic properties of the phenoxy resin obtained in Example 3.

<Method for producing phenoxy resin>
In the present invention, in producing a phenoxy resin by reacting an epoxy compound (A) with a phenol compound (B), a specific epoxy compound is used as the epoxy compound, and a specific bisphenol compound is used as the phenol compound. Is used.

[Epoxy compound (A)]
The epoxy compound (A) includes at least a compound represented by the following formula (A1).

(In the formula, ring Z represents a condensed polycyclic arene ring, R ¹ represents a substituent, R ² represents an alkylene group, R ³ represents a substituent, R ⁴ represents a substituent, and k represents 0 to 0. An integer of 4, m is an integer of 0 or more, n is an integer of 0 to 3, and p is an integer of 0 or more).

In the formula (A1), the condensed polycyclic arene ring represented by the ring Z is a condensed bicyclic arene (for example, C _8-20 condensed bicyclic hydrocarbon such as naphthalene, preferably C _10-16. Examples thereof include fused bicyclic to tetracyclic arene rings such as fused bicyclic arene rings and fused tricyclic arene rings (for example, anthracene and phenanthrene). Preferred examples of the condensed polycyclic arene ring include a naphthalene ring and an anthracene ring, and a naphthalene ring is particularly preferable. The two rings Z may be the same or different rings, and may usually be the same ring.

The substituent represented by the group R ¹ is not particularly limited, but is usually a non-reactive substituent such as a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [for example, In many cases, it may be an alkyl group, an aryl group (C _6-10 aryl group such as a phenyl group), and the like. In particular, it may be a cyano group or an alkyl group (particularly an alkyl group). Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . In addition, when k is plural (two or more), the groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number k is 0 to 2, preferably 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

Examples of the alkylene group represented by the group R ² include C _2-6 alkylene groups such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, tetramethylene group, preferably C _2-4 alkylene group. More preferably, a _C2-3 alkylene group is mentioned. When m 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 rings Z, the groups R ² may be the same or different, and may usually be the same.

The number (number of added moles) m of the oxyalkylene group (OR ² ) can be selected from the range of, for example, about 0 to 25 (for example, 0 to 20) according to the use and desired performance, and is usually 0 to 18 (for example, 0 to 15), preferably 0 to 12 (for example, 0 to 10), more preferably 0 to 8 (for example, 0 to 7). In particular, from the viewpoint of high heat resistance and the like, m may be 0 to 4, preferably 0 to 2, more preferably 0 to 1, particularly 0.

  Further, the total of the two m may be, for example, 0 to 30 (for example, 0 to 25), preferably 0 to 20 (for example, 0 to 18), more preferably 0 to 16 (for example, 0 to 14), In particular, it may be about 0-8.

  Various characteristics (refractive index, heat resistance, etc.) slightly change depending on the sum of the two m. Therefore, the sum of the two m values may be adjusted according to desired characteristics. For example, in the formula (A1), even if the total of two m is relatively small [for example, 0 to 6, preferably 0 to 5, more preferably 0 to 4, particularly 0 to 2 (for example, about 0)]. Good.

  In addition, the compound represented by the formula (A1) may be an assembly of compounds having the same value of m, or an assembly of compounds having different values of m. In the latter case, the value of m and the sum of the two m are average values (arithmetic average or arithmetic average).

Examples of R ³ include non-reactive substituents such as a hydrocarbon group (the hydrocarbon group exemplified above). Representative R ³ includes an alkyl group [for example, a group exemplified in the above R ¹ term such as a methyl group (eg, a C _1-4 alkyl group)].

The substitution number n of R ³ may be 0-3, but is preferably 0-1, particularly 0. When n is 2 or 3, the plurality of R ³ may be the same or different groups.

In addition, examples of the substituent R ⁴ include an alkyl group (eg, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, preferably a C _1-8 alkyl group, more preferably Is a C _1-6 alkyl group), a cycloalkyl group (a C _5-10 cycloalkyl group such as a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _5-6 cycloalkyl group). Hydrocarbons such as aryl groups (for example, C _6-14 aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, preferably C _6-10 aryl group, more preferably C _6-8 aryl group) group; an alkoxy group (methoxy group, an ethoxy group, a propoxy group, _{C 1-12} alkoxy group such as butoxy, preferably _{C 1-8} Al Alkoxy group, more preferably a _{C 1-6} alkoxy group), etc. cycloalkoxy _{(C 5-10} cycloalkoxy group), a group -OR, such as an aryloxy group _(such as _{C 6-10} aryloxy group) wherein , R represents a hydrocarbon group (such as the hydrocarbon group exemplified above)]; an alkylthio group (C _1-20 alkylthio group such as methylthio group, preferably C _1-8 alkylthio group, more preferably C _1-6 alkylthio group). A group such as a group -SR (wherein R is as defined above); an acyl group (a C _1-6 acyl group such as an acetyl group); an alkoxycarbonyl group (a C _1-4 alkoxy such as a methoxycarbonyl group). Carbonyl group etc.); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); nitro group; cyano group; carboxyl group; amino group; Carbamoyl group; substituted amino group (for example, dialkylamino group such as dimethylamino group); sulfonyl group; hydroxyl group; hydroxy (poly) alkoxy group (for example, hydroxy (poly) C _2-4 such as 2-hydroxyethoxy group) An alkoxy group; a mercapto group; a substituent in which these substituents are bonded to each other [for example, an alkoxyaryl group (for example, a C _1-4 alkoxy C _6-10 aryl group such as a methoxyphenyl group), an alkoxycarbonylaryl group ( For example, C _1-4 alkoxy-carbonyl C _6-10 aryl group such as methoxycarbonylphenyl group)] and the like.

