JP2014091790A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition favorable in terms of etchant resistance and adhesiveness to a substrate or base, etc., excellent in terms of film hardness, and capable of forming, by virtue of the high refractive index thereof and the absence of coverage target transparency, a protective film and an insulating film or anti-glare film for a touch panel.SOLUTION: The provided resin composition includes, in attempts to solve problems encountered on high-temperature firing occasions such as yellowish color change, transmissivity loss, aggravation of insulating capacity, deficient stability, etc., oxide particulates, an alkali-soluble resin, and (i) a specified fluorene skeletal compound or (ii) a thermosetting resin and a polyfunctional monomer having at least 4 functional groups. The problems are solved by a resin composition including at least (A) a compound expressed by the general formula (I) or cardo resin and (B) a silane compound having a urethane or amide skeleton.

Description

  The present invention relates to a resin composition for forming a coating film such as a protective film, an insulating film for a touch panel, and an antireflection film.

  In recent years, as electronic devices have become more sophisticated, diversified, and reduced in size and weight, those equipped with a transparent touch panel on the front surface of a display element such as a liquid crystal display are increasing. An increasing number of devices display and select characters, symbols, and patterns displayed on the display element through the transparent touch panel, and switch each function of the device by operating the 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 the 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. The capacitance method detects a position by detecting a 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 includes 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 Correction to liquids (etchant resistance), heat resistance to high-temperature firing process in touch panel manufacturing process, transmittance and insulation when made into a laminated substrate, and coloring by touch panel components such as ITO, It is required to adjust the chromaticity so that a * = 0 and b * = 0.

In addition, when applied to the surface of other layers such as transparent electrode patterns such as ITO, the difference in refractive index increases, causing a “bone-viewing phenomenon” in which the ITO pattern becomes easier to see, which reduces the visibility of the liquid crystal display screen. (Patent Document 4).
In addition, high surface hardness is required for insulating films and protective films used for touch panel applications. Patent Document 5 discloses a method of adding inorganic oxide fine particles to a resin component.
Furthermore, Patent Document 6 discloses a method for improving substrate adhesion using an isocyanate group-containing silane compound.

However, in these methods, problems such as yellowing due to a baking process at a high temperature, low transmittance, deterioration of insulation, and insufficient stability and visibility are observed.
That is, the conventional photosensitive composition is excellent in substrate adhesion, pencil hardness, and resistance, and cannot satisfy all of transmittance, refractive index, insulation, stability, visibility, and the like.
Also, in recent years, transmittance and visibility can be improved by suppressing reflection of light by providing a coating film having a high refractive index on a capacitive touch panel, a liquid crystal display device, an organic EL display device, or the like. It is getting more. The coating film having a high refractive index is, for example, a hard coating layer having a high refractive index, a protective film (Patent Document 7), an antireflection film (Patent Document 8), or the like. However, it is difficult for the hard coat layer to achieve both high refractive index and high hardness characteristics, and the antireflection film has problems such as high production cost in the apparatus and process.

  Therefore, recently, an insulating film, a protective film, and a planarizing film having a high refractive index have been developed. The insulating film is a laminated body for insulating between metal wirings indispensable in the above device. The protective film is a laminate for protecting metal wiring, color filters, organic EL elements, and the like. The planarization film is a laminate for planarizing the base so that there is no difference in thickness when forming a color filter or an organic EL element. Photosensitive resin compositions are widely used for pattern formation of these insulating films, protective films, flattening films, etc. because the number of steps for obtaining the required pattern shape is small and sufficient flatness is obtained. Has been. In order to increase the refractive index, metal oxide fine particles such as titanium and antimony having a high refractive index are generally added (Patent Document 9).

However, when a material having a high refractive index such as metal oxide fine particles is used, the coating film is whitened and the total light transmittance is lowered or a residue is generated on the substrate in the pattern formation process. Such troubles are likely to occur.
That is, a conventional resin composition containing only metal oxide fine particles could not have both a high refractive index, good transmittance, and good developability.

JP 2008-65748 A JP 2009-15490 A JP 2010-44453 A JP-A-08-240800 JP 2000-281863 A JP 2011-102385 A JP 2007-84815 A JP 2009-134238 A JP 2007-084815 A

  The object of the present invention is to provide a protective film, an insulating film for a touch panel or a reflective film because it has good etchant resistance and good adhesion to a substrate and a base, and has excellent film hardness, high refractive index and no visible bones. It aims at providing the resin composition which can form a prevention film.

  As a result of intensive studies to solve the above problems, the present inventors have found that oxide fine particles, alkali-soluble resins, and (i) specific fluorene skeleton compounds or (ii) thermosetting resins and four or more A resin composition containing a polyfunctional monomer having a functional group is provided. At least, the resin composition containing the compound represented by the general formula (I) or the cardo resin (A) and the silane compound (B) having a urethane or amide skeleton is yellowed and transmitted when baked at a high temperature. The present inventors have found that problems such as a low rate, poor insulation, and insufficient stability can be solved, and the present invention has been made based on this finding.

  Forming a protective film, insulating film for touch panel, or anti-reflective film by good etchant resistance and good adhesion to substrates and substrates, excellent film hardness, high refractive index and no bone appearance It is possible to provide a resin composition that can be used.

The present invention relates to the following Embodiments I-VII.
<< Embodiment I >>
Embodiment I is a resin composition that has good adhesion to a substrate, a base, and the like, and can form a coating film such as a protective film having excellent film hardness and etchant resistance, an insulating film for a touch panel, or an antireflection film. For the purpose of provision.
As a result of intensive studies on new means that can solve the above problems, the present inventors have solved the above-mentioned problems with a resin composition containing a hydroxyl group-containing resin and an isocyanate group-containing silane compound having a specific structure. I found that it can be solved.
That is, Embodiment I relates to a resin composition comprising a resin having a hydroxyl group in a side chain, an isocyanate group-containing silane compound represented by the following formula (I-1), and a solvent.

(OCN—R ₁ ) _n —Si— (R ₂ ) _4-n Formula (I-1)
[In Formula (I-1), R ₁ represents an alkylene group having 1 to 5 carbon atoms, R ₂ represents an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group, and n represents an integer of 1 to 3. ]

[式（Ｉ−２）において、ｍは０〜４の整数であり、Ｒ₃はエーテル基、アルキレン基、トリレン基、アリーレン基、カルボニル基、スルホニル基、エステル基、および式（Ｉ−３）で表される構造を有する２価の基からなる群より選ばれるいずれかであり、Ｒ₄は水素原子またはメチル基であり、Ｒ₅はヒドロキシル基、カルボキシル基、および（メタ）アクリロイル基および（メタ）アクリロイルオキシ基からなる群より選ばれるいずれかである。]

［式（Ｉ−３）において、Ｒ_６は脂肪族、脂環式または芳香族の構造を表す。］
樹脂組成物は、さらにアセトフェノン系光重合開始剤またはオキシムエステル系光重合開始剤を含むことが好ましい。樹脂組成物は、さらにフェノール系酸化防止剤、リン系酸化防止剤及びイオウ系酸化防止剤からなる群から選ばれる少なくとも１種の酸化防止剤を含むことが好ましい。酸化防止剤が、樹脂組成物の固形分合計１００重量％中、０．１重量％以上４重量％未満であることが好ましい。 In Embodiment I, the molar ratio of the hydroxyl group of the resin to the isocyanate group of the isocyanate group-containing silane compound is preferably 0.40 to 1.60. It is preferable that the resin is a resin having an ethylenically unsaturated double bond in the side chain, the hydroxyl group equivalent is 300 to 1000 g / mol, and the double bond equivalent is 350 to 1200 g / mol. The solvent preferably contains an alcohol solvent having a boiling point of less than 130 ° C. at 760 mmHg. It is preferable that content of the said alcohol solvent is 25-300 weight part with respect to 100 weight part of solid content of a resin composition. It is preferable that the solvent further contains an ester solvent having a boiling point at 760 mmHg of 200 ° C. or higher and lower than 250 ° C. It is preferable that the resin composition further includes inorganic oxide fine particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, and zinc. The content of the inorganic oxide fine particles is preferably 5% by weight or more and less than 40% by weight in a total solid content of 100% by weight of the resin composition. It is preferable that the resin composition further includes a polyfunctional monomer having 7 or more ethylenically unsaturated double bonds represented by the following formula (I-2).

Expression in (I-2), m is an integer of 0 to 4, R ₃ is an ether group, an alkylene group, a tolylene group, an arylene group, a carbonyl group, a sulfonyl group, an ester group, and formula (I-3) R ₄ is a hydrogen atom or a methyl group, R ₅ is a hydroxyl group, a carboxyl group, and a (meth) acryloyl group and ( It is any selected from the group consisting of (meth) acryloyloxy groups. ]

[In the formula (I-3), R ₆ represents an aliphatic, alicyclic or aromatic structure. ]
The resin composition preferably further contains an acetophenone photopolymerization initiator or an oxime ester photopolymerization initiator. It is preferable that the resin composition further includes at least one antioxidant selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants. It is preferable that the antioxidant is 0.1 wt% or more and less than 4 wt% in the total solid content of 100 wt% of the resin composition.

  The resin composition capable of forming a protective film, an insulating film for a touch panel, an antireflection film, or the like according to Embodiment I has good adhesion to a base material or a base, and further has film hardness and etchant resistance. An excellent resin composition can be provided.

[式（ＩＩ−１）中、Ｒ¹は炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜３０のアルアルキル基、または、炭素数７〜３０のアルカリール基を表し、
Ｘは、炭素数１〜２０のアルキレン基、炭素数６〜２０のアリーレン基、炭素数１〜２０のアルコキシレン基、又は炭素数１〜２０のアルコキシオキシ基、
Ｒ²、Ｒ³およびＲ⁴は互いに独立して、炭素数１〜２０のアルコキシ基、炭素数６〜２０
のアリールオキシ基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜３０のアルアルキル基、炭素数７〜３０のアルカリール基、置換基を有するシロキサン、ハロゲン、ヒドロキシおよび水素を表す。] << Embodiment II >>
The embodiment II has good adhesion to a substrate and a base, and can form a coating film such as a protective film excellent in pencil hardness and etchant resistance, an insulating film for a touch panel or an antireflection film, and is stable over time. An object of the present invention is to provide a resin composition having excellent resistance. As a result of intensive studies on new means that can solve the above-mentioned problems, the present inventors have described the above by using a photosensitive composition containing at least a compound having an ethylenically unsaturated double bond and a silane compound having a specific structure. I found that I could solve the problem.
That is, Embodiment II relates to a photosensitive composition containing at least a compound having an ethylenically unsaturated double bond and a silane compound represented by the following formula (II-1).

[In Formula (II-1), R ¹ 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 Represents an aralkyl group having 7 to 30 carbon atoms or 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, or an alkoxyoxy group having 1 to 20 carbon atoms,
R ² , R ³ and R ⁴ are each independently an alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 30 carbon atoms, alkaryl group having 7 to 30 carbon atoms, siloxane having a substituent, halogen Represents hydroxy and hydrogen. ]

  In Embodiment II, the weight average molecular weight (Mw) of the silane compound is 100 or more and less than 5000, and the content of the silane compound in the total solid content of 100% by weight of the photosensitive composition is 5% by weight or more and 60%. It is preferable that it is less than weight%. The compound having an ethylenically unsaturated double bond preferably includes a compound having a double bond equivalent of 350 g / mol or more and less than 1200 g / mol and a weight molecular weight Mw of 500 or more and less than 40000. It is preferable that the photosensitive resin composition further includes oxide fine particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, and zinc. The content of the oxide fine particles is 5% by weight or more and less than 50% by weight in the total solid content of 100% by weight of the photosensitive composition, and the weight of the silane compound (b) and the weight of the oxide fine particles (c) The ratio (b / c) is preferably 0.4 or more and less than 20.0. The photosensitive composition further contains a solvent, and the solubility of the solvent in water at 20 ° C. is preferably 1 g / 100 ml or more and less than 30 g / 100 ml. The compound having an ethylenically unsaturated double bond preferably contains a compound having an acid value (in terms of solid content) of 30 mgKOH / g or more and less than 200 mgKOH / g. It is preferable that the photosensitive composition further contains tetraalkoxysilane, and the ratio (b / e) of the weight (b) of the silane compound to the weight (e) of the tetraalkoxysilane is 2 or more and less than 20.

  With the resin composition capable of forming a coating film such as the protective film of Embodiment II, the insulating film for touch panel or the antireflection film, the adhesion with the base material or the base is good, and the stability over time is excellent, It is possible to provide a resin composition excellent in pencil hardness and etchant resistance.

［式（ＩＩＩ−Ｉ）中、Ｘ¹及びＸ²は、互いに独立して、ヒドロキシル基、−Ｏ(ＡＯ)_pＨ基（ただし、Ａは、炭素数２〜３のアルキレン基を表し、ｐは１〜１００００００の整数を表す）、アミノ基又はＮ−モノ置換アミノ基を表し、
Ｒ¹〜Ｒ⁴は、互いに独立して、置換されてもよい炭化水素基、置換されてもよいアルコキシ基、Ｎ，Ｎ−ジ置換アミノ基、または、ハロゲン原子を表し、
ｍ１及びｍ２は、互いに独立して、０〜３の整数、ｍ１＋ｍ２＝０〜６の整数であり、ｎ１〜ｎ４は、互いに独立して、０〜４の整数である。ただし、ｍ１＋ｎ１及びｍ２＋ｎ２は、０〜５の整数である。］
また、実施形態ＩＩＩにおいて、ウレタンまたはアミド骨格を有するシラン化合物が、下記式（ＩＩＩ−１）で表わされるシラン化合物であることが好ましい。

[式（ＩＩＩ−１）中、Ｒ³¹は、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜３０のアルアルキル基、炭素数７〜３０のアルカリール基、
Ｘは、炭素数１〜２０のアルキレン基、炭素数６〜２０のアリーレン基、炭素数１〜２０のアルコキシレン基、又は炭素数１〜２０のアルコキシオキシ基、
Ｒ³²、Ｒ³³およびＲ³⁴は、互いに独立して、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜３０のアルアルキル基、炭素数７〜３０のアルカリール基、置換基を有するシロキサン基、ハロゲン原子、ヒドロキシ基および水素である］ << Embodiment III >>
The embodiment III has good etchant resistance and adhesion to a substrate or a base, and has excellent film hardness, high refractive index and no visible bones, for protective film, insulating film for touch panel or antireflection film It aims at providing the resin composition which can form coating films, such as.
Embodiment III relates to a resin composition containing at least a compound represented by the following formula (III-I) or a cardo resin and a silane compound having a urethane or amide skeleton.

[In Formula (III-I), X ¹ and X ² are independently of each other a hydroxyl group, —O (AO) _p H group (wherein A represents an alkylene group having 2 to 3 carbon atoms, p Represents an integer of 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, and n1 to n4 are each independently an integer of 0 to 4. However, m1 + n1 and m2 + n2 are integers of 0-5. ]
In Embodiment III, the silane compound having a urethane or amide skeleton is preferably a silane compound represented by the following formula (III-1).

[In the formula (III-1), R ³¹ represents 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, 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, or an alkoxyoxy 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 having a urethane or amide skeleton is 200 or more and less than 5000, and the content of the silane compound in the total solid content of 100% by weight of the resin composition is 5% by weight or more and 50% or more. It is preferable that it is less than weight%. It is preferable that the weight average molecular weight (Mw) of a cardo resin is 5000-50000. The resin composition preferably further contains fine oxide particles. The oxide fine particles are preferably oxide fine particles of at least one element selected from zirconium and titanium. The content of the oxide fine particles is preferably 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 compound represented by formula (III-I) or the cardo resin preferably has an ethylenically unsaturated double bond. It is preferable that the resin composition further contains a pigment. It is preferable that the pigment contains at least one selected from the group consisting of a red pigment, a blue pigment, and a purple pigment.

  The resin composition capable of forming a protective film, an insulating film for touch panel, an antireflection film, or the like according to Embodiment III has good adhesion to a substrate or a base, and further has film hardness and etchant resistance. An excellent resin composition can be provided.

<< Embodiment IV >>
Embodiment IV aims to provide a resin composition having a high refractive index and excellent developability and transmittance when forming a pattern, and capable of forming a coating film for a protective film, an insulating film for a touch panel or an antireflection film. And

［式（ＩＶ−１）中、Ｒ¹は水素原子、水酸基、フェニル基、トリル基、アミノ基、カルボキシ基、または−(ＣＨ₂)_nＣＨ₃で表されるアルキル基を示し、
Ｒ²は−Ｃ(Ａ)＝ＣＨ₂、 −ＣＯ−Ｃ(Ａ)＝ＣＨ₂、−(Ｂ)−Ｏ−ＣＯ−Ｃ(Ａ)＝ＣＨ₂、−(Ｂ)−Ｃ(Ａ)＝ＣＨ₂、−Ｏ−(Ｂ)−Ｏ−ＣＯ−Ｃ(Ａ)＝ＣＨ₂、−Ｏ−(Ｂ)−Ｃ(Ａ)＝ＣＨ₂、−ＳＨ、−(Ｂ)−ＣＯ−Ｃ(Ａ)＝ＣＨ₂、−Ｏ−(Ｂ)−ＣＯ−Ｃ(Ａ)＝ＣＨ₂、

を示し、
（Ａ）は−Ｈまたは−ＣＨ₃であり、
（Ｂ）は（ＣＨ₂）_n、（ＯＣＨ₂ＣＨ₂）_n、（ＯＣＨ₂ＣＨ₂ＣＨ₂）_n、（ＯＣＨ₂ＣＨ（ＯＨ）ＣＨ₂）_n、または（ＯＣＯＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂）_nであり、
Ｒ³は水素原子、シアノ基、ハロゲン原子またはアルキル基を示す。
ｊ、ｋおよびｍは、互いに独立して０〜４の整数、ｊ＋ｋは０〜５の整数であり、ｎは１〜２０の整数である。］
また、実施形態ＩＶにおいて、アルカリ可溶性樹脂が、下記構成単位（イ）〜（ハ）を有する樹脂を含むことが好ましい。
（イ）カルボキシル基を有する構成単位
（ロ）式（ＩＶ−２）または式（ＩＶ−３）に示す芳香族環基を有する構成単位
（ハ）式（ＩＶ−４）または式（ＩＶ−５）に示す脂肪族環基を有する構成単位

［式（ＩＶ−２）及び（ＩＶ−３）中、Ｒ⁴は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。］

構成単位（イ）〜（ハ）を有する樹脂が、構成単位（ロ）の前駆体と、構成単位（ハ）の前駆体と、エポキシ基を有するエチレン性不飽和単量体とを反応させて共重合体（ｉ１−１）を得て、次に得られた共重合体（ｉ１−１）と不飽和１塩基酸とを反応させて共重合体（ｉ１−２）を得て、さらに得られた共重合体（ｉ１−２）と多塩基酸無水物とを反応させて得られる樹脂（Ｂ１ａ）、
または構成単位（イ）の前駆体と、構成単位（ロ）の前駆体と、構成単位（ハ）の前駆体とを反応させて共重合体（ｉ２−１）を得て、次に得られた共重合体（ｉ２−１）とエポキシ基を有するエチレン性不飽和単量体とを反応させて得られる樹脂（Ｂ１ｂ）であることが好ましい。酸化物微粒子が、ジルコニウム、およびチタニウムから選ばれる少なくとも一つの元素の酸化物微粒子を含むことが好ましい。酸化物微粒子の含有量が、樹脂組成物の固形分１００重量％に対し、１０〜８０重量％であることを特徴とする前記樹脂組成物に関する。樹脂組成物が、さらに式（ＩＶ−６）で示されるシラン化合物を含むことが好ましい。

［式（ＩＶ−６）中、Ｒ³¹は、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜３０のアルアルキル基、炭素数７〜３０のアルカリール基、
Ｘは、炭素数１〜２０のアルキレン基、炭素数６〜２０のアリーレン基、炭素数１〜２０のアルコキシレン基、又は炭素数１〜２０のアルコキシオキシ基、
Ｒ³²、Ｒ³³およびＲ³⁴は、互いに独立して、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜３０のアルアルキル基、炭素数７〜３０のアルカリール基、置換基を有するシロキサン基、ハロゲン原子、ヒドロキシ基、または水素原子である。］ As a result of intensive studies on new means that can solve the above-mentioned problems, the present inventors have found that the above-described problems can be solved by using a resin composition containing oxide fine particles and a fluorene skeleton-containing monomer represented by the formula (IV-1). It was found that can be solved.
That is, Embodiment IV relates to a resin composition comprising oxide fine particles, an alkali-soluble resin, a fluorene skeleton-containing monomer represented by the following formula (IV-1), and an organic solvent.

[In Formula (IV-1), R ¹ represents a hydrogen atom, a hydroxyl group, a phenyl group, a tolyl group, an amino group, a carboxy group, or an alkyl group represented by — (CH ₂ ) _n CH ₃ ;
R ² is _{-C (A) = CH 2,} -CO-C (A) = CH 2, - (B) -O-CO-C (A) = CH 2, - (B) -C (A) = _{CH 2, -O- (B) -O} -CO-C (A) = CH 2, -O- (B) -C (A) = CH 2, -SH, - (B) -CO-C (A ) = CH ₂ , —O— (B) —CO—C (A) = CH ₂ ,

Indicate
(A) is —H or —CH ₃ ;
(B) is (CH ₂ ) _n , (OCH ₂ CH ₂ ) _n , (OCH ₂ CH ₂ CH ₂ ) _n , (OCH ₂ CH (OH) CH ₂ ) _n , or (OCOCH ₂ CH ₂ CH ₂ CH _{2 N} ) and
R ³ represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
j, k and m are each independently an integer of 0 to 4, j + k is an integer of 0 to 5, and n is an integer of 1 to 20. ]
In Embodiment IV, the alkali-soluble resin preferably contains a resin having the following structural units (A) to (C).
(A) Structural unit having a carboxyl group (b) Structural unit having an aromatic ring group represented by formula (IV-2) or formula (IV-3) (C) Formula (IV-4) or formula (IV-5) ) A structural unit having an aliphatic cyclic group

[In formulas (IV-2) and (IV-3), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

A resin having the structural units (a) to (c) reacts with a precursor of the structural unit (b), a precursor of the structural unit (c), and an ethylenically unsaturated monomer having an epoxy group. A copolymer (i1-1) is obtained, and then the copolymer (i1-1) obtained is reacted with an unsaturated monobasic acid to obtain a copolymer (i1-2), which is further obtained. A resin (B1a) obtained by reacting the obtained copolymer (i1-2) with a polybasic acid anhydride,
Alternatively, the precursor of the structural unit (a), the precursor of the structural unit (b), and the precursor of the structural unit (c) are reacted to obtain a copolymer (i2-1), and then obtained. The resin (B1b) obtained by reacting the copolymer (i2-1) with an ethylenically unsaturated monomer having an epoxy group is preferable. The oxide fine particles preferably include oxide fine particles of at least one element selected from zirconium and titanium. The content of the oxide fine particles is 10 to 80% by weight with respect to 100% by weight of the solid content of the resin composition. It is preferable that the resin composition further contains a silane compound represented by the formula (IV-6).

[In the formula (IV-6), R ³¹ represents 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, 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, or an alkoxyoxy 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, or a hydrogen atom. ]

  The weight average molecular weight (Mw) of the silane compound is preferably 200 or more and less than 5000, and the content is preferably 1% or more and less than 20% by weight in a total solid content of 100% by weight of the resin composition. The resin composition preferably further contains a colorant. It is preferable that the colorant includes at least one selected from the group consisting of a red colorant, a blue colorant, and a purple colorant.

  The resin composition capable of forming a protective film, an insulating film for a touch panel or an antireflection film according to Embodiment IV has good adhesion to a base material or a base, and further has film hardness and etchant resistance. An excellent resin composition can be provided.

<< Embodiment V >>
Embodiment V aims to provide a resin composition having a high refractive index, excellent hardness and adhesion, and capable of forming a coating film for a protective film, a touch panel insulating film or an antireflection film.

  As a result of intensive studies on new means that can solve the above problems, the present inventors have found that oxide fine particles, an alkali-soluble resin having a double bond equivalent of 200 or more and less than 500, a thermosetting compound, four or more functional groups. It has been found that the above-mentioned problems can be solved by a resin composition containing a polyfunctional monomer having a group.

  That is, the embodiment V includes oxide fine particles, an alkali-soluble resin having a double bond equivalent of 200 or more and less than 500, a thermosetting compound, and a polyfunctional monomer having four or more functional groups. It relates to a resin composition.

［式（Ｖ−１）中、Ｒ１〜Ｒ６は、それぞれ独立して水素原子、または−ＣＨ２ＯＨ、−ＣＨ２ＯＣＨ３、および−ＣＨ２ＯＣ４Ｈ９からなる群より選ばれるいずれかの置換基を表す。］ Further, in Embodiment V, the oxide fine particles are oxide fine particles of at least one element selected from zirconium and titanium, and the content is 10 to 80% by weight in 100% by weight of the solid content of the resin composition. It is preferable that It is preferable that a thermosetting compound contains the melamine compound represented by a following formula (V-1).

[In Formula (V-1), R1 to R6 each independently represent a hydrogen atom or any one substituent selected from the group consisting of —CH2OH, —CH2OCH3, and —CH2OC4H9. ]

[式（Ｖ−２）において、ｎは０〜４の整数であり、Ｒ７はエーテル基、アルキレン基、トリレン基、アリーレン基、カルボニル基、スルホニル基、エステル基、および式（Ｖ−３）で表される構造を有する２価の基からなる群より選ばれるいずれかであり、Ｒ８は水素原子またはメチル基であり、Ｒ９はヒドロキシル基、カルボキシル基、（メタ）アクリロイル基および（メタ）アクリロイルオキシ基からなる群より選ばれるいずれかである。]

［式（Ｖ−３）において、Ｒ１０は脂肪族、脂環式または芳香族の構造を表す。］
４つ以上の官能基を有する多官能単量体が、４つ以上の官能基を有するフルオレン骨格含有多官能単量体を含むことが好ましい。樹脂組成物が、さらに、下記式（Ｖ−４）で示されるシラン化合物を含むことが好ましい。

[式（Ｖ−４）中、Ｒ^３１は、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜３０のアルアルキル基、炭素数７〜３０のアルカリール基、
Ｘは、炭素数１〜２０のアルキレン基、炭素数６〜２０のアリーレン基、炭素数１〜２０のアルコキシレン基、又は炭素数１〜２０のアルコキシオキシ基、
Ｒ^３２、Ｒ^３３およびＲ^３４は、互いに独立して、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜３０のアルアルキル基、炭素数７〜３０のアルカリール基、置換基を有するシロキサン基、ハロゲン原子、ヒドロキシ基、または水素原子である。］ The thermosetting compound preferably contains an epoxy compound having an epoxy equivalent of 100 or more and less than 500 (g / eq: molecular weight per epoxy group = molecular weight / number of epoxy groups). It is preferable that the epoxy compound having an epoxy equivalent of 100 or more and less than 500 contains a fluorene skeleton. The polyfunctional monomer having four or more functional groups preferably contains a polyfunctional monomer represented by the following formula (V-2).

[In Formula (V-2), n is an integer of 0 to 4, and R7 is an ether group, an alkylene group, a tolylene group, an arylene group, a carbonyl group, a sulfonyl group, an ester group, and the formula (V-3). R8 is a hydrogen atom or a methyl group, R9 is a hydroxyl group, a carboxyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group. Any one selected from the group consisting of groups. ]

[In the formula (V-3), R10 represents an aliphatic, alicyclic or aromatic structure. ]
It is preferable that the polyfunctional monomer having four or more functional groups includes a fluorene skeleton-containing polyfunctional monomer having four or more functional groups. It is preferable that the resin composition further contains a silane compound represented by the following formula (V-4).

[In Formula (V-4), 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, 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, or an alkoxyoxy group having 1 to 20 carbon atoms,
R ³² , R ³³ and R ³⁴ are independently of each other 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, or a hydrogen atom. ]

  The weight average molecular weight (Mw) of the silane compound is preferably 200 or more and less than 5000, and the content is preferably 1% or more and less than 20% by weight in a total solid content of 100% by weight of the resin composition. The resin composition preferably further contains a colorant. It is preferable that the colorant includes at least one selected from the group consisting of a red colorant, a blue colorant, and a purple colorant.

  The resin composition capable of forming a protective film, an insulating film for a touch panel or an antireflection film of Embodiment V has good adhesion to a substrate or a base, and further has film hardness and etchant resistance. An excellent resin composition can be provided.

