JP2013238837A - Photosensitive dry film, and protective film and touch-panel insulating film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a photosensitive dry film comprising a resin composition layer capable of forming a coating film having excellent film hardness and high refractive index as well as exhibiting preferable etchant resistance and adhesion with a base material, an undercoat and the like; and a protective film or touch-panel insulating film using the same.SOLUTION: The resin composition layer of the photosensitive dry film is formed from a resin composition containing at least (A) a cardo resin or a compound represented by the general formula (I) specified in the figure, and (B) a silane compound having a urethane or amide backbone.

Description

  The present invention relates to a photosensitive dry film, and a protective film and an insulating film for a touch panel using the same.

  In recent years, as electronic devices have become more sophisticated, diversified, and smaller and lighter, a transparent touch panel is mounted on the front surface of a display element such as a liquid crystal, and characters, symbols, patterns, etc. displayed on the display element through this transparent touch panel There are an increasing number of devices that perform visual recognition and selection, and switch each function of the device by operating a transparent touch panel.

  The touch panel is, for example, a bank ATM, a vending machine, a personal digital assistant (PDA, UMPC), a copier, a facsimile, a portable game machine, a guide board, a car navigation, a multimedia station (a multifunction terminal installed in a convenience store) ), And rapidly becoming widespread as input devices such as mobile phones, railway vehicle monitoring devices, and answering devices such as quiz programs.

Existing touch panel systems can be classified into a resistive film system, an optical system, an electrostatic capacity system, an ultrasonic system, a pressure system, an electromagnetic wave induction system, an image recognition system, a vibration detection system, and the like.
Specific examples of a touch panel arranged on a display device such as a liquid crystal include a resistance film method and a capacitance method. The resistance film method is a method of detecting a pressed position by voltage, and a capacitance method. Detects the position by capturing the change in capacitance caused by pressing.
As for the electrostatic capacity method, Patent Documents 1 to 3 and the like are disclosed, and an insulating film and a protective film are provided in the laminated structure in order to prevent erroneous recognition of a contact position.

  The performance required for this insulating film and protective film is: adhesion to substrates, bases, and other layers (glass, inorganic materials, metal materials, transparent electrodes such as ITO, organic materials, etc.), etching of ITO and molybdenum There are demands for resistance to liquids (etchant resistance), heat resistance to a high-temperature firing process in the touch panel manufacturing process, and transmittance when a laminated substrate is used. Furthermore, when it is applied to the surface of another layer such as a transparent electrode pattern such as ITO, the refractive index difference becomes large, so that the ITO pattern becomes easy to see, and the visibility of the liquid crystal display screen is lowered.

In addition, an insulating film and a protective film used for touch panel applications are required to have a high surface hardness, and Patent Document 4 discloses a method of adding inorganic oxide fine particles to a resin component.
Further, Patent Document 5 discloses a method for improving adhesion to a substrate using an isocyanate group-containing silane compound.

However, these methods have problems such as yellowing due to a baking process at a high temperature, low transmittance, and insufficient stability.
That is, the conventional resin composition is excellent in substrate adhesion, film hardness, and etchant resistance, and cannot satisfy all of transmittance, refractive index, and stability.

JP 2008-65748 A JP 2009-15490 A JP 2010-44453 A JP 2000-281863 A JP 2011-102385 A

An object of the present invention is to provide a photosensitive dry film comprising a resin composition layer that has good etchant resistance and good adhesion to a substrate and a base, and is excellent in film hardness and capable of forming a coating film having a high refractive index. An object of the present invention is to provide a protective film or an insulating film for a touch panel using the same.
As used herein, the term “high refractive index” means having a refractive index of at least 1.55, preferably 1.57, more preferably 1.60 or higher.

The present invention is a photosensitive dry film comprising a film substrate and a resin composition layer provided on the film substrate, wherein the resin composition layer includes at least the following general formula (I): The photosensitive dry film formed from the resin composition containing the compound or cardo resin (A) shown by these, and the silane compound (B) which has urethane or an amide skeleton.
Formula (I)


[In General Formula (I), X ¹ and X ² are each independently a hydroxyl group, —O (AO) _p H group (wherein A represents an alkylene group having 2 to 3 carbon atoms, p is Represents an integer from 1 to 1000000), represents an amino group or an N-monosubstituted amino group,
R ^{1 to} R ⁴ each independently represent a hydrocarbon group that may be substituted, an alkoxy group that may be substituted, an N, N-disubstituted amino group, or a halogen atom;
m1 and m2 are each independently an integer of 0 to 3, m1 + m2 = 0 to 6;
n1 to n4 are each independently an integer of 0 to 4. However, m1 + n1 and m2 + n2 are integers of 0-5. ]

The present invention also relates to the above photosensitive dry film, wherein the silane compound (B) having a urethane or amide skeleton is a silane compound represented by the following general formula (1).
General formula (1):

[In General Formula (1), R ³¹ is an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon An aralkyl group having 7 to 30 carbon atoms, an alkaryl group having 7 to 30 carbon atoms,
X is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkoxylene group having 1 to 20 carbon atoms,
R ³² , R ³³ and R ³⁴ are each independently an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. A group, an aralkyl group having 7 to 30 carbon atoms, an alkaryl group having 7 to 30 carbon atoms, a siloxane group having a substituent, a halogen atom, a hydroxy group and hydrogen]

  In the present invention, the weight average molecular weight (Mw) of the silane compound (B) having a urethane or amide skeleton is 200 or more and less than 5000, and the silane compound (100% by weight in total solid content of the resin composition) The content of B) is from 5% by weight to less than 50% by weight.

  Moreover, this invention relates to the said photosensitive dry film characterized by the weight average molecular weights (Mw) of cardo resin (A) being 5000-50000.

  Moreover, this invention relates to the said photosensitive dry film characterized by including an oxide fine particle (C) further.

  The present invention also relates to the above photosensitive dry film, wherein the oxide fine particles (C) are oxide fine particles (C) of at least one element selected from zirconium and titanium.

  The present invention also relates to the above photosensitive dry film, wherein the content of the oxide fine particles (C) is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the solid content of the resin composition. .

  Moreover, this invention relates to the said photosensitive dry film characterized by the compound or cardo resin (A) shown by general formula (I) having an ethylenically unsaturated double bond.

  Moreover, this invention relates to the protective film formed using the said photosensitive dry film.

  Moreover, this invention relates to the insulating film for touchscreens formed using the said photosensitive dry film.

Hereinafter, the present invention will be described in detail.
In the present application, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, or “(meth) acrylate”, unless otherwise specified, It shall represent "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid" or "acrylate and / or methacrylate".

First, various components of the resin composition forming the resin composition layer in the photosensitive dry film of the present invention will be described.
<Compound represented by the following general formula (I) or cardo resin (A)>
[Compound represented by the following general formula (I)]
Formula (I)

[In General Formula (I), X ¹ and X ² are each independently a hydroxyl group, —O (AO) _p H group (wherein A represents an alkylene group having 2 to 3 carbon atoms, p is Represents an integer from 1 to 1000000), represents an amino group or an N-monosubstituted amino group,
R ^{1 to} R ⁴ each independently represent a hydrocarbon group that may be substituted, an alkoxy group that may be substituted, an N, N-disubstituted amino group, or a halogen atom;
m1 and m2 are each independently an integer of 0 to 3, m1 + m2 = 0 to 6;
n1 to n4 are each independently an integer of 0 to 4. However, m1 + n1 and m2 + n2 are integers of 0-5. ]

Examples of the N-monosubstituted amino group represented by X ¹ and X ² include an optionally substituted hydrocarbon group (an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, and 6 carbon atoms). N-monosubstituted amino group substituted with 10 to 10 aryl groups).

The substitution position of X ¹ and X ² is not particularly limited and may be any of the o-, m-, and p-positions with respect to fluorene, but the m- and / or p-position is preferred.

In the general formula (I), R ^{1 to} R ⁴ are preferably groups that are non-reactive with respect to reactions such as ester bond forming reaction, urethane bond forming reaction, amide bond forming reaction, and imide bond forming reaction. Examples thereof include a hydrocarbon group, an alkoxy group, an N, N-disubstituted amino group, and a halogen atom. Examples of the hydrocarbon include a linear or branched alkyl group having 1 to 6 carbon atoms (such as a methyl group), a linear or branched alkenyl group having 2 to 6 carbon atoms (such as a vinyl group), and a carbon number having 5 to 6 carbon atoms. A cycloalkyl group (such as a cyclohexyl group), a cycloalkenyl group having 5 to 6 carbon atoms (such as a cyclohexenyl group), an aryl group having 6 to 10 carbon atoms (such as a phenyl group), an aryl-straight chain having 6 to 10 carbon atoms, or Examples include branched alkyl groups having 1 to 4 carbon atoms (such as benzyl group). The alkoxy group includes a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group, the N, N-disubstituted amino group corresponds to the N-monosubstituted amino group, and An amino group (such as a dimethylamino group) disubstituted with a hydrocarbon group is included. Halogen atoms include fluorine, chlorine, bromine and iodine atoms.

  Examples of the substituent when the hydrocarbon group and the alkoxy group have a substituent include alkoxy groups such as methoxy group and phenoxy, aryl groups such as phenyl group, benzyl group and tolyl group, arylene groups such as phenylene group and naphthylene group, There are (meth) acryloyl group, (meth) acryloyloxy group, nitro group, amino group, hydroxy group and the like. Among these, a (meth) acryloyl group, a (meth) acryloyloxy group, and a hydroxy group are preferable. Further, there may be a plurality of substituents. Examples of the hydrocarbon group having a substituent include a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, Examples include 4-methoxybenzyl group, 4-nitrobenzyl group, 2- (meth) acryloyloxyethyl group, 2- (meth) acryloyloxypropyl group, and the like. Of these, a 2- (meth) acryloyloxyethyl group and a 2- (meth) acryloyloxypropyl group are preferable. Examples of the alkoxy group having a substituent include a 4-methoxyphenyl group, 2-methoxy-2-nitroethoxy group, 2-amino-2-phenoxyethoxy group, 2- (meth) acryloyloxyethoxy group, 3 -(Meth) acryloyloxy 2-hydroxypropoxy group etc. are mentioned. Of these, a 2- (meth) acryloyloxyethoxy group and a 3- (meth) acryloyloxy 2-hydroxypropoxy group are preferable.

n1 to n4 are each independently an integer of 0 to 4. n1 and n2 are preferably integers of 0 to 2, more preferably 0 or 1. n3 and n4 are preferably an integer of 0 to 3, more preferably an integer of 0 to 2, particularly 0 or 1.
In many cases, m1 and m2 are each an integer of 0 to 3, preferably an integer of 0 to 2 (especially 0 or 1), and usually 1 (m1 = m2 = 1) and 2 (m1 = m2 = 2), respectively. ) Or 3 (m1 = m2 = 3).

Incidentally, the substitution position of group X ¹ (or X ²⁾ is not particularly limited, may be selected from 2 to 6-position of the phenyl group substituted at position 9 of the fluorene. For example, when m1 (or m2) is 1, the substitution position of the group X ¹ (or X ² ) may be, for example, 2 to 6 position (preferably 2 or 4 position, particularly 4 position), m 1 When (or m2) is 2, it may be, for example, 3,4-position, 3,5-position, and when m1 (or m2) is 3, it is, for example, 3,4,5-position, 2 3,4-position, 2,3,5-position, 2,3,6-position, and the like.

Among the compounds of the general formula (I), a compound where m1 = m2 = 0, that is, bisphenolfluorene [9,9-bisphenylfluorenes] is 9,9-bis [4- (2-acryloyloxyethoxy). ) Phenyl] fluorene, 9,9-bis [4- (3-acryloyloxy 2-hydroxypropoxy) phenyl] fluorene.

Among the compounds of the general formula (I), compounds having m1 = m2 = 1, 2, or 3, that is, bisphenolfluorene [9,9-bis (monohydroxyphenyl) fluorenes], 9,9-bis (dihydroxy) Bisphenolfluorenes (9,9-bis (hydroxyphenyl) fluorenes) such as phenyl) fluorenes, 9,9-bis (trihydroxyphenyl) fluorenes and their C _2-4 alkylene oxide adducts; and bisaniline fluorenes And bisaniline fluorenes (9,9-bis (aminophenyl) fluorenes) such as bis (N-monosubstituted aniline) fluorene are preferred.

Among the bisphenol fluorenes, bisphenol fluorene includes 9,9-bis (4-hydroxyphenyl) fluorene (bisphenol fluorene, BPF); biscresol fluorene (BCF, for example, 9,9-bis (4-hydroxy-3). 9,9-bis (C _1-4 alkylhydroxyphenyl) fluorene such as -methylphenyl) fluorene, 9,9-bis (3-hydroxy-2-methylphenyl) fluorene; 9,9-bis (4-hydroxy- 3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-2,6-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-di-t-butylphenyl) fluorene 9,9-bis (such as di-C _1-4 alkyl-hydroxyphenyl) fluorene; This Corresponds to the compound, bisphenol fluorenes are exemplified substituents R ¹ and R ² are C _3-10 cycloalkyl or C _6-12 aryl group.

As 9,9-bis (dihydroxyphenyl) fluorenes, fluorenes corresponding to the above bisphenol fluorene (9,9-bis (monohydroxyphenyl) fluorenes), for example, 9,9-bis (dihydroxyphenyl) fluorene [ 9,9-bis (3,4-dihydroxyphenyl) fluorene (biscatecholfluorene (BCAF)), 9,9-bis (2,4-dihydroxyphenyl) fluorene, 9,9-bis (2,5-dihydroxyphenyl) ) Fluorene etc.], 9,9-bis (alkyl-dihydroxyphenyl) fluorene [eg 9,9-bis (3,4-dihydroxy-5-methylphenyl) fluorene, 9,9-bis (3,4-dihydroxy) 9,9-bis (C _1-4 alkyl) such as -6-methylphenyl) fluorene Such as 9,9-bis (diC _1-4 alkyl-dihydroxyphenyl) fluorene, such as -dihydroxyphenyl) fluorene, 9,9-bis (2,4-dihydroxy-3,6-dimethylphenyl) fluorene]; Corresponding to the compound, 9,9-bis (dihydroxyphenyl) fluorenes in which the substituents R ¹ and R ² are C _3-10 cycloalkyl or C _6-12 aryl group can be mentioned.

  Examples of 9,9-bis (trihydroxyphenyl) fluorenes include fluorenes corresponding to the 9,9-bis (mono or dihydroxyphenyl) fluorenes, such as 9,9-bis (3,4,5-triene). Hydroxyphenyl) fluorene, 9,9-bis (2,4,6-trihydroxyphenyl) fluorene, 9,9-bis (2,4,5-trihydroxyphenyl) fluorene, 9,9-bis (2,3 , 4-trihydroxyphenyl) fluorene, 9,9-bis (2,3,5-trihydroxyphenyl) fluorene, 9,9-bis (2,3,6-trihydroxyphenyl) fluorene, etc. Bis (trihydroxyphenyl) fluorene and the like are included.

