JP7359559B2 - Light-shielding film, photosensitive resin composition for obtaining the same, and method for producing light-shielding film - Google Patents

Description

The present invention relates to a light-shielding film and a photosensitive resin composition for obtaining the same, which is a light-shielding film using a photosensitive resin composition that has a high transmittance of ultraviolet light and can be hardened to a deep level even by exposure alone. For example, it can be used for flexible displays on substrates whose heat resistance is not very high (plastic substrates, glass substrates, substrates with organic devices such as organic EL or organic TFTs on silicon wafers, etc.). The present invention relates to a light-shielding film that can be formed by photolithography and a photosensitive resin composition for obtaining the same.

Recently, with the aim of making devices more flexible and integrated into one chip, for example, resin films (transparent insulating films) have been applied directly to plastic substrates (plastic films, resin films) such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate). We can form resin film patterns, colored film patterns, and light shielding film patterns directly on substrates with organic devices such as organic EL and organic TFTs on glass substrates and silicon wafers. There is a demand to form a However, the heat resistance temperature of these plastic substrates themselves is generally only about 140°C at most, and for substrates with organic devices, it is at most 120°C, but the heat resistance in actual manufacturing processes is preferably 100°C or less. is the reality.

By the way, if we focus on light-shielding films in particular, conventional light-shielding films using carbon black have high light-shielding properties, but on the other hand, the transmittance of ultraviolet light is low, so photocuring only cures the surface. In order to harden the material deeply, high-temperature heat treatment (post-bake) is usually additionally performed. However, as mentioned above, if you want to use a substrate with relatively low heat resistance, such as a plastic substrate, it is necessary to avoid high-temperature heat treatment. Previously, the curability and solvent resistance of the light-shielding film were ensured by utilizing technology that exposes the light to the back side (post-exposure). The reality is that it costs a lot of money.

Therefore, when used as a light-shielding film, it has a certain degree of light-shielding property, but also has excellent curability and solvent resistance.Moreover, as mentioned above, it has a high transmittance of ultraviolet light and can be cured even with processing methods using light exposure. In other words, there has been a need for a photosensitive resin composition that can both ensure light-shielding properties and photoprocessability.
To address such problems, coloring materials that are transparent in the wavelength range of ultraviolet light have been known (for example, see Patent Document 1), but the invention described in Patent Document 1, The purpose is to lower the dielectric constant of the light-shielding film, and it is not an attempt to process it only by exposure to light, or a method that focuses on its curing properties and solvent resistance. In order to achieve both processability and processability, this publication did not disclose a composition that directly teaches the optimum range of coloring material and its relationship with other components, nor does it disclose a specific light-shielding film obtained using the composition.

Patent No. 5698510

The present invention has been made in view of the above-mentioned problems, and its purpose is to provide a light-shielding film that has excellent light-shielding properties, curing properties, and solvent resistance, while also ensuring reliable processing through exposure. The object of the present invention is to provide a curable photosensitive resin composition and a light-shielding film with excellent curability and solvent resistance obtained therefrom, and to provide a method for manufacturing such a light-shielding film. The light-shielding film according to the present invention can be applied to various displays, display devices such as touch panel sensors, solid-state imaging devices such as image sensors, etc., and especially as a component in the case where these are desired to be made into flexible products.

Therefore, the inventors of the present application have conducted intensive studies regarding the above objectives and problems, and have found that a photosensitive resin composition containing a predetermined alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a coloring material, and a solvent. The inventors have discovered that the above-mentioned problems can be solved by using a colorant that is transparent in a specific ultraviolet wavelength region and optimizing its content, and have completed the present invention.

（Ｒ¹、Ｒ²は、それぞれ独立にＣ１～Ｃ１５のアルキル基、Ｃ６～Ｃ１８のアリール基、Ｃ７～Ｃ２０のアリールアルキル基又はＣ４～Ｃ１２の複素環基を表し、Ｒ³はＣ１～Ｃ１５のアルキル基、Ｃ６～Ｃ１８のアリール基、Ｃ７～Ｃ２０のアリールアルキル基を表す。
ここで、アルキル基およびアリール基はＣ１～Ｃ１０のアルキル基、Ｃ１～Ｃ１０のアルコキシ基、Ｃ１～Ｃ１０のアルカノイル基、ハロゲンで置換されていてもよく、アルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合を含んでいてもよい。また、アルキル基は直鎖、分岐、又は環状のいずれのアルキル基であってもよい。）
〔８〕遮光膜を製造する方法であって、基板上に、前記〔４〕～〔７〕のいずれかに記載の感光性樹脂組成物を塗布し、プリベークした後、紫外線露光装置による露光、及びアルカリ水溶液による現像を行って、遮光膜を形成することを特徴とする遮光膜の製造方法。 That is, the gist of the present invention is as follows.
[1] A light-shielding film obtained by curing a composition containing a photosensitive resin, which satisfies the following (1) to (3).
(1) Optical density (OD) is 0.8 to 4.
(2) The transmittance of light at a wavelength of 365 nm is 10% or more when measured through a light-shielding film with an OD of 1.0.
(3) Film thickness is 0.5 to 5 μm.
[2] The light-shielding film according to [1], wherein the curing is performed only by exposure.
[3] The light-shielding film according to [1] or [2], which is a light-shielding film used for a display device or a solid-state image sensor.
[4] A photosensitive resin composition for obtaining the light-shielding film according to any one of [1] to [3] above,
alkali soluble resin,
a photopolymerizable compound having at least one ethylenically unsaturated bond;
photoinitiator,
Contains colorants and solvents,
A photosensitive resin composition characterized in that the colorant is contained in an amount of 25 to 60% by mass in the total solid content of the composition.
[5] The photosensitive resin composition according to [4], wherein the coloring material is a black organic pigment and/or a mixed color organic pigment.
[6] The colorant contains Pigment Violet 23 (PV23) and Pigment Yellow 139 (P Y 139), and is contained in the total solid content of the composition in an amount of 25 to 48% by mass,
In addition, the PV23 and PY 139 contain 20 to 36% by mass of PV23 and 4 to 12% by mass of PY139, respectively, in the total solid content of the composition, and the mass ratio (PV23/PY139) is 2 to 30% by mass. 4. The photosensitive resin composition according to [4].
[7] The photosensitive resin composition according to any one of [4] to [6], wherein the photopolymerization initiator is an acyloxime photopolymerization initiator having the structure of general formula (1) as a basic skeleton.