ここで、式（１４）中、Ｒ^１は水素原子、水酸基、フェニル基、トリル基、アミノ基、カルボキシ基、または−（ＣＨ_２）_ｎＣＨ_３で表されるアルキル基を示し、
Ｒ^２は−Ｃ（Ａ）＝ＣＨ_２、 −ＣＯ−Ｃ（Ａ）＝ＣＨ_２、−（Ｂ）−Ｏ−ＣＯ−Ｃ（Ａ）＝ＣＨ_２、−（Ｂ）−Ｃ（Ａ）＝ＣＨ_２、−Ｏ−（Ｂ）−Ｏ−ＣＯ−Ｃ（Ａ）＝ＣＨ_２、−Ｏ−（Ｂ）−Ｃ（Ａ）＝ＣＨ_２、−ＳＨ、−（Ｂ）−ＣＯ−Ｃ（Ａ）＝ＣＨ_２、−Ｏ−（Ｂ）−ＣＯ−Ｃ（Ａ）＝ＣＨ_２、

（Ａ）は−Ｈまたは−ＣＨ_３であり、
（Ｂ）は（ＣＨ_２）_ｎ、（ＯＣＨ_２ＣＨ_２）_ｎ、（ＯＣＨ_２ＣＨ_２ＣＨ_２）_ｎ、（ＯＣＨ_２ＣＨ（ＯＨ）ＣＨ_２）_ｎ、または（ＯＣＯＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２）_ｎであり、
Ｒ^３は水素原子、シアノ基、ハロゲン原子またはアルキル基を示し、
ｊ、ｋおよびｍは、互いに独立して０〜４の整数、ｊ＋ｋは０〜５の整数であり、ｎは１〜２０の整数である。
（ｉｉ）熱硬化性樹脂及び４以上の官能基を有する多官能単量体
さらに、実施形態ＶＩにおいて、有機溶剤を含有し、前記（ｉ）及び（ｉｉ）から選択される成分（ｉ）を含有することが好ましい。
前記アルカリ可溶性樹脂が、下記構成単位（イ）〜（ハ）を有する樹脂を含むことが好ましい。
（イ）カルボキシル基を有する構成単位
（ロ）式（２）または式（３）に示す芳香族環基を有する構成単位
（ハ）式（４）または式（５）に示す脂肪族環基を有する構成単位

ここで、式（２）及び（３）中、Ｒ^４は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。

<< Embodiment VI >>
Embodiment VI relates to a resin composition containing fine oxide particles, an alkali-soluble resin, and a component selected from the following (i) and (ii).
(I) Fluorene skeleton compound represented by formula (14)

Here, in Formula (14), R ¹ represents a hydrogen atom, a hydroxyl group, a phenyl group, a tolyl group, an amino group, a carboxy group, or an alkyl group represented by — (CH ₂ ) _n CH ₃ ,
R ² is _{-C (A) = CH 2,} -CO-C (A) = CH 2, - (B) -O-CO-C (A) = CH 2, - (B) -C (A) = _{CH 2, -O- (B) -O} -CO-C (A) = CH 2, -O- (B) -C (A) = CH 2, -SH, - (B) -CO-C (A ) = CH ₂ , —O— (B) —CO—C (A) ═CH ₂ ,

(A) is —H or —CH ₃ ;
(B) is (CH ₂ ) _n , (OCH ₂ CH ₂ ) _n , (OCH ₂ CH ₂ CH ₂ ) _n , (OCH ₂ CH (OH) CH ₂ ) _n , or (OCOCH ₂ CH ₂ CH ₂ CH ₂ ) _N ,
R ³ represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group,
j, k and m are each independently an integer of 0 to 4, j + k is an integer of 0 to 5, and n is an integer of 1 to 20.
(Ii) Thermosetting resin and polyfunctional monomer having 4 or more functional groups Furthermore, in embodiment VI, the organic solvent is contained, and the component (i) selected from the above (i) and (ii) It is preferable to contain.
It is preferable that the alkali-soluble resin contains a resin having the following structural units (A) to (C).
(A) A structural unit having a carboxyl group (b) A structural unit having an aromatic ring group represented by formula (2) or formula (3) (c) An aliphatic ring group represented by formula (4) or formula (5) Units to have

Here, in formulas (2) and (3), R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring.

The resin having the structural units (a) to (c) reacts the precursor of the structural unit (b), the precursor of the structural unit (c), and an ethylenically unsaturated monomer having an epoxy group. To obtain a copolymer (i1-1), and then react the copolymer (i1-1) obtained with an unsaturated monobasic acid to obtain a copolymer (i1-2). A resin (B1a) obtained by reacting the obtained copolymer (i1-2) with a polybasic acid anhydride, or a precursor of the structural unit (a), a precursor of the structural unit (b), A copolymer (i2-1) is obtained by reacting a precursor of the structural unit (c), and then the copolymer (i2-1) obtained and an ethylenically unsaturated monomer having an epoxy group are obtained. It is preferable that it is resin (B1b) obtained by making these react. The oxide fine particles preferably include oxide fine particles of at least one element selected from zirconium and titanium. The content of the oxide fine particles is preferably 10 to 80% by weight in 100% by weight of the solid content of the resin composition.

In Embodiment VI, the alkali-soluble resin preferably has a double bond equivalent of 200 or more and less than 500 and contains a component (ii) selected from (i) and (ii). Furthermore, it is preferable that the silane compound shown by the following formula (V-4) is included.

Here, in the formula (V-4), 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, 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,
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, or an alkoxyoxy 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, or a hydrogen atom.

  The silane compound preferably has a weight average molecular weight (Mw) of 200 or more and less than 5000, and a content of 1% by weight or more and less than 20% by weight in a total solid content of 100% by weight of the resin composition. Furthermore, it is preferable that a colorant is included.

式（１５）において、
Ｒ_１は、炭素数１〜２０のアルキレン基、炭素数１〜２０のアリーレン基、炭素数１〜２０のアルコキシレン基、又は炭素数１〜２０のアルコキシオキシ基、
Ｒ_２は、それぞれ独立して、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜３０のアルアルキル基、炭素数７〜３０のアルカリール基、置換基を有するシロキサン、ハロゲン、ヒドロキシ又は水素を表し
Ｒ_３は水素又は不対電子を表し、
Ｒ_４は炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜３０のアルアルキル基、炭素数７〜３０のアルカリール基又は不対電子を表し、
Ｒ_３及びＲ_４が共に不対電子の場合は、Ｃ及びＮの間は二重結合となり、
ｎは１〜３の整数を表し、同一の基が複数存在する場合はそれぞれ独立して選択される。 << Embodiment VII >>
Embodiment VII relates to a resin composition containing a compound having an ethylenically unsaturated double bond and a silane compound represented by formula (15).

In equation (15),
R ₁ is an alkylene group having 1 to 20 carbon atoms, an arylene group having 1 to 20 carbon atoms, an alkoxylene group having 1 to 20 carbon atoms, or an alkoxyoxy group having 1 to 20 carbon atoms,
R ₂ each independently represents 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, or 7 to 7 carbon atoms. Represents an aralkyl group of 30; an alkaryl group having 7 to 30 carbon atoms; a siloxane having a substituent; a halogen, hydroxy or hydrogen; and R ₃ represents hydrogen or an unpaired electron;
R ₄ 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, an aralkyl group having 7 to 30 carbon atoms, Represents an alkaryl group having 7 to 30 carbon atoms or an unpaired electron,
When R ₃ and R ₄ are both unpaired electrons, a double bond is formed between C and N,
n represents an integer of 1 to 3, and when a plurality of the same groups are present, they are independently selected.

ここで、式（Ｉ−２）において、ｍは０〜４の整数であり、Ｒ_３はエーテル基、アルキレン基、トリレン基、アリーレン基、カルボニル基、スルホニル基、エステル基、および式（Ｉ−３）で表される構造を有する２価の基からなる群より選ばれるいずれかであり、Ｒ_４は水素原子またはメチル基であり、Ｒ_５はヒドロキシル基、カルボキシル基、（メタ）アクリロイル基、および（メタ）アクリロイルオキシ基からなる群より選ばれるいずれかである。

Furthermore, in Embodiment VII, the compound having an ethylenically unsaturated double bond is a resin having a hydroxyl group in a side chain. In Formula (15), R ₁ is an alkylene group having 1 to 5 carbon atoms, R ₂ is preferably an alkoxy group having 1 to 5 carbon atoms or a hydrogen group, R ₃ and R ₄ are both unpaired electrons, and preferably a double bond between C and N. Furthermore, it is preferable to include inorganic oxide fine particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium and zinc. Furthermore, it is preferable to include a polyfunctional monomer having 7 or more ethylenically unsaturated double bonds represented by the following formula (I-2).

Here, in the formula (I-2), m is an integer of 0 to 4, and R ₃ is an ether group, an alkylene group, a tolylene group, an arylene group, a carbonyl group, a sulfonyl group, an ester group, and the formula (I- 3) selected from the group consisting of a divalent group having a structure represented by 3), R ₄ is a hydrogen atom or a methyl group, R ₅ is a hydroxyl group, a carboxyl group, a (meth) acryloyl group, And a (meth) acryloyloxy group.

Here, in the formula (I-3), R ₆ represents an aliphatic, alicyclic or aromatic structure.
Further, it preferably contains an acetophenone photopolymerization initiator or an oxime ester photopolymerization initiator. Furthermore, it is preferable to contain at least one antioxidant selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants.
In Embodiment VII, n is 1, R ₃ is hydrogen, R ₄ is an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or 1 to 20 carbon atoms in the formula (15). It is preferable that it is a C6-C20 aryl group, a C7-C30 aralkyl group, or a C7-C30 alkaryl group. Furthermore, it is preferable to include inorganic oxide fine particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium and zinc. Furthermore, it contains tetraalkoxysilane, and the ratio (b / e) between the weight (b) of the silane compound and the weight (e) of the tetraalkoxysilane is preferably 2 or more and less than 20.

The compound having an ethylenically unsaturated double bond preferably contains a cardo resin having an ethylenically unsaturated double bond. Furthermore, it is preferable to contain the compound shown by Formula (10).

Here, in Formula (10), X ¹ and X ² are each independently a hydroxyl group, —O (AO) _p H group (where A represents an alkylene group having 2 to 3 carbon atoms, p Represents an integer of 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. Furthermore, it is preferable that a colorant is included.

  Further, Embodiment VII relates to a coating film or an insulating film for a touch panel using the above resin composition.

  The silane compound represented by the formula (15) is represented by the above formula (I-1), formula (II-1), formula (III-1), formula (IV-6), or formula (V-4). It is a compound that includes the silane compounds shown.

  The present invention relates to Embodiments I to VII, and the constituent components included in each embodiment are described in detail below.

  In the present specification, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, or “(meth) acrylate”, unless otherwise specified, , “Acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, or “acrylate and / or methacrylate”.

  The term “high refractive index” means having a refractive index of at least 1.55 or more, preferably 1.57 or more, more preferably 1.60 or more. This refractive index is a value at a wavelength of 589 nm when the coating film was measured using an Abbe refractometer (NAGO-4T, manufactured by Atago).

<< Compound having an ethylenically unsaturated double bond (A1) >>
The resin composition of each embodiment can contain the compound (A1) having an ethylenically unsaturated double bond. The compound (A1) having an ethylenically unsaturated double bond is an essential component, particularly in Embodiments II and VII.

  Examples of the compound (A1) having an ethylenically unsaturated double bond include a monomer (A1-1) having an ethylenically unsaturated double bond, or a resin having an ethylenically unsaturated double bond in the side chain ( A1-2).

The compound (A1) having an ethylenically unsaturated double bond includes a monomer (A1-1) having an ethylenically unsaturated double bond, and a resin (A1- 2) and either one or both of them may be included.
The content of the compound (A1) having an ethylenically unsaturated double bond is 5 to 90% by weight from the viewpoint of increasing pencil hardness and imparting solvent resistance in a total of 100% by weight of the solid content of the resin composition. It is preferably 10 to 60% by weight. The content of the monomer (A1-1) having an ethylenically unsaturated double bond is preferably used in an amount of 5 to 80% by weight in a total of 100% by weight of the solid content of the resin composition. In this case, if it is 5% by weight or more, the effect of increasing pencil hardness and imparting solvent resistance is high, and if it is 80% by weight or less, the transmittance is high and the substrate adhesion is excellent. More preferably, it is 10 to 50% by weight. The content of the resin (A1-2) having an ethylenically unsaturated double bond is preferably 5 to 80% by weight from the viewpoint of increasing pencil hardness in the total solid content of 100% by weight of the resin composition. More preferably, it is 10 to 50% by weight.

<Monomer (A1-1) having an ethylenically unsaturated double bond>
Examples of the monomer (A1-1) having an ethylenically unsaturated double bond include the compound (a1) represented by the formula (1), the ethylenically unsaturated monomer (a2) having an acid group, and a hydroxyl group. Having an ethylenically unsaturated monomer (a3), an ethylenically unsaturated monomer having an epoxy group (a4), an ethylenically unsaturated monomer having an isocyanate group (a5), and (a1) to (a5) ) And other ethylenically unsaturated monomers (a6).

[式（１）中、Ｒ⁷およびＲ⁸は、それぞれ独立して、水素原子または置換基を有して
いてもよい炭素数１〜２５の炭化水素基を表す。] <Compound (a1) Represented by Formula (1)>

[In Formula (1), R < ⁷ > and R < ⁸ > represents the C1-C25 hydrocarbon group which may have a hydrogen atom or a substituent each independently. ]

In the formula (1), 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, n Linear or branched alkyl groups such as -propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butylcyclohexyl , Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl An alkyl group substituted with an aryl group such as; 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.

Specific examples of the compound (a1) 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, dibenzyl-2,2 '-[oxybis (methylene)] bis-2-propenoate.
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 (a2)>
Examples of the ethylenically unsaturated monomer (a2) having an acid group include (meth) acrylic acid, itaconic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α of (meth) acrylic acid. An ethylenically unsaturated monomer (unsaturated monobasic acid (a2 ′)) having a carboxyl group such as a monocarboxylic acid such as a substituted haloalkyl, alkoxyl, halogen, nitro, cyano substituent, etc.
Ethylenically unsaturated monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, polybasic acid anhydrides such as tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. Among them, (meth) acrylic acid is particularly preferable among these.

<Ethylenically unsaturated monomer having a hydroxyl group (a3)>
Examples of the ethylenically unsaturated monomer (a3) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth). Acrylate, glycerol (meth)
Examples thereof include hydroxyalkyl (meth) acrylates such as acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more.
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 (a4) having an epoxy group>
Examples of the ethylenically unsaturated monomer (a4) 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 (a5)>
Examples of the ethylenically unsaturated monomer (a5) 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 (a6) other than (a1) to (a5)>
As ethylenically unsaturated monomers (a6) other than (a1) to (a5), 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. The polyfunctional monomer will be described later.

<Resin having an ethylenically unsaturated double bond in the side chain (A1-2)>
As a resin which becomes a skeleton of the resin (A1-2) having an ethylenically unsaturated double bond in the side chain, there are a thermoplastic resin and a thermosetting resin.
The resin serving as the skeleton of the resin having an ethylenically unsaturated double bond in the side chain preferably has a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. It is. Moreover, each resin may be used independently and may be used together.

  Examples of the thermosetting resin 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.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, Examples include 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, 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 (a2) 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.

<Method of introducing acid group into resin>
As a method for introducing an acid group into the resin, a method using an ethylenically unsaturated monomer (a2) having an acid group or an ethylenically unsaturated monomer capable of imparting an acid group after polymerization is used. A method of polymerizing as a saturated monomer component may be used.
When the ethylenically unsaturated monomer (a2) having an acid group is included, the content ratio is not particularly limited, but it is preferably 5 to 70% by weight in the total 100% by weight of all ethylenically unsaturated monomer components, preferably Is preferably 10 to 60% by weight.

Examples of the ethylenically unsaturated monomer capable of imparting an acid group after polymerization include, for example, an ethylenically unsaturated monomer (a3) having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and the like. And an ethylenically unsaturated monomer (a4) having an epoxy group.
When the ethylenically unsaturated monomer (a3) having a hydroxyl group is used, for example, it has a hydroxyl group.

The polybasic acid anhydride is reacted with the hydroxyl group of the copolymer obtained by copolymerizing the ethylenically unsaturated monomer (a3) to be copolymerized with another copolymerizable ethylenically unsaturated monomer. Acid groups (carboxyl groups) can be introduced. Or when using the ethylenically unsaturated monomer (a4) which has an epoxy group, for example, the ethylenically unsaturated monomer (a4) which has an epoxy group, and the other ethylenically unsaturated monomer which can be copolymerized An unsaturated monobasic acid (a2 ′) having a carboxyl group is added to the side chain epoxy group of the copolymer obtained by copolymerizing with a 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 resin composition is a resin 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 is developed with an alkali. The composition can be developed with a liquid. 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 (a4) having an epoxy group and 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 (a4) having an epoxy group include those described in (A1-1). From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) Acrylate is preferred.

As unsaturated monobasic acid (a2 '), what was demonstrated by (A1-1) 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 method (a), for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer (a2) 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 having a hydroxyl group (a3) is used, and other than the unsaturated monobasic acid having another carboxyl group (a2 ′) or (a3) (a2 ′) There is a method in which the isocyanate group of the ethylenically unsaturated monomer (a5) having an isocyanate group is reacted with the side chain hydroxyl group of the copolymer obtained by copolymerizing with the monomer.

  Examples of the ethylenically unsaturated monomer (a3) having a hydroxyl group include those described in (A1-1), and 2-hydroxyethyl (meth) acrylate or glycerol (meta ) Acrylate is preferred.

  Examples of the ethylenically unsaturated monomer (a5) having an isocyanate group include those described in (A1-1).

  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 (a2) having an acid group, such as a compound having a double bond, and the group consisting of alkyl (meth) acrylates described as (a6) in the description in (A1) It is preferable to use one or more of each.

  The resin [A1-2] having an ethylenically unsaturated double bond in the side chain preferably has a double bond equivalent of 350 g / mol or more and less than 1200 g / mol and a molecular weight Mw of 500 or more and less than 40000. When the double bond equivalent is 350 g / mol or more, the curing shrinkage of the resin is small and the substrate adhesion is excellent. When the double bond equivalent is less than 1200 g / mol, sufficient pencil hardness is satisfied. Moreover, when the weight molecular weight Mw is 500 or more, the curing shrinkage of the resin is small and the substrate adhesion is excellent. When the weight molecular weight Mw is less than 40000, the pencil hardness is excellent.

When the double bond equivalent is 350 to 1200 g / mol and the weight molecular weight Mw is 500 or more and less than 40000, it is possible to draw out excellent pencil hardness and substrate adhesion.
In addition, the acid value of the resin [A1-2] is more preferably 30 mgKOH / g or more and less than 200 mgKOH / g from the viewpoint of developability and stability over time of the resin composition. When the acid value is 30 or more, the developability of the resin composition is excellent. When the acid value is less than 200, the silane compound (B) is not hydrolyzed, and the pencil hardness and substrate adhesion of the coating film formed by the resin composition do not decrease with time. In addition, as the resin [A1-2], a resin (A1-2-a) described below is particularly preferable.

<Resin (A1-2-a)>
The resin [A1-2] is a resin (A1-2-a) obtained by copolymerizing the compound (a1) represented by the formula (1) and another compound copolymerizable with the compound (a1). It is particularly preferred.
The description of the compound (a1) is as described in (A1-1).
When the resin (A1-2-a) is obtained by copolymerizing the compound (a1) with another ethylenically unsaturated monomer copolymerizable, the cyclization reaction of the compound (a1) proceeds simultaneously with the polymerization. Thus, a tetrahydropyran ring structure is formed.

  The ratio of the compound (a1) in the ethylenically unsaturated monomer component in obtaining the resin (A1-2-a) is not particularly limited, but is 2 to 55% by weight in the total ethylenically unsaturated monomer component. The amount is preferably 5 to 55% by weight, more preferably 5 to 50% by weight. When the amount of the compound (a1) is 55% by weight or less, it is possible to obtain a low molecular weight during the copolymerization, and no gelation occurs. On the other hand, when it is 2% by weight or more, the coating film performance such as transparency and heat resistance is excellent.

<Other compounds copolymerizable with compound (a1)>
The other compound (a2) that can be copolymerized with the compound (a1) is not particularly limited as long as it can be copolymerized with the compound (a1). In the description in (A1-1), (a2) to (a6) In the above, it is preferable to include a monomer for introducing an acid group to impart alkali solubility, and in addition, a monomer for introducing an ethylenically unsaturated double bond, A side chain type cyclic ether-containing monomer (a6 ′) is preferred.
The method for introducing an acid group and an ethylenically unsaturated double bond into the resin (A1-2-a) is as described above.

<Side Chain Cyclic Ether-Containing Monomer (a6 ′)>
The side chain cyclic ether-containing monomer (a6 ′) 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 ratio of the side-chain cyclic ether-containing monomer (a6 ′) in the monomer component for obtaining the resin (A1-2-a) is not particularly limited, but is 10 to 80 in all monomer components. % By weight is preferable, more preferably 20 to 70% by weight, and still more preferably 30 to 60% by weight. When the amount of the side chain type cyclic ether-containing monomer is 80% by weight or less, the hydrophilicity is not excessively strong, the surface is not whitened during alkali development, the pattern is not lost, and the adhesion to glass is improved. Excellent. When it is 10% by weight or more, performance such as heat resistance is sufficient.

  Other copolymerizable monomers that can be used as other compounds copolymerizable with the compound (a1) other than the side chain type cyclic ether-containing monomer (a6 ′) 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 (A1-2-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 resin composition. When the amount of the resin (A1-2-a) is 10% by weight or more, sufficient substrate adhesion improvement and high heat resistance effects can be obtained. When it is 60% by weight or less, the content of the photocuring component is sufficient, and the pencil hardness of the coating film is excellent.

<Other resins (A1-2b)>
Resin (A1-2) may contain other resin (A1-2-b) in addition to resin (A1-2-a). When the other resin (A1-2-b) is a copolymer, it corresponds to a resin (A1-2-a) that does not contain the compound (a1) as a copolymerization component. It is preferable to use a monomer for introducing a monomer or a monomer for introducing a radical polymerizable double bond as a copolymerization component. Further, the other resin (A1-2-b) may be a thermosetting resin.

<< Resin having a hydroxyl group in the side chain (A2) >>
The resin composition of each embodiment can contain resin (A2) which has a hydroxyl group in a side chain. The resin (A2) having a hydroxyl group in the side chain is an essential component particularly in the embodiment I.
The resin having a hydroxyl group in the side chain (A2) includes a resin obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group and another ethylenically unsaturated monomer copolymerizable, and a carboxyl group. Copolymerized with ethylenically unsaturated monomer and other copolymerizable ethylenically unsaturated monomer, and modified side chain carboxyl group with ethylenically unsaturated monomer having epoxy group Resin or an ethylenically unsaturated monomer having an epoxy group and another copolymerizable ethylenically unsaturated monomer are copolymerized, and the side chain epoxy group is converted to an ethylenically unsaturated monomer having a carboxyl group. Examples include resins formed by modification with a monomer.
When the structure of the resin (A2) is classified,
Resin (A2-a); a resin having a hydroxyl group in the side chain and not having an acid group such as a carboxyl group and an ethylenically unsaturated double bond;
Resin (A2-b); a resin having a hydroxyl group in the side chain and an acid group such as a carboxyl group and having no ethylenically unsaturated double bond,
Resin (A2-c); a resin having a hydroxyl group in the side chain and no acid group such as a carboxyl group and having an ethylenically unsaturated double bond;
Resin (A2-d); 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 mentioned.
Among these, the resin (A2) is preferably a resin (A2-b) or a resin (A2-d) having an acid group such as a carboxyl group in order to exhibit alkali solubility, and also exhibits photosensitivity and pencil hardness. It is preferably a resin (A2-c) or a resin (A2-d) having an ethylenically unsaturated double bond, particularly a resin having both an ethylenically unsaturated double bond and an acid group ( A2-d) is more preferred.

<Method for introducing hydroxyl group>
As a method for introducing a hydroxyl group into the resin (A2), a method (I) of copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another ethylenically unsaturated monomer copolymerizable with a hydroxyl group, There is a method (II) of generating.

Examples of the method (II) for generating a hydroxyl group include copolymerization of an ethylenically unsaturated monomer having a carboxyl group with another ethylenically unsaturated monomer that can be copolymerized, and a carboxyl group in a side chain. Is modified with an ethylenically unsaturated monomer having an epoxy group to produce a hydroxyl group (II-1), or another ethylenic copolymerizable with an ethylenically unsaturated monomer having an epoxy group Examples include a method (II-2) in which an unsaturated monomer is copolymerized and a side chain epoxy group is modified with a compound having a carboxyl group to generate a hydroxyl group.
As a method for introducing a hydroxyl group (I), a resin (A2) can be obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another ethylenically unsaturated monomer copolymerizable. it can.

<Ethylenically unsaturated monomer having a hydroxyl group>
Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate.

<Other copolymerizable ethylenically unsaturated monomers>
As the other copolymerizable ethylenically unsaturated monomer, the compound (a1) represented by the formula (1) described in the column of “Compound having ethylenically unsaturated double bond (A1)”, side Chain-type cyclic ether-containing ethylenically unsaturated monomer (a6 ′), ethylenically unsaturated monomer having acid group (a2), ethylenically unsaturated monomer having epoxy group (a4), other ethylene An unsaturated monomer (a6). One or a plurality of these ethylenically unsaturated monomers can be used and can be prepared in a form that meets the respective requirements. In particular, at least the ethylenically unsaturated monomer (a1) represented by the formula (1) is included. By using a resin obtained by copolymerizing monomers, a coating film excellent in transmittance (transparency), adhesion and etchant resistance can be obtained, which is particularly preferable.

<Ethylenically unsaturated monomer (a1)>
The ethylenically unsaturated monomer (a1) is as described in the column of the compound (A1) having an ethylenically unsaturated double bond.
When the resin (A2) is obtained by copolymerizing the ethylenically unsaturated monomer (a1) with another ethylenically unsaturated monomer copolymerizable, the ethylenically unsaturated monomer ( The cyclization reaction of a1) proceeds to form a tetrahydropyran ring structure.
Although the ratio of the ethylenically unsaturated monomer (a1) in the ethylenically unsaturated monomer component in obtaining the resin (A2) is not particularly limited, it is 2 to 55 in the total ethylenically unsaturated monomer component. % By weight, preferably 5 to 55% by weight, more preferably 5 to 50% by weight. If it is 55% by weight or less, it is possible to obtain a low molecular weight or no gelation during copolymerization. When it is 2% by weight or more, sufficient film performance such as transparency and heat resistance can be obtained.

<Ethylenically unsaturated monomer (a6 ′)>
The ethylenically unsaturated monomer (a6 ′) is a side chain cyclic ether-containing ethylenically unsaturated monomer. Examples of the ethylenically unsaturated monomer (a6 ′) include an ethylenically unsaturated monomer 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. It is.
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 ethylenically unsaturated monomers (a6 ′) can be used singly or as a mixture of two or more at any ratio as required.

  The ratio of the ethylenically unsaturated monomer (a6 ′) in the ethylenically unsaturated monomer component in obtaining the resin (A2) is not particularly limited, but is 3 to 3 in the total ethylenically unsaturated monomer component. 80% by weight, preferably 5 to 70% by weight, more preferably 10 to 60% by weight. If it is 80% by weight or less, the hydrophilicity is appropriate, and the surface is not whitened during alkali development, the pattern is missing, or the adhesion to glass is not deteriorated. When it is 3% by weight or more, performance such as heat resistance is sufficient.

<Ethylenically unsaturated monomer (a2)>
The ethylenically unsaturated monomer (a2) is an ethylenically unsaturated monomer having an acid group. By using the ethylenically unsaturated monomer (a2), an acid group can be introduced into the resin (A2). As a result, the resulting resin composition can be developed with a resin 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 can be developed with an alkaline developer. In order to obtain a resin composition, it is preferable to use the ethylenically unsaturated monomer (a2). The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a polybasic acid anhydride group. These acid groups may be used alone or in combination of two or more.

Specific examples of the ethylenically unsaturated monomer (a2) having an acid group are as described in the column of the compound having an ethylenically unsaturated double bond.
When the ethylenically unsaturated monomer (a2) is contained, the content ratio is not particularly limited, but is 5 to 70% by weight, preferably 10 to 60%, out of the total 100% by weight of all ethylenically unsaturated monomer components. It should be weight percent.