Among the bisphenol fluorenes, alkylene oxide adducts include 1 to 10 moles of C _2-4 alkylene oxide (preferably 1 to 5 moles, particularly 1 to 3 moles) per mole of hydroxyl groups of bisphenol fluorenes. ) Compounds with added degrees. Examples of the compound to which 1 mole of alkylene oxide is added include 9,9-bis (hydroxyalkoxyphenyl) fluorenes [for example, 9,9-bis (4-hydroxyethoxyphenyl) fluorene (bisphenoxyethanol fluorene, BPEF) and the like. 9,9-bis [4- (hydroxyC _2-3 alkoxy) phenyl] fluorene; 9,9-bis (4-hydroxyethoxy-3-methylphenyl) fluorene (biscresol ethanolfluorene, BCEF), 9,9- 9,9-bis (alkylhydroxy C _2-3 alkoxyphenyl) fluorene such as bis (4-hydroxyisopropoxy-3-methylphenyl) fluorene; 9,9-bis (4-hydroxyethoxy-3,5-dimethylphenyl) ) Fluorene, 9,9-bis (4- Mud carboxymethyl isopropoxyphenyl-2,6-dimethylphenyl) 9,9-bis (di-hydroxy C _2-3 alkoxyphenyl, such as fluorene) fluorene; 9,9-bis (4-hydroxyethoxy-3-phenyl) fluorene Roh 9,9-bis (cycloalkyl hydroxy C2-3 alkoxyphenyl) fluorene; 9,9-bis (4-hydroxyethoxy-3-phenylphenyl) fluorene such as 9,9-bis (aryl-hydroxy-C _2-3 alkoxy Phenyl) fluorene, etc.], 9,9-bis [di (hydroxyalkoxy) phenyl] fluorenes corresponding to these compounds {eg, 9,9-bis [3,4-di (2-hydroxyethoxy) phenyl] fluorene 9,9-bis [di (2-hydroxyC _2-3 alkoxy) Enyl] fluorene, etc., 9,9-bis [tri (hydroxyalkoxy) phenyl] fluorenes corresponding to these compounds {eg, 9,9-bis [3,4,5-tri (2-hydroxyethoxy) phenyl] ] 9,9-bis [3,4,5-tri (2-hydroxyC _2-3 alkoxy) phenyl] fluorene etc.] such as fluorene}.

Examples of the bisaniline fluorene (9,9-bis (aminophenyl) fluorenes) include 9,9-bis (monoaminophenyl) fluorenes [for example, 9,9-bis (4-aminophenyl) fluorene ( 9,9-bis (amino-C ₁ ) such as 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9-bis (3-amino-2-methylphenyl) fluorene; _-4 alkylphenyl) fluorene; 9,9-bis (4-amino-3,5-dimethylphenyl) fluorene, 9,9-bis (4-amino-2,6-dimethylphenyl) fluorene, 9,9-bis (4-amino-3,5-di -t- butyl phenyl) fluorene such as 9,9-bis (amino - di C _1-4 alkylphenyl) fluorene; these reduction 9,9-bis (di- or triaminophenyl) fluorenes corresponding to the product; alkylene oxide adducts of these compounds; bisaniline fluorenes corresponding to these compounds, wherein the amino group is an N-monosubstituted amino group Bisaniline fluorenes corresponding to these compounds, wherein the substituents R ¹ and R ² are C _3-10 cycloalkyl or C _6-12 aryl groups.

  Note that bisphenol fluorenes with n = 0 are described in, for example, documents [J. Appl. Polym. Sci., 27 (9), 3289, 1982], JP-A-6-145087, and JP-A-8-217713. According to the method described, it can be produced by condensing fluorenone and phenols using hydrogen chloride gas and mercaptopropionic acid as catalysts. Further, hydrochloric acid water or sulfuric acid may be used in place of the hydrogen chloride gas.

  Bis (monohydroxyphenyl) fluorenes can be synthesized by various synthesis methods, for example, (a) a method of reacting a fluorenone with a phenol in the presence of hydrogen chloride gas and mercaptocarboxylic acid (reference [J. Appl. Polym. Sci., 27 (9), 3289, 1982], JP-A-6-145087, JP-A-8-217713), (b) 9-fluorenone in the presence of an acid catalyst (and alkyl mercaptan). A method of reacting alkylphenols (JP 2000-26349 A), (c) a method of reacting fluorenones and phenols in the presence of hydrochloric acid and thiols (such as mercaptocarboxylic acid) (JP 2002-47227 A). (D), (d) a reaction between fluorenones and phenols in the presence of sulfuric acid and thiols (such as mercaptocarboxylic acid), And a method in which by crystallization in the crystallization solvent is constituted by a kind and a polar solvent to produce a bisphenol fluorene (JP 2003-221352) can be produced by utilizing.

  In addition, 9,9-bis (di- or trihydroxyphenyl) fluorenes can be obtained by using the corresponding polyhydric alcohols (dihydroxy) instead of phenols in the above-mentioned 9,9-bis (monohydroxyphenyl) fluorenes production method. Phenols and trihydroxyphenols). Among these methods, in particular, when the method (c) using hydrochloric acid or the method (d) using a specific crystallization solvent is applied, a product with higher yield and purity may be obtained. Many.

Furthermore, the method for producing 9,9-bis (alkylene oxide adducts of monohydroxyphenylfluorenes) is not particularly limited. For example, 9,9-bis (hydroxyphenyl) fluorenes and the corresponding alkylene oxide (C _{2 -4} alkylene oxide) or alkylene carbonate (C _2-4 alkylene carbonate), if necessary, in the presence of a catalyst (such as a base catalyst), fluorenone and the corresponding phenoxy C _2-4 alcohol An alkylene oxide adduct of 9,9-bis (di- or trihydroxyphenyl) fluorene may be produced by a reaction method (for example, JP-A-11-349657) or the like. , 9-bis (hydroxyphenyl) fluorenes or phenoxy C _2-4 alcohol It can be produced by using corresponding alcohols [9,9-bis (di or trihydroxyphenyl) fluorenes, di or tri (hydroxy C _2-4 alkoxy) benzenes, etc.] instead of thiols.

The bisaniline fluorene in which X ¹ and X ² are amino groups can be prepared by using the corresponding anilines in place of the phenols in the bisphenol fluorene production method.

[Cardo resin]
As the cardo resin referred to in the present invention, an ester bond forming reaction, a transesterification reaction, a urethane bond forming reaction, an amide bond forming reaction, an imide, utilizing the fact that the compound represented by the general formula (I) has active hydrogen. Examples thereof include those obtained by a reaction such as a bond formation reaction.
Some reactions include those having only one cardo skeleton. For example, a (meth) acrylic monomer or an epoxy monomer, which will be described later, that is, a compound represented by the general formula (I), a group having one (meth) acrylic group or epoxy group and capable of reacting with active hydrogen. It is a reaction product with a compound having one (groups capable of reacting with active hydrogen are a carboxyl group, a halogen group, and an isocyanate group. Specifically, (meth) acrylic acid, (meth) acrylic acid chloride (Meth) acryloyloxyethyl isocyanate, epichlorohydrin, etc.). Specifically, 9,9-bis [4- (3-acryloyloxy-2-hydroxy) propoxyphenyl] fluorene, 9,9-bis (4-glycidyloxyphenyl) fluorene (BPFG), 9,9 described later. -Bis (4-glycidyloxy-3-methylphenyl) fluorene and the like.
Other specific examples of the cardo resin include resinous substances (oligomers and resins) such as reaction products of the bisphenol fluorenes and monofunctional compounds [monocarboxylic acids (saturated or unsaturated C _2-10 aliphatic mono Carboxylic acid, saturated or unsaturated C _5-10 alicyclic monocarboxylic acid, aromatic C _6-14 monocarboxylic acid and the like; urethane compound with monoisocyanate compound, etc.]; and the bisaniline fluorenes Reaction products with monofunctional compounds (such as amides with monocarboxylic acids); oligomers and polymers (resins) containing bisphenolfluorenes or bisphenolanilines as constituent monomers (hereinafter referred to simply as “polymers”) And may be referred to as “resin”). Of these, resins (thermoplastic resins and thermosetting resins) are preferable.

  In addition, the molecular weight (weight average molecular weight) of a cardo resin can be selected from about 300-50000, for example, Preferably it is 300-30000, More preferably, it may be about 500-20000. In particular, when the cardo resin is a resin, the weight average molecular weight may be 5,000 to 50,000, preferably 5,000 to 35,000, and more preferably about 10,000 to 20,000. When the cardo resin is an oligomer (or monomer), the weight average molecular weight may be 300 to 10000, preferably 300 to 8000, more preferably about 300 to 5000.

  Examples of bisphenol fluorene resins include thermoplastic resins (polyester resins; polycarbonate resins; polyurethane resins, etc.), thermosetting resins [unsaturated polyester resins; polyurethane resins (urethane resins); epoxy resins; Vinyl ester resins; (meth) acrylic resins obtained by esterification reaction of the bisphenol fluorenes and a polymerizable monomer having a carboxyl group; phenol resins, etc.]. In these resins, the bisphenol fluorenes can be used alone or in combination of two or more.

  Examples of the resin of bisaniline fluorenes include thermoplastic resins (polyamide resins; thermoplastic polyimide resins, thermosetting resins (polyimide resins; aniline resins, etc.), etc. These resins may be used alone or in combination. In these resins, the bisaniline fluorenes can be used alone or in combination of two or more.

(1) Polyester resin (including unsaturated polyester resin)
The polyester-based resin can be obtained by a reaction of a diol component composed of at least the bisphenol fluorenes (9,9-bis (monohydroxyphenyl) fluorenes) and a dicarboxylic acid component. In addition to saturated or unsaturated polyester resins, polyacrylate resins using aromatic dicarboxylic acids as polymerization components are also included.

The diol component of the polyester resin may be configured by combining the bisphenol fluorenes and other diols. Examples of such diols include alkylene glycols (for example, linear chains such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, octanediol, and decanediol. Or branched C _2-12 alkylene glycol, etc.), (poly) oxyalkylene glycol (eg, di to tetra C _2-4 alkylene glycol such as diethylene glycol, triethylene glycol, dipropylene glycol, etc.), alicyclic diol (For example, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane and its alkylene oxide adduct (2,2-bis (4- 2-hydroxyethoxy) cyclohexyl) propane), etc.), aromatic diol (e.g., biphenol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bisphenol AD, bisphenol F and their alkylene oxide (C _2-3 alkylene oxide) adducts (such as 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane) and xylylene glycol). These diols may be used alone or in combination of two or more.

Preferred diols are linear or branched C _2-10 alkylene glycols, particularly C _2-6 alkylene glycols (eg, linear or branched chain such as ethylene glycol, propylene glycol, 1,4-butanediol). C _2-4 alkylene glycol). As the diol, at least ethylene glycol is often used. When such diols (for example, ethylene glycol) are used, the polymerization reactivity can be enhanced and flexibility can be imparted to the resin.

  The ratio (molar ratio) between the bisphenol fluorenes and the diols is, for example, the former / the latter = 100/0 to 50/50, preferably 100/0 to 75/25 (for example, 100/0 to 70/30). More preferably, it may be about 100/0 to 90/10 (for example, 100/0 to 80/20).

  If necessary, the diol component may be used in combination with polyols such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, and the 9,9-bis (di or trihydroxyphenyl) fluorenes.

Examples of the dicarboxylic acid component constituting the polyester-based resin include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and derivatives capable of forming esters thereof [for example, acid anhydrides; acid halides (acid chlorides, etc.); Lower alkyl esters (such as C _1-2 alkyl esters)] and the like. These dicarboxylic acids can be used alone or in combination of two or more.

Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid, hexadecane dicarboxylic acid and other saturated C _3-20 aliphatic dicarboxylic acids. Acids (preferably saturated C _3-14 aliphatic dicarboxylic acids, etc.); unsaturated C _4-20 aliphatic dicarboxylic acids (preferably unsaturated C _4-14 aliphatics, such as maleic acid, fumaric acid, citraconic acid, mesaconic acid) Dicarboxylic acid and the like); derivatives of these that can form esters.
In the unsaturated polyester resin, the ratio of the aliphatic unsaturated dicarboxylic acid (maleic acid or its acid anhydride) is, for example, 10 to 100 mol%, preferably 30 to 100 mol%, based on the entire dicarboxylic acid component. More preferably, it may be about 50 to 100 mol% (for example, 75 to 100 mol%).

Examples of the alicyclic dicarboxylic acid include saturated alicyclic dicarboxylic acids (cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, cycloheptane dicarboxylic acid, etc. C _3-10 cycloalkane-dicarboxylic acid), unsaturated alicyclic dicarboxylic acid (C _3-10 cycloalkene-dicarboxylic acid such as 1,2-cyclohexene dicarboxylic acid, 1,3-cyclohexene dicarboxylic acid, etc.); Cyclic alkane dicarboxylic acids (di- or tricyclo C _7-10 alkane-dicarboxylic acid such as bornane dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid), polycyclic alkene dicarboxylic acids (bornene dicarboxylic acid, norbornene dicarboxylic acid, etc. di- or tricyclic C _7-10 A Ken - dicarboxylic acid), etc. These esters can form derivatives can be exemplified.

Aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, etc.), 4,4'-diphenyldicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, 4 , 4′-diphenylmethane dicarboxylic acid, aromatic C _8-16 dicarboxylic acid such as 4,4′-diphenyl ketone dicarboxylic acid; and ester-forming derivatives thereof.

  The dicarboxylic acid may be used in combination with a polyvalent carboxylic acid such as trimellitic acid or pyromellitic acid, if necessary.

The dicarboxylic acid component is usually at least one selected from aliphatic dicarboxylic acids and alicyclic dicarboxylic acids, in particular, aliphatic dicarboxylic acids (saturated aliphatic dicarboxylic acids or derivatives capable of forming esters thereof, particularly adipic acid, Saturated C _3-14 aliphatic dicarboxylic acids such as suberic acid and sebacic acid) and alicyclic dicarboxylic acids (C _5-10 cycloalkane dicarboxylic acids such as cyclohexane dicarboxylic acid) are preferred.

  In the polyarylate-based resin, a dicarboxylic acid component containing at least an aromatic dicarboxylic acid is used, and the aromatic dicarboxylic acid may be used in combination with another dicarboxylic acid (aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid). Good. The ratio of the aromatic dicarboxylic acid to the other dicarboxylic acid is, for example, the former / the latter (molar ratio) = 100/0 to 10/90, preferably 100/0 to 30/70, more preferably 100/0 to 50. It may be about / 50.

  In the polyester resin, the ratio (molar ratio) of the dicarboxylic acid component and the diol component (bisphenol fluorenes and diols) is usually the former / the latter = 1.5 / 1 to 0.7 / 1, preferably 1. It may be about 2/1 to 0.8 / 1 (particularly 1.1 / 1 to 0.9 / 1).

The weight average molecular weight Mw (polystyrene conversion) of the polyester resin is not particularly limited, and is, for example, 400 to 50 × 10 ⁴ , preferably 500 to 30 × 10 ⁴ (for example, 1000 to 20 × 10 ⁴ ), and more preferably 3000. About 30 × 10 ⁴ . In addition,
In the case of an unsaturated polyester resin, the double bond equivalent may be about 300 to 1500 g / mol, preferably about 350 to 1200 g / mol, and more preferably about 400 to 1100 g / mol. The terminal group of the polyester resin may be a hydroxyl group or a carboxyl group, and may be protected by a protecting group as necessary.

  The polyester-based resin can be produced by subjecting a diol component composed of bisphenolfluorenes and the dicarboxylic acid component to a condensation reaction by a conventional method such as a direct polymerization method (direct esterification method) or a transesterification method. .