(R ¹ and R ² each independently represent a C1 to C15 alkyl group, a C6 to C18 aryl group, a C7 to C20 arylalkyl group, or a C4 to C12 heterocyclic group, and R ³ represents a C1 to C15 Represents an alkyl group, a C6 to C18 aryl group, and a C7 to C20 arylalkyl group.
Here, the alkyl group and aryl group may be substituted with a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C1 to C10 alkanoyl group, or a halogen, and the alkylene moiety is an unsaturated bond, an ether bond, It may contain a thioether bond or an ester bond. Further, the alkyl group may be any linear, branched, or cyclic alkyl group. )
[8] A method for producing a light-shielding film, comprising: coating the photosensitive resin composition according to any one of [4] to [7] above on a substrate, prebaking, and then exposing the composition to an ultraviolet exposure device; and a method for producing a light-shielding film, which comprises performing development with an alkaline aqueous solution to form a light-shielding film.

According to the photosensitive resin composition of the present invention, the optical density (OD) can cover a relatively high range of 0.8 to 4, and the light transmittance at a wavelength of 365 nm is 10% or more at OD 1.0. , it is possible to obtain a light-shielding film with excellent ultraviolet light transmittance, and it is possible to achieve both light-shielding properties and optical processability. The light-shielding film according to the present invention can be applied to various displays, display devices such as touch panel sensors, solid-state imaging devices such as image sensors, etc., and especially as a component in the case where these are desired to be made into flexible products.

The present invention will be explained in detail below.
The present invention relates to a technology for obtaining a light-shielding film by applying optical processing technology such as photolithography, and since the photosensitive resin composition used has characteristics, we will first explain each component of the photosensitive resin composition and their components. The composition ratio will be explained. The photosensitive resin composition of the present invention essentially contains an alkali-soluble resin, a photopolymerizable compound having at least one ethylenically unsaturated bond, a photopolymerization initiator, a colorant, and a solvent. It has that characteristic.

<Coloring material>
The colorant (light-shielding material) in the photosensitive resin composition of the present invention, when formed as a light-shielding film, has a transmittance of 10% for light at a wavelength of 365 nm when measured with a coating film having an optical density (OD) of 1.0. It is necessary to use the above-mentioned pigment, and although there is no limitation, it is preferable to use a black organic pigment, a color-mixing organic pigment, an inorganic black pigment, or a combination thereof. Examples of black organic pigments include perylene black, cyanine black, aniline black, and lactam black. Further, examples of mixed color organic pigments include those obtained by mixing at least two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, etc. to create a pseudo-black color. Examples of inorganic black pigments include chromium oxide, iron oxide, titanium black, titanium oxynitride, and titanium nitride.

These colorants (light-shielding materials) can be used alone or in combination of two or more, but they are more preferably used because they can achieve the above light transmittance when used as a light-shielding film. , Lactam Black as a black organic pigment, Pigment Violet 23 (PV23) and Pigment Yellow 139 ( PY 139) as mixed color organic pigments, and/or as an inorganic black pigment developed by Mitsubishi Materials. Preferably, it includes a titanium black treated to have high UV transmission, such as UB-1.

Regarding such a coloring material (light shielding material), in order to achieve the above light transmittance, the total solid content of the photosensitive resin composition of the present invention (which becomes the solid content when the composition is made into a cured film) is required. It is necessary to contain 25 to 60% by mass (solid content), preferably 30 to 50% by mass.

Among these, when using a colorant containing both Pigment Violet 23 (PV23) and Pigment Yellow 139 (P Y 139), it is particularly important that the colorant is contained in an amount of 25 to 48% by mass in the total solid content of the composition. It is preferable. Furthermore, it is preferable that PV23 and PY 139 be 20 to 36% by mass of PV23 and 4 to 12% by mass of PY139, respectively, in the total solid content of the composition. . At this time, it is preferable that their mass ratio (PV23/PY139) is 2 to 4.

Note that the above-mentioned coloring material in the present invention may be blended after being previously dispersed in a solvent together with a dispersant to form a coloring material dispersion. Here, the solvent for dispersion will be described later, but for example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. are preferably used. Regarding the dispersant to be used, known dispersants such as various polymer dispersants can be used. As specific examples of dispersants, known compounds conventionally used for pigment dispersion (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) may be used without particular restrictions. For example, cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative type dispersants (dispersion aids), etc. can be mentioned. In particular, it has a cationic functional group such as an imidazolyl group, pyrrolyl group, pyridyl group, primary, secondary or tertiary amino group as an adsorption point to the pigment, has an amine value of 1 to 100 mgKOH/g, and has a number average molecular weight. A cationic polymer dispersant having a molecular weight in the range of 1,000 to 100,000 is suitable. The amount of this dispersant to be blended is preferably 1 to 80% by mass based on the colorant, more preferably 30 to 75% by mass in the case of mixed color organic pigments, and 10 to 50% by mass in the case of black pigments. is more preferable.

Furthermore, when preparing the colorant dispersion liquid, in addition to the above-mentioned dispersant, by co-dispersing a part of the alkali-soluble resin described below, it is easier to maintain high exposure sensitivity, and the adhesion during development is improved. It is possible to obtain a photosensitive resin composition that has good properties and is less likely to cause problems with residue. The amount of the alkali-soluble resin blended in the colorant dispersion is preferably 2 to 20% by mass, more preferably 5 to 15% by mass.

Components other than the colorant will also be explained below.
<Alkali-soluble resin>
The alkali-soluble resin in the photosensitive resin composition of the present invention can be used without particular limitation as long as it has a polymerizable unsaturated group and an acidic group in the molecule, but typical An example is an acrylic group or a methacrylic group, and a representative example of the acidic group is a carboxyl group.

The preferred weight average molecular weight (Mw) and acid value range of this alkali-soluble resin vary depending on the skeleton of the resin, but usually Mw is 2,000 to 50,000 and acid value is 60 to 120 mgKOH/g. If Mw is less than 2,000, there is a risk that the adhesion of the pattern during alkaline development will be reduced, and if Mw exceeds 50,000, developability will be significantly reduced, making it impossible to obtain a photosensitive resin composition with an appropriate development time. There is a possibility. In addition, if the acid value is less than 60, residues tend to remain during alkaline development, and if the acid value is greater than 120, the alkaline developer penetrates too quickly, resulting in unfavorable dissolution development and peeling development. Both are undesirable because they are easily stored away. In addition, only one type of alkali-soluble resin may be used, or a mixture of two or more types may be used.