<Ethylenically unsaturated monomer (a4)>
The ethylenically unsaturated monomer (a4) is not particularly limited as long as it is an ethylenically unsaturated monomer having an epoxy group. Specific examples of the ethylenically unsaturated monomer (a4) include, in addition to the description in the column of the compound having an ethylenically unsaturated double bond, for example, β-methylglycidyl (meth) acrylate, β-propylglycidyl ( (Meth) acrylate, β-methylglycidyl-α-ethyl acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5 Examples include 6-epoxyhexyl (meth) acrylate and glycidyl vinyl ether. Among these, glycidyl (meth) acrylate is preferable. These may be used alone or in combination of two or more.
When the ethylenically unsaturated monomer (a4) is included, the content ratio is not particularly limited, but is 5 to 70% by weight, preferably 10 to 60%, out of the total 100% by weight of all ethylenically unsaturated monomer components. It should be weight percent.

<Ethylenically unsaturated monomer (a6)>
Examples of the ethylenically unsaturated monomer (a6) include other ethylenically unsaturated monomers. Examples of the ethylenically unsaturated monomer (a6) include (meth) acrylic acid esters, N-vinylpyrrolidone, styrenes, acrylamides, other vinyl compounds, and macromonomers.
(Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl ( (Meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) Examples include acrylate, tetrahydrofurfuryl (meth) acrylate, and paracumyl EO-modified (meth) acrylate.
As styrenes, styrene and its derivatives, methylstyrene and the like can be used.
Examples of acrylamides include (meth) acrylamide, methylol (meth) acrylamide, alkoxymethylol (meth) acrylamide, diacetone (meth) acrylamide, and the like.
As other vinyl compounds, (meth) acrylonitrile, ethylene, propylene, butylene, vinyl chloride, vinyl acetate and the like can be applied.
Examples of the macromonomer include macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer.
These ethylenically unsaturated monomers (a6) can be used alone or in admixture of two or more at any ratio as required.

<Method of introducing acid group into resin>
The resin (A2) is preferably a resin having an acid group. The method for introducing the acid group is as described in the column of the compound having an ethylenically unsaturated double bond.

<Method of introducing ethylenically unsaturated double bond into resin>
As the method for introducing an ethylenically unsaturated double bond, the ethylenically unsaturated monomer (a4) having an epoxy group described above in the method for introducing an acid group and other ethylenically unsaturated monomers capable of copolymerization are used. An unsaturated monobasic acid is added to the side chain epoxy group of the copolymer obtained by copolymerizing with the monomer, and a polybasic acid having a radical polymerizable double bond in the generated hydroxyl group. Examples include a method of reacting an anhydride to introduce an acid group (carboxyl group) and an ethylenically unsaturated double bond.
Also, copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with an ethylenically unsaturated monomer of an unsaturated monobasic acid having another carboxyl group or another ethylenically unsaturated monomer The method of making the isocyanate group of the ethylenically unsaturated monomer which has an isocyanate group react with the side chain hydroxyl group of the copolymer obtained by this is mentioned.
At this time, when an unsaturated monobasic acid monomer is used, a resin having a hydroxyl group in the side chain and having an acid group of a carboxyl group and an ethylenically unsaturated double bond (A2-d) When an unsaturated monobasic acid monomer is not used, the side chain has a hydroxyl group, does not have an acid group such as a carboxyl group, and has an ethylenically unsaturated double bond. Resin (A2-c) is obtained.
As the ethylenically unsaturated monomer having a hydroxyl group used at this time, in addition to the ethylenically unsaturated monomer having a hydroxyl group described in the introduction method (I) of the hydroxyl group, hydroxyalkyl (meth) acrylate, ethylene oxide, propylene Polyether mono (meth) acrylate obtained by addition polymerization of oxide and / or butylene oxide, (poly) γ-valerolactone, (poly) ε-caprolactone, and / or (poly) 12-hydroxystearic acid Added (poly) ester mono (meth) acrylates can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.
As the ethylenically unsaturated monomer having an isocyanate group, 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, or the like can be used. These ethylenically unsaturated monomers can be used singly or as a mixture of two or more at any ratio as required.

・ Hydroxyl introduction method (II)
Examples of the method (II) for introducing a hydroxyl group include a method for producing a hydroxyl group. As the method (II), for example, an ethylenically unsaturated monomer having a carboxyl group described in the ethylenically unsaturated monomer having an acid group (a2) and other copolymerizable ethylenically unsaturated monomers And a method of producing a hydroxyl group by modifying the side chain carboxyl group with an ethylenically unsaturated monomer (a4) having an epoxy group, or an ethylenically unsaturated group having an epoxy group. The saturated monomer (a4) is copolymerized with another copolymerizable ethylenically unsaturated monomer, and the side chain epoxy group is described as an ethylenically unsaturated monomer having an acid group (a2). The method (II-2) etc. which modify | denaturate with the ethylenically unsaturated monomer which has the carboxyl group produced | generated, and produce | generate a hydroxyl group etc. are mentioned.

  In the method (II) for generating these hydroxyl groups, a double bond can be introduced together with the hydroxyl groups. In the method (II-1), when a part of the side chain carboxyl group is modified with an ethylenically unsaturated monomer having an epoxy group, the side chain has a hydroxyl group and an acid group such as a carboxyl group. And a resin having an ethylenically unsaturated double bond (A2-d) is obtained, and when all of the side chain carboxyl groups are modified with an ethylenically unsaturated monomer having an epoxy group, And a resin (A2-c) having no acid group such as a carboxyl group and having an ethylenically unsaturated double bond. In the method (II-2), a resin (A2-d) 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.

The resin (A2) preferably has an ethylenically unsaturated double bond. Furthermore, it is preferable that an acid group equivalent is 300-1000 g / mol and a double bond equivalent is 350-1200 g / mol. When the hydroxyl group equivalent is 300 g / mol or more, the amount of the hydroxyl group falls within an appropriate range, so that the affinity with the etching solution does not become too high and the etchant resistance is good. When the hydroxyl equivalent is 1000 g / mol or less, the amount of reaction sites between the resin and the isocyanate group of the silane coupling agent is in an appropriate range, and the pencil hardness and substrate adhesion are excellent. When the double bond equivalent is 350 g / mol or more, the curing shrinkage of the resin does not become too large and the substrate adhesion is excellent. When the double bond equivalent is 1200 g / mol or less, sufficient pencil hardness is satisfied. When the hydroxyl group equivalent is 300 to 1000 g / mol and the double bond equivalent is 350 to 1200 g / mol, it is possible to draw out excellent pencil hardness and substrate adhesion.
The theoretical Tg of the resin (A2) can be controlled by the type and blending of the ethylenically unsaturated monomer to be copolymerized, and the weight average molecular weight can be controlled by the polymerization conditions such as the type and amount of the polymerization initiator. Is possible.

  This resin (A2) is synthesized in the presence of a polymerization initiator in an inert gas stream, generally at 50 to 150 ° C. over 2 to 10 hours. The synthesis of the resin may be performed in the presence of a solvent as necessary.

As the polymerization initiator used for the synthesis of the resin (A2), an organic peroxide, an azo compound, or the like can be used. Examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, t-butyl peroxybenzoate and the like. Examples of the azo compound include azo compounds such as 2,2′-azobisisobutyronitrile. The polymerization initiator is preferably used in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.

As a solvent used for the synthesis of the resin (A2), water, a water-miscible organic solvent, acetate ester, ketones, xylene, ethylbenzene and the like can be used. Examples of the water-miscible organic solvent include alcohol solvents such as ethyl alcohol, isopropyl alcohol, and n-propyl alcohol, and mono- or dialkyl ethers of ethylene glycol or diethylene glycol. Examples of the acetic acid ester include ethyl cellosolve acetate and propylene glycol monomethyl ether acetate. Examples of the ketones include cyclohexanone and methyl isobutyl ketone.
The method for the polymerization reaction of the ethylenically unsaturated monomer component is not particularly limited, and various conventionally known polymerization methods can be adopted, 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%. It is good to do.

  The resin (A2) 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 resin composition. If it is 10% by weight or more, sufficient adhesion improvement and high transmittance can be obtained. When it is 60% by weight or less, the content of the photocuring component amount falls within an appropriate range, and sufficient coating film hardness can be obtained.

<< Alkali-soluble resin (A3) >>
The resin composition of each embodiment can contain an alkali-soluble resin (A3). The alkali-soluble resin (A3) is an essential component particularly in Embodiments IV and VI.
The alkali-soluble resin (A3) is a resin having an acid group such as a carboxyl group, a phenolic hydroxyl group, an unsaturated monobasic acid, or a polybasic acid anhydride group in order to exhibit alkali solubility.
Moreover, it is preferable from the point of developability and transmittance | permeability to contain resin (A3-1) containing structural unit (A)-(C) among alkali-soluble resin (A3).
As a method for introducing an acid group into a resin to obtain an alkali-soluble resin (A3), an ethylenically unsaturated monomer having an acid group and another ethylenically unsaturated monomer copolymerizable can be used. There are a method of polymerizing, a method of polymerizing an ethylenically unsaturated monomer capable of giving an acid group after polymerization as an ethylenically unsaturated monomer component, and the like.

The weight average molecular weight (Mw) of the alkali-soluble resin (A3) is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000, still more preferably 5,000 to 30. , 000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.
When the weight average molecular weight (Mw) of the alkali-soluble resin (A3) is 100,000 or less, the interaction between the resins is in an appropriate range, and the viscosity of the photosensitive resin composition is in an appropriate range, so that handling is easy. is there. Further, when the weight average molecular weight (Mw) is 5,000 or more, developability and adhesion to a substrate such as glass are excellent.

The acid value of the alkali-soluble resin (A3) is preferably a resin having an acid value of 20 to 300 KOH-mg / g from the viewpoints of developability and resistance. When the acid value is 20 KOH-mg / g or more, the solubility in the developer is excellent, and it is easy to form a fine pattern. When it is 300 KOH-mg / g or less, a fine pattern remains sufficiently.
The ethylenically unsaturated monomer constituting the alkali-soluble resin (A3) will be described.

<Ethylenically unsaturated monomer having acid group>
By using an ethylenically unsaturated monomer having an acid group, the acid group can be introduced into the resin. As a result, the resulting resin composition can be developed with a resin 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 can be developed with an alkaline developer. Composition. The acid group is as exemplified in the column of the compound having an ethylenically unsaturated double bond. Among these, (meth) acrylic acid is particularly preferable.
When the ethylenically unsaturated monomer having an acid group is included, the content ratio is not particularly limited, but it is 5 to 70% by weight, preferably 10 to 10% in total 100% by weight of all ethylenically unsaturated monomer components. It should be 60% by weight.

<Ethylenically unsaturated monomer capable of imparting acid group after polymerization>
Examples of the ethylenically unsaturated monomer that can impart an acid group after polymerization include, for example, an ethylenically unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, and an epoxy group such as glycidyl (meth) acrylate. And ethylenically unsaturated monomers having
When using an ethylenically unsaturated monomer having a hydroxyl group, for example, it is obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another copolymerizable ethylenically unsaturated monomer. The hydroxyl group of the obtained copolymer can be reacted with a polybasic acid anhydride to introduce an acid group (carboxyl group).
Or, when using an ethylenically unsaturated monomer having an epoxy group, for example, copolymerizing an ethylenically unsaturated monomer having an epoxy group with another copolymerizable ethylenically unsaturated monomer Then, an unsaturated monobasic acid having a carboxyl group is added to the side chain epoxy group of the copolymer thus obtained, and a polybasic acid anhydride is reacted with the generated hydroxyl group to produce an acid group (carboxyl). Group) can be introduced. In this method, when a hydroxyl group and a polybasic acid anhydride having an ethylenically unsaturated double bond 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.

<Other copolymerizable ethylenically unsaturated monomers>
Examples of other copolymerizable ethylenically unsaturated monomers include:
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 or alkenyl (meth) acrylates such as rohexyl (meth) acrylate, allyl (meth) acrylate, or oleyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, β-carboxyethyl (Meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di Various acrylic and methacrylic esters such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isobornyl (meth) acrylate, ester acrylate, epoxy (meth) acrylate, urethane acrylate, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol Divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl- 2,2 '-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene)] bis-2- Examples of monomers and oligomers such as propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate include, but are not limited to, other ethylenically unsaturated monomers. Can be selected, and two or more types can be used in combination. As described above, methyl (meth) acryl methacrylate or ethyl (meth) acrylate is preferably used from the viewpoint of developability.

Other ethylenically unsaturated monomers include, for example,
(Meth) acrylates having a heterocyclic substituent such as tetrahydrofurfuryl (meth) acrylate or 3-methyloxetanyl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate or ethoxypolyethylene glycol (meth) acrylate; or
(Meth) acrylamides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine Etc.

Moreover, as a monomer other than the acrylic monomer, for example,
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; or fatty acid vinyls such as vinyl acetate or vinyl propionate. The monomer other than the acrylic monomer can be used in combination with the acrylic monomer.
In addition, it has an ethylenically unsaturated monomer having a structure represented by formula (2), an ethylenically unsaturated monomer having a structure represented by formula (3), and a structure represented by formula (4) Ethylenically unsaturated monomer, ethylenically unsaturated monomer having the structure represented by formula (5), side chain cyclic ether-containing ethylenically unsaturated monomer, ethylenically unsaturated monomer having an epoxy group The body is mentioned.

One or more of these ethylenically unsaturated monomers can be used and can be prepared in a form that meets their requirements. The resin obtained by reacting the obtained copolymer with an ethylenically unsaturated monomer having an epoxy group has particularly excellent developability and transmittance. It can be obtained and is preferable.
Moreover, the copolymer of the ethylenically unsaturated monomer which has an epoxy group, and another ethylenically unsaturated monomer is obtained, and the obtained copolymer and unsaturated monobasic acid are obtained. A resin obtained by reacting to obtain a copolymer and further reacting the obtained copolymer with a polybasic acid anhydride is particularly preferred because it can provide particularly excellent developability and transmittance.

［式（２）及び（３）中、Ｒ⁴は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。］

以下に、構成単位（イ）、構成単位（ロ）、構成単位（ハ）、及びその他の構成単位について、順に説明する。 <Resin (A3-1) Having Structural Units (A) to (C)>
Furthermore, the alkali-soluble resin (A3-1) preferably has the following structural units (A) to (C) from the viewpoint of developability and transmittance.
(A) a structural unit having a carboxyl group (b) a structural unit having an aromatic ring group represented by formula (2) or formula (3) (c) an aliphatic ring group represented by formula (4) or formula (5) Units to have

[In the formulas (2) and (3), R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

Hereinafter, the structural unit (A), the structural unit (B), the structural unit (C), and other structural units will be described in order.

<Structural unit (b)>
The structural unit (a) has a carboxyl group and functions as an alkali-soluble site during development. From the viewpoint of developability, the content of the structural unit (a) is preferably 2 to 60% by weight based on the weight of all the structural units of the resin (B1). If it is 2% by weight or more, the removability of the unexposed part by the alkaline developer is sufficient. If it is 60% by weight or less, the dissolution rate in the alkali developer is appropriate, and thus the exposed portion is not dissolved.
Examples of the precursor of the structural unit (a) having a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, or α-chloroacrylic acid, and unsaturated dicarboxylic acids such as maleic acid or fumaric acid. And compounds containing a carboxyl group such as an acid and having an ethylenically unsaturated double bond. Moreover, what half-esterified the anhydride of unsaturated dicarboxylic acid, such as maleic anhydride, with the (meth) acrylic compound which has hydroxyl groups, such as hydroxyalkyl (meth) acrylate, can also be used. Among these, (meth) acrylic acid is more preferable, and methacrylic acid is most preferable from the viewpoint of polymerizability (ease of control of molecular weight and the like). These can be used alone or in combination of two or more.

<Structural unit (b)>
The structural unit (b) has a cyclic structure by the aromatic ring group represented by the above formulas (2) and (3), suppresses permeation of ITO etching solution, molybdenum etching solution, etc., and oxidized fine particles (C) Improves compatibility with. From the viewpoint of developability and acid resistance, the content of the structural unit (b) is preferably 2 to 80% by weight based on the weight of all the structural units of the resin (A3). When it is 2% by weight or more, the compatibility, dispersion stability and acid resistance are excellent, and a high-quality coating film can be obtained. On the other hand, when it is 80% by weight or less, the dissolution rate in an alkaline developer is in an appropriate range, the development time is short, and the productivity of the coating film is good.

［式（６）中、Ｒ⁵は、水素原子、またはメチル基であり、Ｒ⁶は、炭素数２若しくは３のアルキレン基であり、Ｒ⁷は、ベンゼン環を有していてもよい炭素数１〜２０のアルキル基であり、ｔは、１〜１５の整数である。］ Examples of the precursor of the structural unit (b) include styrene, α-methylstyrene, benzyl acrylate, benzyl methacrylate, or an ethylenically unsaturated monomer represented by the formula (6).

Wherein (6), R ⁵ is a hydrogen atom or a methyl group,, R ⁶ is an alkylene group having 2 or 3 carbon atoms, R ⁷ is carbon atoms, which may have a benzene ring 1 to 20 alkyl groups, and t is an integer of 1 to 15. ]

Examples of the ethylenically unsaturated monomer represented by the formula (6) include:
New Frontier CEA [EO-modified cresol acrylate, R ⁵ : hydrogen atom, R ⁶ : ethylene group, R ⁷ : methyl group, t = 1 or 2], NP-2 [n-nonylphenoxy polyethylene glycol] Acrylate, R ⁵ : hydrogen atom, R ⁶ : ethylene group, R ⁷ : n-nonyl group, t = 2], or PHE [phenoxyethyl acrylate, R ⁵ : hydrogen atom, R ⁶ : ethylene group, R ⁷ : hydrogen Atoms, t = 1],
Manufactured by Hitachi Chemical Co., Ltd., FA-314A [nonylphenoxy polyethylene glycol acrylate, R ^5: a hydrogen atom, R ^6: an ethylene group, R ^7: n-nonyl group, t = 4], FA-318AS [nonylphenoxy polyethylene glycol acrylate, R ^5: a hydrogen atom, R ^6: an ethylene group, R ^7: n-nonyl group, t = 8]
Daicel, IRR169 [ethoxylated phenyl acrylate (EO 1 mol), R ⁵ : hydrogen atom, R ⁶ : ethylene group, R ⁷ : hydrogen atom, t = 1], or Ebecryl 110 [ethoxylated phenyl acrylate (EO 2 mol), R ⁵ : hydrogen atom, R ⁶ : ethylene group, R ⁷ : hydrogen atom, t = 2],
Aronix M-101A manufactured by Toagosei Co., Ltd. [phenol EO modified (t≈2) acrylate, R ⁵ : hydrogen atom, R ⁶ : ethylene group, R ⁷ : hydrogen atom, t≈2], M-102 [phenol EO modified ( t≈4) acrylate, R ⁵ : hydrogen atom, R ⁶ : ethylene group, R ⁷ : hydrogen atom, t≈4], M-110 [paracumylphenol EO modified (t≈1) acrylate, R ⁵ : hydrogen atom , R ⁶ : ethylene group, R ⁷ : paracumyl, t≈1], M-111 [n-nonylphenol EO-modified (t≈1) acrylate, R ⁵ : hydrogen atom, R ⁶ : ethylene group, R ⁷ : n− Nonyl group, t≈1], M-113 [n-nonylphenol EO-modified (t≈4) acrylate, R ⁵ : hydrogen atom, R ⁶ : ethylene group, R ⁷ : n-nonyl group, t≈4], or M-117 [n-nonyl Phenol PO modified (t≈2.5) acrylate, R ⁵ : hydrogen atom, R ⁶ : propylene group, R ⁷ : n-nonyl group, t≈2.5],
Kyoeisha light acrylate PO-A [phenoxyethyl acrylate, R ⁵ : hydrogen atom, R ⁶ : ethylene group, R ⁷ : hydrogen atom, t = 1], P-200A [phenoxypolyethylene glycol acrylate, R ⁵ : hydrogen atom, R ^6: an ethylene group, R ^7: a hydrogen atom, t ≒ 2], NP-4EA [nonylphenol EO adduct acrylate, R ^5: a hydrogen atom, R ^6: an ethylene group, R ^7: n-nonyl group, t ≒ 4 ], or NP-8EA [[nonylphenol EO adduct acrylate, R ^5: a hydrogen atom, R ^6: an ethylene group, R ^7: n-nonyl group, t ≒ 8], or light ester PO [phenoxyethyl methacrylate, R ⁵ : Methyl group, R ⁶ : propylene group, R ⁷ : hydrogen atom, t = 1],
Manufactured by NOF Corporation Blemmer ANE-300 [nonylphenoxy polyethylene glycol acrylate, R ^5: a hydrogen atom, R ^6: an ethylene group, R ^7: - nonyl group, t ≒ 5], ANP-300 [nonylphenoxy polypropylene glycol acrylate, R ^5: a hydrogen atom, R ^6: a propylene group, R ^7: n-nonyl group, t ≒ 5], 43ANEP-500 [nonylphenoxy - polyethylene glycol - polypropylene glycol - acrylate, R ^5: a hydrogen atom, R ^6: an ethylene group And propylene group, R ⁷ : -nonyl group, t≈5 + 5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ⁵ : hydrogen atom, R ⁶ : ethylene group and propylene group, R ⁷ : n -Nonyl group, t≈9 + 3], 75AN EP-600 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ⁵ : hydrogen atom, R ⁶ : ethylene group and propylene group, R ⁷ : n-nonyl group, t≈5 + 2], AAE-50 [phenoxypolyethylene glycol acrylate, R ^5: a hydrogen atom, R ^6: an ethylene group, R ^7: a hydrogen atom, t = 1], AAE-300 [phenoxy polyethylene glycol acrylate, R ^5: a hydrogen atom, R ^6: an ethylene group, R ^7: hydrogen Atom, t≈5.5], PAE-50 [phenoxypolyethylene glycol methacrylate, R ⁵ : methyl group, R ⁶ : ethylene group, R ⁷ : hydrogen atom, t = 1], PAE-100 [phenoxypolyethylene glycol methacrylate, R ^5: methyl group, R ^6: an ethylene group, R ^7: a hydrogen atom, t = ], Or 43PAPE-600B [phenoxy - polyethylene glycol - polypropylene glycol - methacrylate, R ^5: methyl group, R ^6: an ethylene group and a propylene group, R ^7: a hydrogen atom, t ≒ 6 + 6],
NK ESTER AMP-10G (phenoxyethylene glycol acrylate (EO 1 mol), Shin Nakamura Chemical Co., Ltd., R ⁵ : hydrogen atom, R ⁶ : ethylene group, R ⁷ : hydrogen atom, t = 1], AMP-20G [phenoxyethylene glycol acrylate (EO2mol), R ^5: a hydrogen atom, R ^6: an ethylene group, R ^7: a hydrogen atom, t ≒ 2], AMP-60G [phenoxy ethyleneglycol acrylate (EO6mol), R ^5: a hydrogen atom, R ^6: an ethylene group , R ⁷ : hydrogen atom, t≈6], PHE-1G [phenoxyethylene glycol methacrylate (EO 1 mol), R ⁵ : methyl group, R ⁶ : ethylene group, R ⁷ : hydrogen atom, t = 1],
Biscoat # 192 manufactured by Osaka Organic Chemical Co., Ltd. [phenoxyethyl acrylate, R ⁵ : hydrogen atom, R ⁶ : ethylene group, R ⁷ : hydrogen atom, t = 1], or
Nippon Kayaku SR-339A [2-phenoxy ethyleneglycol acrylate, R ^5: a hydrogen atom, R ^6: an ethylene group, R ^7: a hydrogen atom, t = 1], or SR-504 (ethoxylated nonylphenol acrylate, R ⁵ : Hydrogen atom, R ⁶ : ethylene group, R ⁷ : n-nonyl group] and the like, but not limited thereto, two or more kinds may be used in combination.

In the ethylenically unsaturated monomer represented by the formula (6), the carbon number of the alkyl group represented by R ⁷ is 1 to 20 in consideration of good adhesion to the substrate. Further, considering that the alkyl group becomes an obstacle and suppresses permeation of the ITO etching solution, molybdenum etching solution or the like and increases the acid resistance, the carbon number of the alkyl group of R ⁷ is more preferably 1 to 10. The alkyl group includes not only a linear alkyl group but also a branched alkyl group and an alkyl group having a benzene ring as a substituent.

Examples of the alkyl group having a benzene ring represented by R ⁷ include a benzyl group and a 2-phenyl (iso) propyl group. By increasing one side chain benzene ring, acid resistance is further improved and developability is also improved.

  In the ethylenically unsaturated monomer represented by the formula (6), t is preferably an integer of 1 to 15. When t is 15 or less, the hydrophilicity is in an appropriate range, the effect of solvation is large, the viscosity of the resin (A3) is low, the viscosity of the photosensitive composition using the resin is low, and the fluidity is affected. There is no. From the viewpoint of solvation, t is particularly preferably 1 to 4.

  The precursor of the structural unit (b) is represented by styrene, α-methylstyrene, benzyl acrylate, benzyl methacrylate, or formula (6) from the viewpoint of copolymerization with other precursors and from the viewpoint of acid resistance. Ethylenically unsaturated monomers are preferred. These are particularly preferable because a benzene ring can be introduced into the side chain of the resin (A3). By introducing a benzene ring into the side chain of the resin (A3), the side chain benzene ring suppresses the penetration of the ITO etching solution and the molybdenum etching solution and improves the compatibility with the oxide fine particles (C). There is. Furthermore, benzyl acrylate and / or benzyl methacrylate are most preferable from the viewpoint of developability.

<Structural unit (C)>
The structural unit (c) has a cyclic structure with an aliphatic ring group represented by the above formulas (4) and (5), imparts hardness and acid resistance, and imparts good developability without residue. Based on the weight of all the structural units of the resin (A3), the structural unit (c) is preferably 2 to 40% by weight from the viewpoints of developability, hardness and acid resistance. When it is 2% by weight or more, developability, hardness and acid resistance are sufficient, and a high-quality coating film can be obtained. Further, since the hydrophobicity at the time of development is sufficient, there is no problem of pattern peeling or chipping in the pixel portion. When it is 40% by weight or less, the dissolution rate in an alkali developer is within an appropriate range, the development time is short, and the productivity of the coating film is good.

［式（７）、式（８）中、Ｒ⁹は、水素原子、またはメチル基であり、Ｒ¹⁰は、炭素数２若しくは３のアルキレン基であり、ｑは、０〜１５の整数である。］ Examples of the precursor of the structural unit (c) include an ethylenically unsaturated monomer represented by the formula (7), an ethylenically unsaturated monomer represented by the formula (8), and the like.

[In Formula (7) and Formula (8), R ⁹ is a hydrogen atom or a methyl group, R ¹⁰ is an alkylene group having 2 or 3 carbon atoms, and q is an integer of 0 to 15. . ]

As the ethylenically unsaturated monomer represented by the formula (7), for example,
FANCLIL FA-513A manufactured by Hitachi Chemical Co., Ltd. FA-513A [dicyclopentanyl acrylate, R ⁹ : hydrogen atom, R ¹⁰ : none, q = 0], or FA-513M [dicyclopentanyl methacrylate, R ⁹ : methyl, R ¹⁰ : None, q = 0], etc., but not limited thereto, two or more kinds can be used in combination.

As an unsaturated ethylene monomer represented by the formula (8), for example,
FANCLIL manufactured by Hitachi Chemical Co., Ltd. FA-511A [dicyclopentenyl acrylate, R ⁹ : hydrogen atom, R ¹⁰ : none, q = 0], FA-512A [dicyclopentenyloxyethyl acrylate, R ⁹ : hydrogen atom, R ¹⁰ : Ethylene group, q = 1], FA-512M [dicyclopentenyloxyethyl methacrylate, R ⁹ : methyl group, R ¹⁰ : ethylene group, q = 1], or FA-512MT [dicyclopentenyloxyethyl methacrylate, R ^9: methyl group, R ^10: an ethylene group, q = 1] and others as exemplified, without limitation, can be used in combination of two or more kinds.

<Other structural units>
The other structural unit is not limited as long as it is a structural unit other than the structural unit (b), the structural unit (b), and the structural unit (c), and other ethylenic copolymerizable alkali-soluble resin (A3). The ethylenically unsaturated monomer described as the unsaturated monomer can be used.
Further, these resins (A3) are preferably photosensitive resins having an ethylenically unsaturated double bond in terms of developability and hardness.