Of these, typically the group R ⁴ is a non-reactive substituent such as a hydrocarbon group, —OR (wherein R is as defined above), —SR (wherein R ⁴ is as defined above). The same), an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a substituted amino group, and the like.

Preferred group R ⁴ 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. In particular, R ⁴ represents a hydrocarbon group (particularly an alkyl group) such as an alkyl group [C _1-4 alkyl group (particularly methyl group)] or an aryl group [eg C _6-10 aryl group (particularly phenyl group)]. Group). R ⁴ may be the same or different groups in the same or different rings Z.

In addition, the substitution number p of the group R ⁴ can be appropriately selected depending on the kind of the ring Z and the like, and may be, for example, about 0 to 4 (particularly 0 to 3), preferably 0 to 2, more preferably 0 to 0. It may be about 1 (particularly 0).

  In addition, although the substitution position with respect to the ring Z of an epoxy group (or epoxy group-containing group) is not particularly limited, in the condensed polycyclic arene ring Z, a hydrocarbon ring different from the hydrocarbon ring bonded to the 9-position of fluorene. It is often replaced with. For example, when the ring Z is a naphthalene ring, the substitution position of the epoxy group is often the 5th to 8th positions. (Especially the 2nd and 6th positions).

Typical examples of the compound represented by the formula (A1) include 9,9-bis (glycidyloxynaphthyl) fluorene [for example, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene, 9 , 9-bis (5-glycidyloxy-1-naphthyl) fluorene] in the formula (A1), wherein m is 0; 9,9-bis (glycidyloxyalkoxynaphthyl) fluorene {for example, 9,9 -Bis [6- (2-glycidyloxyethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-glycidyloxyethoxy) -1-naphthyl] fluorene, 9,9-bis [6- ( 3-glycidyloxypropoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2-glycidyloxypropoxy) -2-naphthyl] fur Oren, 9,9-bis [6- (4-glycidyloxy-butoxy) -2-naphthyl] fluorene such as 9,9-bis [(glycidyloxy _{C 2-4} alkoxy) naphthyl] fluorene}, 9,9-bis (Glycidyloxypolyalkoxynaphthyl) fluorene {eg 9,9-bis {6- [2- (2-glycidyloxyethoxy) ethoxy] -2-naphthyl} fluorene, 9,9-bis {5- [2- ( 9,9-bis [(2-glycidyloxyethoxy) ethoxy] -1-naphthyl} fluorene, 9,9-bis {6- [2- (3-glycidyloxypropoxy) ethoxy] -2-naphthyl} fluorene In the formula (A1) such as glycidyloxydi to tetra-C _2-4 alkoxy) naphthyl] fluorene etc., m is 1 or more (for example, Compounds such as 1 to 4, preferably 1 to 3, more preferably 1 to 2, especially 1) are included.

  As the compound represented by the formula (A1), a commercially available product may be used, and a conventional method {for example, a hydroxyl group-containing compound corresponding to the formula (A1) [for example, 9,9-bis (hydroxynaphthyl)] Fluorene, 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorene, etc.] and an epihalohydrin (for example, epichlorohydrin, etc.), etc.} may be used.

(Other epoxy compounds)
The epoxy compound (A) may be composed of only the compound represented by the formula (A1), and may further contain another epoxy compound (A2) as necessary.

  The epoxy compound (A2) is not particularly limited, and may be a monofunctional epoxy compound, but is preferably a bifunctional or higher functional epoxy compound from the viewpoint of improving the reactivity and the molecular weight of the phenoxy resin. Particular preference is given to functional epoxy compounds.

  Bifunctional epoxy compounds include glycidyl ester type compounds, glycidyl ether type compounds, and the like.

  Examples of the glycidyl ester type compounds include aromatic dicarboxylic acids (such as phthalic acid) or their hydrogenated products (such as tetrahydrophthalic acid and hexahydrophthalic acid) and epichlorohydrin, dimer acid glycidyl esters, and the like. Can be mentioned.

  The glycidyl ether type compounds include bisphenol type epoxy resins (bisphenol type epoxy resins or epoxy resins made from bisphenols), naphthalene type epoxy resins (epoxy resins made from naphthalene type epoxy resins or dihydroxynaphthalenes), alicyclic rings Diglycidyl ethers of group diols, diglycidyl ethers of diols having a condensed ring skeleton, diglycidyl ethers (fluorene-based epoxy resins) having a fluorene skeleton not belonging to the category of the formula (A1), and the like.

As the bisphenol-based epoxy resin, for example, bisphenols or their alkylene oxide ( _C2-4 alkylene oxide such as ethylene oxide and propylene oxide) adducts (for example, alkylene oxide has an average of 1 to 10 mol per mol of hydroxy group, preferably 1-6 moles, more preferably adducts added with about 1-4 moles) diglycidyl ether, and epoxy resins obtained by further reaction (addition polymerization) of these diglycidyl ethers. Examples of the bisphenols include bisphenols exemplified in the section of the phenol compound described below [for example, bis (hydroxyphenyl) alkanes such as bisphenol A].