A first example of an alkali-soluble resin that can be preferably applied is an acrylic copolymer having a polymerizable unsaturated group and an acidic group. Examples include resins that are copolymers of (meth)acrylic acid, (meth)acrylic acid esters, and the like and have a (meth)acrylic group and a carboxyl group. For example, in the first step, (meth)acrylic acid and (meth)acrylic acid esters are copolymerized in a solvent, and in the second step, glycidyl (meth) is added to some of the carboxyl groups in the resulting copolymer. ) Polymerizable unsaturated group-containing alkali-soluble resins obtained by reacting acrylates can be exemplified. Another example is a copolymer obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent in the first step, and (meth)acrylic acid in the second step. Examples include polymerizable unsaturated group-containing alkali-soluble resins obtained by reacting and reacting dicarboxylic acid or tricarboxylic acid anhydrides in the third step. For examples that can be preferably used among these copolymers, those specifically shown in JP 2018-141968 can be referred to.

Examples of (meth)acrylic acid esters include various (meth)acrylic esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate. , iso-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylate ) neopentyl acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ( 2-Methylcyclohexyl meth)acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylate Propargyl acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracenyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, cresyl (meth)acrylate, (meth)acrylate Hydrocarbon groups having 1 to 20 carbon atoms, such as triphenylmethyl acid, cumyl (meth)acrylate, ethylene glycol-modified dicyclopentanyl (meth)acrylate, and ethylene glycol-modified dicyclopentenyl (meth)acrylate (meth) ) Acrylic esters can be exemplified.

Examples of copolymerization components that can be used in addition to various (meth)acrylic esters as (meth)acrylic acid esters include styrene or monomaleimide, which may have a substituent on the phenyl group. I can do it. Substituents for the phenyl group of styrene include alkyl groups having 1 to 10 carbon atoms, and monomaleimides include, for example, N-phenylmaleimide and N-cyclohexylmaleimide.

Examples of dicarboxylic acid compounds, tricarboxylic acid compounds, or acid monoanhydrides of these carboxylic acid compounds used in the third step of another example include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, They are phthalic acid, chlorendic acid, trimellitic acid, and acid monoanhydrides thereof, and two or more types can also be used in combination. Among these, tetrahydrophthalic anhydride, succinic anhydride, and trimellitic anhydride can be preferably used.
Regarding the type and blending ratio of (meth)acrylic acid esters, etc., an appropriate combination can be selected in order to satisfy the desired properties of the cured product. In cases where this poses a problem or where it is necessary to improve light resistance, it is preferable to use (meth)acrylic esters that do not contain aromatic groups.

A second example of the alkali-soluble resin is obtained by reacting a compound having two or more epoxy groups with (meth)acrylic acid (this means "acrylic acid and/or methacrylic acid"). Epoxy (meth)acrylate acid obtained by reacting an epoxy (meth)acrylate compound having a hydroxy group with (a) dicarboxylic or tricarboxylic acid monoanhydride and/or (b) tetracarboxylic dianhydride. It is an appendage. Examples of the compound having two or more epoxy groups that can be converted into an epoxy (meth)acrylate acid adduct include bisphenol-type epoxy compounds and novolac-type epoxy compounds.

Bisphenol-type epoxy compounds are epoxy compounds with two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. This reaction generally involves oligomerization of diglycidyl ether compounds, so the bisphenol skeleton is Contains an epoxy compound containing two or more of. Bisphenols used in this reaction include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis( 4-hydroxyphenyl) sulfone, bis(4-hydroxy-3,5-dimethylphenyl) sulfone, bis(4-hydroxy-3,5-dichlorophenyl) sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxyphenyl)hexafluoropropane, -Hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5- dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy- 3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy -3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether , bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4 -Hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4 -Hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9- Bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, etc. . Among these, bisphenols having a fluorene-9,9-diyl group can be particularly preferably used.

(a) The acid monoanhydride of dicarboxylic acid or tricarboxylic acid to be reacted with the epoxy (meth)acrylate is the acid monoanhydride of chain hydrocarbon dicarboxylic acid or tricarboxylic acid, or the acid monoanhydride of alicyclic dicarboxylic acid or tricarboxylic acid. Anhydrides, acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids are used. Here, examples of acid monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralic acid, malonic acid, glutaric acid, There are acid monoanhydrides such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, and even acid monoanhydrides of dicarboxylic acid or tricarboxylic acid into which arbitrary substituents have been introduced. good. In addition, examples of acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, Furthermore, acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which arbitrary substituents have been introduced may be used. Furthermore, examples of acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as phthalic acid, isophthalic acid, and trimellitic acid, and furthermore, dicarboxylic acids or tricarboxylic acids into which arbitrary substituents have been introduced. It may also be an acid monoanhydride.

In addition, as the acid dianhydride of (b) tetracarboxylic acid to be reacted with epoxy (meth)acrylate, acid dianhydride of chain hydrocarbon tetracarboxylic acid, acid dianhydride of alicyclic tetracarboxylic acid, or , dianhydrides of aromatic tetracarboxylic acids are used. Here, examples of acid dianhydrides of chain hydrocarbon tetracarboxylic acids include acid dianhydrides such as butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc. The acid dianhydride of the introduced tetracarboxylic acid may also be used. Examples of acid dianhydrides of alicyclic tetracarboxylic acids include acid dianhydrides such as cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid. Furthermore, it may be an acid dianhydride of tetracarboxylic acid into which any substituent has been introduced. Furthermore, examples of acid dianhydrides of aromatic tetracarboxylic acids include acid dianhydrides such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and biphenyl ethertetracarboxylic acid; It may also be an acid dianhydride of a tetracarboxylic acid into which a substituent has been introduced.

The molar ratio (a)/(b) of (a) dicarboxylic acid or tricarboxylic acid anhydride and (b) tetracarboxylic acid dianhydride to be reacted with epoxy (meth)acrylate is 0.01 to 10. The value is preferably .0, more preferably 0.02 or more and less than 3.0. If the molar ratio (a)/(b) deviates from the above range, it is not preferable because the optimum molecular weight for producing a photosensitive resin composition having good photopatterning properties cannot be obtained. Note that the smaller the molar ratio (a)/(b), the larger the molecular weight, which tends to reduce the alkali solubility.