As specific examples of the unsaturated polyester resin, for example, a compound represented by the following chemical formula (10);
General formula (10)

A compound represented by the following general formula (11):
Formula (11)

(Wherein R ¹⁰ represents oxygen, a carbonyl group, a tetrafluoroethylene group, or a single bond.)

It is obtained by copolymerizing pyromellitic anhydride and at least one selected from terephthalic acid and acid chlorides thereof.

(2) Polycarbonate-based resin As a polycarbonate-based resin, for example, a reaction between a diol component composed of at least the bisphenol fluorenes (9,9-bis (monohydroxyphenyl) fluorenes) and phosgene ( A phosgene method) or a polycarbonate resin obtained by a reaction (transesterification method) of the bisphenolfluorenes (9,9-bis (monohydroxyphenyl) fluorenes) with a carbonate.

  The diol component may be composed of bisphenol fluorenes alone, and is composed of bisphenol fluorenes and other diols (such as the diols exemplified in the above-mentioned polyester resin, particularly aromatic diols and alicyclic diols). May be. Other diols can be used alone or in combination of two or more. Among other diols, aromatic diols such as bisphenols such as bisphenol A, AD, and F are particularly preferable. The ratio of bisphenolfluorenes and diols can be selected from the same range as in the case of the polyester resin.

The molecular weight of the polycarbonate resin is not particularly limited. For example, the weight average molecular weight is 1 × 10 ^{3 to} 100 × 10 ⁴ (for example, 1 × 10 ^{4 to} 100 × 10 ⁴ ), preferably 5 × 10 ³ to 50 × 10 ^4. (For example, 1 × 10 ⁴ to 50 × 10 ⁴ ), more preferably about 1 × 10 ^{4 to} 25 × 10 ⁴ (for example, 1 × 10 ⁴ to 10 × 10 ⁴ ).

(3) Polyurethane resin (urethane resin)
The polyurethane resin can be obtained by a reaction between a diol component composed of at least the bisphenol fluorenes (9,9-bis (monohydroxyphenyl) fluorenes) and a polyisocyanate component.
The diol component constituting the polyurethane resin may be composed of the bisphenol fluorenes (9,9-bis (monohydroxyphenyl) fluorenes) alone, and together with the bisphenol fluorenes, it is exemplified in the section of the polyester resin. You may use together with diols. Furthermore, a diol component containing bisphenol fluorene as a structural unit, for example, a polyester diol produced by a reaction between a diol component composed of bisphenol fluorene and a dicarboxylic acid component, a diol component composed of bisphenol fluorene and an alkylene oxide Polyether diol produced by the above reaction can also be used as the diol component of the polyurethane resin. A diol component can also be used individually or in combination of 2 or more types. If necessary, the diol component may be used in combination with a polyol component such as triol.

  In the diol component, the content of bisphenol fluorenes (or units) is, for example, about 10 to 100 mol%, preferably 20 to 80 mol%, more preferably about 30 to 70 mol% with respect to the entire diol component. May be.

As the diisocyanate compound constituting the polyurethane resin, aromatic diisocyanate [paraphenylene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), naphthalene diisocyanate (NDI), bis ( Isocyanatophenyl) methane (MDI), toluidine diisocyanate (TODI), 1,2-bis (isocyanatophenyl) ethane, 1,3-bis (isocyanatophenyl) propane, 1,4-bis (isocyanatophenyl) butane , Polymeric MDI, etc.], alicyclic diisocyanates [cyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, etc.], fat Diisocyanate diisocyanate compounds such as [hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI), etc.] and the like. These diisocyanate compounds can be used alone or in combination of two or more. If necessary, these diisocyanate compounds may be polyisocyanate compounds (for example, aliphatic triisocyanates such as 1,6,11-undecane triisocyanate methyloctane and 1,3,6-hexamethylene triisocyanate; bicycloheptane triisocyanate). Triisocyanate compounds such as alicyclic triisocyanates, etc.), monoisocyanate compounds (C _1-6 alkyl isocyanates such as methyl isocyanate; C _5-6 cycloalkyl isocyanates such as cycloalkyl isocyanate; C _6- such as phenyl isocyanate) ₁₀ aryl isocyanate and the like). The isocyanate compound includes derivatives such as multimers and modified products of the polyisocyanate compound.
The polyurethane resin is a conventional method, for example, 0.7 to 2.5 mol, preferably 0.8 to 2.2 mol, more preferably about 0.9 to 2 mol of the diisocyanate component with respect to 1 mol of the diol component. It can be obtained by using it in a proportion and causing a urethanization reaction. In addition, when a diisocyanate component of about 0.7 to 1.1 mol is used with respect to 1 mol of a diol component, a thermoplastic resin can be obtained, and an excess mol (for example, about 1.5 to 2.2 mol) is obtained. When a diisocyanate component is used, a thermosetting resin having a free isocyanate group at the terminal can be obtained.

(4) Epoxy resin Epoxy monomers can be obtained by reacting at least the phenol fluorenes with epichlorohydrin, and the epoxy monomers can be obtained alone or copolymerized with other epoxy monomers to form epoxy resins or epoxy oligomers. It becomes. The monool component or polyol component constituting the epoxy resin may be composed of the bisphenol fluorenes alone, and other diols (particularly aromatic diols) exemplified in the section of the bisphenol fluorenes and the polyester resin. Or an alicyclic diol). Other diols can be used alone or in combination of two or more. Of the diols, aromatic diols such as bisphenols such as bisphenol A, AD, and F are particularly preferable. The ratio of bisphenolfluorenes and diols can be selected from the same range as in the case of the polyester resin. Furthermore, the bisphenol fluorenes and other diols as necessary may be used in combination with polyols (for example, phenol novolac).

  Examples of the epoxy monomer include 9,9-bis (glycidyloxyphenyl) fluorenes [for example, 9,9-bis (4-glycidyloxyphenyl) fluorene (BPFG), 9,9-bis (4-glycidyloxy- 9,9-bis (monoglycidyloxyphenyl) fluorenes such as 3-methylphenyl) fluorene (BCFG); 9,9-bis [3,4-di (glycidyloxy) phenyl] fluorene (biscatecholfluorenetetraglycidyl ether) 9,9-bis (diglycidyloxyphenyl) fluorenes; 9,9-bis (triglycidyloxyphenyl) such as 9,9-bis [3,4,5-tri (glycidyloxy) phenyl] fluorene Fluorenes, etc.], 9,9-bis (glycidyloxyalkoxy Nyl) fluorenes [for example, 9,9-bis (4-glycidyloxyethoxyphenyl) fluorene (bisphenoxyethanol fluorenediglycidyl ether) (BPEFG), 9,9-bis (4-glycidyloxyethoxy-3-methylphenyl) 9,9-bis (monoglycidyloxyalkoxyphenyl) fluorenes such as fluorene (BCEFG); 9,9-bis (di or tri (glycidyloxyalkoxy) phenyl) fluorenes corresponding to these] and the like. The weight average molecular weight Mw of the epoxy resin may be, for example, about 300 to 30,000, preferably about 400 to 10,000, and more preferably about 500 to 5,000.

(5) Vinyl ester resin (unsaturated)
The vinyl ester resin is prepared by a conventional method, for example, an epoxy monomer having an bisphenol fluorene unit (oligomer, resin having an epoxy group) and a polymerizable monomer having at least a carboxyl group (unsaturated monocarboxylic acid). It can be obtained by reaction. If necessary, the polymerizable monomer having a carboxyl group is a dicarboxylic acid (aliphatic dicarboxylic acid, alicyclic dicarboxylic acid or aromatic dicarboxylic acid (isophthalic acid, terephthalic acid, etc.)) exemplified in the above-mentioned polyester-based resin. And may be used in combination.

  An unsaturated monocarboxylic acid can be used as the polymerizable monomer having a carboxyl group. As the unsaturated monocarboxylic acid, (meth) acrylic acid can usually be used, and cinnamic acid, crotonic acid, sorbic acid, maleic acid monoalkyl ester (monomethyl malate, etc.) and the like may be used. These monomers may be used alone or in combination of two or more.

  The amount of the unsaturated monocarboxylic acid used is 0.5 to 1.2 mol, preferably 0.7 to 1.1 mol, more preferably 0.8 to 1 mol, based on 1 mol of the epoxy group of the epoxy resin. It may be a degree.

  Vinyl ester resins can also be obtained by reaction of bisphenol fluorenes with glycidyl (meth) acrylate. The usage-amount of glycidyl (meth) acrylate may be 1-3 mol with respect to 1 mol of bisphenol fluorenes, Preferably about 1-2 mol may be sufficient as it.

  Note that typical vinyl ester resins include the vinyl ester resins described in JP-A Nos. 2004-2635 and 2004-2636.

(6) Acrylic resin The (meth) acrylic monomer can be obtained by a reaction between the bisphenolfluorenes and an acrylic polymerizable monomer having a carboxyl group. The (meth) acrylic monomer can be used alone or copolymerized with other acrylic polymerizable monomers to form an acrylic resin.
As the acrylic polymerizable monomer having a carboxyl group, an unsaturated monocarboxylic acid, in particular, (meth) acrylic acid can be used. Cinnamic acid, crotonic acid, sorbic acid, maleic acid monoalkyl ester (monomethyl malate, etc.) ) Etc. may be used. Furthermore, as long as it reacts with active hydrogen, it may be a reactive derivative such as an acid chloride or a C _1-2 alkyl ester instead of an unsaturated carboxylic acid. These monomers may be used alone or in combination of two or more.

  The amount of the unsaturated monocarboxylic acid used is 0.5 to 1.2 mol, preferably 0.7 to 1.1 mol, more preferably 0.8 to 1 mol, based on 1 mol of the hydroxyl group of the bisphenol fluorene. It may be about a mole. Such an acrylic resin is often an oligomer (resin precursor).

The acrylic resin in the form of an oligomer may be polymerized with a copolymerizable monomer as necessary to form an acrylic copolymer. Examples of copolymerizable monomers include carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (meth) acrylic acid C _1-6 alkyl such as methyl (meth) acrylate Examples include esters; vinyl cyanides such as (meth) acrylonitrile; aromatic vinyl monomers such as styrene; vinyl carboxylic acid esters such as vinyl acetate; α-olefins such as ethylene and propylene. These copolymerizable monomers can be used alone or in combination of two or more.

(7) Phenolic resins In the production of phenolic resins, as the bisphenolfluorenes used as monomers, compounds in which n1 and n2 are 0 or X ¹ and X ² are hydroxyl groups in the general formula (I) are used. it can. When n1 and n2 are 1, the substitution positions of R ¹ and R ² are positions that do not hinder the addition reaction of aldehyde.

As the aldehydes, aliphatic C _1-4 aldehydes, usually formaldehyde and paraformaldehyde can be used.

In addition to the bisphenol fluorenes, co-condensation components such as phenols (C _1-4 alkyl-phenols such as phenol and cresol, dihydroxybenzenes such as resorcin), urea, guanamines and melamines are used in combination. Also good. The ratio of the bisphenol fluorenes and the co-condensation component is the former / the latter (molar ratio) = 100/0 to 5/95, preferably 100/0 to 10/90, more preferably about 100/0 to 20/80. There may be.

  The phenolic resin can be produced according to a conventional method for producing a phenolic resin. A novolac type phenolic resin is obtained in the presence of an acid catalyst, and a resol type phenolic resin is obtained in the presence of a base catalyst.

(8) Polyamide resin The polyamide resin can be obtained by reacting bisaniline fluorenes, which are compounds represented by the general formula (I), with dicarboxylic acids.
The diamine component may be composed of bisaniline fluorenes (9,9-bis (monoaminophenyl) fluorenes) alone or in combination of bisaniline fluorenes and diamines. Examples of diamines include chain C _2-14 aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, and dodecanediamine; Cyclic C _6-14 amines such as isophoronediamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, bis (4-amino-3-methyldicyclohexyl) methane; metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, etc. Examples thereof include C _6-20 aromatic diamines; C _7-14 aromatic aliphatic diamines such as m-xylylenediamine. These diamines can be used alone or in combination of two or more.

  The ratio of bisaniline fluorenes to diamines is the former / the latter (molar ratio) = 100/0 to 5/95, preferably 90/10 to 10/90, more preferably about 80/20 to 20/80. is there.

  As the dicarboxylic acids of the polyamide resin, the dicarboxylic acids (aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid) exemplified in the section of the polyester resin can be used. The dicarboxylic acids can be used alone or in combination of two or more.

  In the preparation of the polyamide resin, at least one component selected from aminocarboxylic acid (such as ω-aminoundecanoic acid) and lactam (such as C3-12 lactam such as ε-caprolactam) may be used as a copolymerization component. Good.

(9) Polyimide resin Polyimide resins can be obtained by reacting bisaniline fluorenes, which are compounds represented by the general formula (I), with polycarboxylic acids.
Bisaniline fluorenes (9,9-bis (monoaminophenyl) fluorenes) may be used alone or in combination with a diamine component. Examples of the diamine component include bis (diaminophenyl) alkanes such as diaminophenyl ether and 2,2-bis (3,4-diaminophenyl) propane, in addition to the diamines exemplified in the section of the polyamide-based resin. Diamines can be used alone or in combination of two or more.

  Examples of the raw material polycarboxylic acids include tetracarboxylic acids such as pyromellitic acid or its anhydride, biphenyltetracarboxylic acid or its anhydride, benzophenone tetracarboxylic acid or its anhydride, 2,2-bis (3,4- Examples include bis (dicarboxyphenyl) alkanes such as dicarboxyphenyl) propane or anhydrides thereof, bis (carboxyphenyl) fluoroalkanes such as 2,2-bis (3,4-carboxyphenyl) hexafluoropropane, and bismaleimide. it can. These polycarboxylic acids can be used alone or in combination of two or more.

The unsaturated polyimide resin is a compound represented by the following general formula (11) shown in the section of (1) polyester-based resin;
General formula (11):

(Wherein R ¹⁰ represents oxygen, a carbonyl group, a tetrafluoroethylene group, or a single bond.)

A compound represented by the following general formula (12);
Formula (12):

(Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and each represents hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, and R ¹⁵ represents hydrogen, a carboxyl group or 2 to 2 carbon atoms. 8 represents an alkoxycarbonyl group.)

It is obtained by copolymerizing pyromellitic anhydride and at least one selected from terephthalic acid and acid chlorides thereof.

  The polyimide resin may be thermoplastic or thermosetting.

(10) The bis-anilines fluorenes used as starting material aniline resin aniline resin, wherein in the general formula (I), n1 and n2 is 0 or 1, X ¹ is an amino group or a hydroxyl group (X ^1, at least A compound that is an amino group) can be used. When n1 and n2 are 1, the substitution positions of R ¹ and R ² are positions that do not hinder the addition reaction of aldehyde.

The bisaniline fluorenes may be used alone or in combination with anilines (C _1-4 alkyl-anilines such as aniline and methylaniline, diaminobenzene and the like). The ratio of bisaniline fluorenes to anilines is the former / the latter (molar ratio) = 100/0 to 5/95, preferably 100/0 to 10/90, more preferably about 100/0 to 20/80. is there.

  As the aldehydes, aldehydes (formaldehyde, paraformaldehyde, etc.) described in the section of the phenol resin can be used.

