JP2015209548A - Hydroxyl-containing fluorene-based compound, photosensitive composition containing the compound and transparent film formed with the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition which enables formation of a film excellent in adhesion, chemical resistance and weather resistance in devices of electrical products and a hydroxyl-containing fluorene-based compound contained in the composition.SOLUTION: A hydroxyl-containing fluorene-based compound of formula (1) is provided. In formula (1), Ris a divalent bonding group containing an alicyclic structure or divalent bonding group containing an aromatic ring; Xis a hydrogen atom or a methyl group; Xis a single bond or a methylene group; Xand Xare each a hydrogen atom or a methyl group; Rand Rare each a single bond, an alkyl group, an alkoxy group, an alkoxy ester group or a (meth)acrylate group; and Ris a group containing a (meth)acrylate group.

Description

  The present invention relates to a fluorene compound, and particularly relates to a hydroxyl group-containing fluorene compound, a photosensitive composition containing the fluorene compound, and a transparent film formed from the photosensitive composition.

  A transparent film formed of a fluorene-based compound, for example, a film formed of a fluorene-containing epoxy acrylate resin described in Patent Document 1, has a low dielectric constant, so that it is a device of an electric product such as a liquid crystal display element or an integrated circuit element. Or a protective film or an insulating film of a solid-state imaging device.

  However, such a protective film or insulating film has poor adhesion, chemical resistance, and weather resistance to the device of the electrical product, and is easily degraded by being dropped from the device of the electrical product or affected by temperature, humidity, etc. There is.

JP 2004-083855 A

  In view of the above problems, the present invention provides a photosensitive composition that can form a film having excellent adhesion, chemical resistance, and weather resistance to an electrical device, and a hydroxyl group-containing composition that the photosensitive composition contains. The object is to provide a fluorene compound.

In order to achieve the above object, the present invention is represented by the following general formula (1):
General formula (1)

And in the formula:
R ¹ is

Or

X ¹ is a hydrogen atom or a methyl group, X ² is a single bond or a methylene group, X ³ and X ⁴ are each a hydrogen atom or a methyl group, and R ² and R ³ are each a single bond , A hydroxyl group-containing fluorene compound, wherein R ⁴ is a group containing a (meth) acrylate group, an alkyl group, an alkoxyl group, an alkoxyester group, or a group containing a (meth) acrylate group I will provide a.

  The hydroxyl group-containing fluorene compound preferably contains at least two (meth) acrylate groups.

  The hydroxyl group-containing fluorene compound preferably contains 2 to 10 (meth) acrylate groups.

  In the hydroxyl group-containing fluorene compound, the molecular weight is preferably in the range of 1000 to 6000.

  In addition, the present invention contains the above hydroxyl group-containing fluorene compound, a block copolymer, a photoinitiator, and an organic solvent, and the block copolymer has an acidic group or an anhydride group. Photosensitive composition characterized by having a structure derived from an ethylenically unsaturated monomer and a structure derived from an ethylenically unsaturated monomer other than an ethylenically unsaturated monomer having an acidic group or an anhydride group Offer things.

  In the photosensitive composition, the hydroxyl group-containing fluorene compound preferably has a molecular weight in the range of 1100 to 2500.

  The photosensitive composition preferably further has a polymerizable monomer.

  Moreover, this invention provides the transparent film characterized by being formed with said photosensitive composition.

  According to the configuration of the hydroxyl group-containing fluorene compound, the transparent film formed by the photosensitive composition containing the hydroxyl group-containing fluorene compound of the present invention has excellent adhesion to chemical devices and chemical resistance. And weather resistance.

  An object of the present invention is to provide a hydroxyl group-containing fluorene compound, a photosensitive composition containing the compound, and a transparent film formed from the photosensitive composition. Hereinafter, the present invention will be described with embodiments of the present invention.

First, an embodiment of the hydroxyl group-containing fluorene compound of the present invention will be described.
<< Hydroxyl-containing fluorene compound >>
An embodiment of the hydroxyl group-containing fluorene compound of the present invention is represented by the following general formula (1).
General formula (1)

And in the formula, R ¹ is

Or

X ¹ is a hydrogen atom or a methyl group, X ² is a single bond or a methylene group, and X ³ and X ⁴ are a hydrogen atom or a methyl group, respectively.