（式中、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、それぞれ独立して水素原子、炭素数１～５のアルキル基、ハロゲン原子又はフェニル基を表し、Ｒ⁸は、水素原子又はメチル基を表し、Ａは、－ＣＯ－、－ＳＯ₂－、－Ｃ（ＣＦ₃）₂－、－Ｓｉ（ＣＨ₃）₂－、－ＣＨ₂－、－Ｃ（ＣＨ₃）₂－、－Ｏ－、フルオレン－９，９－ジイル基又は直結合を表し、Ｘは４価のカルボン酸残基を表し、Ｙ1及びＹ2は、それぞれ独立して水素原子又は－ＯＣ－Ｚ－（ＣＯＯＨ）_ｍ（但し、Ｚは２価又は３価カルボン酸残基を表し、ｍは１又は２の数を表す）を表し、ｎは１～２０の整数を表す。） The epoxy (meth)acrylate acid adduct can be produced by a known method, for example, the method described in JP-A-8-278629, JP-A-2008-9401, and the like. First, as a method for reacting (meth)acrylic acid with an epoxy compound, for example, (meth)acrylic acid in an amount equivalent to the epoxy group of the epoxy compound is added to a solvent, and a catalyst (triethylbenzylammonium chloride, 2,6 -diisobutylphenol, etc.), the reaction is carried out by heating and stirring at 90 to 120°C while blowing air. Next, as a method for reacting an acid anhydride with the hydroxyl group of the epoxy acrylate compound, which is a reaction product, a predetermined amount of the epoxy acrylate compound, an acid dianhydride, and an acid monoanhydride are added to a solvent, and a catalyst (odor) is added to the solvent. There is a method in which the reaction is carried out by heating and stirring at 90 to 130°C in the presence of tetraethylammonium chloride, triphenylphosphine, etc.). The epoxy acrylate acid adduct obtained by this method has a skeleton represented by the following general formula (2).

(In the formula, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ⁸ is a hydrogen atom or a methyl group. represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O- , represents a fluorene-9,9-diyl group or a direct bond, X represents a tetravalent carboxylic acid residue, and Y1 and Y2 are each independently a hydrogen atom or -OC-Z-(COOH) _m (however, , Z represents a divalent or trivalent carboxylic acid residue, m represents a number of 1 or 2), and n represents an integer from 1 to 20.)

In addition, examples of alkali-soluble resins other than those mentioned above include, for example, a polyol compound having an ethylenically unsaturated bond in the molecule as the first component, a diol compound having a carboxyl group in the molecule as the second component, and a diol compound having a carboxyl group in the molecule as the second component. Examples include urethane compounds obtained by reacting with diisocyanate compounds. As this type of resin, those shown in JP-A No. 2017-76071 can be referred to.

<Photopolymerizable compound having at least one ethylenically unsaturated bond>
Further, the photosensitive resin composition of the present invention contains a photopolymerizable compound having at least one ethylenically unsaturated bond (hereinafter sometimes simply referred to as a "photopolymerizable compound"). Examples of such photopolymerizable compounds include (meth)acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; , ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate Acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol(meth)acrylate, Sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide modified hexa(meth)acrylate of phosphazene, caprolactone modified dipentaerythritol hexa Examples include (meth)acrylic esters such as (meth)acrylate, dendritic polymers having a (meth)acroyl group, and one or more of these can be used. In addition, the photopolymerizable compound can play the role of crosslinking the molecules of the alkali-soluble resin, and in order to exhibit this function, it is preferable to use a compound having three or more photopolymerizable groups. . Further, the acrylic equivalent, which is the molecular weight of the monomer divided by the number of (meth)acryloyl groups in one molecule, may be 50 to 300, but the more preferable acrylic equivalent is 80 to 200. Note that this photopolymerizable compound does not have a free carboxyl group.

ここで、Ｒ^８は水素原子またはメチル基を表し、Ｒ⁹はＲ¹⁰(ＯＨ)_kのｋ個のヒドロキシル基の内ｌ個のヒドロキシル基を式中のエステル結合に供与した残り部分を表す。好ましいＲ¹⁰(ＯＨ)_kとしては、炭素数２～８の非芳香族の直鎖または分枝鎖の炭化水素骨格に基づく多価アルコールであるか、当該多価アルコールの複数分子がアルコールの脱水縮合によりエーテル結合を介して連結してなる多価アルコールエーテルであるか、またはこれらの多価アルコールまたは多価アルコールエーテルとヒドロキシ酸とのエステルである。ｋおよびｌは独立に２～２０の整数を表すが、ｋ≧ｌである。また、Ｒ¹¹は単結合又は２～６価のＣ１～Ｃ６の炭化水素基であり、ｍはＲ¹¹が単結合であるときは２であり、Ｒ¹¹が２～６価の基であるときは２～６の整数を表す。 Among these photopolymerizable compounds, examples of dendritic polymers having (meth)acroyl groups include, for example, some of the carbon-carbon double bonds in the (meth)acroyl groups of polyfunctional (meth)acrylate compounds. An example is a dendritic polymer obtained by adding a thiol group in a polyvalent mercapto compound to. Specifically, a dendritic polymer obtained by reacting a (meth)acryloyl group of a polyfunctional (meth)acrylate compound of general formula (3) with a thiol group in a polyvalent mercapto compound of general formula (4) is exemplified. can.

Here, R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents the remaining portion after l hydroxyl groups among the k hydroxyl groups of R ¹⁰ (OH) _k are donated to the ester bond in the formula. Preferred R ¹⁰ (OH) _k is a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a plurality of molecules of the polyhydric alcohol are dehydrated alcohols. It is a polyhydric alcohol ether connected via an ether bond by condensation, or an ester of these polyhydric alcohols or polyhydric alcohol ethers and a hydroxy acid. k and l independently represent integers from 2 to 20, with k≧l. Further, R ¹¹ is a single bond or a divalent to hexavalent C1 to C6 hydrocarbon group, m is 2 when R ¹¹ is a single bond, and when R ¹¹ is a divalent to hexavalent group represents an integer from 2 to 6.

Specific examples of the polyfunctional (meth)acrylate compound represented by general formula (3) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and ethylene oxide-modified trimethylol. Propane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate (meth)acrylic acid esters such as These compounds may be used alone or in combination of two or more.