The aniline resin can be produced according to a conventional method for producing aniline resins. In the presence of an acid catalyst, a novolac aniline resin is obtained, and in the presence of a base catalyst, a resole aniline resin is obtained.
<Cardo resin having an ethylenically unsaturated double bond>
The cardo resin used in the present invention may have an ethylenically unsaturated double bond. When the cardo resin has an ethylenically unsaturated double bond, photosensitivity can be imparted to the resin composition.
In order for the cardo resin to have an ethylenically unsaturated double bond, among these, (1) polyester resin, (2) polycarbonate resin, (3) polyurethane resin, (4) epoxy resin, ( 7) A phenolic resin, (8) a polyamide resin, (9) a polyimide resin, and (10) an aniline resin, when a bisaniline fluorene, which is a compound represented by the general formula (I), undergoes a polymerization reaction, The reaction partner should just have an ethylenically unsaturated double bond.
In addition, (5) vinyl ester resin and (6) acrylic resin obtained by polymerization reaction of ethylenically unsaturated double bonds are the ethylenically unsaturated double bonds in the side chain described later after main skeleton formation. An ethylenically unsaturated double bond can be introduced by the method described for the resin [D2], which is a skeleton of a resin having a hydrogen atom. Of course, the said resin obtained by polymerization methods other than the polymerization reaction of an ethylenically unsaturated double bond can introduce an ethylenically unsaturated double bond similarly.

<Other resins>
When the cardo resin is a thermosetting resin, the composition of the present invention may contain an appropriate curing agent. For example, the resin composition containing the epoxy resin or the urethane resin may contain an amine curing agent or the like, and the resin composition containing the unsaturated polyester resin or vinyl ester resin may be an initiator ( Peroxides), polymerization accelerators (organic metal compounds such as octenoic acid metal salts), copolymerizable monomers ((meth) acrylic acid esters, reactive diluents such as styrene), and the like. When a curing agent is used, the curing agent may be composed of the compound (I) or a derivative thereof in order to further improve the dispersibility of the additive. For example, the curing agent for the epoxy resin may be composed of the bisphenol fluorenes or the bisaniline fluorenes.

  The compound represented by the following general formula (I) or the cardo resin (A) may be combined with other resins (thermoplastic resin or thermosetting resin). In particular, the compound represented by the following general formula (I) or the cardo resin (A) in the form of a low molecule or an oligomer may be combined with other resins.

Examples of the thermoplastic resin include olefin resins (polyethylene, polypropylene, polymethylpentene, amorphous polyolefin, etc.), vinyl resins (acrylic resins such as polyvinyl chloride and polymethyl methacrylate, polystyrene and acrylonitrile-styrene). Styrene resins such as resins), polycarbonate resins (such as bisphenol A polycarbonate), polyester resins (polyalkylene arylates such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polyarylate, liquid crystal Polyester), polyacetal resin, polyamide resin (nylon 6, nylon 66, nylon 46, nylon 6T, nylon MXD, etc.) , Polyphenylene ether resin (modified polyphenylene ether, etc.), polysulfone resin (polysulfone, polyether sulfone, etc.), polyphenylene sulfide, polyether ketone, polyether ether ketone, polyether imide, polyamide imide, polyamino bismaleimide, bismaleimide triazine Examples thereof include resins, thermoplastic elastomers, and fluororesins.
Examples of the thermosetting resin include phenol resin, furan resin, urea resin, melamine resin, unsaturated polyester, epoxy resin, urethane resin, silicone resin, polyimide, diallyl phthalate resin, and vinyl ester resin. These resins can be used alone or in combination of two or more.

The ratio (weight ratio) between the other resin and the compound represented by the general formula (I) or the cardo resin (A) is the former / the latter = 99/1 to 1/99 (for example, 90/10 to 10/90). A range of about 99/1 to 50/50, preferably 98/2 to 70/30, and more preferably about 97/3 to 80/20.
<Silane compound (B) having amide or urethane skeleton>
The present invention is characterized in that a silane compound having an amide or urethane skeleton is used for adhesion to the substrate and acid resistance.
The resin composition of the present invention preferably contains a silane compound (B) represented by the following general formula (1).
General formula (1)

[In General Formula (1), R ³¹ is an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon An aralkyl group having 7 to 30 carbon atoms, an alkaryl group having 7 to 30 carbon atoms,
X is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkoxylene group having 1 to 20 carbon atoms,
R ³² , R ³³ and R ³⁴ are each independently an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. Group, an aralkyl group having 7 to 30 carbon atoms, an alkaryl group having 7 to 30 carbon atoms, a siloxane group having a substituent, a halogen atom, a hydroxy group, and hydrogen. ]
When R ³¹ is an alkyl group, an aryl group, an aralkyl group, or an alkaryl group, it becomes a silane compound having an amide skeleton, and when R ³¹ is an alkoxy group or an aryloxy group, it becomes a silane compound having a urethane skeleton.

  Inclusion of the silane compound (B) represented by the general formula (1) improves the transmittance with members used for touch panels such as glass substrates, ITO, and molybdenum, and also improves pencil hardness and substrate adhesion. .

  Examples of the silane compound (B) represented by the general formula (1) include (3-carbamateethyl) propyltriethoxysilane, (3-carbamateethyl) propyltrimethoxysilane, and (3-carbamateethyl) propyltripropoxysilane. , (3-carbamatepropyl) propyltriethoxysilane, (3-carbamatepropyl) propyltrimethoxysilane, (3-carbamatepropyl) propyltripropoxysilane, (3-carbamatebutyl) propyltriethoxysilane, (3-carbamate (Butyl) propyltrimethoxysilane, (3-carbamatebutyl) propyltripropoxysilane, (3-carbamatebutyl) butyltripropoxysilane, (3-carbamatebutyl) propylmethyldiethoxysilane, ( -Carbamate pentyl) propyl triethoxy silane, (3-carbamate hexyl) propyl triethoxy silane, 3-carbamate octyl) pent tilt riboxy silane, (3-carbamate ethyl) propyl silyl trichloride, (3-carbamate ethyl) propyl trimethyl silane , 3-carbamateethyl) propyldimethylsilane, 3-carbamateethyl) propyltributylsilane, 3-carbamateethyl) ethyl-p-xylenetriethoxysilane, 3-carbamateethyl) -p-phenylenetriethoxysilane, and the like. Not limited to these. Further, the silane compound (B) represented by the general formula (1) may be a silanol compound obtained by hydrolysis thereof, or a polyorganosiloxane compound in which they are condensed.

The weight average molecular weight (Mw) of the silane compound (B) is preferably 200 or more and less than 5000, and the content of the silane compound (B) in the total solid content of 100% by weight of the photosensitive composition is 5% by weight or more and 50% by weight. It is preferable that it is less than%. When the weight average molecular weight (Mw) of the silane compound (B) is less than 200, it is not preferable from the viewpoint of availability, and when it is 5000 or more, the substrate adhesion is deteriorated, which is not preferable. Further, when the content is less than 5% by weight, the transmittance and pencil hardness are lowered, and when it is 50% by weight or more, the substrate adhesion and the pencil hardness are lowered, which is not preferable.
The weight average molecular weight (Mw) of the silane compound (B) is more preferably 200 or more and less than 500 from the viewpoint of pencil hardness and substrate adhesion, and the total solid content of the photosensitive composition is 100% by weight. The content of the silane compound (B) is more preferably 10% by weight or more and less than 40% by weight from the viewpoint of substrate adhesion.

Compared with isocyanate group-containing silane compounds such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltripropoxysilane, etc., the silane compound (B) represented by the general formula (1) is heat resistant. The coating film is not easily yellowed due to its excellent properties and is chemically stable, so that it is excellent in stability over time, and the pencil hardness and substrate adhesion are not impaired even after time.
<Oxide fine particles (C)>
The resin composition for obtaining the photosensitive dry film of the present invention comprises oxide fine particles (C).
By using the oxide fine particles (C), it is possible to further improve the heat resistance, pencil hardness, and substrate adhesion, and obtain a coating film having high etchant resistance.
The oxide fine particles may be surface-treated, and are preferably oxide particles of at least one element selected from silicon, aluminum, zirconium, titanium and zinc from the viewpoint of transmittance and pencil hardness. In addition, zirconium or titanium oxide fine particles are particularly preferable from the viewpoint of increasing the refractive index.

  The oxide fine particles (C) are used in plasma dispersion treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding properties with the binder component. A physical surface treatment or a chemical surface treatment with a surfactant or a coupling agent may be performed.

  The average primary particle diameter of the oxide particles (C) is preferably 1 nm to 1000 nm, more preferably 3 nm to 400 nm, and particularly preferably 5 nm to 300 nm. When the average primary particle diameter exceeds 1000 nm, the transparency when cured is reduced, or the surface state when coated is liable to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.

  The average primary particle diameter of the oxide fine particles (C) is measured using, for example, the BET method. Specifically, the specific surface area of the inorganic oxide fine particles obtained by the BET method is obtained, the ratio of volume to surface area is calculated using the specific gravity of the inorganic oxide, and the particles are assumed to be true spheres. There is a method of obtaining the particle diameter from these ratios to obtain the average primary particle diameter.

The oxide particles (C) are preferably used as an organic solvent dispersion. When used as an organic solvent dispersion, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such organic solvents include alcohol solvents such as methanol, ethanol, isopropanol, butanol, and octanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ -Ester solvents such as butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ether solvents such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbon solvents such as benzene, toluene and xylene; dimethyl Examples include amide solvents such as formamide, dimethylacetamide, and N-methylpyrrolidone.
Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, xylene, and propylene glycol monoethyl ether acetate are preferable.

  Commercially available products as silicon oxide fine particle dispersions particularly preferably used in the present invention include MA-ST-MS, IPA-ST, IPA-ST-MS, and IPA-ST- manufactured by Nissan Chemical Industries, Ltd. L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc., hollow silica CS60-IPA manufactured by Catalyst Kasei Kogyo Co., Ltd., etc. Can be mentioned. As powder silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  Commercially available products as aluminum oxide fine particle dispersions preferably used in the present invention include alumina sol-100, alumina sol-200, alumina sol-520 manufactured by Nissan Chemical Industries, Ltd. and AS- manufactured by Sumitomo Osaka Cement Co., Ltd. 150I, AS-150T.

    Examples of products that are commercially available as zirconia oxide fine particle dispersions preferably used in the present invention include ZR-40BL, ZR-30BS, ZR-30AL, ZR-30AH manufactured by Nissan Chemical Industries, Ltd., Sumitomo Osaka Cement ( HXU-110JC manufactured by Co., Ltd. can be mentioned. In addition, an oxide fine particle dispersion of zirconia can be obtained by the method described in Japanese Patent No. 469630.

Examples of products that are commercially available as titanium oxide fine particle dispersions that are preferably used in the present invention include Nanotech manufactured by CI Kasei Co., Ltd. and D-962 manufactured by Sakai Chemical Industry Co., Ltd. In addition, a titanium oxide fine particle dispersion can be obtained by the method described in Japanese Patent No. 469630.

  In addition, oxide fine particle dispersions preferably used in the present invention include oxide fine particle dispersions such as zinc, and commercially available products include Nanotech, manufactured by CI Kasei Co., Ltd.

The addition amount of the oxide fine particles (C) is preferably 5% by weight or more and less than 50% by weight, more preferably 10 to 35% by weight, in the total solid content of 100% by weight in the photosensitive composition. When the addition amount is less than 5% by weight, it is difficult to obtain effects such as improvement in pencil hardness and etchant resistance. On the other hand, when the addition amount exceeds 50% by weight, the adhesion to the substrate is lowered and the transmittance is lowered. Problems may occur.
<Compound (D) having an ethylenically unsaturated double bond>
The resin composition for obtaining the photosensitive dry film of the present invention may contain a compound having an ethylenically unsaturated double bond.
As the compound (D) having an ethylenically unsaturated double bond, a monomer (D1) having an ethylenically unsaturated double bond, or a resin having an ethylenically unsaturated double bond in the side chain [D2] Is mentioned. Unless otherwise specified, the resin [D2] having an ethylenically unsaturated double bond in the side chain does not include the above-mentioned cardo resin having an ethylenically unsaturated double bond.
The compound (D) having an ethylenically unsaturated double bond comprises a monomer (D1) having an ethylenically unsaturated double bond and a resin [D2] having an ethylenically unsaturated double bond in the side chain. One or both of them may be contained, but the content of the monomer (D1) having an ethylenically unsaturated double bond is 100% by weight in total of the solid content of the photosensitive composition. , Preferably in an amount of 5 to 80% by weight. In this case, if the amount of the monomer (D1) is less than 5% by weight, the effect of increasing pencil hardness and imparting solvent resistance cannot be obtained, and if it is more than 80% by weight, the transmittance and the substrate adhesion are decreased. It is easy to happen. More preferably, it is 10 to 50% by weight.

<Monomer (D1) having an ethylenically unsaturated double bond>
The monomer (D1) having an ethylenically unsaturated double bond includes the compound (d1) represented by the general formula (2), the ethylenically unsaturated monomer (d2) having an acid group, and a hydroxyl group. An ethylenically unsaturated monomer (d3), an ethylenically unsaturated monomer having an epoxy group (d4), an ethylenically unsaturated monomer having an isocyanate group (d5), and (d1) to (d5) And ethylenically unsaturated monomers (d6) other than

<Compound (d1) Represented by General Formula (2)>
General formula (2):

[In General Formula (2), R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. ]

In the general formula (2), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ⁷ and R ⁸ is not particularly limited, and examples thereof include methyl, ethyl, linear or branched alkyl groups such as n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butyl An alicyclic group such as cyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; an alkyl group substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a hydrocarbon group which is difficult to be removed by heat are preferable from the viewpoint of heat resistance. R ⁷ and R ⁸ may be the same type of hydrocarbon group or different hydrocarbon groups.

[Compound (d1)]
Specific examples of the compound (d1) include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, Di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n- Butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2 , 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoate Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis (methylene)] Bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t-butyl Chlohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tricyclo Decanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ' -[Oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate and the like. Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred.
These compounds (a1) can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

<Ethylenically unsaturated monomer having acid group (d2)>
Examples of the ethylenically unsaturated monomer (d2) having an acid group include (meth) acrylic acid, itaconic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and (meth) acrylic acid α. Phenols such as ethylenically unsaturated monomers (unsaturated monobasic acid (d2 ′)) having a carboxyl group such as monocarboxylic acids such as haloalkyl, alkoxyl, halogen, nitro, and cyano substituents, and N-hydroxyphenylmaleimide Ethylenically unsaturated monomers having a functional hydroxyl group, tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, polybasic acid anhydrides such as succinic anhydride, maleic anhydride, etc. (Meth) acrylic acid is preferred.

<Ethylenically unsaturated monomer having a hydroxyl group (d3)>
Examples of the ethylenically unsaturated monomer (d3) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth). Examples thereof include hydroxyalkyl (meth) acrylates such as acrylate, glycerol (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Absent.
Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used.

<Ethylenically unsaturated monomer having epoxy group (d4)>
Examples of the ethylenically unsaturated monomer (d4) having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4 epoxybutyl (meth) ) Acrylate and 3,4 epoxy cyclohexyl (meth) acrylate, and these may be used alone or in combination of two or more.

<An ethylenically unsaturated monomer having an isocyanate group (d5)>
Examples of the ethylenically unsaturated monomer (d5) having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. Two or more types can also be used together without doing.