R ² and R ³ are each a group containing a single bond, an alkyl group, an alkoxyl group, an alkoxyester group, or a (meth) acrylate group, and R ⁴ is a group containing a (meth) acrylate group. is there.

  The hydroxyl group-containing fluorene compound preferably contains at least two (meth) acrylate groups, and more preferably contains 2 to 10 (meth) acrylate groups.

  In order to impart excellent developability to the photosensitive composition containing the hydroxyl group-containing fluorene compound and excellent adhesion, chemical resistance and weather resistance to the transparent film formed from the photosensitive composition. The molecular weight of the hydroxyl group-containing fluorene compound is preferably in the range of 1000 to 6000, more preferably in the range of 1100 to 2500.

<Method for producing hydroxyl group-containing fluorene compound>
Regarding the method for producing a hydroxyl group-containing fluorene compound of the present invention, a monomer having two isocyanate groups is reacted with a monomer having a hydroxyl group and a (meth) acrylate group to obtain a first product. The first product is reacted with a hydroxyl group-containing fluorene monomer to obtain the hydroxyl group-containing fluorene compound of the present invention.

  Examples of the monomer having a hydroxyl group and a (meth) acrylate group include dipentaerythritol pentaacrylate and pentaerythritol triacrylate.

  Examples of the monomer having two isocyanate groups include isophorone diisocyanate, toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 1,6-diisocyanate. One or more compounds are selected from the group consisting of hexane (diisocyanatohexane), m-xylylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate (dicycyclohexylmethane-4,4′-disiocyanate), and the like. It is what

  Examples of the fluorene-based monomer containing a hydroxyl group include 9,9′-bis (4-hydroxyphenyl) fluorene [9,9′-bis (4-hydroxyphenyl) fluorene], 9,9′-bis (3, 4-dihydroxyphenyl) fluorene [9,9'-bis (3,4-dihydroxyphenyl) fluorene], 9,9'-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) fluorene [9,9 '-Bis (3-tert-butyl-4-hydroxy-5-methylphenyl) fluorene], 9,9'-bis (2,4-dihydroxyphenyl) fluorene [9,9'-bis (2,4-dihydroxyphenyl) fluorene], 9, '-Bis [4- (3-acryloxy-2-hydroxypropyloxy) phenyl] fluorene {9,9'-bis [4- (3-acryloxy-2-hydroxypropyl) fluorene} fluorene}, 9,9'- One or two or more compounds are selected from the group consisting of bis [4- (2-hydroxyethoxy) phenyl] fluorene {9,9′-bis [4- (2-hydroxyethoxy) phenyl] fluorene} and the like. is there.

  In reacting a monomer having two isocyanate groups with a monomer having a hydroxyl group and a (meth) acrylate group, a catalyst and a solvent can be used. Examples of the catalyst include dibutyltin dilaurate, and examples of the solvent include propylene glycol monomethyl ether acetate.

The following describes an embodiment of the photosensitive composition of the present invention containing a hydroxyl group-containing fluorene compound.
<< Photosensitive composition >>
The photosensitive composition of the present invention contains a hydroxyl group-containing fluorene compound, a block copolymer, a photoinitiator, and an organic solvent. Further, the block copolymer comprises a structure derived from an ethylenically unsaturated monomer having an acidic group or an anhydride group, and an ethylenically unsaturated monomer other than the ethylenically unsaturated monomer having an acidic group or an anhydride group. It has an induced structure.

  The photosensitive composition of the present invention is produced by mixing a hydroxyl group-containing fluorene compound, a block copolymer, a photoinitiator, and an organic solvent by a mixing method known to those skilled in the art. can do. Therefore, detailed description of the mixing method is omitted here.

Hereinafter, the hydroxyl group-containing fluorene-based compound, block copolymer, photoinitiator and organic solvent contained in the photosensitive composition of the present invention will be described.
<Hydroxyl-containing fluorene compound>
Since the hydroxyl group-containing fluorene compound is the same as the above hydroxyl group-containing fluorene compound, a detailed description thereof is omitted here.

  As above, the hydroxyl group-containing fluorene compound preferably contains at least two (meth) acrylate groups, and more preferably contains 2 to 10 (meth) acrylate groups.