<Introduction of ethylenically unsaturated double bond>
In order to introduce an ethylenically unsaturated double bond, an ethylenically unsaturated monomer having an epoxy group or an ethylenically unsaturated monomer having a hydroxyl group is obtained by the following method (i) or method (ii). Can also be used. Since these may become structural units other than other structural units depending on modification, in the case of the resin (A3-1) containing the structural units (A) to (C), It is better to consider the weight ratio of the structural unit (b), the structural unit (b), and the structural unit (c).

<Method (i)>
As the method (i), an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having an epoxy group are used to introduce an ethylenically unsaturated double bond, The method of doing is mentioned.
For example, the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other ethylenically unsaturated monomers is ethylenic. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an unsaturated double bond, further reacting a polybasic acid anhydride with the generated hydroxyl group, introducing an ethylenically unsaturated double bond, and the function of the photosensitive resin And a method (i1) for introducing a carboxyl group having an alkali-soluble function.

That is, the resin (A3) is obtained by reacting a precursor of the structural unit (b), a precursor of the structural unit (c), and an ethylenically unsaturated monomer having an epoxy group. 1), and then the copolymer (i1-1) obtained is reacted with an unsaturated monobasic acid to obtain a copolymer (i1-2). Further, the copolymer (i Resin (A3-1a) obtained by reacting i1-2) with a polybasic acid anhydride is preferable because a coating film exhibiting high Mo adhesion can be obtained.
Moreover, since the carboxyl group of the unsaturated monobasic acid used in this method (i1) forms an ester bond after the addition reaction to the epoxy group, the structural unit (a) of the resin (A3) in this specification includes Not applicable, corresponds to other structural units, and the polybasic acid anhydride forms a carboxyl group after reaction with a hydroxyl group, and thus corresponds to the structural unit (A) of the resin (A3-1) in this specification. .

  Alternatively, a part of the side chain carboxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other ethylenically unsaturated monomers. And the method (i2) of introducing an ethylenically unsaturated double bond and a carboxyl group by addition reaction of an ethylenically unsaturated monomer having an epoxy group.

  That is, the resin (A3-1) reacts with the precursor of the structural unit (a), the precursor of the structural unit (b), and the precursor of the structural unit (c) to produce the copolymer (i2-1). The resin (A3-1b) obtained by reacting the copolymer (i2-1) obtained next with an ethylenically unsaturated monomer having an epoxy group exhibits high surface hardness. It is preferable because a coating film can be obtained.

  In this case, only the structural unit corresponding to the carboxyl group that is not used for the addition reaction with the epoxy group corresponds to the structural unit (A) of the resin (A3-1) in this specification.

  Examples of the ethylenically unsaturated monomer 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-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. Glycidyl (meth) acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step and from the viewpoint of substrate adhesion.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, P-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together. Of these, (meth) acrylic acid is preferred.

  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 also be hydrolyzed. Further, when 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.

<Method (ii)>
As the method (ii), an ethylenically unsaturated double bond is introduced using an ethylenically unsaturated monomer having a hydroxyl group and an ethylenically unsaturated monomer having an isocyanate group to obtain a photosensitive resin. A method is mentioned.

For example, a copolymer obtained by copolymerizing an unsaturated monobasic acid having another carboxyl group or another ethylenically unsaturated monomer using an ethylenically unsaturated monomer having a hydroxyl group There is a method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with the side chain hydroxyl group.
Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate.

Hydroxyalkyl (meta) such as relate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate ) Acrylates, and these may be used alone or in combination of two or more. In addition, polyether mono (meth) acrylates obtained by addition polymerization of the above hydroxyalkyl (meth) acrylates with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.
Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

  The resin (A3-1) 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 resin composition. When the resin (A3-1) is 10% by weight or more, sufficient adhesion improvement and high transmittance are obtained, and when it is 60% by weight or less, the content of the photocuring component is sufficient. The hardness of the coating film can be obtained.

  Resin (A3-1) containing structural units (a) to (c) is composed of a precursor of structural unit (b), a precursor of structural unit (c), and an ethylenically unsaturated monomer having an epoxy group. To obtain a copolymer (i1-1), and then react the copolymer (i1-1) obtained with an unsaturated monobasic acid to obtain a copolymer (i1-2). In addition, the resin (A3-1a) obtained by reacting the obtained copolymer (i1-2) with the polybasic acid anhydride, or the precursor of the structural unit (a), and the structural unit (b) ) And the precursor of the structural unit (c) are reacted to obtain a copolymer (i2-1), and then the copolymer (i2-1) obtained and ethylene having an epoxy group are obtained. A resin composition excellent in compatibility with oxide fine particles and developability is a resin (A3-1b) obtained by reacting a polymerizable unsaturated monomer. In order to things can be, it is more preferable.

The content of the alkali-soluble resin (A3) is preferably selected from the range of 1 to 100% by weight in the total amount of resin of 100% by weight, usually 50 to 100% by weight, preferably 70 to 100% by weight, more preferably Is 80 to 100% by weight.
When it is 1% by weight or more, developability, hardness, acid resistance, and transmittance are sufficient, and a high-quality coating film can be obtained.

Among the alkali-soluble resins (A3), an alkali-soluble resin having a double bond equivalent of 200 or more and less than 500 is an essential component in the embodiment V. Among the alkali-soluble resins (A3), by introducing an ethylenically unsaturated double bond and using an alkali-soluble resin having a double bond equivalent of 200 or more and less than 500, a coating film having excellent hardness can be obtained. The double bond equivalent is more preferably 200 or more and less than 400. When the ethylenically unsaturated double bond equivalent is 200 or more, the hardness of the coating film is in an appropriate range, and adhesion to a metal such as ITO or Mo is high. Moreover, when the ethylenically unsaturated double bond equivalent is less than 500, sufficient hardness of the coating film can be obtained.
The alkali-soluble resin having a double bond equivalent of 200 or more and less than 500 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 resin composition. If the alkali-soluble resin having a double bond equivalent of 200 or more and less than 500 is 10% by weight or more, sufficient hardness and developability can be obtained, and if it is less than 60% by weight, the content of other photocuring components is too high. Sufficient and sufficient film hardness can be obtained.

<< Thermosetting compound (A4) >>
The resin composition of each embodiment can contain a thermosetting compound (A4). The thermosetting compound (A4) is an essential component in the embodiment V. Also in Embodiment VI, it can be an essential component.

  The thermosetting compound (A4) may be a low molecular compound or a high molecular compound, and representative examples include phenolic compounds, furan compounds, urea compounds, melamine compounds, unsaturated polyesters, epoxy compounds, urethane compounds, silicone compounds. , Polyimide, diallyl phthalate compound, vinyl ester compound and the like.

  These compounds can be used singly or in combination of two or more at any ratio as necessary. By adding the thermosetting compound (A4), a coating film having a high hardness can be obtained by reacting during the heating step and forming a network-like coating film structure.

  The thermosetting compound (A4) is preferably used in an amount of 3 to 30% by weight in a total of 100% by weight of the solid content of the resin composition. When the thermosetting compound (A4) is 3% by weight or more, a sufficient hardness-improving effect is obtained. When the thermosetting compound (A4) is 30% by weight or less, the resin is not yellowed, and the transmittance is not lowered accordingly. Among the thermosetting compounds (A3), melamine compounds and epoxy compounds are preferable from the viewpoint of the hardness of the coating film.

Moreover, among the melamine compounds, the melamine compound (A4-1) represented by the formula (9) is preferable because the coating film has high hardness. Among the epoxy compounds, the epoxy equivalent is 100 or more and less than 500. Including a certain epoxy compound (A4-2), particularly preferably an epoxy compound (A4-2a) further containing a fluorene skeleton is preferable because a coating film having high hardness can be obtained while improving the refractive index.
Furthermore, it is preferable to use both of these melamine compounds and epoxy compounds.

<Melamine compound>
The melamine compound may be a low-molecular compound or a high-molecular compound. A melamine in which 1 to 6 hydrogens of amino group (—NH 2) are methylolated, or a water-soluble melamine resin comprising a quantifier thereof, such as Sumitomo Chemical Co., Ltd. ) "Sumitex Resin", or melamine whose methylol group is esterified with a C1-4 aliphatic alcohol, or an oil-soluble melamine resin consisting of its quantity, such as Dainippon Ink Chemical Co., Ltd. "Super Becamine" Or what cross-linked polyester resin and acrylic resin with melamine resin etc. are mentioned.

［式（９）中、Ｒ^１〜Ｒ^６は、それぞれ独立して水素原子、または−ＣＨ_２ＯＨ、−ＣＨ_２ＯＣＨ_３、および−ＣＨ_２ＯＣ_４Ｈ_９からなる群より選ばれるいずれかの置換基を表す。］
式（９）で表されるメラミン化合物（Ａ４−１）としては、例えば以下の市販品が挙げられる。 <Melamine compound represented by formula (9) (A4-1)>
Among melamine compounds, the inclusion of a melamine compound (A4-1) represented by the following formula (9) is preferable because the hardness of the coating film can be increased. The melamine compound (A4-1) is a mixture of a thermosetting melamine compound and / or a partial condensate thereof (a thermosetting melamine compound, a mixture of the partial condensates thereof, or a thermosetting melamine compound and a partial condensate thereof. Mixture).

[In Formula (9), R ^{1 to} R ⁶ are each independently a hydrogen atom or any one selected from the group consisting of —CH ₂ OH, —CH ₂ OCH ₃ , and —CH ₂ OC ₄ H ₉ . Represents a substituent. ]
As a melamine compound (A4-1) represented by Formula (9), the following commercial items are mentioned, for example.

Products in which R ^{1 to} R ⁶ are CH ₂ OCH ₃ include Nicarak MW-30M, Nicarak MW-30, Nicarac MW-22, Nicarac MW-21 (manufactured by Sanwa Chemical Co., Ltd.), and Cymel 300 , Cymel 301, Cymel 303, and Cymel 350 (manufactured by Nippon Cytec Industries, Inc.), etc., R1 to R6 are CH ₂ OH products, Nicalac MS-11, R ^{1 to} R ⁶ are CH ₂ OCH ₃ and CH ₂ OC _As products of ₄ H ₉ , Nicarax MX-45, Nicarak MX-500, Nicarak MX-520, and Nicarac MX-43 (manufactured by Sanwa Chemical Co., Ltd.), Cymel 232, Cymel 235, Cymel 236, and Cymel 238 (Nippon Cytec Industries) As a product in which R ^{1 to} R ⁶ are CH ₂ OC ₄ H ₉ , a mixture of a hexamethylol melamine full alkyl ether compound such as Cymel 506 (manufactured by Nihon Cytec Industries) and / or a partial condensate thereof. (Average polymerization degree is 1-2).
The melamine compound (A4-1) represented by the formula (9) is preferably used in an amount of 3 to 30% by weight in a total of 100% by weight of the solid content of the resin composition. If the melamine compound (A4-1) is 3% by weight or more, a sufficient hardness improvement effect is obtained, and if it is 30% by weight or less, there is no yellowing of the resin, and the transmittance decreases accordingly. Absent.

<Epoxy compound>
The epoxy compound may be a low molecular compound or a high molecular compound, and representative examples include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, and novolac epoxy. Resins, cycloaliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, epoxy resins such as epoxidized oil; brominated derivatives of the above epoxy resins, tris (glycidylphenyl) methane, Triglycidyl isocyanurate etc. are mentioned. Among them, bisphenyl A type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, cycloaliphatic type epoxy resin, glycidyl ester type resin, glycidylamine type resin, tris (glycidylphenyl) methane This is preferable in that the cured density is high and the adverse effect on the developability of the colored composition is small.

  Examples of preferable commercially available epoxy compounds that can be used include EX111, EX201, EX411, EX901, EX4931, manufactured by Nagase ChemteX Corporation, EPPN501H, EPPN502H manufactured by Nippon Kayaku Co., Ltd., JER152, JER1004 manufactured by Japan Epoxy Resin Co., Ltd.

<Epoxy compound having an epoxy equivalent of 100 or more and less than 500 (A4-2)>
Among epoxy compounds, the epoxy equivalent is preferably 100 or more and less than 500, and more preferably 100 or more and less than 250. When the epoxy equivalent is 100 or more, the curability is in an appropriate range, the crosslink density of the film is in an appropriate range, the shrinkage at the time of curing is not excessively increased, and the flatness of the film is obtained. When the epoxy equivalent is 500 or less, the curability is sufficient and the effect of improving the hardness is great. Moreover, the epoxy equivalent in this specification refers to the value defined by “molecular weight / number of epoxy groups: unit g / eq” obtained by calculation from the chemical formula of the epoxy compound, that is, the molecular weight per epoxy group.

  Examples of commercially available epoxy compounds that are preferable as the epoxy compound (A4-2) having an epoxy equivalent of 100 or more and less than 500 include Nagase Chemtex EX111, EX201, EX411, EX901, EX4931, Nippon Kayaku EPPN501H, EPPN502H And JER152 manufactured by Japan Epoxy Resin Co., Ltd.

  The epoxy compound (A4-2) having an epoxy equivalent of 100 or more and less than 500 is preferably used in an amount of 3 to 30% by weight in a total of 100% by weight of the solid content of the resin composition. If the epoxy compound (A4-2) is 3% by weight or more, a sufficient hardness improving effect can be obtained, and if it is 30% by weight or less, the resin does not yellow, and accordingly, the transmittance does not decrease. .

  Moreover, among epoxy compounds (A4-2a) having an epoxy equivalent of 100 or more and less than 500, by using an epoxy compound (A4-2) containing a fluorene skeleton, it is possible to form a coating film having high hardness while improving the refractive index. It is preferable because it can be obtained. The epoxy compound containing a fluorene skeleton will be described later in the column of the fluorene skeleton-containing compound.

<< Compound represented by formula (10) or cardo resin (A5) >>
The resin composition of each embodiment can contain a compound represented by formula (10) or a cardo resin (A5). The compound represented by formula (10) or the cardo resin (A5) is an essential component particularly in Embodiment III.

［式（１０）中、Ｘ¹及びＸ²は、互いに独立して、ヒドロキシル基、−Ｏ(ＡＯ)_pＨ基（ただし、Ａは、炭素数２〜３のアルキレン基を表し、ｐは１〜１００００００の整数を表す）、アミノ基又はＮ−モノ置換アミノ基を表し、
Ｒ¹〜Ｒ⁴は、互いに独立して、置換されてもよい炭化水素基、置換されてもよいアルコキシ基、Ｎ，Ｎ−ジ置換アミノ基、または、ハロゲン原子を表し、
ｍ１及びｍ２は、互いに独立して、０〜３の整数、ｍ１＋ｍ２＝０〜６の整数、好ましくは１〜６の整数であり、ｎ１〜ｎ４は、互いに独立して、０〜４の整数である。ただし、ｍ１＋ｎ１及びｍ２＋ｎ２は、０〜５の整数である。］ <Compound represented by formula (10)>

[In Formula (10), X < ¹ > and X < ² > are respectively independently a hydroxyl group and -O (AO) _pH group (however, A represents a C2-C3 alkylene group, p is 1 Represents an integer of ˜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, preferably 1 to 6, and n1 to n4 are each independently an integer of 0 to 4. is there. 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 Formula (10), R ^{1 to} R ⁴ are preferably groups that are non-reactive with respect to reactions such as ester bond formation reaction, urethane bond formation reaction, amide bond formation reaction, and imide bond formation reaction. Hydrocarbon group, alkoxy group, N, N-disubstituted amino group, halogen atom and the like. 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 formula (10), m1 = m2 = 1, 2, or 3, ie, bisphenolfluorene [9,9-bis (monohydroxyphenyl) fluorenes], 9,9-bis (dihydroxyphenyl) Bisphenol fluorenes (9,9-bis (hydroxyphenyl) fluorenes) such as fluorenes, 9,9-bis (trihydroxyphenyl) fluorenes and their C _2-4 alkylene oxide adducts; and bisaniline fluorenes and bis Bisaniline fluorenes (9,9-bis (aminophenyl) fluorenes) such as (N-monosubstituted aniline) fluorene are preferred.

Of 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 9,9-bis (cycloalkylhydroxyC _2-3 alkoxyphenyl) fluorene; 9,9-bis (arylhydroxy C _2-3 ) such as 9,9-bis (4-hydroxyethoxy-3-phenylphenyl) fluorene Alkoxyphenyl) fluorene, etc.], 9,9-bis [di (hydroxyalkoxy) phenyl] fluorenes corresponding to these compounds {eg, 9,9-bis [3,4-di (2-hydroxyethoxy) phenyl] 9,9-bis fluorene [di (2-hydroxy-C _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-C1-) 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 ( 9,9-bis (amino-diC _1-4 alkylphenyl) fluorene such as 4-amino-3,5-di-t-butylphenyl) fluorene; 9,9-bis (di or triaminophenyl) fluorenes corresponding to the compounds; 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 specification, 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 formula (10) has active hydrogen. Examples thereof include those obtained by reaction such as bond formation reaction.
Some reactions include those having only one cardo skeleton. For example, it is a (meth) acrylic monomer or an epoxy monomer described later, that is, a compound having the formula (10), one (meth) acrylic group or one epoxy group, and one group capable of reacting with active hydrogen. (Groups capable of reacting with active hydrogen are carboxyl groups, halogen groups, and isocyanate groups. 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), (poly) oxyalkylene glycol (for example, di to tetra C2-4 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 ( -(2-hydroxyethoxy) cyclohexyl) propane), etc.), aromatic diols (for example, biphenol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bisphenol AD, bisphenol F and their alkylene oxides (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 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, diphenylether-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. .

（式（１２）中、Ｒ^１０は、酸素、カルボニル基、テトラフルオロエチレン基、または、単結合を表す。） Specific examples of the unsaturated polyester resin include, for example, a compound represented by the following formula (11), a compound represented by the following formula (12), pyromellitic acid anhydride, terephthalic acid and its It is obtained by copolymerizing at least one selected from acid chlorides.

(In formula (12), R ¹⁰ represents oxygen, a carbonyl group, a tetrafluoroethylene group, or a single bond.)

(2) Polycarbonate-based resin As a polycarbonate-based resin, for example, a reaction of a diol component composed of at least the bisphenol fluorenes (9,9-bis (monohydroxyphenyl) fluorenes) with phosgene (for example) 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 An epoxy monomer can be obtained by reacting at least the phenol fluorenes with epichlorohydrin, and the epoxy monomer can be obtained alone or copolymerized with other epoxy monomers to produce an epoxy resin or an epoxy oligomer. 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 the bisphenolfluorene 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) Phenol-based resin In the production of a phenol-based resin, a compound in which n1 and n2 are 0 or X ¹ and X ² are hydroxyl groups in the formula (10) can be used as bisphenolfluorenes as monomers. 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 formula (10), 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 C _3-12 lactam such as ε-caprolactam) is used as a copolymerization component. Also good.

(9) Polyimide resin The polyimide resin can be obtained by reacting bisaniline fluorenes, which are compounds represented by the formula (10), 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.

（式（１３）中、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は、それぞれ同一または異なって、水素または炭素数１〜５の炭化水素基を表し、Ｒ¹⁵は、水素、カルボキシル基または炭素数２〜８のアルコキシカルボニル基を表す。）
ポリイミド樹脂は熱可塑性であってもよく熱硬化性であってもよい。 The unsaturated polyimide resin includes (1) a compound represented by the formula (12) shown in the section of the polyester resin, a compound represented by the following formula (13), pyromellitic acid anhydride, and terephthalic acid. Or at least one selected from acid chlorides thereof.

(In the formula (13), 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 carbon. Represents an alkoxycarbonyl group of formula 2-8.)
The polyimide resin may be thermoplastic or thermosetting.

(10) aniline as the bis aniline fluorenes used as a raw material of the resin aniline resin, in the formula (10), n1 and n2 are 0 or 1, X ¹ is an amino group or a hydroxyl group (X ¹ is at least 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 (C1-4 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-based resin can be produced according to a conventional aniline resin production method. In the presence of an acid catalyst, a novolac aniline-based resin is obtained, and in the presence of a base catalyst, a resol-type aniline-based resin is obtained.

<Cardo resin having an ethylenically unsaturated double bond>
The cardo resin used herein 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) Phenol resin, (8) Polyamide resin, (9) Polyimide resin, and (10) Aniline resin react when polymerizing bisaniline fluorenes, which are compounds represented by formula (10). The other party 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 bond are compounds (A1) having an ethylenically unsaturated double bond after main skeleton formation. The ethylenically unsaturated double bond can be introduced by the method described in the column. Of course, ethylenically unsaturated double bonds may be introduced by other methods.

<Other resins>
In the case where the cardo resin is a thermosetting resin, an appropriate curing agent or the like may be included in the resin composition. 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 formula (10) or the cardo resin (A5) may be combined with other resins (thermoplastic resin or thermosetting resin). In particular, the compound represented by the formula (10) or the cardo resin (A5) 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 formula (10) or the cardo resin (A5) is the former / the latter = 99/1 to 1/99 (for example, 90/10 to 10/90). It can be selected from a range of about, usually 99/1 to 50/50, preferably 98/2 to 70/30, more preferably about 97/3 to 80/20.

<< Fluorene skeleton-containing compound (A6) >>
The resin composition of each embodiment can contain the fluorene skeleton-containing compound (A6) represented by the formula (14). The fluorene skeleton-containing compound (A6) is an essential component particularly in Embodiment IV. It can also be an essential component of Embodiment VI.

［式（１４）中、Ｒ¹は水素原子、水酸基、フェニル基、トリル基、アミノ基、カルボキシ基、または−（ＣＨ₂）_nＣＨ₃で表されるアルキル基を示し、
Ｒ²は−Ｃ(Ａ)＝ＣＨ₂、 −ＣＯ−Ｃ(Ａ)＝ＣＨ₂、−(Ｂ)−Ｏ−ＣＯ−Ｃ(Ａ)＝ＣＨ₂、−(Ｂ)−Ｃ(Ａ)＝ＣＨ₂、−Ｏ−(Ｂ)−Ｏ−ＣＯ−Ｃ(Ａ)＝ＣＨ₂、−Ｏ−(Ｂ)−Ｃ(Ａ)＝ＣＨ₂、−ＳＨ、−(Ｂ)−ＣＯ−Ｃ(Ａ)＝ＣＨ₂、−Ｏ−(Ｂ)−ＣＯ−Ｃ(Ａ)＝ＣＨ₂、

を示し、
（Ａ）は−Ｈまたは−ＣＨ₃であり、
（Ｂ）は（ＣＨ₂）_n、（ＯＣＨ₂ＣＨ₂）_n、（ＯＣＨ₂ＣＨ₂ＣＨ₂）_n、（ＯＣＨ₂ＣＨ（ＯＨ）ＣＨ₂）_n、または（ＯＣＯＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂）_nであり、
Ｒ³は水素原子、シアノ基、ハロゲン原子またはアルキル基を示す。
ｊ、ｋおよびｍは、互いに独立して０〜４の整数、ｊ＋ｋは０〜５の整数であり、ｎは１〜２０の整数である。］ By including the fluorene skeleton compound (A6) represented by the formula (14), the refractive index and developability can be improved.

[In formula (14), R ¹ represents a hydrogen atom, a hydroxyl group, a phenyl group, a tolyl group, an amino group, a carboxy group, or an alkyl group represented by — (CH ₂ ) _n CH ₃ ;
R ² is _{-C (A) = CH 2,} -CO-C (A) = CH 2, - (B) -O-CO-C (A) = CH 2, - (B) -C (A) = _{CH 2, -O- (B) -O} -CO-C (A) = CH 2, -O- (B) -C (A) = CH 2, -SH, - (B) -CO-C (A ) = CH ₂ , —O— (B) —CO—C (A) = CH ₂ ,

Indicate
(A) is —H or —CH ₃ ;
(B) is (CH ₂ ) _n , (OCH ₂ CH ₂ ) _n , (OCH ₂ CH ₂ CH ₂ ) _n , (OCH ₂ CH (OH) CH ₂ ) _n , or (OCOCH ₂ CH ₂ CH ₂ CH _{2 N} ) and
R ³ represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
j, k and m are each independently an integer of 0 to 4, j + k is an integer of 0 to 5, and n is an integer of 1 to 20. ]

The substitution position of R ² is not particularly limited and may be o-, m- or p-position with respect to fluorene, but m- and / or p-position is preferred.
(A) is a -H or -CH _3, from the viewpoint of developability (A) is -H are preferred.
(B) is (CH ₂ ) _n , (OCH ₂ CH ₂ ) _n , (OCH ₂ CH ₂ CH ₂ ) _n , (OCH ₂ CH (OH) CH ₂ ) _n , or (OCOCH ₂ CH ₂ CH ₂ CH ₂ ) and _n, R ⁴ is a hydrogen atom, a cyano group, a halogen atom or an alkyl group, from the viewpoint of developability (B) is _{(OCH 2 CH 2) n,} (OCH 2 CH 2 CH 2) n, ( OCH ₂ CH (OH) CH ₂ ) is preferred.
However, in R ² , (B) is (OCH ₂ CH ₂ ) _n , (OCH ₂ CH ₂ CH ₂ ) _n , (OCH ₂ CH (OH) CH ₂ ) _n , or (OCOCH ₂ CH ₂ CH ₂ CH ₂ ) for _{n, -O- (B) -O-} CO-C (a) = CH 2, -O- (B) -C (a) = CH 2, -O- (B) -CO-C ( It does not become -O- (B)-like A) = CH ₂ or the like.

Further, when R ² is selected as a group containing the above epoxy group, k may be an integer of 1 to 5.

  The fluorene skeleton compound (A6) represented by the formula (14) includes 9,9-bis ((meth) acryloyloxy-branched alkoxy-di to tetraalkylphenyl) fluorenes, 9,9-bis ((meth) acryloyl). Oxy-poly branched alkoxy-dialkylphenyl) fluorenes and the like.

  9,9-bis ((meth) acryloyloxy-branched alkoxy-di to tetraalkylphenyl) fluorenes include, for example, 9,9-bis ((meth) acryloyloxy-branched C3-4 alkoxy-dialkylphenyl) fluorene. {E.g., 9,9-bis [4- (2- (meth) acryloyloxypropoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) -2,5-dimethylphenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) -2,6-dimethylphenyl] fluorene, 9,9-bis [3- (2- ( (Meth) acryloyloxypropoxy) -2,4-dimethylphenyl] fluorene, 9,9-bis [2- (2- (meth) acrylic 9,9-bis ((meth) acryloyloxy-branched C3-4alkoxy-diC1-4alkylphenyl) fluorene such as (royloxypropoxy) -3,4-dimethylphenyl] fluorene, preferably 9,9-bis ( 9,9-bis ((meth) acryloyloxy-branched alkoxy-dialkylphenyl) fluorenes such as 2- (meth) acryloyloxypropoxy-diC1-4alkylphenyl) fluorene}.

The 9,9-bis ((meth) acryloyloxy-polybranched alkoxy-di to tetraalkylphenyl) fluorenes include, for example, 9,9-bis ((meth) acryloyloxy-dibranched C3-4 alkoxy-dialkylphenyl). ) Fluorenes {for example, 9,9-bis ((meth) acryloyl such as 9,9-bis {4- [2- (2- (meth) acryloyloxypropoxy) propoxy] -3,5-dimethylphenyl} fluorene) Oxy-dibranched C3-4alkoxy-diC1-4alkylphenyl) fluorene, preferably 9,9-bis [2- (2- (meth) acryloyloxypropoxy) propoxy-diC1-4alkylphenyl] fluorene} and the like 9,9-bis ((meth) acryloyloxy-dibranched alkoxy-dialkylpheny ), And the like fluorenes.
As the fluorene skeleton compound (A6) represented by the formula (14), a commercially available product can be used. Specifically, NK ester A-BPEF, NK ester A-BPEF-4E (manufactured by Shin-Nakamura Chemical Co., Ltd.), ASF-400 (manufactured by Nippon Steel Chemical Co., Ltd.), Ogsol EA-0200 (manufactured by Osaka Gas Chemical Co., Ltd.) and the like can be mentioned.

  When the fine oxide particles (C) are included in the resin composition, the compatibility with the fine oxide particles (C) is improved by including the fluorene skeleton-containing compound (A6) represented by the formula (14). In addition, problems such as residues remaining during the development process are unlikely to occur, and the effect of improving the refractive index can be obtained.

  The content of the fluorene skeleton compound (A6) represented by the formula (14) is preferably 5% by weight or more and less than 40% by weight in 100% by weight of the total solid content of the resin composition. When the content is 5% by weight or more, sufficient sensitivity and resistance to developability can be obtained, and a sufficient effect of compatibility with the oxidized fine particles (C) can be obtained. On the other hand, when the content is less than 40% by weight, the content of the oxide fine particles (C) and the resin does not decrease, and the balance between the refractive index and developability is good.