<Ethylenically unsaturated monomer (d6) other than (d1) to (d5)>
As ethylenically unsaturated monomers (d6) other than (d1) to (d5), methyl (meth) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (meth) acrylate, t-pentyl (meth) acrylate 1-methylbutyl (meth) acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (Meth) acrylate, isostearyl (meth) acrylate, alkyl (meth) acrylate such as cyclohexyl (meth) acrylate, or alkyl (meth) acrylate described later as (a6 ′),
Allyl (meth) acrylate, oleyl (meth) acrylate, alkenyl (meth) acrylate such as vinyl (meth) acrylate, substituted alkyl (meth) acrylate such as benzyl methacrylate,
Monofunctional monomers such as vinyl compounds such as styrene, methylstyrene, vinyl chloride, vinyl acetate, butadiene, isoprene, cyclopentadiene, cyclohexene,
Monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and malonic acid, Monoesterified products containing free carboxyl groups with dicarboxylic acids such as succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene Tricarboxylic acids such as -1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydride Polyfunctional monomers such as monohydroxy monoacrylates such as xylethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, or oligoesters containing free carboxyl groups with monohydroxy monomethacrylates Although it is mentioned, it is not necessarily limited to these.
These photopolymerizable monomers can be used singly or in combination of two or more at any ratio as required.

Especially, it is preferable that the polyfunctional monomer which has 7 or more ethylenically unsaturated double bonds in 1 molecule is included. By including this, it will be excellent in pencil hardness and etchant tolerance. Moreover, it is preferable that it is a polyfunctional monomer which has 7-16 ethylenically unsaturated double bonds from viewpoints, such as the maintenance of a transmittance | permeability, and pencil hardness and base-material adhesiveness, Furthermore, it is 7-12 pieces. In some cases, it is more preferable because it is excellent in pencil hardness, substrate adhesion, and etchant resistance.
As such a polyfunctional monomer, commercially available products include, for example, Biscoat # 802 (mixture of tripentaerythritol octaacrylate, tetrapentaerythritol decaacrylate, and pentapentaerythritol dodecaacrylate, manufactured by Osaka Organic Chemical Co., Ltd.). be able to.

<Resin [D2] serving as a skeleton of a resin having an ethylenically unsaturated double bond in the side chain>
Examples of the resin [D2] serving as a skeleton of a resin having an ethylenically unsaturated double bond in the side chain include a thermoplastic resin [D2-1] and a thermosetting resin [D2-2].
The resin [D2] which is a skeleton of a resin having an ethylenically unsaturated double bond in the side chain preferably has a spectral transmittance of 80% or more, more preferably 95% in the entire wavelength region of 400 to 700 nm in the visible light region. The above resin. Moreover, each resin may be used independently and may be used together.

  Examples of the thermosetting resin [D2-2] include benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, epoxy resin, urea resin, and phenol resin. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.

The thermoplastic resin [D2-1] is, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. .
As the thermoplastic resin [D2-1], an alkali-soluble vinyl resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer is more preferable.

  The alkali-soluble vinyl resin obtained by copolymerizing the acidic group-containing ethylenically unsaturated monomer (d2) is, for example, a resin having an acidic group such as a carboxyl group, a sulfone group, a phenolic hydroxyl group, or a polybasic acid anhydride group. Can be mentioned. These acid groups may be used alone or in combination of two or more. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  As a method for introducing an acid group into a resin, an ethylenically unsaturated monomer having an acid group (d2) or an ethylenically unsaturated monomer capable of giving an acid group after polymerization is used. A method of polymerizing as a saturated monomer component may be used.

  When the ethylenically unsaturated monomer (d2) having an acid group is included, the content ratio is not particularly limited, but it is preferably 5 to 70% by weight in a total of 100% by weight of all ethylenically unsaturated monomer components. Is preferably 10 to 60% by weight.

Examples of the ethylenically unsaturated monomer that can impart an acid group after polymerization include ethylenically unsaturated monomers (d3) having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and the like. And an ethylenically unsaturated monomer (d4) having an epoxy group.
When the ethylenically unsaturated monomer (d3) having a hydroxyl group is used, for example, an ethylenically unsaturated monomer (d3) having a hydroxyl group and another ethylenically unsaturated monomer that can be copolymerized are used. The hydroxyl group of the copolymer obtained by copolymerization can be reacted with a polybasic acid anhydride to introduce an acid group (carboxyl group). Alternatively, when the ethylenically unsaturated monomer (d4) having an epoxy group is used, for example, the ethylenically unsaturated monomer (d4) having an epoxy group and other ethylenically unsaturated monomers capable of copolymerization are used. An unsaturated monobasic acid having a carboxyl group (d2 ′) is added to the side chain epoxy group of the copolymer obtained by copolymerizing with the monomer, and a polybasic acid is added to the generated hydroxyl group. An anhydride can be reacted to introduce an acid group (carboxyl group). In this method, when the hydroxyl group and the polybasic acid anhydride are reacted without excess or deficiency, the hydroxyl group disappears. On the other hand, a resin having a hydroxyl group in the side chain and an acid group such as a carboxyl group and an ethylenically unsaturated double bond is obtained by reacting a part of the hydroxyl group with a polybasic acid anhydride.

  When an ethylenically unsaturated monomer for imparting an acid group after polymerization is included, the content ratio is not particularly limited, but is 5 to 70% by weight in a total of 100% by weight of all ethylenically unsaturated monomer components. Preferably, it is 10 to 60% by weight.

  By introducing an acid group, the resulting photosensitive composition is a photosensitive composition capable of a crosslinking reaction utilizing the fact that an ester bond is formed by the reaction of an acid group with an epoxy group or a hydroxyl group, or an uncured part. The composition can be developed with an alkali developer. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more.

<Method of introducing ethylenically unsaturated double bond into resin>
In order to have an ethylenically unsaturated double bond in the side chain of the resin, for example, the following methods (a) and (b) are exemplified.

[Method (a)]
As the method (a), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer (d4) having an epoxy group with one or more other monomers. An epoxy group is allowed to undergo an addition reaction with a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and a polybasic acid anhydride is further reacted with the resulting hydroxyl group to produce an ethylenically unsaturated double bond and There is a method of introducing a carboxyl group.

  Examples of the ethylenically unsaturated monomer (d4) having an epoxy group include those described in (D1). From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.

  As unsaturated monobasic acid (d2 '), what was demonstrated by (D1) is mention | raise | lifted, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (a), for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer (d2) having an acid group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the side chain carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (b)]
As the method (b), an ethylenically unsaturated monomer (d3) having a hydroxyl group is used, and other than the unsaturated monobasic acid (d2 ′) having other carboxyl groups and (d3) (d2 ′) There is a method of reacting an isocyanate group of an ethylenically unsaturated monomer (d5) having an isocyanate group with a side chain hydroxyl group of a copolymer obtained by copolymerizing with a monomer.

  Examples of the ethylenically unsaturated monomer (d3) having a hydroxyl group include those described in (D1), and 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate, from the viewpoint of suppressing foreign matter on the coating film. Is preferred.

  Examples of the ethylenically unsaturated monomer (d5) having an isocyanate group include those described in (D1).

  In particular, it contains a carboxyl group such as an unsaturated monocarboxylic acid such as (meth) acrylic acid, crotonic acid, or α-chloroacrylic acid, or an unsaturated dicarboxylic acid such as maleic acid or fumaric acid, and is ethylenically unsaturated. Selected from the group consisting of an ethylenically unsaturated monomer (d2) having an acid group, such as a compound having a double bond, and the group consisting of alkyl (meth) acrylates described as (d6) in the description in (D1) It is preferable to use one or more of each.

The resin [D2] preferably has a double bond equivalent of 350 g / mol or more and less than 1200 g / mol, and a weight molecular weight average (Mw) of 500 or more and less than 40000. When the double bond equivalent is less than 350 g / mol, the resin shrinkage increases and the substrate adhesion may decrease. When the double bond equivalent exceeds 1200 g / mol, sufficient pencil hardness is obtained. Since it may not be able to be satisfied, it is not preferable. In addition, when the weight average molecular weight (Mw) is smaller than 500, the curing shrinkage of the resin is increased, and thus the substrate adhesion may be lowered. When the weight average molecular weight (Mw) exceeds 40000, the pencil hardness is It may deteriorate and is not preferable.
When the double bond equivalent is 350 to 1200 g / mol and the weight average molecular weight (Mw) is 500 or more and less than 40000, it is possible to bring out excellent pencil hardness and substrate adhesion.

  In addition, the acid value of the resin [D2] is more preferably 30 mgKOH / g or more and less than 200 mgKOH / g from the viewpoint of developability and temporal stability of the photosensitive composition. When the acid value is less than 30 mgKOH / g, the developability of the photosensitive composition is lowered, which is not preferable. When the acid value is 200 mgKOH / g or more, the hydrolysis of the silane compound (B) is promoted, and the pencil hardness and substrate adhesion of the coating film formed by the photosensitive composition are decreased with the passage of time. Absent.

[Resin (D2-a)]
The resin [D2] is a resin (A2-a) obtained by copolymerizing the compound (a1) represented by the following general formula (2) and another compound copolymerizable with the compound (a1). Is particularly preferred.
The description of the compound (d1) is as described in (D1).

  When the compound (d1) is copolymerized with another ethylenically unsaturated monomer copolymerizable to obtain the resin (D2-a), the cyclization reaction of the compound (d1) proceeds simultaneously with the polymerization. A tetrahydropyran ring structure is formed.

  The ratio of the compound (d1) in the ethylenically unsaturated monomer component in obtaining the resin (D2-a) is not particularly limited, but is preferably 2 to 50% by weight in the total ethylenically unsaturated monomer component, preferably Is 5 to 55% by weight, more preferably 5 to 50% by weight. If the amount of the compound (d1) is too large, it may be difficult to obtain a low molecular weight product during copolymerization or may be easily gelled. On the other hand, if the amount is too small, the transparency and heat resistance may be increased. There is a possibility that the performance of the coating film becomes insufficient.

[Other compounds copolymerizable with compound (d1)]
The other compound (d2) copolymerizable with the compound (d1) is not particularly limited as long as it can be copolymerized with the compound (d1), and is described as (d2) to (d6) in the description in (D1). It is preferable to include a monomer for introducing an acid group to impart alkali solubility, and other monomers for introducing an ethylenically unsaturated double bond, side chain Type cyclic ether-containing monomer (d6 ′) is preferred.
The method for introducing an acid group and an ethylenically unsaturated double bond into the resin (D2-a) has already been described in the resin [d2].

<Side-chained cyclic ether-containing monomer (d6 ′)>
The side chain type cyclic ether-containing monomer (d6 ′) is, for example, an unsaturated compound containing at least one skeleton selected from the group consisting of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a lactone skeleton. .
Examples of the tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, (meth) acrylic acid tetrahydrofuran-3-yl ester, and the like;
Examples of the furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, and 1-furan. 2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-ene -3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6- (2-furyl) -6-methyl-1-hepten-3-one, and the like;
Examples of the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, and tetrahydropyran 2-methacrylate. 2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and the like;
Examples of the pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone and 4- (1,5-dioxa-6-oxo-7-octenyl) -6. -Methyl-2-pyrone and the like;
Examples of the lactone skeleton include 2-propenoic acid 2-methyl-tetrahydro-2-oxo-3-furanyl ester, 2-propenoic acid 2-methyl-7-oxo-6-oxabicyclo [3.2.1] oct-2- Yl ester, 2-propenoic acid 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-7-yl ester, 2-propenoic acid 2-methyl-tetrahydro-2-oxo- 2H-pyran-3-yl ester, 2-propenoic acid (tetrahydro-5-oxo-2-furanyl) methyl ester, 2-propenoic acid hexahydro-2-oxo-2,6-methanofuro [3,2-b]- 6-yl ester, 2-propenoic acid 2-methyl-2- (tetrahydro-5-oxo-3-furanyl) ethyl ester, 2-propenoic acid 2-methyl ester Ru-decahydro-8-oxo-5,9-methano-2H-furo [3,4-g] -1-benzopyran-2-yl ester, 2-propenoic acid 2-methyl-2-[(hexahydro-2- Oxo-3,5-methano-2H-cyclopenta [b] furan-6-yl) oxy] ethyl ester, 2-propenoic acid 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl) oxy] propyl And 2-propenoic acid 2-methyl-2-oxy-1-oxaspiro [4.5] dec-8-yl ester.
Among these, tetrahydrofurfuryl (meth) acrylate is preferable from the viewpoint of coloring and availability. These side chain type cyclic ether-containing monomers may be used alone or in combination of two or more.

  The proportion of the side-chain cyclic ether-containing monomer (d6 ′) in the monomer component for obtaining the resin (D2-a) is not particularly limited, but is 10 to 80% by weight in the total monomer components. , Preferably 20 to 70% by weight, more preferably 30 to 60% by weight. If the amount of the side chain type cyclic ether-containing monomer is too large, the hydrophilicity becomes too strong and the surface is whitened during alkali development, the pattern is chipped, or the adhesion to a substrate such as glass tends to be lowered. On the other hand, if the amount is too small, performance such as heat resistance may be insufficient.

  Other copolymerizable monomers that can be used as other compounds copolymerizable with the compound (d1) other than the side chain cyclic ether-containing monomer (d6 ′) include methyl (meth) acrylate, Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.

The method for the polymerization reaction of the monomer component is not particularly limited, and various conventionally known polymerization methods can be employed, but the solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are the types and ratios of the monomer components used. Depending on the molecular weight of the target polymer, the polymerization temperature is preferably 40 to 150 ° C. and the polymerization concentration is 5 to 50%, and more preferably, the polymerization temperature is 60 to 130 ° C. and the polymerization concentration is 10 to 40%. It is good to do.
The resin (D2-a) is preferably used in an amount of 10 to 60% by weight in a total of 100% by weight of the solid content of the photosensitive composition. When the amount of the resin (D2-a) is less than 10% by weight, sufficient substrate adhesion improvement and high heat resistance cannot be obtained. When the amount is more than 60% by weight, the content of the photocuring component is decreased. It is difficult to obtain a sufficient pencil hardness of the coating film.
(Other resins (D2-b)
Resin [D2] of the composition of the present invention may contain other resin (D2-b) in addition to resin (D2-a). When the other resin (D2-b) is a copolymer, it corresponds to the resin (D2-a) not containing the compound (d1) as a copolymerization component, and in particular, for introducing the acid group described above. And those containing a monomer for introducing a radical polymerizable double bond as a copolymerization component are preferred. Further, the other resin (D2-b) may be a thermosetting resin.

<Polyfunctional monomer>
As explained in the ethylenically unsaturated monomer (d6) other than (d1) to (d5), the resin composition of the present invention can contain a polyfunctional monomer.
Among these, it is particularly preferable to include a polyfunctional monomer having 7 or more ethylenically unsaturated double bonds in one molecule. By including this, it will be excellent in pencil hardness and etchant tolerance. Moreover, it is preferable that it is a polyfunctional monomer which has 7-16 ethylenically unsaturated double bonds from viewpoints, such as the maintenance of a transmittance | permeability, and pencil hardness and base-material adhesiveness, Furthermore, it is 7-12 pieces. In some cases, it is more preferable because it is excellent in pencil hardness, substrate adhesion, and etchant resistance.