  In order to impart excellent developability to the photosensitive composition containing the hydroxyl group-containing fluorene compound and excellent adhesion, chemical resistance and weather resistance to the transparent film formed from the photosensitive composition. The molecular weight of the hydroxyl group-containing fluorene compound is preferably in the range of 1000 to 6000, more preferably in the range of 1100 to 2500.

<Block copolymer>
The block copolymer has an ethylenically unsaturated group other than a structure derived from an ethylenically unsaturated monomer having an acidic group or an anhydride group and a structure derived from an ethylenically unsaturated monomer having an acidic group or an anhydride group. It has a structure of a saturated monomer.
[Structures derived from ethylenically unsaturated monomers having acidic or anhydride groups]
The acidic group or anhydride group contained in the structure derived from the ethylenically unsaturated monomer having the acidic group or anhydride group can improve the developability of the photosensitive composition. Examples of the ethylenically unsaturated monomer having an acidic group or an anhydride group include an ethylenically unsaturated monomer having one acidic group, an ethylenically unsaturated monomer having two or more acidic groups, and one anhydride. One or two or more compounds are selected from the group consisting of an ethylenically unsaturated monomer containing a group, an ethylenically unsaturated monomer containing two or more anhydride groups, and the like.

  Examples of the ethylenically unsaturated monomer containing one acidic group include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, α-chloro-acid. One or more compounds are selected from the group consisting of methacrylic acid (α-chloro-acidic acid), 2-ethylacrylic acid (2-Ethylacrylic acid), cinnamic acid, and the like.

  Examples of the ethylenically unsaturated monomer containing two or more acidic groups include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid ( One or two or more compounds are selected from the group consisting of mesaconic acid.

  Examples of the ethylenically unsaturated monomer containing one anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, mesaconic anhydride, and the like. One or two or more compounds are selected from the group consisting of:

  Examples of the ethylenically unsaturated monomer containing the two anhydride groups include bicyclo (2.2.2) oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicyclo (2 2.2)) oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride) or the like.

In the block copolymer, a structure derived from an ethylenically unsaturated monomer having the acidic group or anhydride group, and an ethylenically unsaturated monomer other than the ethylenically unsaturated monomer having the acidic group or anhydride group The content of the structure derived from the ethylenically unsaturated monomer having an acidic group or an anhydride group is in the range of 10 to 90 parts by weight based on 100 parts by weight in total with the derived structure.
[An ethylenically unsaturated monomer other than an ethylenically unsaturated monomer having an acid group or an anhydride group]
In order to improve the properties of the photosensitive composition such as heat resistance, developability, adhesion, chemical resistance, solvent resistance, etc., ethylenicity other than the ethylenically unsaturated monomer having the acidic group or anhydride group described below. Can have unsaturated monomers.

  Examples of the ethylenically unsaturated monomer other than the structure derived from the ethylenically unsaturated monomer having an acidic group or an anhydride group include, for example, an ethylenic compound containing an allyl group and two (meth) acrylate groups. One or more compounds are selected from the group consisting of an ethylenic compound, a vinyl nitrile compound, an aromatic ethylenic compound, and other ethylenic compounds.

  As the ethylenic compound containing the allyl group, for example, one or more compounds may be selected from the group consisting of allyl acrylate, allyl methacrylate, and the like. is there.

  Examples of the ethylenic compound containing two (meth) acrylate groups include 2,2-dimethyl-1,3-propylene glycol diacrylate and ethylene glycol. Diacrylate (ethylene glycol diacrylate), ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), dicyclopentenyl diacrylate (dicypentylene diacrylate), dicyclopentenyl diacrylate (dicyclopentyl dipropylene diacrylate) iacrylate), propylene glycol dimethacrylate (propylene glycol dimethacrylate), 2,2-dimethyl-1,3-propylene glycol diacrylate (2,2-dimethyl-1,3-propylene glycol diacrylate), 2,2-dimethyl-1 , 3-propylene glycol dimethacrylate (2,2-dimethyl-1,3-propylene dimethylacrylate), triethylene glycol diacrylate, triethylene glycol dimethyl acrylate, triethylene glycol dimethyl methacrylate Tetraethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tri (2-hydroxyethyl) isocyanate diacrylate [tri (2-hydroxyethyl) isocynate 2-isocyanate diisocyanate] One or more compounds are selected from the group consisting of [tri (2-hydroxyethyl) isocynate dimethacrylate] and the like.