Specific examples of the polyvalent mercapto compound represented by the general formula (4) include trimethylolpropane tri(mercaptoacetate), trimethylolpropane tri(mercaptopropionate), pentaerythritol tetra(mercaptoacetate), and pentaerythritol tri(mercaptoacetate). mercaptoacetate), pentaerythritol tetra (mercaptopropionate), dipentaerythritol hexa (mercaptoacetate), dipentaerythritol hexa (mercaptopropionate), and the like. These compounds may be used alone or in combination of two or more.

<Photopolymerization initiator>
Examples of the photopolymerization initiator in the photosensitive resin composition of the present invention include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert - Acetophenones such as butylacetophenone, benzophenones such as benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5 -Biimidazole compounds such as diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1 ,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3 ,4-oxadiazole and other halomethylthiazole compounds, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1, 3,5-triazine, 2-phenyl-4, 6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3, 5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloroR-methyl) -1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)- Halomethyl-S- such as 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine Triazine compounds, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione- 2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-o -O-acyloxime compounds such as acetate, sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone , anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, 2-mercapto Examples include thiol compounds such as benzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine.

（Ｒ¹、Ｒ²は、それぞれ独立にＣ１～Ｃ１５のアルキル基、Ｃ６～Ｃ１８のアリール基、Ｃ７～Ｃ２０のアリールアルキル基又はＣ４～Ｃ１２の複素環基を表し、Ｒ³はＣ１～Ｃ１５のアルキル基、Ｃ６～Ｃ１８のアリール基、Ｃ７～Ｃ２０のアリールアルキル基を表す。
ここで、アルキル基およびアリール基はＣ１～Ｃ１０のアルキル基、Ｃ１～Ｃ１０のアルコキシ基、Ｃ１～Ｃ１０のアルカノイル基、ハロゲンで置換されていてもよく、アルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合を含んでいてもよい。また、アルキル基は直鎖、分岐、又は環状のいずれのアルキル基であってもよい。）

〔式（５）中、Ｒ¹²およびＲ¹³はそれぞれ独立に、炭素数１～１０の直鎖状もしくは分岐状のアルキル基であるか、炭素数４～１０のシクロアルキル基、シクロアルキルアルキル基もしくはアルキルシクロアルキル基であるか、または炭素数１～６のアルキル基で置換されていてもよいフェニル基である。Ｒ¹⁴はそれぞれ独立に、炭素数２～１０の直鎖状もしくは分岐状のアルキル基またはアルケニル基であり、当該アルキル基またはアルケニル基中の－ＣＨ₂－基の一部が－Ｏ－基で置換されていてもよい。さらに、これらＲ¹²～Ｒ¹⁴の基中の水素原子の一部がハロゲン原子で置換されていてもよい。〕 Among these, it is particularly preferable to use O-acyloxime compounds (including ketooximes). Specific examples of the compound group include O-acyloxime photopolymerization initiators having the structure of the following general formula (1) or general formula (5) as a basic skeleton. In the present invention, among them, it is preferable to use an O-acyloxime photopolymerization initiator having a molar extinction coefficient of 10,000 L/(mol·cm) or more at 365 nm. Moreover, two or more kinds of these photopolymerization initiators can also be used. Note that the photopolymerization initiator as used in the present invention is used to include a sensitizer.

(R ¹ and R ² each independently represent a C1 to C15 alkyl group, a C6 to C18 aryl group, a C7 to C20 arylalkyl group, or a C4 to C12 heterocyclic group, and R ³ represents a C1 to C15 Represents an alkyl group, a C6 to C18 aryl group, and a C7 to C20 arylalkyl group.
Here, the alkyl group and aryl group may be substituted with a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C1 to C10 alkanoyl group, or a halogen, and the alkylene moiety is an unsaturated bond, an ether bond, It may contain a thioether bond or an ester bond. Further, the alkyl group may be any linear, branched, or cyclic alkyl group. )

[In formula (5), R ¹² and R ¹³ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group or cycloalkylalkyl group having 4 to 10 carbon atoms. or an alkylcycloalkyl group, or a phenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms. R ¹⁴ is each independently a linear or branched alkyl group or alkenyl group having 2 to 10 carbon atoms, and some of the -CH ₂ - groups in the alkyl group or alkenyl group are -O- groups. May be replaced. Furthermore, some of the hydrogen atoms in these groups R ¹² to R ¹⁴ may be substituted with halogen atoms. ]

<Solvent>
Examples of the solvent used in the photosensitive resin composition of the present invention include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, and terpenes such as α- or β-terpineol. Ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol Glycols such as toll, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, etc. Ethers, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate By dissolving and mixing them, a uniform solution-like composition can be obtained, and the solution can be adjusted to a desired viscosity for use.

<Other ingredients>
In addition to the above components, the photosensitive resin composition of the present invention may optionally contain resins other than the alkali-soluble resins, curing agents and curing accelerators for these resins, thermal polymerization inhibitors, antioxidants, plasticizers, etc. Additives such as additives, fillers, leveling agents, antifoaming agents, coupling agents, and surfactants can be added. Examples of resins other than the alkali-soluble resins mentioned above include resins that do not have photoradical reactivity such as epoxy resins, and examples of curing agents and curing accelerators for these resins include acid anhydrides, amine compounds, and imidazole. Examples thereof include type compounds and the like. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, silica, mica, alumina, etc., and examples of the leveling agent and antifoaming agent include silicone-based, fluorine-based, and acrylic compounds. Further, examples of the silane coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane, and examples of the surfactant include fluorine-based interface Examples include active agents, silicone surfactants, and the like.

The preferred proportions of each component in the solid content (the solid content includes monomer components that become solid content after curing) of the photosensitive resin composition of the present invention are as follows: The amount of the photopolymerizable compound is 10 to 60 parts by weight, and the amount of the photopolymerization initiator is 2 to 40 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin and the photopolymerizable compound. More preferably, the photopolymerizable compound is in an amount of 30 to 50 parts by weight per 100 parts by weight of the alkali-soluble resin, and the photopolymerization initiator is in an amount of 100 parts by weight in total of the alkali-soluble resin and the photopolymerizable compound. 3 to 30 parts by mass.

The photosensitive resin composition of the present invention contains the above-mentioned essential components (alkali-soluble resin, at least one A photopolymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a coloring agent) are contained in a total amount of 80% by mass, preferably 90% by mass or more. The amount of the solvent varies depending on the target viscosity, but it is preferably contained in the photosensitive resin composition in the range of 60 to 90% by mass.