<< 7 or more polyfunctional monomers >>
The polyfunctional monomer having 7 or more ethylenically unsaturated double bonds is preferably, for example, a polyfunctional monomer represented by the following general formula (20).
Formula (20):

[In General Formula (20), m is an integer of 0 to 4, and R ₂₃ is an ether group, an alkylene group, a tolylene group, an arylene group, a carbonyl group, a sulfonyl group, an ester group, or a general formula (3). Wherein R ₂₄ is a hydrogen atom or a methyl group, R ₂₅ is a hydroxyl group, a carboxyl group, and a (meth) acryloyl group, and (meta ) Any one selected from the group consisting of acryloyloxy groups. ]

General formula (3):

[In General Formula (3), R ₆ represents an aliphatic, alicyclic or aromatic structure. ]

Among the compounds represented by the general formula (20), R ₂₃ is preferably an ether group or a divalent group having a structure represented by the general formula (3) in terms of pencil hardness and substrate adhesion. .

  As what is represented by General formula (3), the compound etc. which are obtained by making dipentaerythritol penta (meth) acrylate and tetrabasic acid dianhydride react are mentioned, for example.

Specific examples of tetrabasic acid dianhydrides include pyromellitic anhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclo Pentanetetracarboxylic dianhydride, oxydiphthalic anhydride, ethylene glycol bisanhydro trimellitate, glycerin bis (anhydro trimellitate monoacetate), benzophenone tetracarboxylic dianhydride, methylcyclohexylene tetracarboxylic dianhydride And the like.

Among the polyfunctional monomers in which R ₂₃ is an ether group in the general formula (20), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetra Pentaerythritol deca (meth) acrylate, pentapentaerythritol undeca (meth) acrylate, or pentapentaerythritol dodeca (meth) acrylate is preferred.
Among these, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, or pentapentaerythritol dodeca (meth) acrylate is most preferable. It may be included.

  As such a polyfunctional monomer, commercially available products include, for example, Biscoat # 802 (mixture of tripentaerythritol octaacrylate, tetrapentaerythritol decaacrylate, and pentapentaerythritol dodecaacrylate, manufactured by Osaka Organic Chemical Co., Ltd.). be able to.

In the general formula (20), when R ₂₃ is a divalent group having a structure represented by the general formula (3), m = 1 and R ₂₅ is a (meth) acryloyl group or (meth) acryloyl An oxy group is more preferable in terms of pencil hardness.

  Examples of such a polyfunctional monomer include TO-2323, TO-2324, TO-2325, TO-2326, TO-2327, and TO-2328 (manufactured by Toa Gosei Co., Ltd.). .

  The content of the polyfunctional monomer is preferably 5 to 80% by weight in a total of 100% by weight of the solid content of the resin composition. In this case, if the amount of the polyfunctional monomer is less than 5% by weight, the effect of increasing the surface hardness and imparting solvent resistance cannot be obtained, and if it is more than 80% by weight, the transmittance decreases and the substrate adhesion decreases. Cheap. More preferably, it is 10 to 50% by weight.

《Other polyfunctional monomers》
In the present invention, in addition to the above polyfunctional monomer, other polyfunctional monomers may be contained. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples thereof include various acrylic esters and methacrylic esters such as pentaerythritol hexa (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and propylene oxide-modified trimethylolpropane tri (meth) acrylate.

  Further, it may contain a polyfunctional monomer having an acid group, for example, an esterified product of a poly (meth) acrylate containing a free hydroxyl group of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; And esterified products with monohydroxyalkyl (meth) acrylates. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like monohydroxy oligoacrylates or monohydroxy oligomethacrylates And monoesterified products containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. be able to.

Moreover, the compound represented by following General formula (5) can also be used preferably.
General formula (5):
_{(H 2 C = C (R} 9) COO) h -X- (OCOCH (R 9) CH 2 S (R 50) COOH) i ··· (5)
[In General Formula (5), R ₉ is a hydrogen atom or a methyl group, R ₅₀ is a hydrocarbon group having 1 to 12 carbon atoms, X is an (h + i) -valent organic group having 3 to 60 carbon atoms, h is 2 to 2 An integer of 18, i represents an integer of 1 to 3. ]

Here, the compound represented by the general formula (5) can be easily obtained, for example, by the following method.
(1) A method of adding a mercapto compound to an obtained compound after esterifying the compound giving an organic group represented by X with acrylic acid to acrylate, and (2) a compound giving an organic group represented by X Is modified with a polyisocyanate compound, and then the resulting compound is acrylated with an acrylate compound having a hydroxyl group, and then a mercapto compound is added to the obtained compound. (3) An organic group represented by X is given. A method in which a compound is esterified with acrylic acid to be acrylated, then modified with a polyisocyanate compound, and a mercapto compound is added to the obtained compound.

  Examples of the compound giving an organic group represented by X include pentaerythritol, pentaerythritol modified caprolactone, pentaerythritol modified polyisocyanate, dipentaerythritol, dipentaerythritol caprolactone modified, dipentaerythritol polyisocyanate Denatured products can be mentioned.

  Examples of the mercapto compound include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.

<Solvent>
Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butylal N-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, cyclopentanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl acetate Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol Methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, ethanol, n-propanol, iso-propanol, n-butanol, 2-butanol, Examples thereof include n-octanol and n-hexanol, which are used alone or in combination.

Among these solvents, an alcohol solvent is preferably included. In addition to improving the stability of the silane compound (B) having an amide or urethane skeleton by including an alcohol solvent, the hydrolysis reaction rate of the silane compound is controlled moderately, pencil hardness, and substrate adhesion , And a coating film excellent in etchant resistance can be obtained.
Further, among alcohol solvents, methanol (bp 65 ° C.), ethanol (bp 78 ° C.), 1-propanol (bp 83 ° C.), 1-butanol (bp 117 ° C.), ethylene glycol monohexyl ether (bp 98 ° C.), etc. at 760 mmHg It is particularly preferable to include an alcohol solvent having a boiling point of less than 130 ° C.

  The content of the alcohol solvent is preferably 25 to 300 parts by weight with respect to 100 parts by weight of the solid content of the resin composition. In the case of 25 to 300 parts by weight, the drying time of the alcohol-based solvent is improved in the drying process at the time of film formation, so that the reaction with the base material of the silane compound (B) having an amide or urethane skeleton proceeds efficiently. . In addition, the silane compound (B) having an amide or urethane skeleton is preferable for maintaining a good self-condensation reaction rate, improving storage stability and improving coatability.

  In consideration of the drying property of the solvent, it is preferable to include a high boiling point solvent of 160 ° C. or higher in die coating or printing methods. For example, 3-methoxy-3-methyl-1-butanol (bp 174 ° C.), 1, 3 -Butanediol (bp 203 ° C.), 3-methyl-1,3-butanediol (bp 203 ° C.), 2-methyl-1,3-propanediol (bp 213 ° C.), diisobutyl ketone (bp 168.1 ° C.), ethylene glycol mono Butyl ether (bp 171.2 ° C.), ethylene glycol monohexyl ether (bp 208.1 ° C.), ethylene glycol monobutyl ether acetate (bp 191.5 ° C.), ethylene glycol dibutyl ether (bp 203.3 ° C.), diethylene glycol monomethyl ether (bp 194.0) ℃), Diechi Glycol monoethyl ether (bp 202.0 ° C.), diethylene glycol diethyl ether (bp 188.4 ° C.), diethylene glycol monoisopropyl ether (bp 207.3 ° C.), propylene glycol monobutyl ether (bp 170.2 ° C.), propylene glycol diacetate (bp 190 0.0 ° C.), dipropylene glycol monomethyl ether (bp 187.2 ° C.), dipropylene glycol monoethyl ether (bp 197.8 ° C.), dipropylene glycol monopropyl ether (bp 212.0 ° C.), dipropylene glycol dimethyl ether (bp 175 ° C.) ), Tripropylene glycol monomethyl ether (bp 206.3 ° C.), ethyl 3-ethoxypropionate (bp 169.7 ° C.), 3-methoxybutene Rubacetate (bp 172.5 ° C.), 3-methoxy-3-methylbutyl acetate (bp 188 ° C.), γ-butyrolactone (bp 204 ° C.), N, N-dimethylacetamide (bp 166.1 ° C.), N-methylpyrrolidone (bp 202 ° C), p-chlorotoluene (bp162.0 ° C), o-diethylbenzene (bp183.4 ° C), m-diethylbenzene (bp181.1 ° C), p-diethylbenzene (bp183.8 ° C), o-dichlorobenzene (bp180) 0.5 ° C), m-dichlorobenzene (bp 173.0 ° C), n-butylbenzene (bp183.3 ° C), sec-butylbenzene (bp178.3 ° C), tert-butylbenzene (bp169.1 ° C), cyclo Hexanol (bp 161.1 ° C), cyclohexyl acetate (bp 73 ° C.), include such methylcyclohexanol (bp174 ℃), preferably high-boiling solvent or 160 ° C. 5 to 50 wt% based on the total amount of solvent.

  The solvent can be used in an amount of 200 to 4000 parts by weight based on 100 parts by weight of the total solid content in the resin composition of the present invention.

<Photopolymerization initiator>
In the resin composition for obtaining the photosensitive dry film of the present invention, the composition is cured by ultraviolet irradiation, and a photopolymerization initiator is added to form a coating film by a photolithography method. It can be prepared in the form of an alkali development type resin composition.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Acetophenone photopolymerization initiators such as 1-one,
1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl]-, 1- (o-acetyloxime) and other oxime ester photopolymerization initiators,
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal,
Benzophenone photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide,
Thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone,
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloro) Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-tri Triazine photopolymerization initiators such as azine,
Borate photopolymerization initiator, carbazole photopolymerization initiator,
Imidazole-based photopolymerization initiators and the like are used, and these can be used alone or in admixture of two or more.

Among them, acetophenone photopolymerization initiators and oxime ester photopolymerization initiators are preferable because they have high sensitivity and can be added in a small amount, so that the transmittance increases.
Among acetophenone photopolymerization initiators and oxime ester photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1 , 2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], especially 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, , 2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)] is less yellowed during the heating process, has a high transmittance as an insulating film, and particularly has a wavelength of around 400 nm. Since a resin composition with a high rate can be provided, it is more preferable. These may be used alone or in combination.
The photopolymerization initiator is preferably used in an amount of 1 to 30% by weight in a total of 100% by weight of the solid content of the resin composition, and more preferably 1 to 10% by weight from the viewpoint of transmittance. .

The resin composition of the present invention further includes α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4 as a sensitizer. , 4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone and the like can be used in combination.
The sensitizer can be used in an amount of 0.1 to 150 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

<Antioxidant>
The resin composition for obtaining the photosensitive dry film of the present invention may contain an antioxidant. The antioxidant can suppress a decrease in transmittance due to yellowing or the like due to the heating process. Therefore, by including an antioxidant, yellowing during the heating step can be prevented, and a coating film having a high transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Among these antioxidants, phenol-based antioxidants, phosphorus-based antioxidants and sulfur-based antioxidants are preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Among phenol-based compounds, hindered phenol-based antioxidants having high steric hindrance are particularly preferable.

[Phenolic antioxidant]
For example, 2,6-di-t-butyl-4-ethylphenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 , 5-triazine, 2,2-thio-diethylenebis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, N, N'-hexamethylenebis (3,5-di- t-butyl-4-hydroxy-
Hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,6- Di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-methoxyphenol, triethylene glycol-bis {3- (3-t-butyl- 5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, pentaerythrityl-tetrakis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Roxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenyl) benzene, and the like can be used alone or in combination of two or more. May be.

Among them, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t- A hindered phenolic antioxidant selected from the group consisting of butyl-4-hydroxybenzylphosphonate-diethyl ester and tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate is: It is preferable from the viewpoint of photocurability.

[Phosphorus antioxidant]
Although what is marketed can be used as phosphorus antioxidant, Tris [2,4-di- (tert) -butylphenyl] phosphinetris [2-[[2,4,8,10-tetrakis ( 1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11- Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl) oxy] ethyl] amine, ethylbisphosphite (2,4-ditert-butyl-6-) It is preferable that it is at least one compound selected from the group consisting of these, and these may be used alone or in combination of two or more.

[Sulfur antioxidants]
A sulfur-based antioxidant is an antioxidant containing sulfur in the molecule. As such a sulfur-containing antioxidant, commercially available ones can be used, but dioctadecyl 3,3′-thiodipropanoate, dimyristyl-3,3′-thiodipropionate, dipalmityl-3,3′- Thiodipropionate, distearyl-3,3′-thiodipropionate, 4,4′-thiobis-3-methyl-6-tert-butylphenol, thiodiethylenebis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], and is preferably at least one compound selected from the group consisting of these, and one or more of these may be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  The content of the antioxidant is preferably 0.1 wt% or more and less than 4 wt% in the total solid content of the resin composition of 100 wt%. If the amount is less than 0.1% by weight, it is difficult to obtain the yellowing prevention effect due to insufficient antioxidant, and if it is more than 4% by weight, the radicals generated at the time of UV exposure are captured. Curing of the product may be insufficient.

<Other ingredients>
In the resin composition for obtaining the photosensitive dry film of the present invention, a monofunctional monomer, a surfactant, a storage stabilizer, a leveling agent, a light stabilizer and the like can be used as necessary.

<Storage stabilizer>
Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 5% by weight in a total of 100% by weight of the resin composition.

《Leveling agent》
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-330 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in a total of 100% by weight of the resin composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.
<Production method of resin composition>
The resin composition for obtaining the photosensitive dry film of the present invention includes a compound represented by the general formula (I) or a cardo resin (A), a silane compound (B) having a urethane or amide skeleton, and oxide fine particles (C). If necessary, it can be obtained by stirring and mixing a compound having an ethylenically unsaturated double bond, a polyfunctional monomer, a photopolymerization initiator, an antioxidant, a leveling agent, and other components.
The resin composition for obtaining the photosensitive dry film of the present invention is 5 μm or larger coarse particles, preferably 1 μm or larger coarse particles, more preferably 0.8 μm, by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove coarse particles of 5 μm or more, mixed dust and foreign matters.

<Resin composition layer>
The resin composition layer in the present invention can be obtained by coating the resin composition dissolved in a solvent on a film substrate and then drying the solvent. Although the thickness of the resin composition layer after coating / solvent drying is not specifically limited, Usually, it is preferable that it is the range of 0.5-20 micrometers.
<Film base>
If the film base material in this invention is a film form, it will not specifically limit, A conventionally well-known thing can be used. For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide, polyester, polyethylene, polycarbonate, polyvinyl butyrate, polypropylene, vinyl chloride and the like can be exemplified, and a film having good peelability such as a separate film is preferable. . Further, the film substrate may be composed of a single material or may be a laminate of a plurality of layers, and the thickness is not limited as long as it is not contrary to the gist of the present invention, but usually 2 to 400 μm. A range is preferable.

<Photosensitive dry film>
Since the resin composition layer of the present invention and the cured product thereof are characterized by excellent alkali developability, they can be suitably used for applications in which a coating film forming process including photocuring, alkali development, and post-cure is used.
After the photosensitive dry film of the present invention is laminated to a desired substrate, bubbles and the like are removed and adhered to a circuit by lamination or vacuum lamination. After this pasting step, there may be a case where the radiation curing is performed through a separate film, or a case where the development pattern is brought into contact after the separation film is peeled to perform the radiation curing. After radiation curing, a pattern is formed by developing, and a film having excellent resistance is formed by heat curing as post-cure. The post cure is preferably 80 ° C. to 200 ° C. for 10 minutes to 2 hours. Further, in order to further improve the resistance of the coating film, an active energy ray can be irradiated as necessary after post-curing. By irradiating the active energy ray after the post cure, the coating film durability can be further improved.