  Examples of the vinyl nitrile compound include a group consisting of acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-chloromethacrylonitrile, or a group consisting of α-chloromethacrylonitrile, Two or more compounds are selected.

  As the aromatic ethylenic compound, for example, one or more compounds are selected from the group consisting of styrene, methylstyrene, methoxystyrene and the like.

Examples of the other ethylenic compounds include isooctyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, and C ₆ -C ₁₂ cycloalkyl group (Cycyl). ) One or two or more compounds are selected from the group consisting of acrylates, C ₆ -C ₁₂ cycloalkyl group methacrylates, and the like.

[Photoinitiator]
When the photoinitiator is irradiated with an energy ray, an active substance capable of causing a crosslinking reaction, such as a free radical, a cation, and an anion, is obtained. Examples of the photoinitiator include a phosphine oxide compound, an acetophenone compound, a benzoin compound, a benzophenone compound, a carbonyl group compound, and an aminocarbonyl group. ) -Based compounds, anthraquinone triazine-based compounds, oxime-based compounds, amine-based compounds, alkoxy group anthracene-based compounds, thioxanthone-based compounds, and the like. One or two or more compounds are selected. Further, the content of the photoinitiator is in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the photosensitive composition.

[Organic solvent]
Examples of the organic solvent include benzene, toluene, xylene, methanol, ethanol, ethylene glycol monopropyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol methyl ether, and diethylene glycol methyl ether. Methyl acid propionate, Ethyl ethoxypropionate, Ethyl lactate, Tetrahydrofuran, Ethylene glycol monomethyl ether Ethylene glycol monoethyl ether, Ethylene glycol monoethyl ether, Ethyl glycol monoethyl ether, Ethyl glycol monoethyl ether, Ethyl glycol monoethyl ether, Ethyl glycol monoethyl ether, Ethyl glycol monoethyl ether (Diethylene monobutyl ether), propylene glycol methyl ether acetate (abbreviated as “PGMEA”), propylene Glycol monoethyl ether acetate, propylene glycol propyl ether acetate, methyl isobutyl ketone, ethyl ether, methyl ether ketone, ethyl ether ketone Formamide (abbreviated as “DMF”), N, N-dimethylacetamide (N, N-dimethylacetamide, abbreviated as “DMAc”), N-methylpyrrolidone (abbreviated as “NMP”), γ- Butyrolactone From gamma-butyrolactone) group and the like, it is those selected one or two or more compounds.

  The content of the organic solvent is in the range of 60 to 80 parts by weight with respect to 100 parts by weight of the total amount of the photosensitive composition.