The method for forming the light-shielding film in the present invention is a normal photolithography method, but as mentioned above, high-temperature heat treatment (particularly, It is preferable not to perform post-baking, and it is more preferable that curing can be achieved by exposure alone. That is, first, a photosensitive resin composition is applied onto a substrate such as a plastic substrate or a substrate with an organic device, and then the solvent is dried (prebaking), and the resulting coating film is irradiated with ultraviolet rays through a photomask. The exposed areas are cured, and a pattern is formed by performing further development using an alkaline aqueous solution to elute the unexposed areas, and if necessary, post-baking (thermal baking) may be performed as post-curing. The pre-bake and post-bake temperatures need to be set to below baking temperature = (heat-resistant temperature - 10) °C, taking into account the heat-resistant temperature of the substrate used, such as a plastic substrate or an organic device substrate.

The substrate used in the production method of the present invention, that is, the substrate on which the photosensitive resin composition having the above-mentioned specific composition is applied, is a film made of resin such as PET or PEN (plastic substrate). Here, the heat-resistant temperature is the temperature at which problems such as deformation do not occur even if the substrate is exposed during processing processes such as forming a light-shielding film on the substrate, and for resin films, it also changes depending on the degree of stretching processing. However, it is necessary that the temperature does not exceed at least the glass transition temperature (Tg). Further, the substrate may include a resin film on which electrodes such as ITO or gold are deposited or patterned.

In addition, examples of other substrates used in the manufacturing method of the present invention include glass substrates, silicon wafers, polyimide films, etc., which have high heat resistance themselves, but have thin films with low heat resistance formed on the substrate. I can list things. Specific examples include substrates with organic devices in which organic EL (OLED) and organic thin film transistors (TFT) are formed on glass, silicon wafers, and polyimide films. Note that the allowable temperature limit of substrates with low heat resistance, which are particularly targeted in the present invention, such as resin films and substrates with organic devices, is approximately 80 to 140° C., although it varies depending on the type of resin and device. Note that the substrate with an organic device includes one in which a protective film, a protective film, etc. are formed after the organic device is formed. This is because even if these protective films or protective films themselves have a heat resistance of 150°C or higher, in order to ensure the functionality of the organic device, if the heat resistance is substantially only 140°C or lower, the organic device cannot be attached. This is because it corresponds to a board.

Methods for applying the solution of the photosensitive resin composition onto these substrates include the known solution dipping method, spray method, and methods using a roller coater machine, land coater machine, slit coater machine, and spinner machine. The method can also be adopted. By these methods, a film is formed by applying the film to a desired thickness and then removing the solvent (prebaking). Prebaking is performed by heating with an oven, hot plate, or the like. The heating temperature and heating time in the prebaking are appropriately selected depending on the solvent used, and is carried out, for example, at a temperature of 60 to 110° C. (the upper limit is set to the heat-resistant temperature of the substrate −10° C.) for 1 to 3 minutes.

Exposure performed after prebaking is performed by an ultraviolet exposure device, and by exposing through a photomask, only the portions of the resist corresponding to the pattern are exposed. The exposure device and its exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultra-high-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a far-ultraviolet lamp, etc., and the photosensitive resin composition in the coating film is photocured. Preferably, photocuring is performed by irradiating a certain amount of light with a wavelength of 365 nm.

Alkaline development after exposure is performed for the purpose of removing the resist in unexposed areas, and a desired pattern is formed by this development. Examples of developing solutions suitable for this alkaline development include aqueous solutions of carbonates of alkali metals and alkaline earth metals, aqueous solutions of alkali metal hydroxides, and particularly sodium carbonate, potassium carbonate, lithium carbonate, etc. It is best to develop at a temperature of 23 to 28°C using a weakly alkaline aqueous solution containing 0.05 to 3% by mass of carbonates such as carbonates. Can be formed precisely.

After development, it is preferable to finish there, but if necessary, heat treatment (set at a temperature of about 80 to 140 degrees Celsius (upper limit set at -10 degrees Celsius, the heat-resistant temperature of the substrate) for 20 to 90 minutes ( Post-bake) may also be performed. This post-baking is performed for the purpose of increasing the adhesion between the patterned resin film and the substrate. Similar to pre-baking, this is done by heating with an oven, hot plate, etc. A more preferable range of heat treatment conditions for post-bake is a temperature of 90 to 120° C. (upper limit set at -10° C., the heat-resistant temperature of the substrate) and a heating time of 30 to 60 minutes. The patterned light-shielding film of the present invention is formed through the steps of the photolithography method described above.

The light-shielding film of the present invention obtained through such a process has an optical density (OD) of 0.8 to 4, and furthermore, the OD was measured as a film with a thickness of 1.0. It is preferable that the transmittance of light having a wavelength of 365 nm is 10% or more. At this time, the film thickness is preferably 0.5 to 5 μm. In the present invention, a light-shielding film that can be cured only by light processing using exposure, and that can be made into a light-shielding film that has desired cured properties (solvent resistance, etc.) without undergoing a post-bake heating process that exceeds the heat-resistant temperature of the substrate. It is good that The thickness of the light-shielding film depends on the design of the display device, etc., so when designing the formulation of the photosensitive resin composition of the present invention, for example, the OD should be set to 1.0 to 2.5/μm. It is better to set In particular, in the case of a system in which PV23 and PY139 are used together as colorants, it is preferably applied that the OD is 1.0 to 1.8/μm.

As described above, the method for producing a light shielding film of the present invention is most preferably capable of curing by only exposure without heat treatment, and at the same time, it is possible to cure the substrate by an operation such as alkaline development until the substrate has a low heat resistance temperature. It can be suitably used to form a light shielding film thereon. Specifically, when using a substrate with a low heat-resistant temperature, various insulating films, colored films for color filters, partition materials for organic EL pixel formation (for when RGB is formed by inkjet method, etc.), insulation for touch panels, etc. It is useful for forming films, light-shielding films, etc., and these resin film patterned substrates are used for display devices such as liquid crystals and organic EL, solid-state imaging devices, and touch panel materials (mainly used for displays and touch panels). It is possible to make the board

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. A preparation example of a photosensitive resin composition used in the method for manufacturing a light-shielding film of the present invention will be explained, and evaluation results of the characteristics of a cured product of the photosensitive resin composition will be explained.