As a naphthalene type epoxy resin, for example, naphthalenediol or its alkylene oxide ( _C2-4 alkylene oxide such as ethylene oxide and propylene oxide) adduct (for example, alkylene oxide has an average of 1 to 10 mol per mol of hydroxy group, preferably Is 1-6 mol, more preferably an adduct added by about 1-4 mol) diglycidyl ether (for example, 1,5-di (glycidyloxy) naphthalene, 1,6-di (glycidyloxy) naphthalene, 2, Di (glycidyloxy) naphthalenes such as 6-di (glycidyloxy) naphthalene, 2,7-di (glycidyloxy) naphthalene, 2,7-di (2-methyl-2,3-epoxypropoxy) naphthalene; 2′-diglycidyloxybinaphthalene, bis (2-glycol Such as diglycidyl ether of bis-naphthols, such as bis (glycidyloxy naphthyl) C _1-6 alkane such as Gilles oxy naphthyl) methane and the like.

  Examples of diglycidyl ethers of alicyclic diols include 1,4-cyclohexanedimethanol diglycidyl ether.

  Examples of diglycidyl ethers of diols having a condensed ring skeleton include 9-phenyl-2,7-diglycidyloxy-1,3,4,5,6,8-hexamethylxanthene.

Examples of the fluorene-based epoxy resin include compounds in which the ring Z is a benzene ring in the formula (A1), such as 9,9-bis (glycidyloxyphenyl) fluorene [for example, 9,9-bis (4-glycidyl). Oxyphenyl) fluorene], 9,9-bis (alkyl-glycidyloxyphenyl) fluorene [e.g., 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, 9,9-bis (4-glycidyloxy) 9,9-bis (mono- or di-C _1-4 alkyl-glycidyloxyphenyl) fluorene] such as 3,5-dimethylphenyl) fluorene, 9,9-bis (aryl-glycidyloxyphenyl) fluorene [eg 9 9, 9-bis (4-glycidyloxy-3-phenylphenyl) fluorene , 9-bis (mono or di-C _6-10 aryl-glycidyloxyphenyl) fluorene], 9,9-bis (glycidyloxyalkoxyphenyl) fluorene [eg, 9,9-bis (4- (2-glycidyloxyethoxy) ) Phenyl) fluorene, etc.].

  These epoxy compounds (A2) may be used alone or in combination of two or more.

  When combining an epoxy compound (A1) and an epoxy compound (A2) (especially a bifunctional epoxy compound), these ratios are about the former / the latter (molar ratio) = about 99.9 / 0.1 / 1/99. Can be selected from a range, for example 99.5 / 0.5 to 10/90 (eg 99/1 to 30/70), preferably 99/1 to 40/60 (eg 98/2 to 50/50), Preferably, it may be about 95/5 to 60/40 (particularly 90/10 to 70/30).

  The ratio of the epoxy compound (A1) to the entire epoxy compound (A) can be selected from a range of about 10 mol% or more (for example, 20 mol% or more), for example, 30 mol% or more (for example, 40 mol% or more), preferably May be 50 mol% or more (for example, 60 mol% or more), more preferably 70 mol% or more (particularly 80 mol% or more), or 90 mol% or more (for example, 95 mol% or more). In the present invention, even when the epoxy compound (A1) is contained in a relatively high proportion as described above, the polymerization can proceed efficiently.

[Phenol compound (B)]
The phenol compound (B) includes at least a compound represented by the following formula (B1).

(Wherein, ^{R 5} represents a hydrogen atom or a hydrocarbon group, ^{R 6} and ^{R 7} represents a substituent, q is an integer of 0 to 4, r is an integer of 0 to 5).

In the formula (B1), examples of the hydrocarbon group represented by the group R ⁵ include an alkyl group (eg, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group). ), A cycloalkyl group (such as a C _5-10 cycloalkyl group such as a cyclohexyl group), an aryl group (eg, a C _6-14 aryl group such as a phenyl group, tolyl group, xylyl group, naphthyl group, etc.) A hydrocarbon group etc. are mentioned.

Among these hydrocarbon groups, an alkyl group (particularly, a C _1-8 alkyl group), an aryl group can be used because the molecular weight and glass transition temperature of the phenoxy resin can be improved, and film retention (self-supporting) and heat resistance can be improved. Groups (especially phenyl groups) are preferred. Even when the hydrocarbon group is a C _1-4 alkyl group (particularly a C _1-2 alkyl group such as a methyl group), high heat resistance can be maintained.

  Although the bonding position (substitution position) of the hydroxyl group with respect to the benzene ring is not particularly limited, it is often the 3-5 position and is usually the 4 position.

Moreover, the group R ⁶ hydroxyl groups is another substituent group on the benzene ring substituted, it can be exemplified exemplified substituents as the substituent R ⁴ in the formula (A1). Among the substituents, the group R ⁶ includes an alkyl group (eg, a C _1-6 alkyl group such as a methyl group), a cycloalkyl group (eg, a C _5-8 cycloalkyl group such as a cyclohexyl group), An aryl group (eg, a C _6-10 aryl group such as a phenyl group), an aralkyl group (eg, a C _6-8 aryl-C _1-2 alkyl group), an alkoxy group (eg, a C _1-4 alkoxy group), a halogen Atoms are preferred.

The number of substitution q of the group R ⁶ can be selected from an integer of 0 to 4, and may be, for example, 0 to 3, preferably 0 to 2, and more preferably 0 to 1 (particularly 0).

Examples of the group R ⁷ that is a substituent of the benzene ring that is not substituted with a hydroxyl group include the substituents exemplified as the substituent R ^{1 in the} formula (A1). Of the above substituents, the group R ⁷ is preferably a cyano group or an alkyl group (particularly a C _1-6 alkyl group), and particularly preferably a C _1-4 alkyl group (particularly a methyl group).

Incidentally, the substitution number r of ^{R 7} radical may be selected from the integers from 0 to 5, for example 0-3, preferably 0-2, more preferably 0-1 may be (especially 0) about.