  The photosensitive composition of the present invention preferably further includes other polymerizable monomer in order to improve the degree of crosslinking and hardness. Examples of the polymerizable monomer include 4-methyl-1,2,3,6-tetrahydrophthalic anhydride (ethylene-1,2,3,6-tetrahydrophthalic anhydride), ethylene glycol diacrylate (ethylene glycol diacrylate). ), Ethylene glycol dimethacrylate, polyethylene glycol diacrylate containing 2 to 14 ethylene oxide groups, polyethylene glycol dimethacrylate containing 2 to 14 ethylene oxide groups (Polyethylene glyc l dimethacrylate), trimethylolpropane diacrylate (trimethylol propane diacrylate), trimethylol propane dimethacrylate (trimethylol propane dimethacrylate), trimethylolpropane triacrylate (trimethylol propane triacrylate), trimethylolpropane trimethacrylate (trimethylol propane trimethacrylate), pentaerythritol Triacrylate (pentaerythritol triacrylate), pentaerythritol trimethacrylate (pentaerythritol trimethacrylate) Propylene glycol diacrylate (propylene glycol diacrylate) containing pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate (propyleneoxide group), 2-14 propylene oxide groups (propylene oxide group) Containing propylene glycol dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pen Data methacrylate (dipentaerythritol pentamethacrylate), dipentaerythritol hexaacrylate (dipentaerythritol hexaacrylate, abbreviated "DPHA"), dipentaerythritol hexa methacrylate (dipentaerythritol hexamethacrylate), trimethylolpropane triglycidyl ether acrylic acid (trimethylolpropanetriglycidylether acrylic acid), bisphenol A diglycidyl Phthalic acid diester of ether acrylic acid (bisphenol A diglycylether acrylic acid) and β-hydroxyethyl (meth) acrylate (Phthalate diesters of β-hydroxyethyl (meth) acrylate), toluene diisocyanate, ditrimethylolpropane tetraacrylate, 2-isylacrylic acid. ], Ethoxylated pentaerythritol tetraacrylate (content of ethoxy group is 4 mol), ethoxylated pentaerythritol tetraacrylate (content of ethoxy group is 35 mol), ethoxy Group of trimethylolpropane triacrylate (ethoxylated tripropylpropylene triacrylate, ethoxy group content: 9 mol), ethoxy grouped trimethylolpropane triacrylate (ethoxy group content: 3 mol), propoxyl grouped trimethylolpropane triacrylate (Propoxylated trimethylpropylene triacrylate, propoxyl group content is 4 mol), nonaethylene glycol diacrylate, and a compound obtained by reacting dipentaerythritol hexaacrylate with caprolactone. -modified caprolactone), trimethylolpropane propoxylate triacrylate (trimethylolpropanepropoxylate triacrylate), Taiwan S. M.M. S TECHNOLOGY CO. , Products of product number BPSG manufactured by LTD, KAYARAD DPHA-40H manufactured by Nippon Kayaku Co., Ltd., products manufactured by Shin-Nakamura Chemical Co., Ltd. (for example, U-4HA, U-6HA, U-6LPA, U-15HA, UA-32P, U-324A, U-4H, U-6H), products manufactured by Negami Kogyo Co., Ltd. (for example, UN-9000H, UN-3320HA, UN-3320HB, UN-3320HC, UN- 901, UN-1200TPK, UN-904, etc.), etc., and one or more compounds are selected.

  As long as the effect of this invention is acquired, the photosensitive composition of this invention can have an additive further. Examples of the additive include additives such as a leveling agent and an adhesion promoter.

  Examples of the smoothing agent include a product of product number F-479 manufactured by DIC Corporation. Examples of the adhesion promoter include Taiwan S.I. M.M. S TECHNOLOGY CO. , Ltd., product number A-174, and the like.

The following describes embodiments of the transparent film of the present invention.
<Transparent film>
The transparent film is formed of the above-described photosensitive composition, and has excellent transparency, hardness, adhesion, chemical resistance, and weather resistance with respect to an electrical device. It is suitable for the dielectric layer and protective layer of the touch panel.

Hereinafter, the present invention will be described using evaluation results of each example and each comparative example.
<Example 1>
In a reaction vessel, 3.900 g of isophorone diisocyanate was dissolved in 30.924 g of propylene glycol monomethyl ether acetate, and stirred and mixed uniformly to obtain a first composition. Then, nitrogen was injected into the reaction environment to fill it, and the first composition was heated to 45 ° C.

  Next, 9.205 g of dipentaerythritol pentaacrylate and 0.024 g of dibutyltin dilaurate are dissolved in 25.109 g of propylene glycol monomethyl ether acetate and mixed uniformly to obtain a second composition. It was.

The first composition was measured for an absorption peak derived from N = C = O having a wave number of 2260 cm ⁻¹ with an infrared spectrophotometer, and the intensity of the first absorption peak was obtained. Then, after slowly dropping the second composition into the first composition over about 2 hours, an absorption peak derived from N═C═O having a wave number of 2260 cm ⁻¹ is measured with an infrared spectrometer, When the intensity of the absorption peak was half of the initial intensity, nitrogen injection was stopped and the reaction vessel was cooled to obtain a first product.

10.646 g of 9,9′-bis [4- (3-acryloxy-2-hydroxypropyloxy) phenyl] fluorene and 24.833 g of propylene glycol monomethyl ether acetate were mixed uniformly to obtain a third A composition was obtained. After the third composition was heated to 80 ° C., the first product was slowly dropped into the third composition and reacted for 4 hours to obtain a second product. The second product has 29.1 wt% of a hydroxyl group-containing fluorene compound. The structural formula of the hydroxyl group-containing fluorene compound is shown in the general formula (2).
General formula (2)

<Example 2>
In a reaction vessel, 3.900 g of isophorone diisocyanate was dissolved in 29.455 g of propylene glycol monomethyl ether acetate, and stirred and mixed uniformly to obtain a first composition. Then, nitrogen was injected into the reaction environment to fill it, and the first composition was heated to 45 ° C.