First, an example of synthesis of an alkali-soluble resin will be shown. Evaluation of the resin in the synthesis example was performed as follows.
[Solid content concentration]
A glass filter [weight: W ₀ (g)] was impregnated with 1 g of the resin solution obtained in the synthesis example, weighed [W ₁ (g)], and the weight after heating at 160°C for 2 hours [W ₂ ( g)] from the following formula.
Solid content concentration (wt%) = 100 x (W ₂ - W ₀ )/(W ₁ - _{W 0} ).

[Acid value]
It was determined by dissolving a resin solution in dioxane and titrating it with a 1/10N-KOH aqueous solution using a potentiometric titration device [manufactured by Hiranuma Sangyo Co., Ltd., trade name COM-1600].

[Molecular weight]
Gel permeation chromatography (GPC) [manufactured by Tosoh Corporation, product name HLC-8220GPC, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2 columns) + TSKgelSuperH-3000 (1 column) + TSKgelSuperH-4000 (1 column) + TSKgelSuper-H5000 (1 bottle) [manufactured by Tosoh Corporation], temperature: 40℃, speed: 0.6ml/min], and the weight average molecular weight (Mw) was calculated as a standard polystyrene [PS-oligomer kit, manufactured by Tosoh Corporation]. I asked for it.

Further, the abbreviations used in the synthesis examples and comparative synthesis examples are as follows.
DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: Styrene AA: Acrylic acid SA: Succinic anhydride BPFE: Bisphenol fluorene type epoxy compound (reaction between 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane) thing.)
BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: Tetrahydrophthalic anhydride PTMA: Pentaerythritol tetra(mercaptoacetate)
DPHA: Mixture of dipentaerythritol pentaacrylate and hexaacrylate AIBN: Azobisisobutyronitrile TDMAMP: Trisdimethylaminomethylphenol HQ: Hydroquinone TEA: Triethylamine TEAB: Tetraethylammonium bromide BzDMA: Benzyldimethylamine PGMEA: Propylene glycol monomethyl ether acetate

[Synthesis example 1]
300 g of PGMEA was placed in a 1 L four-necked flask equipped with a reflux condenser, and the temperature was raised to 120° C. after purging the inside of the flask with nitrogen. A monomer mixture (a mixture of 77.1 g (0.35 mol) of DCPMA, 49.8 g (0.35 mol) of GMA, and 10 g of AIBN dissolved in 31.2 g (0.30 mol) of St) was added into this flask from the dropping funnel. The mixture was added dropwise over a period of time and further stirred at 120°C for 2 hours to obtain a copolymer solution.
Next, after purging the inside of the flask with air, 24.0 g of AA (95% of glycidyl groups), 0.8 g of TDMAMP, and 0.15 g of HQ were added to the obtained copolymer solution, and the mixture was heated at 120°C. The mixture was stirred for 6 hours to obtain a polymerizable unsaturated group-containing copolymer solution.
Furthermore, 30.0 g of SA (90% of the number of moles added of AA) and 0.5 g of TEA were added to the obtained copolymer solution containing polymerizable unsaturated groups, and the mixture was reacted at 120° C. for 4 hours. An alkali-soluble copolymer resin solution (a)-1 was obtained. The solid content concentration of the resin solution was 46% by mass, the acid value (solid content equivalent) was 76 mgKOH/g, and the Mw by GPC analysis was 5300.

[Synthesis example 2]
114.4 g (0.23 mol) of BPFE, 33.2 g (0.46 mol) of AA, 157 g of PGMEA, and 0.48 g of TEAB were placed in a 500 ml four-neck flask equipped with a reflux condenser, and the mixture was heated at 100 to 105°C. The reaction was stirred for 20 hours under heating. Next, 35.3 g (0.12 mol) of BPDA and 18.3 g (0.12 mol) of THPA were placed in a flask and stirred for 6 hours while heating at 120 to 125°C to form an alkali-soluble resin containing a polymerizable unsaturated group. (a)-2 was obtained. The resulting resin solution had a solid content concentration of 56.1% by mass, an acid value (solid content equivalent) of 103 mgKOH/g, and an Mw of 3600 by GPC analysis.

[Synthesis example 3]
Add 20 g of PTMA (0.19 mol of mercapto group), 212 g of DPHA (2.12 mol of acrylic group), 58 g of PGMEA, 0.1 g of HQ, and 0.01 g of BzDMA into a 1 L four-necked flask, and react at 60 ° C. for 12 hours. A dendritic polymer solution (b)-2 (solid content concentration: 80% by mass) was obtained. The disappearance of thiol groups in the obtained dendritic polymer was confirmed by iodometry. The Mw of the obtained dendritic polymer was 10,000.

(Preparation of photosensitive resin composition)
For each solid content concentration (Pcon, mass %) of the coloring material in the total solid content, Examples 1 to 9 were formulated using mixed color organic pigments (PV23, PY139) as the coloring agent, and formulations using a black organic pigment ( Examples 10 to 16 were formulations using carbon black (lactam black), and Comparative Example 1 was a formulation using carbon black as a colorant (Tables 1 and 2). Each component used in the formulation is as follows, and all numbers in the table are parts by mass. All other than the solvent are the amounts of solid content (including photopolymerizable monomers that become solid content after photoreaction), and in the actual preparation of the photosensitive resin composition, component a is the amount of the resin solution obtained in the synthesis example. The d and e components are added as a dispersion in which the d and e components are dispersed in a solvent.

[a] Alkali-soluble resin:
(a)-1: Resin obtained in the above Synthesis Example 1 (a)-2: Resin obtained in the above Synthesis Example 2 [b] Photopolymerizable compound:
(b)-1: Mixture of dipentaerythritol pentaacrylate and hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name DPHA, acrylic equivalent weight 106)
(b)-2: Resinlike polymer obtained in Synthesis Example 3 [c] Photopolymerization initiator:
(c)-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime) (manufactured by BASF Japan, product name Irgacure OXE02)
(c)-2: Oxime ester photopolymerization initiator [ADEKA COOLS NCI-831, manufactured by ADEKA, with the skeleton of general formula (1) and a molar absorption coefficient of 23,000 L/(mol・cm)]
[d] Colorant:
(d)-1: Pigment Violet 23 (PV23) (Hostaperm Violet RL-NF manufactured by Clariant)
(d)-2: Pigment Yellow 139 (PY139) (Paliotol Yellow D 1819 manufactured by BASF)
(d)-3: Pigment Blue 15:6 (PB15:6) (Heliogen Blue D 6700 T manufactured by BASF)
(d)-4: Lactam black (Irgaphor (registered trademark) Black S 0100 CF manufactured by BASF)
(d)-5: Carbon black (MA100 manufactured by Mitsubishi Chemical Corporation)
[e] Dispersant: Cationic polymer dispersant (Ajisper PB821 manufactured by Ajinomoto Fine Techno)
[f] Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

[evaluation]
The following evaluations were performed using the photosensitive resin compositions of Examples 1 to 16 and Comparative Example 1.