Typical examples of the compound represented by the formula (B1) include bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenolacetophenone), 1 , 1-bis (4-hydroxyphenyl) -1-phenylpropane, 1,1-bis (4-hydroxyphenyl) -1-phenylbutane, 1,1-bis (4-hydroxyphenyl) -1-phenylpentane, Bis (hydroxyphenyl) alkanes such as 1,1-bis (4-hydroxyphenyl) -1-phenylhexane; bis (hydroxyphenyl) diphenylmethanes such as bis (4-hydroxyphenyl) diphenylmethane (bisphenolbenzophenone) It is done. Of these compounds, bis (hydroxyphenyl) C _1-4 alkanes such as 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP) are preferred.

(Other phenolic compounds)
The phenol compound (B) may be composed of only the compound represented by the formula (B1), and may further contain another phenol compound (B2) as necessary.

  The phenol compound (B2) is not particularly limited and may be a compound having one phenolic hydroxyl group, but has two or more phenolic hydroxyl groups from the viewpoint of improving the reactivity and the molecular weight of the phenoxy resin. Compounds are preferred, and compounds having two phenolic hydroxyl groups are preferred. Such phenol compounds include dihydroxyarene, bisphenols and the like.

Examples of the dihydroxyarene include dihydroxy C _6-20 arenes (preferably dihydroxy C _6-10 arenes) such as dihydroxybenzene (hydroquinone, resorcinol, etc.) and dihydroxynaphthalene.

  Bisphenols (bisphenol compounds) include phenolic compounds having no fluorene skeleton (non-fluorene bisphenols), phenolic compounds having a fluorene skeleton (fluorene bisphenols), and the like.

Non-fluorene bisphenols include, for example, biphenols such as 4,4′-dihydroxybiphenyl; bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis ( 4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy) Phenyl) 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, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, bis (hydroxyphenyl) alkanes such as bis (4-hydroxyphenyl) diphenylmethane [eg bis (hydroxyphenyl) C _1-10 alkane]; Bis (hydroxybiphenylyl) alkanes such as 2-bis (4-hydroxy-3,3′-biphenylyl) propane; Bis such as 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Hydroxyphenyl) cycloalkanes; bis (hydroxyphenyl) ethers such as 4,4′-dihydroxydiphenyl ether; bis (hydroxyphenyl) sulfones such as 4,4′-dihydroxydiphenylsulfone; -Bis such as dihydroxydiphenyl sulfoxide Hydroxyphenyl) sulfoxides; bis (hydroxyphenyl) sulfides such as 4,4′-dihydroxydiphenylsulfide; bis (hydroxyphenyl-) such as 4,4 ′-(o, m, p-phenylenediisopropylidene) diphenol Alkyl) arenes and the like.

Examples of the fluorene-based bisphenols include 9,9-bis (hydroxyphenyl) fluorenes {for example, 9,9-bis (hydroxyphenyl) fluorene [for example, 9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis (alkyl-hydroxyphenyl) fluorene [eg 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene 9,9-bis (mono or diC _1-4 alkyl-hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxyphenyl) fluorene [eg, 9,9-bis (4-hydroxy-3- 9,9-bis such phenylphenyl) fluorene (mono- or _{di-C 6-10} aryl - hydro Phenyl) fluorene]], 9,9-bis (hydroxynaphthyl) fluorenes [eg, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9,9-bis (5-hydroxy-1-naphthyl) ) 9,9-bis (hydroxyaryl) fluorenes such as 9,9-bis (hydroxynaphthyl) fluorene].

  The phenol compound (B2) may be used alone or in combination of two or more.

Among these phenolic compounds (B2), phenolic compounds having no fluorene skeleton such as non-fluorene-based bisphenol compounds [more specifically, two phenolic hydroxyl groups are preferred because they have excellent reactivity and can improve the molecular weight of the phenoxy resin. A phenol compound having a group and no fluorene skeleton (non-fluorene compound)] is preferable, and bis (hydroxyphenyl) alkanes (particularly, bis (hydroxyphenyl) C _1-6 alkanes such as bisphenol A) are particularly preferable. .

  When combining the phenolic compound (B1) and the phenolic compound (B2) (especially bis (hydroxyphenyl) alkanes), the molar ratio of the two is about phenol (B1) / phenol (B2) = 99/1 to 1/99. For example, 95/5 to 5/95, preferably 90/10 to 10/90 (eg 70/30 to 30/70), more preferably 60/40 to 40/60 (especially 55 / 45 to 45/55).

  In the reaction, the ratio of the epoxy compound (A) to the phenol compound (B) is, for example, the former / the latter (molar ratio) = 2/1 to 0.5 / 1, preferably 1.5 / 1 to 0.7. / 1, more preferably about 1.2 / 1 to 0.8 / 1 (particularly 1.1 / 1 to 0.9 / 1).