<< Silane compound (B) >>
The resin composition of each embodiment can contain a silane compound (B).
Including a silane compound is preferable because adhesion to a glass substrate, ITO, or the like is improved.
Examples of the silane compound include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl. Methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-a Nopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxy Examples include silane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane.
These silane compounds can be used alone or in admixture of two or more at any ratio as required.

[式（１５）において、
Ｒ_１は、炭素数１〜２０のアルキレン基、炭素数１〜２０のアリーレン基、炭素数１〜２０のアルコキシレン基、又はアルコキシオキシ基を表し、
Ｒ_２は、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜３０のアルアルキル基、炭素数７〜３０のアルカリール基、置換基を有するシロキサン、ハロゲン、ヒドロキシ又は水素を表し、
Ｒ_３はそれぞれ独立して水素又は不対電子を表し、
Ｒ_４は炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜３０のアルアルキル基、炭素数７〜３０のアルカリール基又は不対電子を表し、
Ｒ_３及びＲ_４が共に不対電子対の場合は、Ｃ及びＮの間は二重結合となり、
ｎは１〜３の整数を表し、同一の基が複数存在する場合はそれぞれ独立して選択される。」 Among the silane compounds (B), the silane compound (B) represented by the following formula (15) is an essential component particularly in Embodiments III and VII.

[In Formula (15),
R ₁ represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 1 to 20 carbon atoms, an alkoxylene group having 1 to 20 carbon atoms, or an alkoxyoxy group,
R ₂ 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, and an aralkyl group having 7 to 30 carbon atoms. Represents an alkaryl group having 7 to 30 carbon atoms, a siloxane having a substituent, halogen, hydroxy or hydrogen,
Each R ₃ independently represents hydrogen or an unpaired electron;
R ₄ 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, an aralkyl group having 7 to 30 carbon atoms, Represents an alkaryl group having 7 to 30 carbon atoms or an unpaired electron,
When R ₃ and R ₄ are both unpaired electron pairs, a double bond is formed between C and N,
n represents an integer of 1 to 3, and when a plurality of the same groups are present, they are independently selected. "

When R ₄ is an alkyl group, aryl group, aralkyl group, or alkaryl group, the silane compound has an amide skeleton, and when R ³¹ is an alkoxy group or an aryloxy group, the silane compound has a urethane skeleton.

  By including the silane compound (B) represented by the formula (15), adhesion with a member used for a touch panel such as a glass substrate, ITO, molybdenum, and transmittance are improved, and pencil hardness and substrate adhesion are improved. improves.

In the formula (15), R ₁ is an alkylene group having 1 to 5 carbon atoms, R ₂ is an alkoxy group or hydrogen group having 1 to 5 carbon atoms, R ₃ and R ₄ are both unpaired electrons, and C and The silane compound that represents a double bond between N is an essential component of Embodiment I as the silane compound represented by the formula (I-1). By including an isocyanate group-containing silane compound in the resin composition, adhesion to a member used for a touch panel such as a glass substrate, ITO, or molybdenum is improved.
In formula (15), n is 1, R ₃ is hydrogen, R ₄ 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, and the number of carbon atoms A silane compound which is an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or an alkaryl group having 7 to 30 carbon atoms is represented by the formula (II-1) as a silane compound represented by the formula II. It is an essential ingredient. The silane compound represented by the formula (II-1) is very thermally and chemically stable because it does not have a highly reactive site such as an isocyanate group. Therefore, the coating film is hardly yellowed. In addition, the resin composition has very high temporal stability, and is very excellent in pencil hardness, substrate adhesion, and developability.

Examples of the silane compound (B) represented by the formula (15) include (3-carbamateethyl) propyltriethoxysilane, (3-carbamateethyl) propyltrimethoxysilane, (3-carbamateethyl) propyltripropoxysilane, (3-carbamatepropyl) propyltriethoxysilane, (3-carbamatepropyl) propyltrimethoxysilane, (3-carbamatepropyl) propyltripropoxysilane, (3-carbamatebutyl) propyltriethoxysilane, (3-carbamatebutyl ) Propyltrimethoxysilane, (3-carbamatebutyl) propyltripropoxysilane, (3-carbamatebutyl) butyltripropoxysilane, (3-carbamatebutyl) propylmethyldiethoxysilane, (3 Carbamate pentyl) triethoxysilane, (3-carbamate-hexyl) triethoxysilane, 3-carbamate-octyl) pen tilt butoxy silane,
(3-carbamateethyl) propylsilyltrichloride, (3-carbamateethyl) propyltrimethylsilane, 3-carbamateethyl) propyldimethylsilane, 3-carbamateethyl) propyltributylsilane, 3-carbamateethyl) ethyl-p-xylenetri Examples include, but are not limited to, ethoxysilane, 3-carbamateethyl) -p-phenylenetriethoxysilane, and the like. Further, the silane compound (B) represented by the formula (15) may be a silanol compound obtained by hydrolysis thereof or a polyorganosiloxane compound in which they are condensed.

  In Embodiment I, the molar ratio of the hydroxyl group of the resin (A2) having a hydroxyl group in the side chain to the isocyanate group of the silane compound (B) is preferably 0.40 to 1.60. A molar ratio of 0.40 or more is preferable because of excellent adhesion and significantly improved transmittance. The case of 1.60 or less is preferable because the pencil hardness is improved. The silane compound (B) is preferably used in an amount of 0.1 to 30% by weight in a total of 100% by weight of the solid content of the resin composition. When the content is 0.1% by weight or more, the adhesion improving effect is excellent. When the content is 30% by weight or less, the resin, polyfunctional monomer, photopolymerization initiator, and the like in the resin composition are relatively suitable. Therefore, characteristics such as substrate adhesion and pencil hardness tend to be improved.

In Embodiment II, the weight average molecular weight (Mw) of the silane compound (B) is 100 or more and less than 5000, and the content of the silane compound (B) in the total solid content of the resin composition is 100% by weight or more. Preferably it is less than 60% by weight. When the weight average molecular weight (Mw) of the silane compound (B) is 100 or more, the substrate adhesion is good, and when it is less than 5000, the pencil hardness is good. When the content is 5% by weight or more, the pencil hardness is good, and when it is less than 60% by weight, the substrate adhesion and the transmittance are excellent. Furthermore, it is more preferable that the weight average molecular weight (Mw) of the silane compound (B) is 200 or more and less than 500 from the viewpoint of pencil hardness and substrate adhesion, and the total solid content of the resin composition is 100% by weight. The content of the silane compound (B) is more preferably 10% by weight or more and less than 50% by weight from the viewpoint of substrate adhesion.
In Embodiment III, the weight average molecular weight (Mw) of the silane compound (B) 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 5% by weight. The amount is preferably less than 50% by weight. When the weight average molecular weight (Mw) of the silane compound (B) is 200 or more, it is preferable from the viewpoint of availability, and when it is less than 5000, the substrate adhesion is good. If the content is 5% by weight or more, the transmittance and pencil hardness are good, and if it is less than 50% by weight, the substrate adhesion and the pencil hardness are high. Furthermore, it is more preferable that the weight average molecular weight (Mw) of the silane compound (B) is 200 or more and less than 500 from the viewpoint of pencil hardness and substrate adhesion, and the total solid content of the resin 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.
In Embodiments IV and V, the weight average molecular weight (Mw) of the silane compound (B) is more preferably 200 or more and less than 5000 from the viewpoint of adhesion to the metal substrate and developability, and the content of the silane compound (B). Is more preferably 1% by weight or more and less than 20% by weight in the total solid content of 100% by weight of the resin composition from the viewpoint of adhesion to the metal substrate and developability. More preferably, they are 1 weight% or more and less than 10 weight%. When the weight average molecular weight (Mw) of the silane compound (B) is 200 or more, it is preferable from the viewpoint of availability. When the weight average molecular weight (Mw) is less than 5000, the adhesion to the metal substrate and the developability are preferable. Moreover, when the content is 1% by weight or more, the transmittance and developability are excellent, and when it is less than 20% by weight, not only the adhesion to the substrate and the hardness but also the developability is preferable.

<< Oxide fine particles (C) >>
The resin composition of each embodiment can contain oxide fine particles (C). The oxide fine particles (C) are an essential component particularly in Embodiments IV to VI.

  The oxide fine particles may be surface-treated. From the viewpoint of colorlessness when the resin composition is cured, or from the viewpoint of transmittance and pencil hardness, oxide particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, and zinc It is preferable. Of these, from the viewpoint of transmittance, oxide particles of silicon, zirconium, or aluminum are preferable, and silicon oxide particles are particularly preferable. Zirconium or titanium oxide fine particles are preferable from the viewpoint of increasing the refractive index. From the viewpoint of refractive index, it preferably contains oxide fine particles of at least one element selected from aluminum, antimony, zirconium, cerium, titanium, zinc and the like, having a refractive index of 1.55 or more, and zirconium or titanium oxide fine particles Is preferred.

  By using the oxide fine particles (C), it is possible to further improve heat resistance, pencil hardness, and substrate adhesion, and obtain a coating film having high etchant resistance. In addition, by using the oxide fine particles (C), a coating film having high hardness and good chemical resistance can be obtained.

  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, and any of these is preferable within this range, but 3 nm to 400 nm is more preferable, 3 nm to 100 nm is more preferable, and 5 nm to 300 nm is more preferable. 5 nm to 30 nm is particularly preferable. When the average primary particle size is 1000 nm or less, the transparency of the cured product does not decrease, and the surface state of the coating is good. 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 monomethyl ether acetate are preferable.

  Commercially available products as silicon oxide fine particle dispersions include MA-ST-MS, IPA-ST, IPA-ST-MS, IPA-ST-L, and IPA-ST-ZL manufactured by Nissan Chemical Industries, Ltd. , 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 and the like, and hollow silica CS60-IPA manufactured by Catalyst Chemical Industry Co., Ltd. can be exemplified. 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 zirconia oxide fine particle dispersions include ZR-40BL, ZR-30BS, ZR-30AL, ZR-30AH, etc. manufactured by Nissan Chemical Industries, Ltd., HXU-110JC, manufactured by Sumitomo Osaka Cement 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.

  Commercially available products as aluminum oxide fine particle dispersions include Alumina Sol-100, Alumina Sol-200, Alumina Sol-520 manufactured by Nissan Chemical Industries, Ltd., AS-150I, AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd. Can be mentioned.

  Examples of products that are commercially available as titanium oxide fine particle dispersions 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, the oxide fine particle dispersion liquid preferably used includes an oxide fine particle dispersion liquid such as zinc, and the commercially available product includes Nanotech manufactured by CI Kasei Co., Ltd.

  In Embodiments IV to VI, the content of the oxide fine particles (C) is preferably 10 to 80% by weight and more preferably 20 to 70% by weight in 100% by weight of the total solid content in the resin composition. If the addition amount is 10% by weight or more, the effect of improving the hardness and the refractive index is high, while if it is 80% by weight or less, the developability and the transmittance can be excellent.

  In Embodiments I to III and VII, the addition amount of the oxide fine particles (C) is preferably 5% by weight or more and less than 40% by weight in the total solid content of 100% by weight in the resin composition, and is 5% by weight or more and 50% by weight or less. Less than, more preferably 10 to 35% by weight. When the addition amount is 5% by weight or more, the pencil hardness and etchant resistance are improved, and when it is 40% by weight or less, the substrate adhesion and the transmittance are excellent. The ratio (b / c) between the weight (b) of the silane compound (B) represented by the formula (15) and the weight (c) of the oxide fine particles (C) is 0.4 or more and less than 20.0. It is preferable that it is 1.0 or more and less than 10.0. When the ratio (b / c) is 0.4 or more, the effect of improving the adhesion to the substrate is sufficiently obtained, and the insulating property does not deteriorate. When the ratio (b / c) is less than 20.0, pencil hardness and etchant resistance are good.

<< Solvent (D) >>
The resin composition of each embodiment can contain a solvent (D). The solvent (D) is an essential component in the embodiment I. Further, among the solvents, the organic solvent is an essential component in the embodiment IV.

  Solvents include alcohol solvents such as methanol, ethanol, isopropanol, butanol, octanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl Ester solvents such as ether acetate, propylene glycol monoethyl ether acetate and 1,3-butylene glycol diacetate; Ether solvents such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene Solvent: Amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

The solvent is preferably used in an amount of 25 to 6000 parts by weight, more preferably 200 to 4000 parts by weight, based on 100 parts by weight of the total solid content in the resin composition.
Furthermore, specific examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,4-dioxane, 2-heptanone, 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-butyl alcohol, 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, ethylene glycol mono Hexyl 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 , Cyclopentanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopro 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 propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, Propyl acetate Dibasic acid esters, and the like, used alone or in combination.

  Among these solvents, an alcohol solvent is preferably included. When the silane compound (B) is contained in the resin composition, the stability of the silane compound (B) can be improved by including an alcohol solvent, and the hydrolysis reaction rate of the silane compound is moderate. It is possible to obtain a coating film excellent in pencil hardness, substrate adhesion, and etchant resistance.

  Furthermore, 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 of the silane compound (B) with the substrate proceeds efficiently. Moreover, it is preferable in order to keep the self-condensation reaction rate of the silane compound (B) good, improve the storage stability, and improve the coatability.

  Considering the drying property of the solvent in particular, it is preferable to include a high boiling point solvent of 160 ° C. or higher in die coating or printing methods. Examples of such a solvent include 3-methoxy-3-methyl-1-butanol (bp 174 ° C.), 1,3-butanediol (bp 203 ° C.), and 3-methyl-1,3-butanediol (bp 203 ° C.). 2-methyl-1,3-propanediol (bp 213 ° C.), diisobutyl ketone (bp 168.1 ° C.), ethylene glycol monobutyl 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 ° C.), diethylene 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 ° 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-methoxybutyl acetate (bp 172.5 ° C.), 3-methoxy-3-methylbutyl acetate (b 188 ° C.), γ-butyrolactone (bp 204 ° C.), N, N-dimethylacetamide (bp 166.1 ° C.), N-methylpyrrolidone (bp 202 ° C.), p-chlorotoluene (bp 162.0 ° C.), o-diethylbenzene (bp 183) .4 ° C.), m-diethylbenzene (bp 181.1 ° C.), p-diethylbenzene (bp 183.8 ° C.), o-dichlorobenzene (bp 180.5 ° C.), m-dichlorobenzene (bp 173.0 ° C.), n-butyl Benzene (bp183.3 ° C), sec-butylbenzene (bp178.3 ° C), tert-butylbenzene (bp169.1 ° C), cyclohexanol (bp161.1 ° C), cyclohexyl acetate (bp173 ° C), methylcyclohexanol ( bp 174 ° C.) and the like.

  The solvent preferably contains a solvent having a solubility in water at 20 ° C. of 0.1 g / 100 ml or more and less than 30 g / 100 ml. When the silane compound (B) is contained in the resin composition, if the solubility of the solvent in water is less than 30 g / 100 ml, the silane compound (B) is not hydrolyzed during the production of the resin composition. The composition does not become cloudy, and the substrate adhesion of the coating film is excellent. If the solubility of the solvent in water is 1 g / 100 ml or more, the amount of water in the resin composition is sufficient, siloxane bonds are formed by hydrolysis, and the substrate adhesion of the coating film is excellent.

  Examples of the solvent having a solubility in water at 20 ° C. of 0.1 g / 100 ml or more and less than 30 g / 100 ml include cyclohexanone (8.7 g / 100 ml), propylene glycol monomethyl ether acetate (16.0 g / 100 ml), 1,3 -Butylene glycol diacetate (5.0 g / 100 ml), cyclohexanol acetate (0.2 g / 100 ml), and the like, but are not limited thereto. The solubility in water at 20 ° C. can be obtained by mixing 100 g of water at 20 ° C. with 100 g of solvent at 20 ° C., separating only the aqueous layer, and determining the difference between the weight of the water tank and the weight of water. .

  The content of the solvent whose solubility in water at 20 ° C. is 0.1 g / 100 ml or more and less than 30 g / 100 ml is used in an amount of 25 to 6000% by weight with respect to 100% by weight of the total solid content in the resin composition. be able to.

  Furthermore, it is more preferable to include an alcohol solvent having a boiling point of less than 130 ° C. at 760 mmHg and a solvent having a boiling point of not less than 130 ° C. and less than 250 ° C. at 760 mmHg because wettability to the substrate is improved. The solvent having a boiling point at 760 mmHg of 130 ° C. or higher and lower than 250 ° C. is preferably an ester solvent, and most preferably an ester solvent at 760 mmHg of 200 ° C. or higher and lower than 250 ° C. In particular, when reacting the silane compound (B) with the resin (A2) having a hydroxyl group in the side chain, if the solvent has a boiling point of less than 250 ° C. at 760 mmHg, the volatility is appropriate. The condensation reaction is not inhibited, and the adhesion to the substrate is not deteriorated.

  Examples of alcohol solvents having a boiling point at 760 mmHg of 130 ° C. or higher and lower than 250 ° C. include 1,3-butanediol (bp 207.5 ° C.), 1,3-butylene glycol (bp 207.5 ° C.), 2-heptanone (bp 151). .3 ° C.), 3-methoxy-3-methyl-1-butanol (bp 174 ° C.), 3-methyl-1,3-butanediol (bp 203 ° C.), 3-methoxybutanol (bp 161 ° C.), ethylene glycol monotertiary Butyl ether (bp 152.5 ° C.), ethylene glycol monobutyl ether (bp 171 ° C.), ethylene glycol monopropyl ether (bp 150 ° C.), ethylene glycol monomethyl ether (bp 124.1 ° C.), diethylene glycol monobutyl ether (bp 230 ° C.), diethyl Glycol monomethyl ether (bp 194 ° C.), cyclohexanol (bp 161 ° C.), dipropylene glycol monoethyl ether (bp 197.8 ° C.), dipropylene glycol monobutyl ether (bp 230.6 ° C.), dipropylene glycol monopropyl ether (bp 210 ° C.) ), Dipropylene glycol monomethyl ether (bp 190 ° C.), diacetone alcohol (bp 169.2), tripropylene glycol monomethyl ether (bp 243 ° C.), propylene glycol phenyl ether (bp 243 ° C.), propylene glycol monoethyl ether (bp 133 ° C.), Propylene glycol monobutyl ether (bp 170.2 ° C), propylene glycol monopropyl ether (bp 150 ° C), benzyl Lucol (bp 205 ° C.), 1-methylcyclohexanol (bp 168 ° C.), 2-methylcyclohexanol (bp 172 ° C.), 4-methylcyclohexanol (bp 172 ° C.), octanol (bp 195 ° C.), 2-methyl-1,3- Examples include propanediol (bp 123 ° C.), isobutyl alcohol (bp 108 ° C.), ethylene glycol monoisopropyl ether (bp 42 ° C.), propylene glycol monomethyl ether (bp 120 ° C.), and these can be used alone or in combination.

Among these, diethylene glycol monobutyl ether (bp 230 ° C.), 1,3-butanediol (bp 207.5 ° C.), 3-methyl-1,3-, which are alcohol solvents having a boiling point at 760 mmHg of 200 ° C. or higher and lower than 250 ° C. It is preferable to use butanediol (bp 203 ° C.), dipropylene glycol monobutyl ether (bp 230.6 ° C.), and 1,3-butylene glycol (bp 207.5 ° C.).
Examples of solvents other than alcohols having a boiling point at 760 mmHg of 130 ° C. or higher and lower than 250 ° C. include 1,2,3-trichloropropane (bp 156 ° C.), 1,3-butylene glycol diacetate (bp 232 ° C.), 3, 3 , 5-trimethylcyclohexanone (bp 188 ° C.), ethyl 3-ethoxypropionate (bp 166 ° C.), 1,4-butanediol diacetate (bp 220 ° C.), 3-methoxy-3-methylbutyl acetate (bp 188 ° C.), 3- Methoxybutyl acetate (bp 171 ° C), 4-heptanone (bp 149 ° C), m-diethylbenzene (bp 182 ° C), m-dichlorobenzene (bp 173 ° C), N, N-dimethylacetamide (bp 165 ° C), N, N-dimethylformamide (Bp 153 ° C), n-buty Benzene (bp183.3 ° C), N-methylpyrrolidone (bp202 ° C), o-chlorotoluene (bp158.9 ° C), o-diethylbenzene (bp183 ° C), o-dichlorobenzene (bp180 ° C), p-chlorotoluene ( bp162.4 ° C), p-diethylbenzene (bp184 ° C), sec-butylbenzene (bp173 ° C), tert-butylbenzene (bp169 ° C), γ-butyrolactone (bp204 ° C), isophorone (bp215.2 ° C), ethylene glycol Diethyl ether (bp 121.4 ° C.), ethylene glycol dibutyl ether (bp 202 ° C.), ethylene glycol monoethyl ether (bp 135 ° C.), ethylene glycol monoethyl ether acetate (bp 156.3 ° C.), ethylene glycol monobutyl Chill ether acetate (bp 192 ° C.), ethylene glycol monomethyl ether acetate (bp 145 ° C.), diisobutyl ketone (bp 168 ° C.), diethylene glycol diethyl ether (bp 180 ° C.), diethylene glycol dimethyl ether (bp 162 ° C.), diethylene glycol monoethyl ether acetate (bp 218 ° C.), Diethylene glycol monobutyl ether acetate (bp 246.8 ° C), cyclohexanol acetate (bp 173 ° C), cyclohexanone (bp 155.6 ° C), cyclopentanone (bp 130 ° C), dipropylene glycol dimethyl ether (bp 175 ° C), dipropylene glycol methyl ether acetate (Bp 209 ° C.), propylene glycol diacetate (bp 190 ), Propylene glycol monoethyl ether acetate (bp 158 ° C.), propylene glycol monomethyl ether acetate (bp 146 ° C.), propylene glycol monomethyl ether propionate (bp 160 ° C.), n-amyl acetate (bp 149 ° C.), isoamyl acetate (bp 142 ° C.) And dibasic acid esters.
These solvents can be used singly or in combination of two or more at any ratio as required.

Among these solvents, ester solvents are preferable, propylene glycol diacetate (bp 190 ° C.) and diethylene glycol monoethyl ether acetate (bp 218 ° C.) are preferable, 1,3-butylene glycol diacetate (bp 232 ° C.), 1,4 -Butanediol diacetate (bp 220 ° C.) is particularly preferred.
Furthermore, as a solvent, in order to adjust the volatility of the solvent, a solvent other than an alcohol having a boiling point of less than 130 ° C. at 760 mmHg or a solvent having a boiling point of 250 ° C. or higher at 760 mmHg may be used as long as the effects of the present invention are not impaired. For example, propyl acetate (bp 96.6 ° C.), n-propyl acetate (bp 102 ° C.), n-butyl acetate (bp 126 ° C.), isobutyl acetate (bp 118 ° C.), 3,5,5-trimethyl-2- It may contain cyclohexen-1-one (bp 289 ° C.), triacetin (bp 258 ° C.), tripropylene glycol monobutyl ether (bp 276 ° C.), 1,6-hexanediol diacetate (bp 260 ° C.), and the like.

<< Polyfunctional monomer (D) >>
The resin composition of each embodiment can contain a polyfunctional monomer (D). Among them, a polyfunctional monomer having four or more functional groups is an essential component in the embodiment V. Moreover, it can be made into an essential component in Embodiment VI.

  By including a polyfunctional monomer having four or more functional groups, a coating film having excellent hardness can be obtained.

The content of all the polyfunctional monomers in the resin composition is preferably 5 to 80% by weight, more preferably 10 to 10% of the total 100% by weight of the solid content of the resin composition from the viewpoint of increasing pencil hardness. 50% by weight.
Specific examples of the polyfunctional monomer having four or more functional groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexaacrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, dipentaerythritol penta (meth) acrylate and acid anhydride Examples thereof include a reaction product, a reaction product of pentaerythritol homopolymer and acrylic acid.
In addition, it may have an acid group, for example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid, Examples thereof include esterified products with hydroxyalkyl (meth) acrylates. Specific examples include monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, malonic acid, succinic acid, glutaric acid, terephthalate. Monoesterified product containing free carboxyl group with dicarboxylic acid such as acid; propane-1,2,3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, benzene-1,2,3 Tetracarboxylic acids such as 1,4-tetracarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate It can be given free carboxyl group-containing oligo ester of monohydroxy monoacrylate or monohydroxy monomethacrylate and the like.
These polyfunctional monomers can be used singly or in combination of two or more at any ratio as required.

Examples of commercially available polyfunctional monomers having four or more functional groups include, for example, Aronix M-400, Aronix M-460, Aronix M-402, Aronix M-510, Aronix M-520 (Toagosei). KAYARADT-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60, KAYARAD DPCA120 (manufactured by Nippon Kayaku Co., Ltd.), Biscote # 802, Biscote # 2500, Biscote # 1000 (Osaka Organic) Chemical Industry Co., Ltd.).
The content of the polyfunctional monomer having four or more functional groups is preferably 5 to 80% by weight in a total of 100% by weight of the solid content of the resin composition. If it is 5% by weight or more, the effects of increasing hardness and imparting solvent resistance are sufficiently obtained. When it is 80% by weight or less, the transmittance is high and the adhesion is high. More preferably, it is 10 to 50% by weight.

<Polyfunctional monomer (D1) represented by Formula (16)>
Among polyfunctional monomers having 4 or more functional groups, in particular, polyfunctional monomers having 7 or more ethylenically unsaturated double bonds (D1) in one molecule represented by the following formula (16) ) Is preferable because a coating film with higher hardness (pencil hardness) and substrate adhesion can be obtained. Moreover, it can be excellent in etchant resistance.

[式（１６）において、ｎは０〜４の整数であり、Ｒ^７はエーテル基、アルキレン基、トリレン基、アリーレン基、カルボニル基、スルホニル基、エステル基、および式（１７）で表される構造を有する２価の基からなる群より選ばれるいずれかであり、Ｒ^８は水素原子またはメチル基であり、Ｒ^９はヒドロキシル基、カルボキシル基、（メタ）アクリロイル基および（メタ）アクリロイルオキシ基からなる群より選ばれるいずれかである。]

［式（１７）において、Ｒ^１０は脂肪族、脂環式または芳香族の構造を表す。］ From the viewpoint of maintaining transmittance, the balance between pencil hardness and substrate adhesion, etc., it is preferably a polyfunctional monomer having 7 to 16 ethylenically unsaturated double bonds, and more preferably 7 to 12 In some cases, it is more preferable because it is excellent in pencil hardness, substrate adhesion, and etchant resistance.

[In the formula (16), n is an integer of 0 to 4, and R ⁷ is represented by an ether group, an alkylene group, a tolylene group, an arylene group, a carbonyl group, a sulfonyl group, an ester group, and the formula (17). R ⁸ is any one selected from the group consisting of divalent groups having a structure, R ⁸ is a hydrogen atom or a methyl group, R ⁹ is a hydroxyl group, a carboxyl group, a (meth) acryloyl group and a (meth) acryloyloxy group. One selected from the group consisting of ]

[In the formula (17), R ¹⁰ represents an aliphatic, alicyclic or aromatic structure. ]

Among the compounds represented by the formula (16), it is preferable in terms of hardness and adhesion that R ⁷ is an ether group or a divalent group having a structure represented by the formula (17).

R ⁷ is an ether group, for example, a compound obtained by reacting dipentaerythritol penta (meth) acrylate with polyfunctional isocyanate, dipentaerythritol penta (meth) acrylate and tetrabasic acid dianhydride are reacted. And a compound obtained by reacting dipentaerythritol penta (meth) acrylate with a polyfunctional epoxy compound.

  Specific examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.

  Specific examples of tetrabasic acid dianhydrides include pyromellitic anhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride. , Cyclopentanetetracarboxylic dianhydride, oxydiphthalic anhydride, ethylene glycol bisanhydro trimellitate, glycerin bis (anhydro trimellitate monoacetate), benzophenone tetracarboxylic dianhydride, methylcyclohexylene tetracarboxylic acid A dianhydride etc. can be mentioned.

  Specific examples of the polyfunctional epoxy compound include tris (glycidylphenyl) methane, triglycidyl isocyanurate, bis (3,4-epoxycyclohexylmethyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl). Examples thereof include adipate, methylene bis (3,4-epoxycyclohexane), bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and novolak type epoxy resin.

Among the polyfunctional monomers in which R7 is an ether group in the formula (16), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol 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 (D1) represented by the formula (16), commercially available products include, for example, Bisquat # 802 (poly (pentaerythritol) acrylate (reaction product of pentaerythritol homopolymer and acrylic acid). Osaka Organic Chemical Industry Co., Ltd.).