  Next, 9.205 g of dipentaerythritol pentaacrylate and 0.021 g of dibutyltin dilaurate are dissolved in 23.637 g of propylene glycol monomethyl ether acetate and mixed uniformly to obtain a second composition. It was.

The first composition was measured for an absorption peak derived from N═C═O having a wave number of 2260 cm ⁻¹ with an infrared spectrophotometer to obtain the intensity of the first absorption peak. Then, after slowly dropping the second composition into the first composition over about 2 hours, an absorption peak derived from N═C═O having a wave number of 2260 cm ⁻¹ is measured with an infrared spectrometer, When the intensity of the absorption peak was half of the initial intensity, nitrogen injection was stopped and the reaction vessel was cooled to obtain a first product.

7.694 g of 9,9′-bis [4- (2-hydroxyethoxy) phenyl] fluorene and 17.951 g of propylene glycol monomethyl ether acetate were uniformly mixed to obtain a third composition. After the third composition was heated to 65 ° C., the first product was slowly dropped into the third composition and reacted for 4 hours to obtain a second product. The second product has 28.9 wt% of a hydroxyl group-containing fluorene compound. The structural formula of the hydroxyl group-containing fluorene compound is shown in the general formula (3).
General formula (3)

<Comparative Example 1>
In a reaction vessel, 17.340 g of the compound of the general formula (3) was dissolved in 42.66 g of propylene glycol monomethyl ether acetate and mixed uniformly to obtain a first composition. Then, nitrogen was injected into the reaction environment to fill it, and the first composition was heated to 45 ° C. .

  Then, 1.855 g of 2-acryloyloxyethyl isocyanate was dissolved in 4.330 g of propylene glycol monomethyl ether acetate and mixed uniformly to obtain a second composition.

After slowly dropping the second composition into the first composition over about 1 hour, the nitrogen injection was stopped and the reaction vessel was cooled to obtain the first product. The first product has 29.0 wt% of a fluorene-based compound not containing a hydroxyl group. The structural formula of the fluorene-based compound not containing the hydroxyl group is as shown in the general formula (4).
General formula (4)

<Application example 1>
3.385 g of the compound of the general formula (2) and 10 g of a block copolymer (manufactured by Taiwan Daxin Materials, (meth) acrylate-based adhesive resin. A block copolymer having at least three blocks, The blocks are derived from the following monomers: (1): ethylenically unsaturated monomer having an acidic group, (2): ethylenically unsaturated monomer other than (1), (3): having an epoxy group An unsaturated monomer, and the block copolymer has an acid value of 88.47 mg / g and a viscosity of 2463 cps), 0.8 g of Irgacure (registered trademark) 907 (manufactured by BASF SE, Germany), 50 g of PGMEA, 3 g of UN-904 (manufactured by Negami Kogyo Co., Ltd.) and 0.5 g of 4-methyl-1,2,3,6-tetrahydrophthalic anhydride (4-methyl- , 2, 3, 6-tetrahydrophthalic anhydride) (manufactured by Waterstone, USA), 0.5 g of BPSG (manufactured by SMS TECHNOLOGY CO., LTD. Of Taiwan), and 0.1 g of F-479 (DIC ( Co., Ltd.) and 0.8 g of A-174 (manufactured by Taiwan SMS TECHNOLOGY CO., LTD) were mixed to obtain a photosensitive composition of Application Example 1. And after apply | coating this photosensitive composition to an ITO board | substrate, and forming a coating film, this coating film is irradiated with an ultraviolet-ray with irradiation energy 150mJ / cm < ² > using an exposure apparatus, and 30 minutes at 230 degreeC. The transparent film of 2 μm was formed on the ITO substrate to obtain a laminate composed of the transparent film and the ITO substrate.