  The reaction between the epoxy compound (A) and the phenol compound (B) may be performed in the presence of a catalyst (reaction catalyst). The catalyst is not particularly limited, and examples thereof include hydroxides (eg, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide), amines [eg, Aliphatic amines (e.g., triethylamine, tri-n-propylamine, tri-n-butylamine, triisopropylamine, diisopropylethylamine, dicyclohexylethylamine, diethylcyclohexylamine, tribenzylamine, N, N, N ', N'- Tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropanediamine, 1-methylpiperidine, 1-ethylpiperidine, 1,2,2 ′, 6,6′-pentamethylpiperidine, 1-methylpyrrolidine, 1-ethylpyrrolidine, 4-methylmorpholine, 4 Aliphatic tertiary amines such as ethylmorpholine and 2,6-dimethylpiperazine), aromatic amines (eg, aromatic tertiary amines such as N, N-dimethylaniline and N, N-diethylaniline), complex Cyclic amines [pyridine, lutidine, collidine, 4- (dimethylamino) pyridine, 4-pyrrolidinopyridine, imidazole compounds (imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, etc.), 1,5- Diazabicyclo [4.3.0] nonene, 1,8-diazabicyclo [5.4.0] undecene etc.)], quaternary ammonium salts (eg tetramethylammonium bromide, benzyltrimethylammonium bromide etc.), phosphines (For example, triphenylphosphine, tributylphosphine Etc.), phosphonium salts (e.g., n- butyl triphenyl phosphonium bromide), and the like. These catalysts may be used alone or in combination of two or more.

  Although the ratio of a catalyst is based also on the kind of catalyst, it is 0.001-30 weight part with respect to 100 weight part of total amounts of an epoxy compound (A) and a phenolic compound (B), for example, Preferably 0.005- It may be about 10 parts by weight, more preferably about 0.01 to 5 parts by weight (for example, 0.02 to 3 parts by weight), or 1 part by weight or less [for example, 0.001 to 0.9 parts by weight, preferably 0.003-0.5 part by weight, more preferably about 0.005-0.3 part by weight (particularly 0.01-0.1 part by weight)].

The reaction may be performed in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, hydrocarbons (for example, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane; aromatic hydrocarbons such as toluene and xylene) ), Alcohols (eg, alkanols such as methanol, ethanol, propanol, butanol), ethers (eg, dialkyl ethers such as diethyl ether; 1,3-dimethoxypropane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether) (Poly) alkylene glycol dialkyl ethers such as: cyclic ethers such as tetrahydrofuran and 1,4-dioxane), ketones (eg, alkanones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone); Cycloalkanones such as non), esters (e.g., methyl acetate, ethyl acetate, etc.), amides (e.g., N- methylformamide, N, such as N- dimethylformamide N- mono- or _{di-C 1-4} alkyl N-methylacetamide, N-mono- or di-C _1-4 alkylacetamide such as N, N-dimethylacetamide; N-methylpyrrolidone, etc.), nitriles (for example, acetonitrile, propionitrile, etc.), sulfoxides ( Examples thereof include organic solvents such as dimethyl sulfoxide) and sulfones (for example, cyclic sulfones such as sulfolane). The solvent may be a mixed solvent of an organic solvent and an inorganic solvent (such as water). Moreover, you may use the amine as said catalyst as a solvent. These solvents may be used alone or in combination of two or more.

  The proportion of the solvent can be selected from a range of about 1 to 1000 parts by weight, for example, 5 to 800 parts by weight, preferably 10 to 500 parts by weight, with respect to 100 parts by weight of the total amount of the epoxy compound (A) and the phenol compound (B). Part, more preferably about 50 to 300 parts by weight (particularly 100 to 200 parts by weight). In addition, by adjusting the amount of the solvent, it is easy to efficiently adjust the viscosity in the reaction system and to efficiently suppress side reactions (for example, cyclization reaction).

  The reaction may be performed under heating. When performed under heating, the reaction temperature may be, for example, about 50 to 300 ° C, preferably 100 to 250 ° C, more preferably about 150 to 200 ° C. The reaction time may be, for example, 30 minutes to 24 hours, preferably 1 to 18 hours, more preferably about 2 to 12 hours. The reaction may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed under reduced pressure, normal pressure, or increased pressure (usually normal pressure).

  The product (phenoxy resin) may be separated and purified by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. .

<Phenoxy resin>
The phenoxy resin of the present invention is obtained by the reaction described above. Such a phenoxy resin is a resin (or polymer) having a skeleton (or a repeating unit or a structural unit) derived from the epoxy compound (A) and the phenol compound (B). [In other words, it is a polymer having at least a structural unit (or repeating unit) represented by the following formula (1)].

(In the formula, X represents a residue of the phenol compound (B), R ^3a represents a hydrogen atom or R ³ , and Z, R ¹ , R ² , R ³ , R ⁴ , k, m, and p are the same as above) .

  In the formula (1), X represents a residue of the phenol compound (B) (that is, a group obtained by removing two phenolic hydroxyl groups from the phenol compound (B)). For example, the phenol compound (B) is bisphenol acetophenone. In this case, X represents a group represented by the following formula (1,1,1-triphenylethane-4,4′-diyl group).

In Formula (1), R ^3a is a hydrogen atom or R ³ (or a group corresponding to R ³ ), particularly a hydrogen atom.

  The phenoxy resin of the present invention seems to be obtained through efficient polymerization and has a relatively high molecular weight despite having a 9,9-fused polycyclic aryl skeleton. The weight average molecular weight of such a phenoxy resin may be 15000 or more (for example, 15,000 to 300,000) in terms of polystyrene in gel permeation chromatography (GPC), for example, 20,000 to 300,000 (for example, 25,000 to 200,000), preferably Is 28000 to 100,000 (for example, 30000 to 50000), more preferably about 31000 to 40000 (particularly 32000 to 35000). If the molecular weight is too small, there is a possibility that the film retention is lowered.

  In addition, the terminal group of phenoxy resin is not specifically limited, Any of terminal groups derived from an epoxy compound (A), a terminal group derived from a phenol compound (B), etc. may be sufficient. The epoxy equivalent of the phenoxy resin of the present invention can be selected from the range of, for example, about 500 to 300,000 g / eq, for example, 1000 to 100,000 g / eq, preferably 5000 to 80000 g / eq (for example, 10,000 to 50000 g / eq), and more preferably. Is about 15000-40000 g / eq (particularly 20000-35000 g / eq).