The insulating film obtained by using the photosensitive dry film of the present invention can be cured by a known radiation curing method to obtain a cured product. As active energy rays, electron beams, ultraviolet rays, and visible light of 400 to 500 nm are used. Can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source to be irradiated. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) for ultraviolet light and visible light of 400 to 500 nm. Specifically, an ultra-high pressure mercury lamp, a xenon mercury lamp, or a metal halide lamp is often used because of the point light source and the stability of luminance. The active energy dose to be irradiated, can be set appropriately in the range of 5~2000mJ / cm ^2, it is preferably in the range on the easy of 50~1000mJ / cm ² management process. Further, these active energy rays can be used in combination with heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

As the base material of the insulating film formed using the photosensitive dry film of the present invention, it can be applied to metal, metal oxides such as ITO, molybdenum, ceramics, glass, plastic, wood, slate, etc. It is not limited. Specific types of plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, melamine resin, and the like. Examples of the shape of the substrate include a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber shape, but are not particularly limited.

The photosensitive dry film of the present invention may be used for any of a protective film application, a flat film application, and a touch panel insulating film application, and in each application, pattern formation by photolithography is particularly preferable.

Hereinafter, the present invention will be described by way of examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
Prior to Examples, the compound represented by the general formula (I) or the cardo resin (A), the method for measuring the weight average molecular weight of the silane compound (B) having an amide or urethane skeleton, the compound represented by the general formula (I) or A method for calculating the double bond equivalent of the cardo resin (A) will be described.

(Weight average molecular weight (Mw) of compound represented by general formula (I) or cardo resin (A))
As for the weight average molecular weight (Mw) of the compound (A) having a fluorene skeleton, “HLC-8220GPC” (manufactured by Tosoh Corporation) is used as the apparatus, and “TSK-GEL SUPER HZM-N” is connected in series as the column. Polystyrene equivalent molecular weight measured using THF as a solvent.
(Weight average molecular weight (Mw) of silane compound (B) having amide or urethane skeleton)
The weight average molecular weight (Mw) of the silane compound (B) having an amide or urethane skeleton was calculated by analyzing the molecular weight distribution with a gel permeation chromatography (GPC) analyzer (Shodex GPC system manufactured by Showa Denko KK).

(Double bond equivalent of compound represented by general formula (I) or cardo resin (A))
Double bond equivalent is a measure of the amount of double bonds contained in a molecule. If the compounds have the same molecular weight, the amount of double bonds introduced increases as the double bond equivalent value decreases. .
The double bond equivalent was calculated by the following formula.
[Double bond equivalent] = [Molecular weight of monomer component having double bond] / [Composition ratio of monomer component having double bond in resin]
(Production example of compound represented by general formula (I) or cardo resin (A))
<Example of production of cardo resin solution A1-1>

  Dry air was introduced into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas introduction tube, and 200 parts of a 50% PGMEA solution of 9,9-bis (4-hydroxyethoxyphenyl) fluorene (BPEF) was added. 67.6 parts of phthalic acid and 1.0 part of triphenylphosphine were charged, and stirring was continued at 100 ° C. for 10 hours. After cooling to room temperature, A1-1 having a solid content of 30% was obtained by diluting with PGMEA. The weight average molecular weight was 3000.

BPEF: “Bisphenoxyethanol fluorene” (Osaka Gas Chemical Co., Ltd.); 9,9-bis (4-hydroxyethoxyphenyl) fluorene

(Cardo resin solution (A1-2, A1-3, A1-4))
A resin solution (A1) having a weight average molecular weight as shown in Table 1 was prepared in the same manner as the resin solution (A1-1) except that the composition and the amount (parts by weight) shown in Table 1 were changed. -2, A1-3, A1-4) were obtained.
<Example of production of cardo resin solution A2-1>

(Production example of photosensitive polyester resin)
Dry air was introduced into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube, and 9,9-bis [4- (3-acryloyloxy-2-hydroxy) propoxyphenyl] fluorene (ASF- 400) of 50% PGMEA solution, 40 parts of phthalic anhydride and 1.0 part of triphenylphosphine were added, and stirring was continued at 100 ° C. for 10 hours. After cooling to room temperature, A2-1 having a solid content of 30% was obtained by diluting with PGMEA. The weight average molecular weight was 7000.
<Production example of cardo resin A3-1>

(Example of production of non-photo acrylic resin)
50% PGMEA of 9,9-bis [4- (3-acryloyloxy-2-hydroxy) propoxyphenyl] fluorene (ASF-400) in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube 200 parts of the solution was added, heated to 80 ° C. while introducing dry nitrogen, and a mixture of 20 parts of methacrylic acid and 13 parts of 2,2′-azobisisobutyronitrile was added dropwise at the same temperature over 1 hour. A polymerization reaction was performed. After the completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of PGMEA was added, followed by stirring at the same temperature for 3 hours to obtain a copolymer. It was. After cooling to room temperature, A3-1 containing a photopolymerizable functional group having a solid content of 30% and a carboxyl group was obtained by diluting with PGMEA. The weight average molecular weight was 4000.

(Cardo resin solution (A3-2, A3-3, A3-4))
A resin solution (A3) having a weight average molecular weight as shown in Table 3 was prepared in the same manner as the resin solution (A3-1) except that the composition and the blending amount (parts by weight) shown in Table 3 were changed. -2, A3-3, and A3-4) were obtained.

PGMEA: propylene glycol monomethyl ether acetate ASF-400 (50%); propylene glycol monomethyl ether acetate of “9,9-bis (4-hydroxyphenyl) fluorene glycidyl ether acrylic acid adduct” (manufactured by Nippon Steel Chemical Co., Ltd.) Solution (adjusted to a solid content of 50%); 9,9-bis [4- (3-acryloyloxy-2-hydroxy) propoxyphenyl] fluorene MAA: methacrylic acid

<Production example of cardo resin A4-1>

(Production example of photo acrylic resin)
50% PGMEA of 9,9-bis [4- (3-acryloyloxy-2-hydroxy) propoxyphenyl] fluorene (ASF-400) in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube 200 parts of the solution was added, heated to 80 ° C. while introducing dry air, and a mixture of 35 parts of methacrylic acid and 8 parts of 2,2′-azobisisobutyronitrile was added dropwise at the same temperature over 1 hour. A polymerization reaction was performed. After the completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of PGMEA was added, followed by stirring at the same temperature for 3 hours to obtain a copolymer. It was. Subsequently, 20 parts of tetrahydrophthalic anhydride were charged and stirring was continued for 10 hours at the same temperature. After cooling to room temperature, A4-1 containing a photopolymerizable functional group having a solid content of 40% and a carboxyl group was obtained by diluting with PGMEA. The weight average molecular weight was 8000.
<Method for Producing Silane Compound (B-1) Having Amide or Urethane Skeleton>
(Silane compound having amide or urethane skeleton (B-1)
Prepare a flask with a cooling tube as a reaction vessel, and stir well 100 g of 3-isocyanatopropyltrimethoxysilane ("Y-5187" manufactured by Momentive Performance Materials Japan) and 100 g of methanol (manufactured by Kishida Chemical Co., Ltd.). A mixture was prepared, purged with nitrogen, and heated in an oil bath while stirring to raise the temperature of the reaction vessel to 60 ° C. After the temperature of the reaction vessel was stabilized at 60 ° C., the mixture was stirred for 6 hours. After confirming the completion of the reaction by FT-IR spectrum, the temperature of the reaction vessel was lowered to room temperature, and the sample was taken out and stored in a container purged with nitrogen. As a result of analyzing the molecular weight distribution with a gel permeation chromatography (GPC) analyzer (Shodex GPC system manufactured by Showa Denko KK), the weight average molecular weight (Mw) was about 237.
<Method for producing silane compound (B-2) having amide or urethane skeleton>
(Silane compound having amide or urethane skeleton (B-2)
Prepare a flask equipped with a cooling tube as a reaction tank, and thoroughly stir and mix 100 g of 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 g of ethanol (manufactured by Kishida Chemical Co., Ltd.). After substituting with nitrogen, the temperature of the reaction vessel was raised to 60 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 60 ° C., the mixture was stirred for 6 hours. After confirming the completion of the reaction by FT-IR spectrum, the temperature of the reaction vessel was lowered to room temperature, and the sample was taken out and stored in a container purged with nitrogen. As a result of analyzing the molecular weight distribution with a gel permeation chromatography (GPC) analyzer (Shodex GPC system manufactured by Showa Denko KK), the weight average molecular weight (Mw) was about 293.
<Method for Producing Silane Compound (B-3) Having Amide or Urethane Skeleton>
(Silane compound having amide or urethane skeleton (B-3)
Prepare a flask equipped with a cooling tube as a reaction vessel, and stir and mix 100 g of 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 g of 2,8-ethyl-1-tetradecanol well. The prepared product was purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 60 ° C. After the temperature of the reaction vessel was stabilized at 60 ° C., the mixture was stirred for 10 hours. After confirming the completion of the reaction by IR spectrum, the temperature of the reaction vessel was lowered to room temperature, and the sample was taken out and stored in a container purged with nitrogen. As a result of analyzing the molecular weight distribution with a gel permeation chromatography (GPC) analyzer (Shodex GPC system manufactured by Showa Denko KK), the weight average molecular weight (Mw) was about 520.
<Method for producing silane compound (B-4) having amide or urethane skeleton>
(Silane compound having amide or urethane skeleton (B-4)
Prepare a flask equipped with a cooling tube as a reaction tank, and mix well with 100 g of 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) and 50 g of ethanol (manufactured by Kishida Chemical Co., Ltd.). After substituting with nitrogen, the temperature of the reaction vessel was raised to 60 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 60 ° C., the mixture was stirred for 8 hours. After confirming the completion of the reaction by FT-IR spectrum, the temperature of the reaction vessel was lowered to room temperature to obtain 150 g of an ethanol solution of (3-carbamateethyl) propyltriethoxysilane having a solid content of 79% by weight.
A 100 mL four-necked flask equipped with a Dimroth-type cooling condenser, a Dean Stark, a stirrer, and a thermometer was prepared by sufficiently substituting with nitrogen, and then 100 g of the ethanol solution of (3-carbamateethyl) propyltriethoxysilane, Ethanol (25 mL) and sodium acetate (0.06 g) were charged, and water (1.3 g) was slowly added. The mixture was aged at 30 to 40 ° C. for 1 hour under normal pressure and then aged for 2 hours under reflux. After aging, the solvent was gradually extracted at normal pressure, and when the kettle temperature reached 105 ° C., the heating was stopped and the system was cooled. The obtained solution was filtered, and dried under reduced pressure at 120 ° C. for 1 hour to obtain 35 g of a siloxane oligomer that was a transparent oily product. As a result of analyzing the molecular weight distribution with a gel permeation chromatography (GPC) analyzer (Shodex GPC system manufactured by Showa Denko KK), the weight average molecular weight (Mw) was about 4000.
<Method for producing silane compound (B-5) having amide or urethane skeleton>
(Silane compound having amide or urethane skeleton (B-5)
Prepare a flask equipped with a cooling tube as a reaction tank, and mix well with 100 g of 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) and 50 g of ethanol (manufactured by Kishida Chemical Co., Ltd.). After substituting with nitrogen, the temperature of the reaction vessel was raised to 60 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 60 ° C., the mixture was stirred for 8 hours. After confirming the completion of the reaction by FT-IR spectrum, the temperature of the reaction vessel was lowered to room temperature to obtain 150 g of an ethanol solution of (3-carbamateethyl) propyltriethoxysilane having a solid content of 79% by weight.
A 100 mL four-necked flask equipped with a Dimroth-type cooling condenser, a Dean Stark, a stirrer, and a thermometer was prepared by sufficiently substituting with nitrogen, and then 100 g of the ethanol solution of (3-carbamateethyl) propyltriethoxysilane, Ethanol (25 mL) and sodium acetate (0.06 g) were charged, and water (1.3 g) was slowly added. The mixture was aged at 30 to 40 ° C. for 1.5 hours under normal pressure and then aged for 3 hours under reflux. After aging, the solvent was gradually extracted at normal pressure, and when the kettle temperature reached 105 ° C., the heating was stopped and the system was cooled. The obtained solution was filtered and dried under reduced pressure at 120 ° C. for 1 hour to obtain 34 g of a siloxane oligomer which was a transparent oily product. As a result of analyzing the molecular weight distribution with a gel permeation chromatography (GPC) analyzer (Shodex GPC system manufactured by Showa Denko KK), the weight average molecular weight (Mw) was about 5500.
<Method for producing oxide fine particle (C) dispersion>
(Production of dispersant (Ti-1))
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 80.0 parts of biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), pentaerythritol triacrylate (2) (Japan) Kayaku Co., Ltd., trade name: KAYARAD PET-30) 250.0 parts, hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) 0.16 parts, cyclohexanone 141.2 parts were charged, and the temperature was raised to 85 ° C. . Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 33.9 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst. The mixture was stirred at 85 ° C. for 6 hours and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent, had a solid content of 70%, and a weight average molecular weight (Mw) of about 3130.
(Production of dispersant (Ti-2))
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 36.6 parts of pyromellitic anhydride was added, and it was made to react at 120 degreeC for 2 hours, and the dispersing agent (Ti-2) was obtained. The obtained dispersant (Ti-2) was a white wax-like solid at room temperature.
(Production of dispersant (Zr))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 80.0 parts of biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), pentaerythritol triacrylate (1) (Osaka) Organic Chemical Industry Co., Ltd., trade name: Biscoat # 300) 250.0 parts, hydroquinone (Wako Pure Chemical Industries, Ltd.) 0.16 parts, cyclohexanone 141.2 parts were charged, and the temperature was raised to 85 ° C. . Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 33.9 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) were added as a catalyst. The mixture was stirred at 85 ° C. for 6 hours and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent and had a solid content of 70% and a weight average molecular weight (Mw) of about 2830.
(Production of oxide fine particle dispersion (C-1, C-2, C-3))
Using the dispersant (Ti-1), the dispersant (Ti-2), and the dispersant (Zr), metal oxide dispersion was performed according to the formulation shown in Table 4 to prepare an oxide fine particle dispersion (the blending amount was Indicates the amount of solids). Dispersion methods are pre-dispersion (using zirconia beads (1.25 mm) as a medium and dispersing for 1 hour with a paint shaker) and main dispersion (using zirconia beads (0.1 mm) as a medium). (Dispersion with machine UAM-015). The obtained oxide fine particle dispersion was diluted with PGMEA and adjusted to the solid content of Table 4.

TiO ₂ : “TTO-51 (A)” manufactured by Ishihara Sangyo Co., Ltd. (average primary particle size: 20 nm)
ZrO ₂ : “PCS-60” manufactured by Nippon Electric Works Co., Ltd. (average primary particle size: 20 nm)
MIBK: Methyl isobutyl ketone (manufactured by Kyowa Hakko Chemical Co., Ltd.) Metobuta: 3-methoxy-1-butanol (manufactured by Daicel Chemical Industries, Ltd.)