When R ¹⁰ is a divalent group having a structure represented by formula (17), if n = 1 and R ⁹ is a (meth) acryloyl group or a (meth) acryloyloxy group, the hardness Is more preferable.

  Commercially available products as such a polyfunctional monomer (D1) represented by the formula (16) include, for example, TO-2323, TO-2324, TO-2325, TO-2326, TO-2327 and TO-2328 ( Toa Gosei Co., Ltd.).

The content of the polyfunctional monomer (D1) represented by the formula (16) is preferably used in an amount of 30 to 100% by weight in the polyfunctional monomer having 4 or more functional groups. When it is 30% by weight or more, sufficient effects of increasing hardness and imparting good adhesion can be obtained.
The content of the polyfunctional monomer (D1) represented by the formula (16) is preferably used in an amount of 5 to 80% by weight in the total of 100% by weight of the solid content of the resin composition. . If it is 5% by weight or more, the effects of increasing pencil hardness, imparting etchant resistance, and imparting solvent resistance are sufficiently obtained, and if it is 80% by weight or less, the transmittance and substrate adhesion are high. More preferably, it is 10 to 50% by weight.

［式（１８）中、Ｒ¹⁴は水素原子、水酸基、フェニル基、トリル基、アミノ基、カルボキシ基、または−(ＣＨ_２)_ｔＣＨ_３で表されるアルキル基を示し、
Ｒ^１５は−Ｃ(Ａ)＝ＣＨ_２、−ＣＯ−Ｃ(Ａ)＝ＣＨ_２、−(Ｂ)−Ｏ−ＣＯ−Ｃ(Ａ)＝ＣＨ_２、
−(Ｂ)−Ｃ(Ａ)＝ＣＨ_２、−Ｏ−(Ｂ)−Ｏ−ＣＯ−Ｃ(Ａ)＝ＣＨ_２、−Ｏ−(Ｂ)−Ｃ(Ａ)＝ＣＨ_２、−(Ｂ)−ＣＯ−Ｃ(Ａ)＝ＣＨ_２、−Ｏ−(Ｂ)−ＣＯ−Ｃ(Ａ)＝ＣＨ_２、
を示し、
（Ａ）は−Ｈまたは−ＣＨ_３であり、
（Ｂ）は(ＣＨ_２)_ｔ、(ＯＣＨ_２ＣＨ_２)_ｔ、(ＯＣＨ_２ＣＨ_２ＣＨ_２)_ｔ、(ＯＣＨ_２ＣＨ(ＯＨ)ＣＨ_２)_ｔ、または(ＯＣＯＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２)_ｔであり、
Ｒ^１６は水素原子、シアノ基、ハロゲン原子またはアルキル基を示す。
ｐは０〜３の整数、ｑは２〜５の整数、ｒは０〜４の整数、ｐ＋ｑは２〜５の整数であり、ｔは１〜２０の整数である。］ <Fluorene skeleton-containing polyfunctional monomer (D2) having four or more functional groups>
Moreover, from the point of the hardness of a coating film, it is preferable to contain especially the polyfunctional monomer (D2) containing a fluorene skeleton among the polyfunctional monomers which have a 4 or more functional group. Specific examples of the fluorene skeleton-containing polyfunctional monomer (D2) include, but are not limited to, compounds represented by the following formula (18). By using such a fluorene skeleton-containing polyfunctional monomer (D2) having four or more functional groups, high hardness can be obtained while improving the refractive index.

[In the formula (18), R ¹⁴ represents a hydrogen atom, a hydroxyl group, a phenyl group, a tolyl group, an amino group, a carboxy group, or an alkyl group represented by — (CH ₂ ) _t CH ₃ ;
R ¹⁵ is _{-C (A) = CH 2,} -CO-C (A) = CH 2, - (B) -O-CO-C (A) = CH 2,
- (B) -C (A) = CH 2, -O- (B) -O-CO-C (A) = CH 2, -O- (B) -C (A) = CH 2, - (B _{) -CO-C (A) =} CH 2, -O- (B) -CO-C (A) = CH 2,
Indicate
(A) is —H or —CH ₃ ;
(B) is (CH ₂ ) _t , (OCH ₂ CH ₂ ) _t , (OCH ₂ CH ₂ CH ₂ ) _t , (OCH ₂ CH (OH) CH ₂ ) _t, or (OCOCH ₂ CH ₂ CH ₂ CH ₂ ) _t ,
R ¹⁶ represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
p is an integer of 0 to 3, q is an integer of 2 to 5, r is an integer of 0 to 4, p + q is an integer of 2 to 5, and t is an integer of 1 to 20. ]

The substitution position of R ¹⁵ is not particularly limited, and may be o-, m-, or p-position with respect to fluorene, but m- and / or p-position is preferred.
(A) is —H or —CH ₃ and (A) is preferably —H from the viewpoint of developability.
(B) is (CH ₂ ) _t , (OCH ₂ CH ₂ ) _t , (OCH ₂ CH ₂ CH ₂ ) _t , (OCH ₂ CH (OH) CH ₂ ) _n, or (OCOCH ₂ CH ₂ CH ₂ CH ₂ ) _n , and (B) is preferably (OCH ₂ CH ₂ ) _t , (OCH ₂ CH ₂ CH ₂ ) _t , (OCH ₂ CH (OH) CH ₂ ) from the viewpoint of developability.
However, R ¹⁵ is (B) is (OCH ₂ CH ₂ CH ₂ ) _t , (OCH ₂ CH ₂ CH ₂ ) _t , (OCH ₂ CH (OH) CH ₂ ) _t, or (OCOCH ₂ CH ₂ CH ₂ CH ₂ ) for _{t, -O- (B) -O-} CO-C (a) = CH 2, -O- (B) -C (a) = CH 2, -O- (B) -CO-C ( a) = as CH ₂ etc., -O- (B) - and it does not become.
Specific examples of the fluorene skeleton-containing polyfunctional monomer (D2) include 9,9-bis {4- [2- (2- (meth) acryloyloxypropoxy) propoxy] -5- [2- (2- ( (Meth) acryloyloxypropoxy) propoxy] fluorene and the like.
The content of the fluorene skeleton-containing polyfunctional monomer (D2) is preferably 30% by weight or more and less than 100% by weight in the polyfunctional monomer having four or more functional groups. When the content is less than 30% by weight, a sufficient effect of increasing the refractive index can be obtained.

<Other polyfunctional monomers>
In addition to the polyfunctional monomer having four or more functional groups, the polyfunctional monomer may contain other polyfunctional monomers having less than four functional groups. For example, trimethylolpropane tri (meth) acrylate And various acrylic esters such as pentaerythritol tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and propylene oxide-modified trimethylolpropane tri (meth) acrylate, and methacrylates. These polyfunctional monomers may have an acid group.
Moreover, the compound represented by following formula (19) can also be used preferably.
Formula (19):
_{(H 2 C = C (R} 9) COO) h -X- (OCOCH (R 9) CH 2 S (R 10) COOH) i

[In Formula (19), R ₉ is a hydrogen atom or a methyl group, R ₁₀ is a hydrocarbon group having 1 to 12 carbon atoms, X is an (h + i) -valent organic group having 3 to 60 carbon atoms, and h is 2 to 18 And i represents an integer of 1 to 3. ]

Here, the compound represented by Formula (19) can be easily obtained by the following method, for example.
(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 mercapto compounds include mercaptoacetic acid, 2-mercaptopropionic acid,
Examples include 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.

<< Colorant >>
The resin composition of each embodiment can contain a colorant.
By using the colorant, for example, in the case of a panel, the hue of the resin composition can be corrected in order to adjust the chromaticity a * = 0 and b * = 0.

  In particular, depending on the coating film forming step and the constituent components of the resin composition, the coating film may shift to a yellowish hue. In such a case, it is preferable to add a colorant to the resin composition to adjust the hue and form a more excellent protective film and touch panel insulating film.

The content of the colorant is preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight, out of a total of 100% by weight of the solid content of the resin composition, from the viewpoint of maintaining the transmittance of the coating film. It is.
Examples of the colorant include pigments such as inorganic pigments and organic pigments, and dyes such as oil-soluble dyes, acid dyes, direct dyes, basic dyes, mordant dyes, acid mordant dyes, and pigments (E1) in terms of heat resistance. Is preferred.

Among the colorants, the pigment has a great effect of correcting the chromaticity shift. In particular, when at least one selected from the group consisting of a red pigment, a blue pigment, and a violet pigment is included, the hue of the coating film can be easily adjusted to an appropriate chromaticity range, and a superior protective film and touch panel can be used. It is preferable because an insulating film can be formed.
For example, when the resin composition contains oxide fine particles (C), although it varies depending on the type and content of the oxide fine particles (C), a * is about −0.7 to −0.01 for the hue. b * may shift by about +0.01 to 2.4. In such a case, the hue of the resin composition is a * <0, b *> 0. Therefore, in order to adjust the hue to red (a * is in the + direction) and blue (b * is in the − direction) in order to set the hue to a * = 0 and b * = 0, a red pigment and a blue pigment are used. And a pigment containing at least one selected from the group consisting of purple pigments. When a purple pigment or a blue pigment and a red pigment are used, it is preferable because a coating film having more excellent hue can be obtained.

<Pigment>
As the pigment, organic or inorganic pigments can be used alone or in admixture of two or more at any ratio as required. Among the pigments, pigments having high color developability and high heat resistance, particularly organic pigments are preferable.

In addition, among the pigments, it is preferable to include at least one selected from the group consisting of a red pigment, a blue pigment, and a purple pigment because the hue of the coating film can be easily adjusted to an appropriate chromaticity range.
Specific examples of organic pigments that can be preferably used are shown below by color index numbers, but are not limited thereto.

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254, more preferably C.I. I. Pigment Red 177, 209, 224, 242, or 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 or 58.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, or 180.

<Miniaturization of pigment>
The pigment is preferably used after being refined. There are no particular limitations on the method of miniaturization, and for example, any of wet grinding, dry grinding, and dissolution precipitation can be used. Etc., and may be miniaturized.
It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. If it is 5 nm or more, it can be sufficiently dispersed in an organic solvent. When the thickness is 90 nm or less, a sufficient contrast ratio can be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded with heating using a kneader, and then washed with water to remove the water-soluble inorganic salt and water-soluble organic solvent. It is a process to remove.

  Examples of the kneader include a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, and a sand mill. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

  When preparing a pigment dispersion, it is preferable to add a pigment derivative in order to prevent aggregation of the pigment and maintain a finely dispersed state of the pigment. The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the pigment. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by weight or less, and most preferably 35 parts by weight or less with respect to 100 parts by weight of the pigment.

<Dye>
A dye is also preferably used as the colorant. The dyes may be used alone or in admixture of two or more at any ratio as necessary, and may be used in combination with the above-mentioned pigment. Furthermore, it is preferable that at least one selected from the group consisting of a red dye, a blue dye, and a purple dye is included from the viewpoint of correcting the chromaticity of a touch panel constituent member such as titanium oxide that is added as necessary.
Examples of the form of the dye include those having any form of various dyes such as oil-soluble dyes, acid dyes, direct dyes, basic dyes, mordant dyes, and acid mordant dyes.
The dye may be used in the form of a lake, or may be in the form of a salt-forming compound of a dye and a nitrogen-containing compound.

The dye is not particularly limited as long as it is generally referred to as a dye. Among them, triphenylmethane dye, diphenylmethane dye, quinoline dye, thiazine dye, thiazole dye, xanthene dye, flavin Dyes, auramine dyes, safranine dyes, phloxine dyes, methylene blue dyes, and the like can be used.
Dyes have good spectral characteristics and excellent color developability, but have problems with light resistance and heat resistance. There may not be.

Therefore, in order to improve these disadvantages, in the case of a basic dye, it is preferable to use a salt-forming compound salted with an organic acid or perchloric acid. As the organic acid, organic sulfonic acid or organic carboxylic acid is preferably used. Of these, naphthalenesulfonic acid such as tobias acid and perchloric acid are preferably used in terms of resistance.
In the case of acidic dyes and direct dyes, a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, and the like, and a salt formed using a resin component having these functional groups It is preferable in terms of resistance to use as a salt compound or as a salt-forming compound obtained by sulfonamidation to obtain a sulfonic acid amide compound.

<Method for adding colorant>
As a method for adding the colorant, the colorant may be added to the resin composition as it is. Or you may add to a resin composition as a coloring composition mixed in colorant carriers, such as resin, and / or a solvent. Although it may add by what kind of method, it is preferable to add as a coloring composition at the point which is excellent in the transparency of a resin composition especially.

  The coloring composition comprises a colorant dispersed in a colorant carrier and / or solvent such as a resin such as a thermoplastic resin and a resin having an ethylenically unsaturated double bond, preferably together with a dispersion aid. It can be produced by finely dispersing using means (colorant dispersion).

  Examples of the dispersing means include a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor. When two or more colorants are included, these colorants and the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. In addition, when the colorant has high solubility due to dyes or the like, specifically, it is highly soluble in the solvent to be used. There is no need to manufacture.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing re-aggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has brightness, contrast ratio, and Viscosity stability is improved.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more. When a dye derivative is used, those having a quinophthalone skeleton and an azo skeleton are preferable from the viewpoint of lightness.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324, 21407, 21715 or Lactimon, Lactimon-WS or Bykumen, etc., Japan Lubrizol SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, manufactured by Ciba Japan , 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 45 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajimoto Fine Techno Co., Ltd. PB821, PB822, PB824, etc. are mentioned.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin-type dispersant and the surfactant is 0.1 parts by weight or more, the added effect is sufficiently obtained, and when it is 55 parts by weight or less, the dispersibility is good.

<< tetraalkoxysilane >>
The resin composition of each embodiment can contain tetraalkoxysilane.
Examples of tetraalkoxysilane include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

  In particular, when the silane compound (B) is contained in the resin composition, hydrolysis with water in the resin composition is preferentially performed with tetraalkoxysilane by containing tetraalkoxysilane together, and silane Hydrolysis of the compound (B) can be prevented. The ratio (b / e) of the weight (b) of the silane compound (B) and the weight (e) of the tetraalkoxysilane is preferably 2 or more and less than 20. When the ratio (b / e) of the weight (b) of the silane compound (B) to the weight (e) of the tetraalkoxysilane is 2 or more, the hydrolysis of the tetraalkoxysilane is small during the formation of the coating film, and the silane compound (B ), And the pencil hardness and substrate adhesion of the coating film are excellent. When the ratio (b / e) of the weight (b) of the silane compound (B) to the weight (e) of the tetraalkoxysilane is less than 20, the effect of preventing the hydrolysis of the silane compound (B) by the tetraalkoxysilane is great. .

<< photopolymerization initiator >>
The resin composition of each embodiment can contain a photopolymerization initiator. When making a resin composition into the photosensitive resin composition, it is preferable to contain a photoinitiator.
In order to cure the composition by ultraviolet irradiation and form a coating film by photolithography, it can be prepared in the form of a solvent development type or alkali development type photosensitive composition by adding a photopolymerization initiator.

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,
Examples include imidazole-based photopolymerization initiators. 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)] has a high transmittance as an insulating film because it does not turn yellow during the heating step, and particularly has a transmittance around 400 nm. Is more preferable because it can provide a photosensitive composition having a high value. 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. .
When the resin composition of the present embodiment is a photosensitive resin composition, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrene is further used as a sensitizer. Compounds such as quinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone Can also be used together.
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 of each embodiment can 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 specification may be a compound having an ultraviolet absorption function, a radical scavenging function, or a peroxide decomposition function. Specific examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds. An ultraviolet absorber, antioxidant, etc. 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-t-butyl-4-hydroxyphenyl) propionate}, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Examples include propionate and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenyl) benzene. .
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-based antioxidant>
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%. When it is 0.1% by weight or more, a yellowing prevention effect is sufficiently obtained, and when it is less than 4% by weight, radicals generated during UV exposure are not captured and the resin composition is not sufficiently cured. .

<< Other ingredients >>
In the resin composition according to each embodiment, a monofunctional monomer, a surfactant, a storage stabilizer, a leveling agent, a light stabilizer, and the like can be used as necessary.

<Monofunctional monomer>
Examples of the monofunctional monomer include ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxypropyl succinic acid. Acid, 2-methacryloyloxypropyl succinic acid, methoxyethylene glycol acrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, Methoxydipropylene glycol Acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, and commercially available products such as 2-acryloyloxyethyl succinic acid (trade name M-5300) Can be mentioned.
These monofunctional monomers can be used singly or as a mixture of two or more at any ratio as required.

<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 methyl ethers thereof, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. 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 resin composition on the transparent substrate, it is preferable to add a leveling agent. 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 and low water solubility, and when added to a resin composition, It has the feature of low surface tension reducing ability, and also has good wettability to the glass plate despite its low surface tension reducing ability. In the addition amount in which defects of the coating film due to foaming do not appear, 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 of each embodiment can be obtained by stirring and mixing essential components and, if necessary, other components.

  For example, in the case of the resin composition according to Embodiment VII, the compound (A) having an ethylenically unsaturated double bond, the silane compound (B) represented by the formula (15), and other components as necessary. It can be obtained by stirring and mixing.

  Moreover, in the case of the resin composition by Embodiment VI, it has oxide fine particles, alkali-soluble resin, (i) fluorene frame | skeleton compound shown by Formula (14), or (ii) thermosetting resin, and 4 or more functional groups. A polyfunctional monomer and, if necessary, other components can be obtained by stirring and mixing.

  The resin composition of each embodiment is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove dust and foreign matters.

<< Coating film >>
The obtained resin composition is applied on a glass substrate, ITO, molybdenum, other metal film, organic film, etc. by spin coating, spin coating, casting coating, roll coating, roll transfer, etc. A coating film can be formed by application by the above.

  In addition, the resin composition may be used for any of a protective film application, a flat film application, a touch panel insulating film application, an antireflection film application, and in each application, a pattern may be formed by a printing method. Of course, pattern formation by lithography is particularly preferred.

When forming a coating film by photolithography, a resin composition (photosensitive resin composition) prepared as a solvent development type or an alkali development type is spray-coated, spin-coated, slit-coated, or roll-coated on a transparent substrate. Apply by a coating method such as If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, the uncured portion can be removed by dipping in a solvent or an alkali developer or spraying the developer with a spray or the like to form a cured coating film. Furthermore, in order to accelerate | stimulate superposition | polymerization of the photosensitive resin composition, it can also heat as needed.
In development, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.

In order to increase UV exposure sensitivity, a film that prevents polymerization inhibition by oxygen by coating and drying a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin after coating and drying the photosensitive resin composition. After forming, UV exposure can also be performed.
In addition, the resin composition of the present embodiment may be used for any of protective film applications, flat film applications, insulating film applications, and antireflection film applications, and film formation is also possible with touch panels, liquid crystal display devices, and organic EL devices. Any of them may be formed, and since it has a high refractive index and good developability, it can also be used as a protective film, a flat film, an insulating film, or an antireflection film.

  Furthermore, when used as an antireflection film, the refractive index and film thickness of the resin composition can be variously selected according to the optical design, and the refractive index is particularly in the range of 1.60 to 1.80 and Further, by coating with a film thickness of 0.05 to 0.5 μm, it is possible to further improve the antireflection ability or improve the bone appearance phenomenon. When the film thickness is reduced to 1 μm or less, the coating film hardness is lowered, so that appropriate adjustment is necessary depending on the purpose of use. Moreover, the effect of reducing interference fringes can be obtained by setting the film thickness to 0.5 μm or less.

  Embodiments I to VII of the present invention will be described below with Examples I to V. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

<< Example I >>
The following examples relate to embodiment I. This also applies to Embodiment VII.
Prior to the examples, methods for measuring the weight average molecular weight of the resin, the hydroxyl value of the resin, and the double bond equivalent of the resin will be described.

(Weight average molecular weight of resin)
The weight average molecular weight (Mw) of the resin was measured using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, TSK-GEL SUPER HZM-N connected in series as a column, and THF as a solvent. The molecular weight in terms of polystyrene.

(Hydroxyl equivalent of resin)
The hydroxyl group equivalent is a measure of the amount of hydroxyl group contained in the molecule. If the compounds have the same molecular weight, the amount of hydroxyl group introduced increases as the value of the hydroxyl group equivalent decreases.
The hydroxyl equivalent was calculated by the following formula.
[Hydroxyl equivalent] = [Molecular weight of monomer component having hydroxyl group] / [Composition ratio of monomer component having hydroxyl group in resin]

(Double bond equivalent of resin)
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]

(Resin hydroxyl group / Substituent X (molar ratio))
(1) Resin hydroxyl group (molar ratio) and substituent X (molar ratio) are calculated by the following formula.
[Resin hydroxyl group (molar ratio)] = [resin solid content weight / hydroxyl group equivalent]
[Substituent X (molar ratio)] = [Solid weight of silane compound represented by formula (15)] / [Molecular weight of silane compound represented by formula (15)]
(2) Calculate (resin hydroxyl group / substituent X (molar ratio)) from the value obtained in (1) by the following formula.
[Resin hydroxyl group / substituent X (molar ratio)] = [Resin hydroxyl group (molar ratio)] / [Substituent X (molar ratio)]
Then, the manufacturing method of resin (I-A1) solution which has a hydroxyl group in a side chain, and other resin (I-A2) solutions is demonstrated.

<Method for Producing Resin (I-A1) Solution>
(Resin solution (I-A1-2))
Process 1
PGMEA 100 parts is put into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heated to 80 ° C. while injecting nitrogen gas into the vessel, 25.0 parts of styrene at the same temperature, A mixture of 1.0 part of 2-hydroxyethyl methacrylate, 30.0 parts of cyclohexyl methacrylate, 27.0 parts of methacrylic acid and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. went. 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 40 parts of PGMEA was added, followed by stirring at the same temperature for 3 hours to obtain a copolymer. It was.
Process 2
Next, dry air was introduced into the reaction vessel, charged with 45.0 parts of glycidyl methacrylate, 37.0 parts of PGMEA, 1.0 part of dimethylbenzylamine, and 0.1 part of methoquinone, and then continued stirring at the same temperature for 10 hours. It was. After cooling to room temperature, the resin solution (A1-2) having a weight average molecular weight, a hydroxyl value, and a double bond equivalent as shown in Table I-1 having a solid content of 40% was obtained by diluting with PGMEA.

(Resin solution (I-A1-3, I-A1-4, I-A1-6, I-A1-7, I-A1-10))
Table I-1 or Table I-2 was prepared in the same manner as in the resin solution (I-A1-2) except that the composition and amount (parts by weight) described in Table I-1 or Table I-2 were changed. Resin solutions having the weight average molecular weight, hydroxyl value and double bond equivalent as shown in I-2 (I-A1-3, I-A1-4, I-A1-6, I-A1-7, I-A1 -10) was obtained respectively.

(Resin solution (I-A1-5))
Process 1
In a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, 100 parts of PGMEA was charged and heated to 80 ° C. while injecting nitrogen gas into the vessel, and 4.0 parts of styrene at the same temperature, A mixture of 4.0 parts of cyclohexyl methacrylate, 46.6 parts of glycidyl methacrylate, 20.0 parts of 2-hydroxyethyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. went. 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.
Process 2
Next, dry air was introduced into the reaction vessel, charged with 28.2 parts of methacrylic acid, 100 parts of PGMEA, 1 part of dimethylbenzylamine and 0.1 part of methoquinone, and then continued stirring at the same temperature for 10 hours.
Process 3
Further, 120.0 parts of tetrahydrophthalic anhydride was charged, and stirring was continued at the same temperature for 10 hours. After cooling to room temperature, the resin solution (I-A1-5) having a weight average molecular weight, a hydroxyl value, and a double bond equivalent as shown in Table I-1 having a solid content of 40% was obtained by diluting with PGMEA. .

(Resin solution (I-A1-8, I-A1-9))
Except having each changed to the composition of Table I-1, and a compounding quantity (part by weight), it adjusted by the method similar to a resin solution (I-A1-5), and the weight average molecular weight as shown in Table II-2 , Resin solutions having hydroxyl value and double bond equivalent (I-A1-8, I-A1-9) were obtained.

(Resin solution (I-A1-11))
Process 1
150 parts of PGMEA is placed in a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 20.0 parts of methacrylic acid at the same temperature. , A mixture of 30.0 parts of 2-hydroxyethyl methacrylate, 10.0 parts of styrene, 50.0 parts of cyclohexyl methacrylate, and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. went. Thereafter, stirring was continued at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, a resin solution (I-A1-11) having a weight average molecular weight and a hydroxyl value as shown in Table I-2 having a solid content of 40% was obtained by diluting with PGMEA.

<Method for Producing Other Resin (I-A2) Solution>
(Resin solution (I-A2-1))
Process 1
PGMEA 100 parts is put into a reaction vessel equipped with a stirrer, a thermometer, a dripping device, a reflux condenser, and a gas introduction pipe, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 10.0 parts of methacrylic acid at the same temperature. , 22.5 parts of 2-hydroxyethyl methacrylate, 20.0 parts of styrene, 30.0 parts of cyclohexyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile were added dropwise over 1 hour to carry out the polymerization reaction. went. 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 20 parts of PGMEA was added, followed by stirring at the same temperature for 3 hours to obtain a copolymer. It was.
Process 2
Subsequently, the temperature of the reaction vessel was cooled to 70 ° C., and dry air was further introduced into the reaction vessel, and 50.0 parts of 2-methacryloyloxyethyl isocyanate, 37 parts of PGMEA, 0.1 part of dibutyltin dilaurate, 0.1 part of methoquinone 0.1 Then, stirring was continued at the same temperature for 10 hours. After cooling to room temperature, the resin solution (I-A2-1) having a weight average molecular weight and a double bond equivalent as shown in Table I-2 having a solid content of 40% was obtained by diluting with PGMEA.

(Resin solution (I-A2-2))
Process 1
PGMEA 100 parts is put into a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 30.0 parts of methacrylic acid at the same temperature. A mixture of 40.0 parts of styrene, 30.0 parts of cyclohexyl methacrylate, and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. 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 40 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, a resin solution (I-A2-2) having a weight average molecular weight and a double bond equivalent as shown in Table I-2 having a solid content of 40% was obtained by diluting with PGMEA.

PGMEA: propylene glycol monomethyl ether acetate St: styrene HEMA: 2-hydroxyethyl methacrylate CHMA: cyclohexyl methacrylate MAA: methacrylic acid MMA: methyl methacrylate GMA: glycidyl methacrylate THPA: tetrahydrophthalic anhydride (4-cyclohexene-1,2-dicarboxylic acid) Anhydride)

[Example I-1]
(Resin composition I-1)
A mixture of 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 I-1.
Resin Solution I-A1-2 20.86 parts Polyfunctional monomer 4.00 parts (V # 802 “Biscoat # 802” (manufactured by Osaka Organic Chemical Co., Ltd.))
Isocyanate group-containing silane compound 6.35 parts (3-isocyanatopropyltriethoxysilane)
Photopolymerization initiator 1.30 parts (IRGACURE OX-01 (manufactured by BASF); 1,2-octadion-1- [4
-(Phenylthio)-, 2- (o-benzoyloxime)])
Leveling agent 1.00 parts (BYK-330 2% (by Big Chemie); PGMEA solution of polyether structure-containing dimethylsiloxane (adjusted to 1% solid content)))
Solvent 66.49 parts (propylene glycol monomethyl ether acetate)

[Examples I-2 to I-37, Comparative Examples I-1 to I-5]
(Resin compositions I-2 to I-42 (I-R2 to I-R42))
The composition shown in Tables I-3 to I-11 and the mixture of the blending amount (parts by weight) were stirred and mixed so as to be uniform, then filtered through a 1 μm filter, and the same method as the resin composition I-1 Thus, resin compositions I-2 to I-42 (I-R1 to I-R42) respectively corresponding to Examples I-2 to I-37 and Comparative Examples I-1 to I-5 were obtained.