  In addition, the phenoxy resin whose terminal (terminal group) is derived from the epoxy compound (A) (or epoxy group) is a point of storage stability, modified with thermosetting property or epoxy group (for example, reacted with acrylic acid or the like). For example, modification to introduce an acryloyl group), and dimensional stability.

  The glass transition temperature (Tg) of the phenoxy resin of the present invention is a glass transition temperature measured by a differential scanning calorimeter (DSC) and may be 50 ° C. or higher, for example, 50 to 200 ° C., preferably 60 to 180 ° C. Preferably it is about 80-150 degreeC, 100 degreeC or more may be sufficient especially, for example, about 110-180 degreeC (especially 120-150 degreeC) may be sufficient. The glass transition temperature by dynamic viscoelasticity analysis (DMA) method is, for example, 30 to 200 ° C, preferably 50 to 150 ° C (eg 90 to 130 ° C), more preferably 95 to 125 ° C (particularly 100 to 120 ° C). ) Degree. If the glass transition temperature is too low, the heat resistance may be reduced.

  The phenoxy resin of the present invention is excellent in electrical insulation and may have a dielectric constant (relative dielectric constant) (1 GHz) of 5 or less, for example, 1.5 to 5, preferably 2 to 4, more preferably 3. It is about -3.8 (especially 3.2-3.6). Further, the dielectric loss tangent (1 GHz) may be 0.05 or less, for example, 0.01 to 0.05, preferably 0.015 to 0.04, preferably 0.02 to 0.035 (particularly 0.002). 025 to 0.03).

  The phenoxy resin of the present invention is excellent in heat resistance and may have a linear expansion coefficient (α1 and α2) of 100 ppm or less, for example, 10 to 100 ppm, preferably 20 to 80 ppm, more preferably 30 to 70 ppm (particularly 40 ppm). ˜65 ppm).

  Although the phenoxy resin of the present invention has a 9,9-bis-fused polycyclic aryl skeleton, it is excellent in moldability and usually can form a self-supporting film (formation alone). Therefore, the present invention includes such a self-supporting film.

  In addition, the phenoxy resin (or free-standing film) of the present invention often has excellent mechanical properties (for example, high elastic modulus). For example, the phenoxy resin of the present invention may have a temperature at which the storage elastic modulus measured by the DMA method is 10 MPa, which may be 90 ° C. or higher (particularly 95 ° C. or higher), for example, 90 to 150 ° C., preferably 95 to 130. It may be a phenoxy resin at about 100 ° C., more preferably about 100 to 120 ° C. (especially 105 to 115 ° C.).

  The phenoxy resin (or self-supporting film) of the present invention may have a tensile strength in a tensile test of 50 MPa or more, for example, 50 to 300 MPa, preferably 60 to 200 MPa, more preferably 70 to 150 MPa (particularly 80 to 100 MPa). It may be a degree. The tensile modulus may be 2000 MPa or more, for example, 2000 to 10000 MPa, preferably 2500 to 5000 MPa, more preferably about 3000 to 4000 MPa (particularly 3200 to 3500 MPa).

  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, the various components (and their abbreviations) used are as follows.

(Bifunctional epoxy compound)
Epicoat 828: Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, “Epicoat 828”, epoxy equivalent 187 g / eq
BNFG: 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene [9,9-bis (6-hydroxy-2-naphthyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd.) and epichlorohydrin Synthesized by reaction]
(Phenol compound)
Bisphenol A (BisA): manufactured by Tokyo Chemical Industry Co., Ltd. Bisphenol acetophenone (BisAP): manufactured by Tokyo Chemical Industry Co., Ltd. Bishydroxytetraphenylmethane (BisTP): manufactured by Tokyo Chemical Industry Co., Ltd. BNF: 9,9-bis (6-hydroxy) -2-Naphthyl) fluorene, manufactured by Osaka Gas Chemical Co., Ltd. (catalyst)
2E4MZ: 2-ethyl-4-methylimidazole: manufactured by Tokyo Chemical Industry Co., Ltd. Further, in the examples, various measurements were performed as follows.

(Molecular weight)
Tetrahydrofuran was used as an eluent, and gel permeation chromatography (Tosoh Corp.) equipped with two continuous linear polystyrene gel columns (Tosoh TSKgel GMH _HR- L) at 30 ° C. (flow rate: 1.00 mL / min). ) “HLC-8120GPC”)), measured with polystyrene standards.

(Glass transition temperature (DSC))
Using a differential scanning calorimeter (“DSC 6220” manufactured by SII), measurement was performed at a rate of 10 ° C./min in a temperature range of 30 ° C. to 220 ° C.

(Glass transition temperature (DMA) and dynamic viscoelasticity)
Using a dynamic viscoelasticity measuring apparatus (Rhesol-G5000, manufactured by UBM Co., Ltd.), the measurement was performed at a frequency of 1 Hz and a temperature rising rate of 3 ° C./min. The glass transition temperature (Tg) was a tan δ peak. In the dynamic viscoelasticity measurement, the temperature at a storage elastic modulus of 10 MPa was read.

(Dielectric properties)
Using a PNA-L network analyzer (“N5230A” manufactured by Agilent Technologies) and a cavity resonator (“CP431” manufactured by Kanto Electronics Application Development Co., Ltd.), a cavity at a test temperature of 23 ° C., 50% RH, and a frequency of 1 GHz It was measured by a resonator perturbation method (according to ASTM D 2520).