<Evaluation of development characteristics (pattern line width/pattern linearity)>
Each photosensitive resin composition obtained above was coated on a 125 mm x 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.2 μm, and heated at 90°C. Prebaked for 1 minute. After that, the exposure gap was adjusted to 100 μm, a negative photomask with line/space = 10 μm/50 μm was placed over the dried coating film, and ultra-high pressure mercury lamp with i-line illuminance of 30 mW/cm ² was used to deliver ultraviolet light of 50 mJ/cm ² . was irradiated to perform a photocuring reaction on the photosensitive area.

Next, this exposed coated plate was heated at 25°C with a 0.04% potassium hydroxide aqueous solution at a shower pressure of 1 kgf/cm ² for +10 seconds and +20 seconds from the development time (break time = BT) at which the pattern began to appear. After development, spray washing at 5 kgf/cm ² pressure is performed to remove the unexposed parts of the coating film to form a resin film pattern on the glass substrate, and then heat post drying at 100°C for 60 minutes using a hot air dryer. Baked. The line width and pattern linearity of the obtained resin film pattern with respect to the mask width of 20 μm lines were evaluated.

Pattern line width: Measure the pattern line width with a mask width of 20 μm using a length measuring microscope (Nikon Corporation "XD-20"). If it is within 20 ± 2 μm, mark it as ○, and if it is outside the range of 20 ± 2 μm, mark it as ×. did.
Pattern linearity: Observe the 20 μm mask pattern after post-baking with an optical microscope. ○ indicates that no peeling from the substrate or jagged edges of the pattern is observed, △ indicates that it is observed in some areas, and △ indicates that it is observed throughout. was evaluated as ×.
Note that the pattern line width and pattern linearity were evaluated for BT+10 seconds and BT+20 seconds.

<Evaluation of OD/μm>
Each photosensitive resin composition containing the colorant obtained above was applied onto a 125 mm x 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 μm. , prebaked at 90°C for 1 minute. Thereafter, without covering with a negative photomask, 80 mJ/cm ² of ultraviolet rays were irradiated using an ultra-high pressure mercury lamp with i-line illuminance of 30 mW/cm ² to perform a photocuring reaction.

Next, this exposed coated plate was developed for 60 seconds at 25°C with a 0.05% potassium hydroxide aqueous solution at a shower pressure of 1 kgf/cm ² , and then washed with spray water at a pressure of 5 kgf/cm ² , and then washed with hot air. Heat post-baking was performed at 100° C. for 60 minutes using a dryer. The OD value of this coated plate was evaluated using a Macbeth transmission densitometer. In addition, the thickness of the light-shielding film formed on the coated plate was measured, and the value obtained by dividing the OD value by the film thickness was defined as OD/μm.

<Evaluation of solvent resistance>
The solvent resistance of the formed coating film (light-shielding film) was evaluated using a coated plate (glass plate with light-shielding film) prepared in the same manner as in the case of OD evaluation. Rub the surface continuously with a cloth dipped in PGMEA 20 times and observe the surface condition. If there is no dissolution or scratches on the coating surface, the solvent resistance is ○, and the coating surface is not dissolved or softened. If the film was scratched by scratches, the solvent resistance was evaluated as ×. In addition, if the dissolution or scratches were limited to only a small part, the score was rated as △.

Claims (7)

A light-shielding film obtained by curing a composition containing a photosensitive resin, only a black organic pigment and/or a mixed color organic pigment as a coloring material, and an O-acyloxime photopolymerization initiator, comprising the following (1) to A light-shielding film characterized by satisfying (3).
(1) Optical density (OD) is 0.8 to 4.
(2) The transmittance of light at a wavelength of 365 nm is 10% or more when measured through a light-shielding film with an OD of 1.0.
(3) Film thickness is 0.5 to 5 μm. The light-shielding film according to claim 1, which is a light-shielding film used for a display device or a solid-state image sensor. A photosensitive resin composition for obtaining a light shielding film according to claim 1 or 2,
alkali soluble resin,
a photopolymerizable compound having at least one ethylenically unsaturated bond;
O-acyloxime photopolymerization initiator,
Contains only a black organic pigment and/or a mixed color organic pigment as a coloring agent, and a solvent,
A photosensitive resin composition characterized in that the colorant is contained in an amount of 25 to 60% by mass in the total solid content of the composition. The colorant contains Pigment Violet 23 (PV23) and Pigment Yellow 139 (PY139), and is contained in the total solid content of the composition in an amount of 25 to 48% by mass,
In addition, the PV23 and PY139 contain 20 to 36% by mass of PV23 and 4 to 12% by mass of PY139, respectively, in the total solid content of the composition, and the mass ratio (PV23/PY139) is 2 to 4. The photosensitive resin composition according to claim 3, characterized in that: 5. The photosensitive resin composition according to claim 3, wherein the photopolymerization initiator is an acyloxime photopolymerization initiator having the structure of general formula (1) as a basic skeleton.

(R ¹ and R ² each independently represent a C1 to C15 alkyl group, a C6 to C18 aryl group, a C7 to C20 arylalkyl group, or a C4 to C12 heterocyclic group, and R ³ represents a C1 to C15 Represents an alkyl group, a C6 to C18 aryl group, and a C7 to C20 arylalkyl group.
Here, the alkyl group and aryl group may be substituted with a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C1 to C10 alkanoyl group, or a halogen, and the alkylene moiety is an unsaturated bond, an ether bond, It may contain a thioether bond or an ester bond. Further, the alkyl group may be any linear, branched, or cyclic alkyl group. ) A method for producing a light-shielding film, the method comprising applying the photosensitive resin composition according to any one of claims 3 to 5 on a substrate, prebaking, and then exposing to an ultraviolet exposure device and developing with an alkaline aqueous solution. A method for producing a light-shielding film, the method comprising: forming a light-shielding film. 7. The light-shielding film according to claim 6, wherein the light-shielding film is formed by post-baking at a temperature of 80° C. or higher and a heat-resistant temperature of the substrate −10° C. or lower after the development with the alkaline aqueous solution. Production method.