<Inorganic oxide fine particle dispersion>
ZR-40BL (Nissan Chemical Co., Ltd.); tetramethylammonium hydroxide dispersion of fine zirconia oxide particles (solid content 40%)
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, tripentaerythritol octaacrylate, DPCA30; Kayacure DPCA30 (manufactured by Nippon Kayaku Co., Ltd.)
Caprolactone-modified dipentaerythritol hexaacrylate M-402; Aronix M-402 (manufactured by Toagosei Co., Ltd.); dipentaerythritol hexaacrylate << isocyanate group-containing silane compound (B) >>
・ 3-Isocyanatopropyltriethoxysilane ・ 3-Isocyanatepropyltrimethoxysilane << other organic group-containing silane compounds >>
・ 3-glycidoxypropyltrimethoxysilane ・ 3-acryloxypropyltrimethoxysilane ・ N-phenyl-3-aminopropyltrimethoxysilane << photoinitiator >>
OXE-01; IRGACURE OX-01 (manufactured by BASF); 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)]
・ Irg. 907; IRGACURE907 (manufactured by BASF); 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one-Irgacure 819 (manufactured by BASF); bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide (Leveling agent)
-BYK-330 2% (manufactured by Big Chemie); polyether structure-containing dimethylsiloxane PGMEA solution (adjusted to 1% solids)
<< Solvent (C) >>
・ PGMEA: Propylene glycol monomethyl ether acetate ・ Ethanol (Kishida Chemical Co., Ltd.)
Butanol (made by Kishida Chemical Co., Ltd.); 1-butanol, 1,3-BGDA (made by Daicel Chemical Industries, Ltd.); 1,3-butylene glycol diacetate, 1,6-HDDA (made by Daicel Chemical Industries, Ltd.); 6-Hexanediol diacetate << Antioxidant >>
IRGANOX 1010 (manufactured by BASF); pentaerythritol tetrakis [3- (3
, 5-Di-tert-butyl-4-hydroxyphenyl) propionate]
IRGANOX 1035 (manufactured by BASF); thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
TINUVIN123 (manufactured by BASF); decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reactivity of 1,1-dimethylethyl hydroperoxide and octane Creature

<< Example II >>
The following examples relate to embodiment II. This also applies to Embodiment VII.
Prior to Examples, a compound having an ethylenically unsaturated double bond, a weight average molecular weight of a silane compound, a double bond equivalent of a compound having an ethylenically unsaturated double bond, and a compound having an ethylenically unsaturated double bond A method for measuring the acid value of will be described.

(Weight average molecular weight (Mw) of the compound having an ethylenically unsaturated double bond)
It was measured in the same manner as the weight average molecular weight of the resin relating to Example I.

(Weight average molecular weight of silane compound (Mw))
Analysis and calculation were performed in the same manner as the weight average molecular weight of the silane compound related to Example I.

(Double bond equivalent of compound having ethylenically unsaturated double bond)
The calculation was performed in the same manner as the double bond equivalent of the resin related to Example I.

(Acid value of a compound having an ethylenically unsaturated double bond)
The acid value (JIS acid value) of a compound having an ethylenically unsaturated double bond can be determined by the following method.
The acid value is obtained by dissolving 1 g of a sample in a titration solvent mixed with xylene and dimethylformamide (1 + 1), titrating with a 0.1 mol / L potassium hydroxide / ethanol solution by potentiometric titration, and setting the inflection point on the titration curve as the end point. The acid value is calculated from the titration amount until the end point of the potassium hydroxide solution.
Calculation of acid value The obtained result is substituted into the following formula to calculate the acid value.
A = (BC) × f × D / S
(A: Acid value (mgKOH / g), B: Addition amount of potassium hydroxide solution in this test (mL), C: Addition amount of potassium hydroxide solution in blank test (measured without using measurement sample) (mL ), F: factor of potassium hydroxide solution, D: concentration converted value 5.611 mg / mL (0.1 mol / LKOH 1 mL of potassium hydroxide equivalent), S: sample (g))
Subsequently, a resin (II-A2-a) solution containing a compound represented by formula (1) as a copolymer component, and another resin (II-A2-) not containing a compound represented by formula (1) as a copolymer component. b) A method for producing the solution will be described.

<Method for Producing Other Resin (II-A2-b) Solution>
(Resin solution (II-A-1))
In a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, 100 parts of PGMEA was charged, heated to 70 ° C. while injecting nitrogen gas into the vessel, 30.0 parts of styrene at the same temperature, A mixture of 23.4 parts of 2-hydroxyethyl methacrylate, 43.5 parts of cyclohexyl methacrylate, 3.1 parts of methacrylic acid and 1 part of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. went. After completion of the dropwise addition, the mixture was further reacted at 70 ° C. for 3 hours, then 0.2 parts of azobisisobutyronitrile dissolved in 50 parts of PGMEA was added, and then the copolymer was continuously stirred for 3 hours at the same temperature. Got. After cooling to room temperature, the resin solution (II-A-1) having a weight average molecular weight and acid value as shown in Table II-1 having a solid content of 40% by weight was obtained by diluting with PGMEA.

<Method for Producing Resin (II-A2-a) Solution>
(Resin solution (II-A-2-2))
Process 1
PGMEA 100 parts in a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction pipe, heated to 70 ° C. while injecting nitrogen gas into the vessel, 5.0 parts of styrene at the same temperature, A mixture of 15.9 parts of cyclohexyl methacrylate, 31.7 parts of methacrylic acid, and 1 part of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 70 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 40 parts of PGMEA was added, followed by stirring at the same temperature for 3 hours. Got.
Process 2
Next, dry air was introduced into the reaction vessel, charged with 50.0 parts of glycidyl methacrylate, 37.0 parts of PGMEA, 0.3 part of dimethylbenzylamine, and 0.1 part of methoquinone, and then continued stirring at the same temperature for 10 hours. It was. A resin solution (II-A-2-2) having a weight average molecular weight, an acid value, and a double bond equivalent as shown in Table II-1 having a solid content of 40% by weight after being cooled to room temperature and diluted with PGMEA Got.

(Resin solution (II-A-2-3 to II-A-2-9))
Except for changing the composition, blending amount (parts by weight) and reaction temperature described in Table II-1, respectively, the resin solution (II-A-2-2) was adjusted in the same manner as in Table II-1. Resin solutions (II-A-2-3, II-A-2-4, II-A-2-5, II-A-2-6) having a weight average molecular weight, acid value and double bond equivalent as shown II-A-2-7, II-A-2-8, and II-A-2-9) were obtained.

PGMEA: propylene glycol monomethyl ether acetate St: styrene HEMA: 2-hydroxyethyl methacrylate CHMA: cyclohexyl methacrylate MAA: methacrylic acid GMA: glycidyl methacrylate

<Method for producing silane compound>
(Silane compound (II-B-1))
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 130 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 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 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 5,500.

(Silane compound (II-B-2))
Prepare a flask with a cooling tube as a reaction tank, 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 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.

(Silane compound (II-B-3))
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.

[Example II-1]
(Photosensitive composition II-1 (II-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 photosensitive composition II-1.

Resin solution II-A-1 35.24 parts Polyfunctional monomer (V # 802 “Biscoat # 802” (manufactured by Osaka Organic Chemical Co., Ltd.)) 4.00 parts Silane compound II-B-1
(Siloxane oligomer molecular weight about 5,500) 0.60 parts Photopolymerization initiator (IRGACURE OXE-01 (manufactured by BASF); 1,2-octadion-1- [4
-(Phenylthio)-, 2- (o-benzoyloxime)])) 1.30 parts Leveling agent (BYK-330 2% (manufactured by Big Chemie)); Polyether structure-containing dimethylsiloxane PGMEA solution (solid content 1% Adjustment))) 1.00 parts propylene glycol monomethyl ether acetate 37.87 parts ethanol (manufactured by Kishida Chemical Co.) 20.00 parts

[Examples II-2 to II-19, Comparative Examples II-1 to II-4]
(Photosensitive composition II-2 to II-23 (II-R2 to II-R23))
After stirring and mixing the mixture shown in Tables II-2 to II-5 in a uniform amount and a blending amount (parts by weight), the mixture was filtered through a 1 μm filter, and the same as for photosensitive composition II-1 By the method, photosensitive compositions II-2 to II-23 (II-R2 to II-R23) corresponding to Examples II-2 to II-19 and Comparative Examples II-1 to II-4, respectively, were obtained.
Regarding these photosensitive compositions, the molecular weight Mw of the silane compound used and the content of the photosensitive composition with respect to the total solid content, the double bond equivalent and molecular weight Mw of the resin having an ethylenic double bond in the side chain, photosensitivity The solid content of the composition, the content of inorganic fine particles relative to the total solid content of the photosensitive composition, the ratio (b / c) of the weight (b) of the silane compound to the weight (c) of the oxide fine particles, the weight of the silane compound ( The ratio (b / e) between b) and the weight (e) of tetraalkoxysilane is shown in Table II-2 to Table II-5 below.

<Oxide fine particles>
ZR-40BL (Nissan Chemical Co., Ltd.); tetramethylammonium hydroxide dispersion of fine zirconia oxide particles (solid content 40%)
PMA-ST (manufactured by Nissan Chemical Co., Ltd.); PGMEA dispersion of silicon oxide fine particles (solid content 30%)

<< Monomer having an ethylenically unsaturated double bond >>
・ V # 802; Biscote # 802 (Osaka Organic Chemical Co., Ltd.)
Mixture of tripentaerythritol octaacrylate and tetrapentaerythritol decaacrylate pentapentaerythritol dodecaacrylate, tripentaerythritol octaacrylate DPCA30; Kayacure DPCA30 (manufactured by Nippon Kayaku Co., Ltd.)

<< Tetraalkoxysilane (E) >>
TEOS: Tetraethoxysilane (manufactured by Wako Pure Chemical Industries)
<< Silane compound >>
KBM-573: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBE-9007: 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

<< Photopolymerization initiator >>
OXE-01; IRGACURE OX-01 (manufactured by BASF); 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)]
・ Irg. 907; IRGACURE907 (manufactured by BASF); 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one

《Leveling agent》
-BYK-330 2% (manufactured by Big Chemie); polyether structure-containing dimethylsiloxane PGMEA solution (adjusted to 1% solids)
"solvent"
・ PGMEA: Propylene glycol monomethyl ether acetate ・ Ethanol (Kishida Chemical Co., Ltd.)
・ 1,3-BGDA (manufactured by Daicel Chemical Industries); 1,3-butylene glycol diacetate

<< Example III >>
The following examples relate to embodiment III. This also applies to Embodiment VII.
Prior to the examples, the compound represented by formula (10) or the cardo resin, the method for measuring the weight average molecular weight of the silane compound having an amide or urethane skeleton, the double bond equivalent of the compound represented by formula (10) or the cardo resin The calculation method and the measurement method of the average primary particle diameter of the pigment will be described.

(Weight average molecular weight (Mw) of compound represented by formula (10) or cardo resin)
It was measured in the same manner as the weight average molecular weight of the resin relating to Example I.

(Weight average molecular weight (Mw) of silane compound having amide or urethane skeleton)
Calculation was performed in the same manner as the weight average molecular weight of the silane compound related to Example II.

(Measurement method of average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Production example of compound represented by formula (10) or cardo resin)
<Production example of cardo resin solution (III-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, (III-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 (III-A1-2, III-A1-3, III-A1-4)>
Except having each changed to the composition of Table III-1, and a compounding quantity (part by weight), it adjusted by the method similar to a resin solution (III-A1-1), and the weight average molecular weight as shown in Table III-1 Resin solutions (III-A1-2, III-A1-3, III-A1-4) having

<Production Example of Cardo Resin Solution (III-A2-1)>
(Production example of photosensitive polyester resin)
Dry air was introduced into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a 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, it was diluted with PGMEA to obtain III-A2-1 having a solid content of 30%. The weight average molecular weight was 7000.

<Production Example of Cardo Resin (III-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, it was diluted with PGMEA to obtain III-A3-1 containing a photopolymerizable functional group having a solid content of 30% and a carboxyl group. The weight average molecular weight was 4000.

<Production Example of Cardo Resin (III-A3-2 to III-A3-4)>
Similarly to the production example of the cardo resin (III-A3-1), a cardo resin having a solid content of 30% was obtained, and the weight average molecular weight was measured.

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 (III-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, by diluting with PGMEA, III-A4-1 containing a photopolymerizable functional group having a solid content of 40% and a carboxyl group was obtained. The weight average molecular weight was 8000.

<Production Example of Acrylic Resin Solution (III-H-1)>
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 20 parts of methacrylic acid at the same temperature, A mixture of 10 parts of methyl methacrylate, 55 parts of n-butyl methacrylate, 15 parts of benzyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of dropping, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain an acrylic resin solution. Got. After cooling to room temperature, an acrylic resin solution (III-H-1) containing a carboxyl group not containing a photopolymerizable functional group having a solid content of 20% was obtained by diluting with cyclohexanone. The weight average molecular weight was 40,000.

<Method for Producing Silane Compound (III-B-1) Having Amide or Urethane Skeleton>
(Silane compound having amide or urethane skeleton (III-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 (III-B-2) Having Amide or Urethane Skeleton>
(Silane compound having amide or urethane skeleton (III-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 (III-B-3) Having Amide or Urethane Skeleton>
(Silane compound having amide or urethane skeleton (III-B-3)
Prepare a flask with a cooling tube as a reaction tank, 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 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 (III-B-4) Having Amide or Urethane Skeleton>
(Silane compound having amide or urethane skeleton (III-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 (III-B-5) Having Amide or Urethane Skeleton>
(Silane compound having amide or urethane skeleton (III-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 dispersion>
(Production of dispersant (Ti))
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: KAYARADPET-30) 250.0 parts, hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) 0.16 parts and cyclohexanone 141.2 parts were charged and heated 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 (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 (III-C-1, III-C-2))
Using the dispersant (Ti) and the dispersant (Zr), metal oxide dispersion was performed according to the formulation shown in Table III-3 to prepare an oxide fine particle dispersion (the blend amount indicates the solid content). Dispersion method is pre-dispersion (using zirconia beads (1.25 mm) as media and dispersing for 1 hour with a paint shaker) and main dispersion (using zirconia beads (0.1 mm) as media). (Dispersion with machine UAM-015). The obtained oxide fine particle dispersion was diluted with PGMEA and adjusted to the solid content of Table III-3.

ＴｉＯ₂：石原産業（株）製「ＴＴＯ−５１（Ａ）」（平均一次粒子径：２０ｎｍ）
ＺｒＯ₂：日本電工（株）製「ＰＣＳ−６０」（平均一次粒子径：２０ｎｍ）
ＭＩＢＫ：メチルイソブチルケトン（協和発酵ケミカル（株）製）
メトブタ：３−メトキシ−１−ブタノール（ダイセル化学工業（株）製）

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 fine pigment>
(Blue refined pigment (III-F-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“Rionol Blue ES” manufactured by Toyo Ink Mfg. Co., Ltd.), 800 parts of crushed salt, and 100 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) at 70 ° C. for 12 hours. Kneaded. The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts of blue refinement | purification pigments (III-F-1). The average primary particle diameter of the obtained pigment was 28.3 nm.

(Red fine pigment (III-F-2))
Diketopyrrolopyrrole red pigment C.I. I. 120 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan Co., Ltd.), 1000 parts of crushed salt and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts of red refined pigments (III-F-2). The average primary particle diameter of the obtained pigment was 24.8 nm.

(Yellow fine pigment (III-F-3))
Nickel complex yellow pigment C.I. I. 100 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 95 parts of yellow fine pigment (III-F-3). The average primary particle diameter of the obtained pigment was 39.2 nm.

(Purple refined pigment (III-F-5))
Dioxazine-based purple pigment C.I. I. 120 parts of Pigment Violet 23 (“FastViolet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 118 parts of purple refined pigments (III-F-5). The average primary particle diameter of the obtained pigment was 26.4 nm.

・樹脂型顔料分散剤 ： ８．０部
（ビックケミー・ジャパン社製 ＢＹＫ−１１１）
・アクリル樹脂溶液（Ｈ−１） ：６０．０部
・シクロヘキサノン ：１２．０部
（赤色顔料分散体（ＩＩＩ−Ｇ−Ｒ））
下記の組成の混合物を使用し、青色顔料分散体（Ｇ−Ｂ）と同様にして赤色顔料分散体
（ＩＩＩ−Ｇ−Ｒ）を得た。
・赤色微細化顔料（ＩＩＩ−Ｆ−２） ：１０．０部
・アントラキノン系顔料(Ｃ.Ｉ. Ｐｉｇｍｅｎｔ Ｒｅｄ １７７) ： ２．０部
（チバ・ジャパン社製「クロモフタールレッドＡ２Ｂ」）
・黄色微細化顔料（ＩＩＩ−Ｆ−３） ： ４．０部
・ジケトピロロピロール系顔料誘導体 ： ４．０部 <Example of production of pigment dispersion>
(Blue pigment dispersion (III-GB))
The mixture having the composition shown below was uniformly stirred and mixed, and then dispersed with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, followed by filtration with a 5 μm filter. A blue pigment dispersion (III-GB) was obtained.

Blue refined pigment (III-F-1): 18.0 parts Copper phthalocyanine derivative: 2.0 parts

-Resin type pigment dispersant: 8.0 parts (BYK-111 manufactured by BYK Japan)
-Acrylic resin solution (H-1): 60.0 parts-Cyclohexanone: 12.0 parts (red pigment dispersion (III-GR))
A red pigment dispersion (III-GR) was obtained in the same manner as the blue pigment dispersion (GB) using a mixture having the following composition.
Red refined pigment (III-F-2): 10.0 partsAnthraquinone pigment (CI Pigment Red 177): 2.0 parts (Chromotar Red A2B manufactured by Ciba Japan)
Yellow refined pigment (III-F-3): 4.0 parts Diketopyrrolopyrrole pigment derivative: 4.0 parts

・樹脂型顔料分散剤 ： ８．０部
（日本ルーブリゾール社製「ソルスパース ２００００」）
・アクリル樹脂溶液（ＩＩＩ−Ｈ−１） ：６０．０部
・シクロヘキサノン ：１２．０部

-Resin type pigment dispersant: 8.0 parts ("Solsperse 20000" manufactured by Nippon Lubrizol)
Acrylic resin solution (III-H-1): 60.0 parts Cyclohexanone: 12.0 parts

(Purple pigment dispersion (III-G-V))
A purple pigment dispersion (III-GV) was obtained in the same manner as the blue pigment dispersion (GB) using a mixture having the following composition.

-Purple refined pigment (III-F-5): 20.0 parts-Resin-type pigment dispersant: 8.0 parts (BYK-111 manufactured by Big Chemie Japan)
Acrylic resin solution (III-H-1): 60.0 parts Cyclohexanone: 12.0 parts

[Example III-1]
(Photosensitive composition 1 (III-R1))
A mixture of 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 III-1.

Silane compound having a urethane skeleton 45.97 parts U-201; “Yuriano U-201” (manufactured by Arakawa Chemical Industries, Ltd.)
Compound of formula (10) 6.00 parts ASF-400; “9,9-bis (4-hydroxyphenyl) fluorene glycidyl ether acrylic acid adduct” (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

[Examples III-2 to III-29, Comparative Examples III-1 to III-2]
(Resin compositions III-2 to III-29 (III-R2 to III-R31))
The composition shown in Tables III-4 to III-10 and the mixture of the blending amount (parts by weight) were stirred and mixed so as to be uniform, then filtered through a 1 μm filter, and the same method as that for the resin composition III-1 Thus, resin compositions III-2 to III-31 (III-R2 to III-R31) respectively corresponding to Examples III-2 to III-29 and Comparative Examples III-1 and III-2 were obtained.

<< Compound or Cardo Resin Shown by Formula (10) >>
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 a skeleton >>
U-201: Polyurethane-silica hybrid (Arakawa Chemical Industries, Ltd .; “Yuliano U-201”)
AC601; Epoxy-silica hybrid (Arakawa Chemical Industries, Ltd .; “Composeran AC601”)

<Oxide fine particle 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 << photoinitiator >>
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

<Evaluation of resin composition>
The resin compositions (III-R26, III-R30) were evaluated by the following evaluation methods. The results are shown in Table III-10.

(Measurement of refractive index)
The resin composition (III-R26, III-R30) was applied to a 100 mm × 100 mm, 0.7 mm thick PEN film using a bar coater, and then heated at 100 ° C. for 30 minutes to dry. The refractive index of 589 nm was measured for the obtained film using an Abbe refractometer (manufactured by Atago, NAR-4T).

(Visibility evaluation)
A substrate was prepared by sputtering ITO on glass. Thereafter, ITO was patterned using a hydrochloric acid-nitric acid etching solution. The resin composition (III-R26, III-R30) was applied to the ITO pattern substrate by the same method as “Measurement of transmittance” described in Embodiment I. However, the finished film thickness was adjusted to 0.05, 0.40, 0.60, and 2.0 μm. The obtained board | substrate was confirmed visually from both sides, and the difficulty of seeing the boundary of the part with ITO and the part without ITO was determined.
◎: Not visible at all ○: Almost invisible △: Looks thin ×: Visible

  Example III-26 having a refractive index in the range of 1.60 to 1.80 has better visibility than Comparative Example III-1, and particularly has a film thickness in the range of 0.05 to 0.4 μm. The visibility of was good.

<< Example IV >>
The following examples relate to embodiment IV. This also applies to Embodiment VI.
Prior to the examples, a method for measuring the weight average molecular weight of the resin, the acid value of the resin, the weight average molecular weight of the silane compound, and the average primary particle diameter of the pigment will be described.

(Weight average molecular weight of resin)
Polymerization average molecular weight (Mw) of the resin is TSKgel column (manufactured by Tosoh Corporation), GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC), and measured in terms of polystyrene measured using THF as a developing solvent. It is a weight average molecular weight (Mw).

(Resin acid value)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the resin solution and stirred to dissolve uniformly, and an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) is used with a 0.1 mol / L KOH aqueous solution as a titrant. ) And the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Weight average molecular weight of silane compound (Mw))
The measurement was performed in the same manner as in the case of the polymerization average molecular weight (Mw) of the resin.

(Measurement method of average primary particle diameter of pigment)
The average primary particle size was determined by the same method as “Method for measuring average primary particle size of pigment” described in Embodiment III.

  Then, the manufacturing method of the oxide fine particle dispersion, the alkali-soluble resin solution, the silane compound, the colorant, the pigment dispersion, and the dye-containing solution used in Examples and Comparative Examples will be described.

<Method for producing oxide fine particle dispersion>
(Production of dispersant (Ti))
The same dispersant (Ti) was produced in the same manner as in “Production of Dispersant (Ti)” described in Example III.

(Production of dispersant (Zr))
The same dispersant (Ti) was produced in the same manner as in “Production of Dispersant (Zr)” described in Example III.

(Production of oxide fine particle dispersion (IV-A-1, IV-A-2))
Using a dispersant (Ti) and a dispersant (Zr), metal oxide dispersion was carried out according to the formulation shown in Table IV-1 to prepare an oxide fine particle dispersion (the blend amount indicates the solid content). Dispersion method is pre-dispersion (using zirconia beads (1.25 mm) as media and dispersing for 1 hour with a paint shaker) and main dispersion (using zirconia beads (0.1 mm) as media). (Dispersion with machine UAM-015). The obtained oxide fine particle dispersion was diluted with propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMEA), and adjusted to the solid content of Table IV-1.

TiO ₂ : “TTO-51 (A)” manufactured by Ishihara Sangyo Co., Ltd. (average primary particle size: 20 nm)
ZrO ₂ 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.)

<Method for producing alkali-soluble resin solution>
(Preparation of resin solution (IV-B-1))
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 70.0 parts of propylene glycol monoethyl ether acetate, heated to 80 ° C., and the reaction vessel was filled with nitrogen. After the substitution, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) )) A mixture of 7.4 parts and 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a resin solution having a solid content of 30% by weight and a weight average molecular weight of 26000.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether acetate was added to obtain a resin solution (IV-B-1) which is an alkali-soluble resin.

<< Method for Producing Resin (IV-B1) Solution >>
(Preparation of resin solution (IV-B1-1))
A reactor equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device was charged with 70.0 parts of PGMEA, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. A mixture of 67.2 parts of benzyl methacrylate, 18.4 parts of methacrylic acid, 14.4 parts of dicyclopentanyl methacrylate, and 0.4 parts of 2,2′-azobisisobutyronitrile is added dropwise over 2 hours to polymerize the reaction. Went. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% by weight.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMEA was added to the previously synthesized resin solution so that the nonvolatile content was 40% by weight. A resin solution (B1-1) was prepared. The solid content acid value was 46.8 mgKOH / g, and the weight average molecular weight was 32,000.

(Preparation of resin solution (IV-B1-2))
A synthetic reaction is performed in the same manner as in the resin solution (IV-B1-1) except that dicyclopentanyl methacrylate in the resin solution (IV-B1-1) is changed to dicyclopentenyl methacrylate, and the resin solution (IV-B1) -2) was prepared. The weight average molecular weight was 12500.

(Preparation of resin solution (IV-B1-3))
Put 100 parts of PGMEA in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirring device in a separable four-necked flask, and heat it to 120 ° C. while injecting nitrogen gas into the vessel. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate and 1.0 part of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was purged with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours. The reaction was terminated when the value reached 0.8, and a resin solution having a weight average molecular weight of about 12,000 was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added, reacted at 120 ° C. for 4 hours, PGMEA was added so that the nonvolatile content was 40%, and the resin corresponding to the resin (A3-1a) A solution (IV-B1-3) was prepared.

(Preparation of resin solution (IV-B1-4))
Put 182 parts of PGMEA in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirring device in a separable four-necked flask, and heat to 100 ° C. while injecting nitrogen gas into the vessel. A mixture of 70.5 parts benzyl methacrylate, 22.0 parts dicyclopentanyl methacrylate, 43.0 parts methacrylic acid, 136 parts propylene glycol monomethyl ether acetate, and 3.6 parts azobisisobutyronitrile over 2 hours. The solution was added dropwise and further stirred at 100 ° C. for 5 hours to carry out a polymerization reaction.
Next, the inside of the flask was purged with air, 0.9 part of trisdimethylaminomethylphenol and 0.145 part of hydroquinone were added to 35.5 parts of glycidyl methacrylate, the reaction was continued at 110 ° C. for 6 hours, and the solid content acid value = 0. The reaction was terminated when the amount reached 0.8 mgKOH / g, and PGMEA was added so that the non-volatile content was 40% to prepare a resin solution (IV-B1-4) corresponding to the resin (A3-1b). The weight average molecular weight was 13000.

<Method for producing silane compound>
(Silane compound (IV-D-1))
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.

(Silane compound (IV-D-2)
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 colorant>
<Pigment>
(Blue refined pigment (IV-E-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“Rionol Blue ES” manufactured by Toyo Ink Mfg. Co., Ltd.), 800 parts of crushed salt, and 100 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) at 70 ° C. for 12 hours. Kneaded. The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts of blue refinement | purification pigments (IV-E-1). The average primary particle diameter of the obtained pigment was 28.3 nm.

(Red fine pigment (IV-E-2))
Diketopyrrolopyrrole red pigment C.I. I. 120 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan Co., Ltd.), 1000 parts of crushed salt and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts of red refined pigments (IV-E-2). The average primary particle diameter of the obtained pigment was 24.8 nm.

(Purple refined pigment (IV-E-3))
Dioxazine-based purple pigment C.I. I. 120 parts of Pigment Violet 23 (“FastViolet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 118 parts of purple refined pigments (IV-E-3). The average primary particle diameter of the obtained pigment was 26.4 nm.

"dye"
(Xanthene salt forming compound (IV-E-4))
In the following procedure, C.I. I. A xanthene salt-forming compound (IV-E-4) comprising acid red 52 and a resin having a cationic group in the side chain was produced.
51 parts of a vinyl resin was added to 2000 parts of water, and after sufficient stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound (IV-E-4) between Acid Red 52 and a resin having a cationic group in the side chain was obtained. At this time, C.I. I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

・樹脂型顔料分散剤 ： ８．０部
（ビックケミー・ジャパン社製 ＢＹＫ−１１１）
・樹脂溶液（ＩＶ−Ｂ−１） ：６０．０部
・シクロヘキサノン ：１２．０部 <Method for producing pigment dispersion>
(Blue pigment dispersion (IV-GB))
The mixture having the composition shown below was uniformly stirred and mixed, and then dispersed with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, followed by filtration with a 5 μm filter. A blue pigment dispersion (IV-GB) was obtained.

Blue refined pigment (IV-E-1): 18.0 parts Copper phthalocyanine derivative: 2.0 parts

-Resin type pigment dispersant: 8.0 parts (BYK-111 manufactured by BYK Japan)
Resin solution (IV-B-1): 60.0 parts Cyclohexanone: 12.0 parts

・樹脂型顔料分散剤 ： ８．０部
（日本ルーブリゾール社製「ソルスパース ２００００」）
・樹脂溶液（ＩＶ−Ｂ−１） ：６０．０部
・シクロヘキサノン ：１２．０部
（紫色顔料分散体（ＩＶ−Ｇ−Ｖ））
下記の組成の混合物を使用し、青色顔料分散体（ＩＶ−Ｇ−Ｂ）と同様にして紫色顔料分散体（ＩＶ−Ｇ−Ｖ）を得た。

・紫色微細化顔料（ＩＶ−Ｅ−３） ：２０．０部
・樹脂型顔料分散剤 ： ８．０部
（ビックケミー・ジャパン社製 ＢＹＫ−１１１）
・樹脂溶液（ＩＶ−Ｂ−１） ：６０．０部
・シクロヘキサノン ：１２．０部 (Red pigment dispersion (IV-GR))
A red pigment dispersion (IV-GR) was obtained in the same manner as the blue pigment dispersion (IV-GB) using a mixture having the following composition.