(Linear expansion coefficient)
A thermomechanical analyzer (“TMA8310” manufactured by Rigaku Corporation) was used, and measurement was performed in a compressed mode (load 49 mN) in a nitrogen stream at room temperature to 300 ° C. and 5 ° C./min.

(Mechanical properties by tensile test)
A universal material testing machine (“5528 type” manufactured by Instron) was used, and in accordance with JIS K 7162, the test piece was IBA type and measured at 23 ° C. and 50% RH.

(Comparative Example 1)
23 parts by weight of Epicoat 828 (0.9 equivalents relative to the phenolic compound), 28 parts by weight of BNF, 29 parts by weight of cyclohexanone and 0.02 parts by weight of 2E4MZ were mixed and stirred at 165 ° C. for 8 hours. Reaction was performed to obtain a reaction product.

  The weight average molecular weight of the reaction product was 11,000. Moreover, the reaction liquid (solid content concentration of about 40%) containing the reaction product was applied on a cellulose triacetate film (“TAC100” manufactured by Fuji Film Co., Ltd.) and dried at 80 ° C. for 10 minutes. The dried film (thickness 20 μm) was peeled from the cellulose triacetate film, but it was fragile and divided into strips, clearly not forming a self-supporting film. In addition, since the self-supporting film could not be formed, the glass transition temperature (DMA) and the elastic modulus could not be measured.

(Comparative Example 2)
In Comparative Example 1, the reactants were prepared in the same manner as in Comparative Example 1, except that each component was changed to 21 parts by weight of BNFG, 7 parts by weight of BisA, 15 parts by weight of cyclohexanone, and 0.02 parts by weight of 2E4MZ. Obtained.

  The weight average molecular weight of the reactant was 25000, the glass transition temperature (DSC) of the reactant was 105 ° C, and the glass transition temperature (DMA) was 91 ° C. Moreover, when the reaction material was applied and dried in the same manner as in Comparative Example 1, it was confirmed that the dried film was cleanly peelable from the film and formed a self-supporting film. In the dynamic viscoelasticity measurement, the temperature at a storage elastic modulus of 10 MPa was 106 ° C.

Example 1
Comparative Example 1 and Comparative Example 1 except that each component was 30 parts by weight BNFG, 6 parts by weight BisA, 7 parts by weight BisAP, 356 parts by weight cyclohexanone, 0.09 parts by weight 2E4MZ. A reaction product was obtained in the same manner.

  The weight average molecular weight of the reactant was 32100, the glass transition temperature (DSC) of the reactant was 130 ° C, and the glass transition temperature (DMA) was 107 ° C. Moreover, when the reaction material was applied and dried in the same manner as in Comparative Example 1, it was confirmed that the dried film was cleanly peelable from the film and formed a self-supporting film. In the dynamic viscoelasticity measurement, the temperature at a storage elastic modulus of 10 MPa was 110 ° C.

(Example 2)
In Comparative Example 1, each component was changed to 30 parts by weight of BNFG, 3.4 parts by weight of BisA, 9.8 parts by weight of BisAP, 65 parts by weight of cyclohexanone, 0.02 parts by weight of 2E4MZ, A reaction product was obtained in the same manner as in Comparative Example 1.

  The weight average molecular weight of the reactant was 25100, the glass transition temperature (DSC) of the reactant was 106 ° C., and the glass transition temperature (DMA) was 82 ° C. Moreover, when the reaction material was applied and dried in the same manner as in Comparative Example 1, it was confirmed that the dried film was cleanly peelable from the film and formed a self-supporting film. In the dynamic viscoelasticity measurement, the temperature at a storage elastic modulus of 10 MPa was 101 ° C.

(Example 3)
Comparative Example 1 except that each component was 30 parts by weight BNFG, 8 parts by weight BisA, 4.2 parts by weight BisAP, 63 parts by weight cyclohexanone, 0.02 parts by weight 2E4MZ in Comparative Example 1. In the same manner as in 1, a reaction product was obtained.

  The weight average molecular weight of the reactant was 21300, the glass transition temperature (DSC) of the reactant was 102 ° C., and the glass transition temperature (DMA) was 79 ° C. Moreover, when the reaction material was applied and dried in the same manner as in Comparative Example 1, it was confirmed that the dried film was cleanly peelable from the film and formed a self-supporting film. In the dynamic viscoelasticity measurement, the temperature at a storage elastic modulus of 10 MPa was 95 ° C.

(Comparative Example 3)
Comparative Example 1 except that each component in Comparative Example 1 was 40 parts by weight BNFG, 8 parts by weight BisA, 11.3 parts by weight BisTP, 88 parts by weight cyclohexanone, 0.02 parts by weight 2E4MZ. In the same manner as in 1, a reaction product was obtained.

  The weight average molecular weight of the reaction product was 17,500. In addition, when the reaction product was applied and dried in the same manner as in Comparative Example 1, the dried film was peelable from the film and formed a self-supporting film, but the film was brittle, so the glass transition temperature ( DMA) and elastic modulus could not be measured.

  These results are shown in the table below.

  As is clear from the results in Table 1, the polymerization proceeded more by introducing the fluorene skeleton into the glycidyl ether side and causing the reaction. Furthermore, by using bisphenol acetophenone as the phenol compound, the polymerization further progressed, and the molecular weight and heat resistance were improved.

(Comparative Example 4)
Comparative Example 1 was the same as Comparative Example 1 except that each component was changed to 23 parts by weight of Epicoat 828, 14.5 parts by weight of BisA, 56.25 parts by weight of cyclohexanone, and 0.02 parts by weight of 2E4MZ. To obtain a reaction product. Moreover, when the reaction material was applied and dried in the same manner as in Comparative Example 1, the dried film was peelable from the film, and a self-supporting film was formed.