<Production Example of Resin Composition>
(Resin composition 1 (R1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a resin composition 1.
Silane compound having urethane skeleton (B) 45.97 parts U-201; “Yuriano U-201” (manufactured by Arakawa Chemical Industries, Ltd.)
Compound (A) represented by formula (I) 6.00 parts ASF-400; “acrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorene glycidyl ether” (manufactured by Nippon Steel Chemical Co., Ltd.); 9 , 9-bis [4- (3-acryloyloxy-2-hydroxy) propoxyphenyl] fluorene photoinitiator 0.20 part OXE-01; “IRGACURE OXE-01” (manufactured by BASF); 1,2-octadione -1- [4- (phenylthio)-, 2- (o-benzoyloxime)])
Leveling agent 1.00 parts BYK-330 2%; BYK-330 (manufactured by Big Chemie); polyether structure-containing dimethylsiloxane propylene glycol monomethyl ether acetate solution (adjusted to 2% solid content)))
Solvent 46.83 parts PGMEA; propylene glycol monomethyl ether acetate

(Resin compositions 2-33 (R2-R33))
After stirring and mixing the mixture shown in Tables 5 to 10 and the blending amount (parts by weight) uniformly, the mixture was filtered through a 1 μm filter, and resin composition 2 was obtained in the same manner as resin composition 1. To 27 (R2 to R27, R30 to R33) and comparative resin compositions 1 and 2 (R28 and R29) were obtained.

<< Compound represented by formula (I) or cardo resin (A) >>
BPEF-A; bisphenoxyethanol fluorene acrylate, BPEF-A (manufactured by Osaka Gas Chemical Company); 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene; ASF-400; “9,9- Acrylic acid adduct of glycidyl ether of bis (4-hydroxyphenyl) fluorene "(manufactured by Nippon Steel Chemical Co., Ltd.); 9,9-bis [4- (3-acryloyloxy-2-hydroxy) propoxyphenyl] fluorene << urethane or amide Silane compound having skeleton (B) >>
U-201; polyurethane-silica hybrid (Arakawa Chemical Industries, Ltd .; “Yuriano U-20”)
1 ")
AC601; Epoxy-silica hybrid (Arakawa Chemical Industries, Ltd .; “Composeran AC601”
")
<< Oxide fine particle (C) dispersion >>
PMA-ST (manufactured by Nissan Chemical Co., Ltd.); PGMEA dispersion of silicon oxide fine particles (solid content 30%)
《Polyfunctional monomer》
・ V # 802; Biscote # 802 (Osaka Organic Chemical Co., Ltd.)
Mixture of tripentaerythritol octaacrylate and tetrapentaerythritol decaacrylate pentapentaerythritol dodecaacrylate

<< Photopolymerization initiator >>
OXE-01; IRGACUREOXE-01 (manufactured by BASF); 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)]

《Leveling agent》
-BYK-330 2% (manufactured by Big Chemie); polyether structure-containing dimethylsiloxane PGMEA solution (adjusted to 2% solid content)
"solvent"
・ PGMEA; Propylene glycol monomethyl ether acetate

<Production of photosensitive dry film>
[Examples 1-31, Comparative Examples 1 and 2]
The resin compositions R1 to R33 were uniformly coated on a 12 μPET film (S-12 manufactured by Toray DuPont Co., Ltd.) so that the dry film thickness was 2 μm, dried at 100 ° C. for 5 minutes, and then cooled to room temperature. The photosensitive dry film of Examples 1-27 and Comparative Examples 1-2 was obtained by laminating a biaxially oriented polypropylene film (OPP film) on the surface of the photosensitive resin composition.
<Evaluation of photosensitive dry film>
The photosensitive dry films were evaluated by the following evaluation methods. The results are shown in Tables 11-15.

(Measurement of transmittance after additional firing)
The OPP film was peeled off from the photosensitive dry film, and vacuum laminated to a glass substrate (Corning Glass Eagle 2000). The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. Next, ultraviolet exposure was performed using an ultrahigh pressure mercury lamp at an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² . Furthermore, the obtained substrate was heated at 230 ° C. for 20 minutes and allowed to cool. The substrate returned to room temperature was heated at 260 ° C. for 60 minutes and allowed to cool. Using a microspectrophotometer ("OSP-100" manufactured by Olympus Optical Co., Ltd.), the transmittance of the obtained coating film at a wavelength of 400 nm was determined by a liquid immersion method. The film thickness was measured with a stylus type film thickness meter DECTAC-3 manufactured by ULVAC.
<Evaluation criteria>
Transmittance 95% or more: Practical level (judgment ○)
Transmittance <95%: Level not suitable for practical use (judgment x)

(Measurement of refractive index)
The OPP film was peeled off from the photosensitive dry film and vacuum-laminated to a 100 μPET film (Toray Lumirror U34 # 100). The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. Next, using an ultra-high pressure mercury lamp, UV exposure was performed at an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² , and then heated and dried at 100 ° C. for 30 minutes. The obtained film was measured using a multi-wavelength Abbe refractometer (manufactured by Atago, DR-M2 <use of circulating constant temperature water bath 60-C3>) while maintaining a temperature of 25 ° C. and measuring a refractive index at 589 nm.

(Measurement of pencil hardness)
The OPP film was peeled off from the photosensitive dry film and vacuum-laminated on the following measurement substrate. The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. Next, ultraviolet exposure was performed using an ultrahigh pressure mercury lamp at an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² . Further, the ITO film was heated at 150 ° C. for 20 minutes, and the glass substrate was heated at 230 ° C. for 20 minutes. The surface hardness of the insulating film was measured by a scratch hardness (pencil method) test according to JIS K5600-5-4.
<Measurement substrate>
(1) 125μ ITO film (Toyobo 300R)
(2) Glass (Corning Glass Eagle 2000)

(Measurement of ITO adhesion)
The OPP film is peeled off from the photosensitive dry film, vacuum-laminated on a 125 μITO film (300R manufactured by Toyobo Co., Ltd.), and then irradiated with ultraviolet light at an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² using a super high pressure mercury lamp from above the 12 μPET film. After exposure, an evaluation sample was prepared by heating at 150 ° C. for 20 minutes. About the obtained board | substrate, the base-material adhesiveness of the coating film was evaluated by the adhesiveness (cross-cut method) test according to JISK5600-5-6, and the number of peeling in 25 grids was counted.
<Evaluation criteria>
Number of cross-cuts peeled off 0 → Excellent level (judgment ◎)
Number of cross-cuts less than 1 (edge peel; level at which cross-cuts are peeled off) → Practical level (Judgment ○)
Number of peeled grids: 1 or more and 3 or less → Practical level (judgment △)
Number of peeled grids greater than 3 → Levels that impede practical use (judgment ×)

(Measurement of Mo adhesion)
The OPP film is peeled off from the photosensitive dry film, vacuum-laminated on a Mo film manufactured by Toho Kaken Co., Ltd., and then exposed to ultraviolet light at an illuminance of 20 mW / cm 2 and an exposure amount of 50 mJ / cm ² using a super high pressure mercury lamp on the 12 μPET film. After that, an evaluation sample was prepared by heating at 230 ° C. for 20 minutes. About the obtained board | substrate, the base-material adhesiveness of the coating film was evaluated by the adhesiveness (cross-cut method) test according to JISK5600-5-6, and the number of peeling in 25 grids was counted.
<Evaluation criteria>
Number of cross-cuts peeled off 0 → Excellent level (judgment ◎)
Number of cross-cuts less than 1 (edge peel; level at which cross-cuts are peeled off) → Practical level (Judgment ○)
Number of peeled grids 1 or more and 3 or less → Practical level (judgment △ ○)
Number of peeled grids: 3 or more and 5 or less → Practically practically no problem (judgment △)
Number of peeled grids greater than 5 → Practical hindrance level (judgment ×)

(ITO etchant resistance)
After forming a coating film on the ITO substrate by the same method as that prepared for the measurement of the ITO adhesion, it was immersed in an ITO etchant; nitric acid / hydrochloric acid / water = 0.1 / 1/1 at 40 ° C. for 5 minutes to obtain pure After washing with water, it was left for 24 hours. The obtained substrate was evaluated for substrate adhesion of the coating film by an adhesion (cross-cut method) test according to JIS K5600-5-6, and the number of peels in 25 grids was counted.
<Evaluation criteria>
Number of cross-cuts peeled off 0 → Excellent level (judgment ◎)
Number of peeled grids 1 or more and less than 3 → Practical level (Judgment ○)
Number of peeled grids 3 or more and 5 or less → Practical level (judgment △)
Number of peeled grids greater than 5 → Practical hindrance level (judgment ×)

(Mo etchant resistance)
After forming a coating film on the ITO base material by the same method as that prepared for the measurement of Mo adhesion, it was immersed in ITO etchant; nitric acid / hydrochloric acid / water = 0.1 / 1/1 at 40 ° C. for 5 minutes, and pure After washing with water, it was left for 24 hours. The obtained substrate was evaluated for substrate adhesion of the coating film by an adhesion (cross-cut method) test according to JIS K5600-5-6, and the number of peels in 25 grids was counted.
<Evaluation criteria>
Number of cross-cuts peeled off 0 → Excellent level (judgment ◎)
Number of peeled grids 1 or more and less than 3 → Practical level (Judgment ○)
Number of peeled grids 3 or more and 5 or less → Practical level (judgment △ ○)
Number of peeled grids 5 or more and 10 or less → Practically no problem (judgment △)
Number of peeled grids greater than 10 → Levels that impede practical use (judgment ×)

(Mo etchant resistance)
After being applied on the Mo substrate in the same manner as that prepared for measuring Mo adhesion, it was immersed in Mo etchant; phosphoric acid / acetic acid / nitric acid / water = 80/5/5/10 at 40 ° C. for 5 minutes, After washing with pure water, it was left for 24 hours. The obtained substrate was evaluated for substrate adhesion of the coating film by an adhesion (cross-cut method) test according to JIS K5600-5-6, and the number of peels in 25 grids was counted.
Number of cross-cuts peeled off 0 → Excellent level (judgment ◎)
Number of peeled grids 1 or more and less than 3 → Practical level (Judgment ○)
Number of peeled grids 3 or more and 5 or less → Practical level (judgment △)
Number of peeled grids greater than 5 → Practical hindrance level (judgment ×)

  As shown in Tables 11 to 15, a resin composition containing a compound represented by the general formula (I) or a cardo resin (A) and a silane compound (B) having a urethane or amide skeleton is applied to a film substrate and dried. By using the photosensitive dry film thus obtained, good results were obtained in terms of transmittance, heat resistance, pencil hardness, adhesion to substrates such as ITO and Mo, etchant resistance, and refractive index.

  Especially, when the structure of the silane compound (B) is represented by the general formula (1), good results were obtained in transmittance, pencil hardness, and substrate adhesion.

  When Examples 1 and 2 and Comparative Examples 1 and 2 are compared, Example 1 containing a compound represented by general formula (I) or a cardo resin (A) and a silane compound (B) having a urethane or amide skeleton, No. 2 showed good results in pencil hardness, substrate adhesion and etchant resistance.

  When Examples 1-4 are compared, when the structure of the silane compound (B) having a urethane or amide skeleton is represented by the general formula (1), good results are obtained in transmittance, pencil hardness, and Mo adhesion. It was.

  When Examples 3 to 6 and Example 9 are compared, Examples 5, 6, and 9 in which the weight average molecular weight (Mw) of the silane compound (B) having a urethane or amide skeleton is 200 or more and less than 5000 are pencil hardness and ITO. The result was excellent in adhesion. Further, when Examples 7 to 11 are compared, Examples 8, 9, and 10 in which the content of the silane compound (B) in the total solid content of 100% by weight of the resin composition is 5% by weight or more and less than 50% by weight. Gave good results in transmittance and pencil hardness.

  When Examples 9, 12, 13, 14 or Examples 15-18 are compared, Examples 12, 13 or Examples in which the molecular weight of the compound represented by the general formula (I) or the cardo resin (A) is 5000 to 50000 16 and 17 resulted in excellent pencil hardness.

  Furthermore, when Examples 13 and 19 were compared, Example 13 combined with a monomer having a fluorene skeleton obtained a high refractive index without impairing etchant resistance.

  When Examples 19, 20, 21, and 22 were compared, in Examples 20, 21, and 22 containing oxide fine particles (C), the pencil hardness was improved, and the substrate adhesion and the Mo etchant resistance were improved. In Examples 21 and 22 containing titanium or zirconium having a high refractive index, not only the refractive index but also the ITO etchant resistance was improved.

  When Examples 21, 23, 24, and 25 are compared, the content of the oxide fine particles (C) is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the solid content of the resin composition, The result was a high pencil hardness of 24.

  When Examples 24, 26, and 27 were compared, when the cardo resin (A) had an ethylenic double bond, the pencil hardness was high.

Claims (10)

A photosensitive dry film comprising a film substrate and a resin composition layer provided on the film substrate, wherein the resin composition layer is at least a compound represented by the following general formula (I) or A photosensitive dry film formed from a resin composition containing a cardo resin (A) and a silane compound (B) having a urethane or amide skeleton.
Formula (I)


[In General Formula (I), X ¹ and X ² are each independently a hydroxyl group, —O (AO) _p H group (wherein A represents an alkylene group having 2 to 3 carbon atoms, p is Represents an integer from 1 to 1000000), represents an amino group or an N-monosubstituted amino group,
R ^{1 to} R ⁴ each independently represent a hydrocarbon group that may be substituted, an alkoxy group that may be substituted, an N, N-disubstituted amino group, or a halogen atom;
m1 and m2 are each independently an integer of 0 to 3, m1 + m2 = 0 to 6;
n1 to n4 are each independently an integer of 0 to 4. However, m1 + n1 and m2 + n2 are integers of 0-5. ] The photosensitive dry film according to claim 1, wherein the silane compound (B) having a urethane or amide skeleton is a silane compound represented by the following general formula (1).
General formula (1):

[In General Formula (1), R ³¹ is an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon An aralkyl group having 7 to 30 carbon atoms, an alkaryl group having 7 to 30 carbon atoms,
X is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkoxylene group having 1 to 20 carbon atoms,
R ³² , R ³³ and R ³⁴ are each independently an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. A group, an aralkyl group having 7 to 30 carbon atoms, an alkaryl group having 7 to 30 carbon atoms, a siloxane group having a substituent, a halogen atom, a hydroxy group and hydrogen]   The weight average molecular weight (Mw) of the silane compound (B) having a urethane or amide skeleton is 200 or more and less than 5000, and the content of the silane compound (B) in the total solid content of 100% by weight of the resin composition is The photosensitive dry film according to claim 1 or 2, wherein the content is 5% by weight or more and less than 50% by weight.   The photosensitive dry film according to claim 1, wherein the cardo resin (A) has a weight average molecular weight (Mw) of 5000 to 50000.   The photosensitive dry film according to claim 1, further comprising oxide fine particles (C) in the resin composition.   6. The photosensitive dry film according to claim 5, wherein the oxide fine particles (C) are oxide fine particles (C) of at least one element selected from zirconium and titanium.   7. The photosensitive property according to claim 5, wherein the content of the oxide fine particles (C) is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the solid content of the resin composition. Dry film.   The photosensitive dry film according to claim 1, wherein the compound represented by the general formula (I) or the cardo resin (A) has an ethylenically unsaturated double bond.   The protective film formed using the photosensitive dry film in any one of Claims 1-8.   The insulating film for touchscreens formed using the photosensitive dry film in any one of Claims 1-8.