-Red fine pigment (IV-E-2): 10.0 parts-Anthraquinone pigment (CI Pigment Red 177): 2.0 parts ("Chromophthal Red A2B" manufactured by Ciba Japan)
・ Diketopyrrolopyrrole pigment derivative: 4.0 parts

-Resin type pigment dispersant: 8.0 parts ("Solsperse 20000" manufactured by Nippon Lubrizol)
Resin solution (IV-B-1): 60.0 parts Cyclohexanone: 12.0 parts (purple pigment dispersion (IV-G-V))
A purple pigment dispersion (IV-G-V) was obtained in the same manner as the blue pigment dispersion (IV-GB) using a mixture having the following composition.

・ Purple refined pigment (IV-E-3): 20.0 parts ・ Resin type pigment dispersant: 8.0 parts (BYK-111 manufactured by BYK Japan)
Resin solution (IV-B-1): 60.0 parts Cyclohexanone: 12.0 parts

<Method for producing dye-containing solution>
(Xanthene salt forming compound-containing solution (IV-G-V2))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a xanthene-based salt-forming compound-containing solution (IV-G-V2).

Xanthene salt forming compound (IV-E-4): 20.0 parts PGMEA: 80.0 parts

[Example IV-1]
(Photosensitive composition (IV-R1))
After stirring and mixing a mixture having the following composition to be uniform, it is filtered through a 1 μm filter,
A resin composition (IV-R1) was obtained.

PMA-ST 3.33 parts “PMA-ST” (manufactured by Nissan Chemical Co., Ltd.); PGMEA dispersion of silicon oxide fine particles (solid content 30%)
Resin solution (IV-B-1) 36.98 parts Monomer; A-BPEF 4.00 parts "NK ester A-BPEF" (manufactured by Shin-Nakamura Chemical Co., Ltd.)
OXE-01 0.20 parts "IRGACURE OXE-01" (manufactured by BASF); 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)])
Leveling agent: BYK-330 2% 1.00 part "BYK-330" (manufactured by Big Chemie); polyether structure-containing dimethylsiloxane in propylene glycol monomethyl ether acetate solution (adjusted to 2% solids)
Solvent; 54.49 parts cyclohexanone

[Examples IV-2 to IV-18, Comparative Examples IV-1 to IV-3]
(Resin composition (IV-2 to IV-R22))
After stirring and mixing the mixture shown in Tables IV-2 to IV-6 in a uniform amount and a blending amount (parts by weight), the mixture was filtered through a 1 μm filter and the same as the resin composition (IV-R1). By this method, resin compositions (IV-R2 to IV-R22) corresponding to Examples IV-2 to IV-19 and Comparative Examples IV-1 to IV-3, respectively, were obtained.

<Oxide fine particle dispersion>
PMA-ST; “PMA-ST” (manufactured by Nissan Chemical Co., Ltd.); PGMEA dispersion of silicon oxide fine particles (solid content 30%)
・ Al2O3 solution; Aluminum oxide dispersion (Wako Chemical Co., Ltd.); Solid 23% aluminum oxide dispersion, particle size 44nm
《Other resins》
MW-30; “Nikarak MW-30” (manufactured by Sanwa Chemical Co., Ltd.)

<< Monomer containing fluorene skeleton represented by formula (14) >>
A-BPEF: “NK ester A-BPEF” (manufactured by Shin-Nakamura Chemical Co., Ltd.)
ASF-400; “acrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorene glycidyl ether” (manufactured by Nippon Steel Chemical Co., Ltd.)
EA-0200; “Ogsol EA-0200” (Osaka Gas Chemical Co., Ltd.)
《Other monomers》
DPCA30; “KAYARAD DPCA30” (manufactured by Nippon Kayaku Co., Ltd.)

<< Silane compound having urethane or amide skeleton >>
U-201; “Yuriano U-201” (manufactured by Arakawa Chemical Industries, Ltd.); polyurethane-silica hybrid << photopolymerization initiator >>
-OXE-01; "IRGACURE OXE-01" (manufactured by BASF)
1,2-octadione-1- [4- (phenylthio)-, 2- (o-benzoyloxime)]
《Leveling agent》
-BYK-330 2%; "BYK-330" (manufactured by Big Chemie)
Propylene glycol monomethyl ether acetate solution of polyether structure-containing dimethylsiloxane (adjusted to 2% solids)

<Evaluation of resin composition>
The resin compositions (IV-R17, IV-R20, IV-R21) were evaluated by the evaluation methods shown below. The results are shown in Table IV-7.

(Measurement of refractive index)
The refractive index was measured by the same method as “measurement of refractive index” described in Example III.

(Visibility evaluation)
A substrate was prepared by sputtering ITO on glass. Thereafter, ITO was patterned using a hydrochloric acid-nitric acid etching solution. The resin composition (IV-R17, IV-R20, IV-R21) was applied to the ITO pattern substrate by the same method as “Measurement of transmittance” described in Embodiment I. However, the finished film thickness was adjusted to 0.05, 0.40, 0.60, and 2.0 μm. The obtained board | substrate was confirmed visually from both sides, and the difficulty of seeing the boundary of the part with ITO and the part without ITO was determined.
◎: Not visible at all ○: Almost invisible △: Looks thin ×: Visible

  When Example IV-17 and Comparative Examples IV-1 and IV-2 were compared, when the resin composition of the present application having a refractive index of 1.60 to 1.80 was used, the visibility was good, particularly the film A coating film with good visibility was obtained when the thickness was in the range of 0.05 to 0.4 μm.

<< Example V >>
The following examples relate to embodiment V. This also applies to Embodiment VI.
Prior to the examples, a method for measuring the weight average molecular weight of the resin, the double bond equivalent of the resin, the acid value of the resin, the weight average molecular weight of the silane compound, and the average primary particle diameter of the pigment will be described.

(Weight average molecular weight of resin)
A weight average molecular weight (Mw) was obtained by the same method as “polymerization average molecular weight of resin” described in Example IV.

(Double bond equivalent of resin)
The double bond equivalent of the resin was calculated in the same manner as the “double bond equivalent of resin” described in Example I.

(Resin acid value)
The acid value per solid content of the resin was calculated by the same method as “Resin acid value” described in Example IV.

(Weight average molecular weight of silane compound (Mw))
The weight average molecular weight (Mw) of the silane compound was obtained by the same method as “polymerization average molecular weight of silane compound” described in Example IV.

(Measurement method of average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by the same method as “Method for measuring average primary particle diameter of pigment” described in Example III.
Subsequently, the oxide fine particle dispersion, the alkali-soluble resin solution, the fluorene skeleton-containing polyfunctional monomer, the silane compound, the colorant, the pigment dispersion, and the method for producing the dye-containing solution used in Examples and Comparative Examples are described. To do.

<Method for producing oxide fine particle dispersion>
(Production of dispersant (Ti))
The reaction was carried out in the same manner as in “Production of dispersant (Ti)” in Example III. 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 (Zr))
The reaction was carried out in the same manner as in “Production of dispersant (Zr)” in Example III. 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 (VA-1, VA-2))
Using a dispersant (Ti) and a dispersant (Zr), metal oxide dispersion was performed according to the formulation shown in Table V-1, and an oxide fine particle dispersion was prepared (the blend amount indicates the solid content). Dispersion method is pre-dispersion (using zirconia beads (1.25 mm) as media and dispersing for 1 hour with a paint shaker) and main dispersion (using zirconia beads (0.1 mm) as media). (Dispersion with machine UAM-015). The obtained oxide fine particle dispersion was diluted with propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMEA), and adjusted to the solid content of Table V-1.

ＴｉＯ２：石原産業（株）製「ＴＴＯ−５１（Ａ）」（平均一次粒子径：２０ｎｍ）
ＺｒＯ２：日本電工（株）製「ＰＣＳ−６０」（平均一次粒子径：２０ｎｍ）
ＭＩＢＫ：メチルイソブチルケトン（協和発酵ケミカル（株）製）
メトブタ：３−メトキシ−１−ブタノール（ダイセル化学工業（株）製）

TiO2: “TTO-51 (A)” manufactured by Ishihara Sangyo Co., Ltd. (average primary particle size: 20 nm)
ZrO2: “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.)

<Method for producing alkali-soluble resin solution>
(Preparation of resin solution (V-B-1))
Process 1
PGMEA 100 parts in a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction pipe, heated to 70 ° C. while injecting nitrogen gas into the vessel, 5.0 parts of styrene at the same temperature, A mixture of 15.9 parts of cyclohexyl methacrylate, 31.7 parts of methacrylic acid, and 1 part of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 70 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 40 parts of PGMEA was added, followed by stirring at the same temperature for 3 hours. Got.
Process 2
Next, dry air was introduced into the reaction vessel, charged with 50.0 parts of glycidyl methacrylate, 37.0 parts of PGMEA, 0.3 part of dimethylbenzylamine, and 0.1 part of methoquinone, and then continued stirring at the same temperature for 10 hours. It was. After cooling to room temperature, a resin solution (V-B-1) having a solid content of 40% by weight, a weight average molecular weight of 45,000, an acid value of 20, and a double bond equivalent of 300 was obtained by dilution with PGMEA.

(Preparation of resin solution (V-B-2))
Process 1
100 parts of PGMEA was put into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, heated to 70 ° C. while injecting nitrogen gas into the vessel, 10.0 parts of styrene at the same temperature, A mixture of 38.9 parts of cyclohexyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 17.4 parts of methacrylic acid, and 1 part of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. . After completion of the dropwise addition, the mixture was further reacted at 70 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 40 parts of PGMEA was added, followed by stirring at the same temperature for 3 hours. Got.
Process 2
Next, dry air was introduced into the reaction vessel, charged with 25.0 parts of glycidyl methacrylate, 37.0 parts of PGMEA, 0.3 part of dimethylbenzylamine and 0.1 part of methoquinone, and then stirred at the same temperature for 10 hours. It was. After cooling to room temperature, a resin solution (V-B-2) having a solid content of 40% by weight, a weight average molecular weight of 45,000, an acid value of 20, and a double bond equivalent of 600 was obtained by dilution with PGMEA.

<Method for producing fluorene skeleton-containing polyfunctional monomer>
(Fluorene skeleton-containing polyfunctional monomer (V-D2-1))
36 g (about 0.2 mol) of 9-fluorenone, 88 g (about 0.8 mol) of catechol, 0.7 ml of β-mercaptopropionic acid, and 60 g of 1,4-dioxane were placed in a reactor and heated at 80 ° C. 5 ml of 98% sulfuric acid was added dropwise. After completion of the reaction, 200 ml of MIBK (methyl isobutyl ketone) and 100 ml of water were added for extraction. Excess sulfuric acid was removed by performing the same operation three times. After solvent concentration, MIBK 100 ml and toluene 200
After adding ml, the mixture was cooled to 10 ° C. to obtain 65 g of biscatechol fluorene [9,9-bis (3,4-dihydroxyphenyl) fluorene].
38 g (about 0.1 mol) of the obtained biscatechol fluorene, diethylene glycol 1
00 g, 1 g of 1-methylimidazole, and 150 g of ethylene carbonate (about 1.7 g
Mol) was placed in a reactor and heated to 100 ° C. to carry out the reaction. After completion of the reaction, 500 ml of IPA (isopropanol) was added and cooled to 10 ° C. to obtain 40 g of a polyhydric alcohol to which an ethylene oxide unit was added as white crystals. As a result of analyzing the obtained polyhydric alcohol, it was found that it was a polyhydric alcohol in which 4.5 mol of an ethoxy group was added to 1 mol of biscatechol fluorene used as a raw material.
A reactor equipped with 40 g (0.06 mol) of the obtained polyhydric alcohol, 43 g (0.6 mol) of acrylic acid, 1 g of 70% by weight methanesulfonic acid aqueous solution, 0.01 g of hydroquinone and 100 mL of toluene, with a Dean-Stark trap attached. The esterification reaction was performed for 5 hours under toluene reflux. Water generated during the esterification reaction was removed by a Dean-Stark trap to obtain 45 g of a fluorene skeleton-containing polyfunctional monomer (V-D2-1) which is a tetraacrylate of the polyhydric alcohol. When analyzed by high performance liquid chromatography, the purity of tetraacrylate was 98%.

<Method for producing silane compound>
(Silane compound (VE-1))
By the same method as the silane compound (IV-D-1) of Example IV, a silane compound (VE-1) having a weight average molecular weight (Mw) of about 293 was obtained.

(Silane compound (VE-2))
By the same method as the silane compound (IV-D-2) of Example IV, a silane compound (VE-2) having a weight average molecular weight (Mw) of about 4000 was obtained.

<Method for producing colorant>
<Pigment>
(Blue refined pigment (V-F-1))
In the same manner as in “Blue refined pigment (IV-E-1)” in Example IV, 98 parts of blue refined pigment (VF-1) were obtained. The average primary particle diameter of the obtained pigment was 28.3 nm.

(Red refined pigment (VF-2))
115 parts of red micropigmented pigment (VF-2) was obtained in the same manner as in Example IV “Red micropigmented pigment (IV-E-2)”. The average primary particle diameter of the obtained pigment was 24.8 nm.

(Purple refined pigment (VF-3))
In the same manner as in “Purple refined pigment (IV-E-3)” of Example IV, 118 parts of purple refined pigment (VF-3) was obtained. The average primary particle diameter of the obtained pigment was 26.4 nm.

"dye"
(Xanthene salt forming compound (VF-4))
In the same manner as in “Xanthene salt-forming compound (IV-E-4)” in Example IV, 32 parts of C.I. I. A salt-forming compound (VF-4) between Acid Red 52 and a resin having a cationic group in the side chain was obtained. At this time, C.I. in the salt-forming compound (VF-4). I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

・樹脂型顔料分散剤 ： ８．０部
（ビックケミー・ジャパン社製 ＢＹＫ−１１１）
・樹脂溶液（Ｖ−Ｂ−１） ：６０．０部
・シクロヘキサノン ：１２．０部 <Method for producing pigment dispersion>
(Blue pigment dispersion (VGB))
The mixture having the composition shown below was uniformly stirred and mixed, and then dispersed with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, followed by filtration with a 5 μm filter. A blue pigment dispersion (VGB) was obtained.

Blue refined pigment (VF-1): 18.0 parts Copper phthalocyanine derivative: 2.0 parts

-Resin type pigment dispersant: 8.0 parts (BYK-111 manufactured by BYK Japan)
Resin solution (V-B-1): 60.0 parts Cyclohexanone: 12.0 parts

・樹脂型顔料分散剤 ： ８．０部
（日本ルーブリゾール社製「ソルスパース ２００００」）
・樹脂溶液（Ｖ−Ｂ−１） ：６０．０部
・シクロヘキサノン ：１２．０部 (Red pigment dispersion (VGR))
Using a mixture having the following composition, a red pigment dispersion (VGR) was obtained in the same manner as the blue pigment dispersion (VGB).

Red fine pigment (VF-2): 10.0 partsAnthraquinone pigment (CI Pigment Red 177): 2.0 parts ("Chromophthal Red A2B" manufactured by Ciba Japan)
・ Diketopyrrolopyrrole pigment derivative: 4.0 parts

-Resin type pigment dispersant: 8.0 parts ("Solsperse 20000" manufactured by Nippon Lubrizol)
Resin solution (V-B-1): 60.0 parts Cyclohexanone: 12.0 parts

(Purple pigment dispersion (VGV))
Using a mixture having the following composition, a purple pigment dispersion (VGV) was obtained in the same manner as the blue pigment dispersion (VGB).

-Purple refined pigment (VF-3): 20.0 parts-Resin type pigment dispersant: 8.0 parts (BYK-111 manufactured by Big Chemie Japan)
Resin solution (V-B-1): 60.0 parts Cyclohexanone: 12.0 parts

<Method for producing dye-containing solution>
(Xanthene salt forming compound-containing solution (VG-V2))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a xanthene-based salt-forming compound-containing solution (VG-V2).

Xanthene salt-forming compound (VF-4): 20.0 parts PGMEA: 80.0 parts

[Example V-1]
(Photosensitive composition (R1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a resin composition (R1).

・ Oxide fine particles (A); 4.35 parts of Al2O3 solution “Aluminum oxide dispersion solution” (manufactured by Wako Chemical Co., Ltd.): solid content 23% aluminum oxide dispersion solution, particle size 44 nm
-Alkali-soluble resin (B); resin solution (B-1) 29.58 parts-Thermosetting compound (C-1); Nicarak MW-30 2.96 parts "Nicarac MW-30" (Sanwa Chemical Co., Ltd.) Manufactured by the same company): a mixture containing a compound in which R1 to R6 of the formula (9) are CH2OCH3.
-Polyfunctional monomer (D) having four or more functional groups; 4.00 parts of M-402 “Aronix M-402” (manufactured by Toagosei Co., Ltd.)
-Photopolymerization initiator: OXE-02 0.20 part "IRGACURE OXE-01" (manufactured by BASF); 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)] )
-Leveling agent: BYK-330 2% 1.00 part "BYK-330" (manufactured by Big Chemie); Polypropylene structure-containing dimethylsiloxane propylene glycol monomethyl ether acetate solution (adjusted to 2% solid content)
Solvent: 57.91 parts of cyclohexanone

[Examples V-2 to V-18, Comparative Examples V-1 to V-3]
(Resin composition (V-R2 to V-R21))
After stirring and mixing the mixture shown in Tables V-2 to V-6 in a uniform manner and a blending amount (parts by weight), the mixture was filtered through a 1 μm filter and the same as the resin composition (V-R1). By this method, resin compositions (V-R2 to V-R21) corresponding to Examples V-2 to V-18 and Comparative Examples 1 to 3, respectively, were obtained.

・ＪＥＲ１００４；（下記式で表されるエポキシ樹脂）（ジャパンエポキシレジン社製）
エポキシ当量９２５（ｇ/eq）

・ＥＧ−２００；フルオレン系エポキシ樹脂 （大阪ガスケミカル株式会社製）
エポキシ当量２９２（ｇ/eq） The abbreviations in Table V-2 to Table V-6 are written.
<Oxide fine particles>
-Al2O3 solution; aluminum oxide dispersion solution (manufactured by Wako Chemical Co., Ltd.); solid content 23% aluminum oxide dispersion solution, particle size 44 nm
<< thermosetting compound >>
MW-30: Melamine compound “Nicalak MW-30” (manufactured by Sanwa Chemical Co., Ltd.)
EX4931; epoxy compound (epoxy resin represented by the following formula) (manufactured by Nagase Chemtech)
Epoxy equivalent 384 (g / eq)

・ JER1004; (epoxy resin represented by the following formula) (manufactured by Japan Epoxy Resin Co., Ltd.)
Epoxy equivalent 925 (g / eq)

・ EG-200; fluorene epoxy resin (Osaka Gas Chemical Co., Ltd.)
Epoxy equivalent 292 (g / eq)

<< Polyfunctional monomer having four or more functional groups >>
M-402 (containing a monomer having 4 functional groups);
"Aronix M-402" (manufactured by Toa Gosei Co., Ltd.)
Biscoat # 802 (containing 8 functional group monomers); polyfunctional monomer poly (pentaerythritol) acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
《Other monomers》
・ M-350; “Aronix M-350” (manufactured by Toa Gosei Co., Ltd.)

<< Silane compound having urethane or amide skeleton >>
U-201; “Yuriano U-201” (manufactured by Arakawa Chemical Industries, Ltd.); polyurethane-silica hybrid << photopolymerization initiator >>
-OXE-01; "IRGACURE OXE-01" (manufactured by BASF)
1,2-octadione-1- [4- (phenylthio)-, 2- (o-benzoyloxime)]
《Leveling agent》
-BYK-330 2%; "BYK-330" (manufactured by Big Chemie)
Propylene glycol monomethyl ether acetate solution of polyether structure-containing dimethylsiloxane (adjusted to 2% solids)

<Evaluation of resin composition>
The resin compositions (V-R1 to V-R21) were evaluated by the evaluation methods shown below. The results are shown in Table V-7.

(Measurement of refractive index)
The refractive index at a wavelength of 589 nm was measured in the same manner as in “Measurement of refractive index” described in Example IV.

(Visibility evaluation)
A substrate was prepared by sputtering ITO on glass. Thereafter, ITO was patterned using a hydrochloric acid-nitric acid etching solution. Resin compositions (V-R18, V-R19) were applied to the ITO pattern substrate in the same manner as in “Measurement of transmittance” described in Embodiment I. However, the finished film thickness was adjusted to 0.05, 0.40, 0.60, and 2.0 μm. The obtained board | substrate was confirmed visually from both sides, and the difficulty of seeing the boundary of the part with ITO and the part without ITO was determined.
◎: Not visible at all ○: Almost invisible △: Looks thin ×: Visible

Comparing Example V-18 and Comparative Example V-1, when the resin composition of the present application having a refractive index of 1.60 to 1.80 is used, the visibility is good, and the film thickness is particularly preferably 0.00. When it was in the range of 05 to 0.4 μm, a coating film with good visibility was obtained.
From the above results, it is possible to obtain a coating film excellent in refractive index, hardness, adhesion, and hue with the resin composition of the present application, and the coating film is a protective film, a flat film, an insulating film, or an antireflection film. As a result, it was confirmed that it had excellent performance.

Claims (24)

Oxide fine particles,
A resin composition comprising an alkali-soluble resin and a component selected from the following (i) and (ii):
(I) A fluorene skeleton-containing compound represented by the formula (14)

Here, in Formula (14), R ¹ represents a hydrogen atom, a hydroxyl group, a phenyl group, a tolyl group, an amino group, a carboxy group, or an alkyl group represented by — (CH ₂ ) _n CH ₃ ,
R ² is _{-C (A) = CH 2,} -CO-C (A) = CH 2, - (B) -O-CO-C (A) = CH 2, - (B) -C (A) = _{CH 2, -O- (B) -O} -CO-C (A) = CH 2, -O- (B) -C (A) = CH 2, -SH, - (B) -CO-C (A ) = CH ₂ , —O— (B) —CO—C (A) ═CH ₂ ,

(A) is —H or —CH ₃ ;
(B) is (CH ₂ ) _n , (OCH ₂ CH ₂ ) _n , (OCH ₂ CH ₂ CH ₂ ) _n , (OCH ₂ CH (OH) CH ₂ ) _n , or (OCOCH ₂ CH ₂ CH ₂ CH ₂ ) _N ,
R ³ represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group,
j, k and m are each independently an integer of 0 to 4, j + k is an integer of 0 to 5, and n is an integer of 1 to 20.
(Ii) A polyfunctional monomer having a thermosetting resin and four or more functional groups. In addition, it contains an organic solvent,
The resin composition of Claim 1 containing the component (i) selected from said (i) and (ii). The resin composition according to claim 2, wherein the alkali-soluble resin contains a resin having the following structural units (A) to (C).
(A) A structural unit having a carboxyl group (b) A structural unit having an aromatic ring group represented by formula (2) or formula (3) (c) An aliphatic ring group represented by formula (4) or formula (5) Units to have

Here, in formulas (2) and (3), R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring.

The resin having the structural units (a) to (c) reacts the precursor of the structural unit (b), the precursor of the structural unit (c), and an ethylenically unsaturated monomer having an epoxy group. To obtain a copolymer (i1-1), and then react the copolymer (i1-1) obtained with an unsaturated monobasic acid to obtain a copolymer (i1-2). A resin (B1a) obtained by reacting the obtained copolymer (i1-2) with a polybasic acid anhydride, or a precursor of the structural unit (a), a precursor of the structural unit (b), A copolymer (i2-1) is obtained by reacting a precursor of the structural unit (c), and then the copolymer (i2-1) obtained and an ethylenically unsaturated monomer having an epoxy group are obtained. The resin composition according to claim 3, wherein the resin composition is a resin (B1b) obtained by reacting with.   The resin composition according to claim 2, wherein the oxide fine particles include oxide fine particles of at least one element selected from zirconium and titanium.   6. The resin composition according to claim 5, wherein the content of the oxide fine particles is 10 to 80% by weight in 100% by weight of the solid content of the resin composition. The alkali-soluble resin has a double bond equivalent of 200 or more and less than 500,
The resin composition of Claim 1 containing the component (ii) selected from said (i) and (ii). Furthermore, the silane compound shown by following formula (V-4) is included, The resin composition of Claim 1 characterized by the above-mentioned.

Here, in the formula (V-4), 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, 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,
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, an alkoxyoxy 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, or a hydrogen atom.   The silane compound has a weight average molecular weight (Mw) of 200 or more and less than 5000, and a content of 1% by weight or more and less than 20% by weight in a total solid content of 100% by weight of the resin composition. The resin composition according to claim 8.   Furthermore, a coloring agent is included, The resin composition of Claim 1 characterized by the above-mentioned. The resin composition containing the compound which has an ethylenically unsaturated double bond, and the silane compound shown by Formula (15).

In equation (15),
R ₁ represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 1 to 20 carbon atoms, an alkoxylene group having 1 to 20 carbon atoms, or an alkoxyoxy group having 1 to 20 carbon atoms,
R ₂ each independently represents 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, or 7 to 7 carbon atoms. Represents an aralkyl group of 30; an alkaryl group having 7 to 30 carbon atoms; a siloxane having a substituent; a halogen, hydroxy or hydrogen; and R ₃ represents hydrogen or an unpaired electron;
R ₄ 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, an aralkyl group having 7 to 30 carbon atoms, Represents an alkaryl group having 7 to 30 carbon atoms or an unpaired electron,
When R ₃ and R ₄ are both unpaired electrons, a double bond is formed between C and N,
n represents an integer of 1 to 3, and when a plurality of the same groups are present, they are independently selected. The compound having an ethylenically unsaturated double bond is a resin having a hydroxyl group in a side chain,
In the formula (15), R ₁ is an alkylene group having 1 to 5 carbon atoms, R ₂ is an alkoxy group or hydrogen group having 1 to 5 carbon atoms, R ₃ and R ₄ are both unpaired electrons, and C and N The resin composition according to claim 11, which represents a double bond.   The resin composition according to claim 12, further comprising inorganic oxide fine particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium and zinc. The resin composition according to claim 12, further comprising a polyfunctional monomer having 7 or more ethylenically unsaturated double bonds represented by the following formula (I-2).

Here, in the formula (I-2), m is an integer of 0 to 4, and R ₃ is an ether group, an alkylene group, a tolylene group, an arylene group, a carbonyl group, a sulfonyl group, an ester group, and the formula (I- 3) selected from the group consisting of a divalent group having a structure represented by 3), R ₄ is a hydrogen atom or a methyl group, R ₅ is a hydroxyl group, a carboxyl group, a (meth) acryloyl group, And a (meth) acryloyloxy group.

Here, in the formula (I-3), R ₆ represents an aliphatic, alicyclic or aromatic structure.   The resin composition according to claim 12, further comprising an acetophenone photopolymerization initiator or an oxime ester photopolymerization initiator.   The resin composition according to claim 12, further comprising at least one antioxidant selected from the group consisting of a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. In the formula (15), n is 1, R ₃ is hydrogen, R ₄ 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, or 6 carbon atoms. The resin composition according to claim 11, which is an aryl group having ˜20, an aralkyl group having 7 to 30 carbon atoms, or an alkaryl group having 7 to 30 carbon atoms.   The resin composition according to claim 17, further comprising inorganic oxide fine particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, and zinc.   Furthermore, it contains tetraalkoxysilane, and the ratio (b / e) of the weight (b) of the silane compound and the weight (e) of the tetraalkoxysilane is 2 or more and less than 20. The photosensitive composition as described in any one of.   The resin composition according to claim 17, wherein the compound having an ethylenically unsaturated double bond contains a cardo resin having an ethylenically unsaturated double bond. Furthermore, the resin composition of Claim 17 containing the compound shown by Formula (10).

Here, in Formula (10), X ¹ and X ² are each independently a hydroxyl group, —O (AO) _p H group (where A represents an alkylene group having 2 to 3 carbon atoms, p Represents an integer of 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.   Furthermore, a coloring agent is included, The resin composition of Claim 11 characterized by the above-mentioned.   The resin composition for coating films which consists of any one of Claims 1-22.   A resin composition for an antireflective film comprising any one of claims 1 to 22.