  Table 2 shows the results of evaluating the dielectric properties and mechanical properties of the tensile tests of the films obtained in Comparative Example 2, Example 1 and Comparative Example 4.

  As is clear from the results in Table 2, the film of Example 1 had a low dielectric constant and a large dielectric loss tangent, and thus showed excellent electrical insulation properties as the films of Comparative Examples 2 and 4. Moreover, the film of an Example had a smaller linear expansion coefficient than Comparative Examples 2 and 4, and showed the outstanding heat resistance. Further, the films of the examples had higher tensile strength and tensile elastic modulus than those of Comparative Examples 2 and 4, and exhibited excellent mechanical properties.

  In the present invention, despite having a 9,9-bis-fused polycyclic aryl skeleton, the phenoxy resin can be made high molecular weight efficiently. Such a phenoxy resin is excellent in moldability and can form a self-supporting film alone.

  Such a phenoxy resin of the present invention can be used as a thermoplastic resin, or can be used as a thermosetting resin or a thermosetting resin composition by combining with a curing agent.

  Such a resin composition (phenoxy resin composition) contains other components such as other phenoxy resins and additives [for example, stabilizers (antioxidants, ultraviolet absorbers, light-resistant stabilizers, heat stabilizers, etc. Flame retardants, flame retardant aids, plasticizers, impact modifiers, fillers (or reinforcing agents), dispersants, antistatic agents, antibacterial agents, lubricants, curing agents (eg amine-based curing agents, acids) Anhydride-based curing agent and the like] may be included. These other components may be used alone or in combination of two or more. In addition, the resin composition containing a hardening | curing agent can be used as a thermosetting resin composition (thermosetting phenoxy resin composition) as mentioned above.

  Such a phenoxy resin (or a composition thereof) or a molded body thereof according to the present invention has excellent characteristics such as high heat resistance, high refractive index, high strength and high elasticity, and high electrical insulation, Applications, for example, electrical laminates such as electrical laminates, insulating varnishes, etc., interlayer insulation films, insulation films such as anisotropic conductive films, transparent plastic substrates, optical materials such as optical waveguides, resin modification It can be suitably used as an agent, sealant, adhesive, film and the like.

Claims (11)

An epoxy compound (A) containing a compound represented by the following formula (A1) is reacted with a compound represented by the following formula (B1) and a phenol compound (B) containing bis (hydroxyphenyl) alkanes, A method for producing a phenoxy resin.

(In the formula, ring Z represents a naphthalene ring, R ¹ represents a cyano group, a halogen atom or a hydrocarbon group , R ² represents an alkylene group, R ³ represents a hydrocarbon group , R ⁴ represents a hydrocarbon group, group -OR (wherein R is a hydrocarbon group), group -SR (wherein R is a hydrocarbon group), acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, carboxyl group, amino group, carbamoyl A group, a substituted amino group, a hydroxyl group, a hydroxy (poly) alkoxy group, a mercapto group or a group in which these substituents are bonded to each other , k is an integer of 0 to 4, m is an integer of 0 or more, and n is 0 to 0. An integer of 3 and p is an integer of 0 or more)

(Wherein R ⁵ represents a hydrogen atom or a hydrocarbon group, R ⁶ represents a hydrocarbon group, a group —OR (wherein R is a hydrocarbon group), a group —SR (wherein R is a hydrocarbon group) , Acyl groups, alkoxycarbonyl groups, halogen atoms, nitro groups, cyano groups, carboxyl groups, amino groups, carbamoyl groups, substituted amino groups, hydroxyl groups, hydroxy (poly) alkoxy groups, mercapto groups, or these substituents bonded together indicates the group, ^{R 7} represents a cyano group, a halogen atom or a hydrocarbon group, q is an integer of 0 to 4, r is an integer of 0 to 5) In Formula (A1), R ¹ is an alkyl group, k is 0 to 1, R ² is a C _2-4 alkylene group, m is 0 to 10, n is 0, R ⁴ is an alkyl group or an aryl group, and p is 0. The method according to claim 1, which is ˜4.   The method according to claim 1 or 2, wherein m is 0 in formula (A1).   The method according to any one of claims 1 to 3, wherein the compound represented by the formula (A1) is 9,9-bis (glycidyloxynaphthyl) fluorene.   The method in any one of Claims 1-4 in which an epoxy compound (A) contains the compound represented by Formula (A1) in the ratio of 50 mol% or more. The method according to any one of claims 1 to 5, wherein in formula (B1), R ⁵ and R ⁶ are alkyl groups or aryl groups, q is 0 to 2, R ⁷ is an alkyl group, and r is 0 to 1.   An epoxy compound (A) comprising a compound represented by the formula (A1) according to claim 1, and a phenol compound comprising a compound represented by the formula (B1) according to claim 1 and a bis (hydroxyphenyl) alkane ( A phenoxy resin obtained by reaction with B) having a weight average molecular weight of 15000 or more.   The phenoxy resin according to claim 7, wherein the temperature at which the storage elastic modulus measured by dynamic viscoelasticity analysis is 10 MPa is 95 ° C or higher.   The phenoxy resin according to claim 7 or 8, wherein the glass transition temperature measured by a differential scanning calorimeter (DSC) is 100 ° C or higher.   The molded object formed with the phenoxy resin in any one of Claims 7-9.   The molded article according to claim 10, which is a self-supporting film.

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