<Application Example 2 and Comparative Application Example 1>
In Application Example 2 and Comparative Application Example 1, a photosensitive composition, a transparent film, and a laminate were prepared according to the same procedure as in Application Example 1 with the types and amounts of each component shown in Table 1 below.
<Evaluation method>
[Adhesion]
A cross-cut method of cutting a lattice pattern perpendicular to a transparent film in a laminate with a cross-cut tester (manufactured by ZEHNTNER, Switzerland, model number ZCC 2087) with respect to the laminates in Application Example 1, Application Example 2, and Comparative Application Example 1. The measurement was performed. The rank of evaluation is as follows.
5B: The edge of the cut is completely smooth, and there is no peeling to the eyes of any lattice.
4B: There is a small peeling in the transparent film at the intersection of the cuts. The area of the peeling is less than 5% with respect to the total area of the transparent film in the lattice pattern.
3B: The transparent film is partially or completely peeled along the edge of the cut, or the eye part is partially or completely peeled off. The area of peeling is in the range of 6% to 14% with respect to the total area of the transparent film in the lattice pattern.
2B: The transparent film is partially or completely peeled along the edge of the cut, or the eye part is partially or completely peeled off. The area of peeling is in the range of 15% to 35% with respect to the total area of the transparent film in the lattice pattern.
1B: The transparent film is partially or completely peeled along the edge of the cut, or the eye part is partially or completely peeled off. The area of peeling is in the range of 36% to 65% with respect to the total area of the transparent film in the lattice pattern.
0B: The transparent film is partially or completely peeled along the edge of the cut, or the eye part is partially or completely peeled off. The area of peeling is 66% or more with respect to the total area of the transparent film in the lattice pattern.

[Weatherability]
The oven temperature was set to 85 ° C., the relative humidity was set to 85%, and the laminates in Application Example 1, Application Example 2 and Comparative Application Example 1 were left in the oven for 24 hours, and then measured by the above cross-cut method. went. The rank of evaluation is the same as above.

[chemical resistance]
The laminates in Application Example 1, Application Example 2, and Comparative Application Example 1 were immersed in a sodium hydroxide solution having a temperature of 50 ° C. and a concentration of 5 wt% for 30 minutes. And after drying, it measured by said cross-cut method. The rank of evaluation is the same as above.

  According to the above evaluation results, the transparent film formed by the photosensitive composition containing the hydroxyl group-containing fluorene compound of the present invention has excellent adhesion, chemical resistance, and weather resistance, particularly hydroxyl group. It has better chemical resistance and weather resistance than a transparent film formed by a photosensitive composition containing a fluorene-based compound containing no fluorene.

  The transparent film formed from the photosensitive composition containing the hydroxyl group-containing fluorene compound of the present invention has excellent adhesion, chemical resistance, and weather resistance, and is therefore suitable for general protective layers, particularly electrical products. It is suitable for the dielectric layer and protective layer of the device.

Claims (8)

It is represented by the following general formula (1),
General formula (1)

And in the formula:
R ¹ is

Or

And
X ¹ is a hydrogen atom or a methyl group,
X ² is a single bond or a methylene group,
Each of X ³ and X ⁴ is a hydrogen atom or a methyl group;
R ² and R ³ are each a group containing a single bond, an alkyl group, an alkoxyl group, an alkoxyester group, or a (meth) acrylate group,
R ⁴ is a hydroxyl group-containing fluorene compound, wherein R ⁴ is a group containing a (meth) acrylate group.   The hydroxyl group-containing fluorene compound according to claim 1, wherein the hydroxyl group-containing fluorene compound contains at least two (meth) acrylate groups.   The hydroxyl group-containing fluorene compound according to claim 1, comprising 2 to 10 (meth) acrylate groups.   The hydroxyl group-containing fluorene compound according to any one of claims 1 to 3, wherein the molecular weight is in the range of 1000 to 6000. The hydroxyl group-containing fluorene compound according to any one of claims 1 to 4,
A block copolymer;
A photoinitiator;
An organic solvent,
The block copolymer is
It has a structure derived from an ethylenically unsaturated monomer having an acidic group or an anhydride group and a structure derived from an ethylenically unsaturated monomer other than an ethylenically unsaturated monomer having an acidic group or an anhydride group The photosensitive composition characterized by the above-mentioned.   6. The photosensitive composition according to claim 5, wherein the hydroxyl group-containing fluorene compound has a molecular weight in the range of 1100 to 2500.   The photosensitive composition according to claim 5, further comprising a polymerizable monomer.   A transparent film formed from the photosensitive composition according to claim 5.