JP2016071244A - Photosensitive resin composition, cured product and production method of the same, production method of resin pattern, cured film, liquid crystal display device, organic el display device, and touch panel display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition exhibiting a high optical density and excellent sensitivity of a cured product obtained therefrom and having excellent adhesiveness of a thin line of the cured product after developed, a cured product obtained by curing the photosensitive resin composition, a cured film and a production method of the cured film, a production method of a resin pattern, and a liquid crystal display device, an organic EL display device and a touch panel display device including the cured film.SOLUTION: The photosensitive resin composition comprises: a polymer component having a structural unit a1 having a group in which an acid group is protected by an acid decomposable group, a structural unit a2 having a crosslinking group and a structural unit a3 having an acid group, at least in any polymer, as a component A; a photoacid generator as a component B; a solvent as a component C; and carbon black as a component S. The content of the component S is 35 to 60 mass% with respect to the total solid content of the photosensitive resin composition.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the resin composition of the present invention” or “the composition of the present invention”). Moreover, the resin pattern manufacturing method using the said photosensitive resin composition, the hardened | cured material formed by hardening | curing the said photosensitive resin composition, the cured film formed by hardening | curing the said photosensitive resin composition, and the said cured film The present invention relates to various image display devices used.
More specifically, a photosensitive resin composition suitable for forming a black matrix (light-shielding color filter) of a color filter used for a liquid crystal display device, an organic EL display device, a touch panel display device, etc., and a cured film using the same It relates to a manufacturing method.

A color filter used in a liquid crystal display device includes a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast. Also in the solid-state imaging device, a black matrix is provided for the purpose of preventing noise and improving image quality. In general, a black matrix contains a polymerizable composition in which a light-shielding black color material is dispersed, a polymerizable compound, a polymerization initiator, and other components to form a polymerizable composition, which is then patterned. Manufactured by.
As a conventional photosensitive resin composition, what was described in patent document 1 or 2 is known.

JP 2006-251296 A JP-A-5-341530

In recent years, it is preferable that the black matrix used in the liquid crystal display device, the organic EL display device, and the touch panel display device can be made thinner in order to obtain a display device with a high aperture ratio. Therefore, it is required to be able to be resolved with a smaller exposure amount and to have excellent adhesion even if the completed pattern is a fine line. The compositions described in Patent Documents 1 and 2 have not been sufficient in terms of sensitivity and fine wire adhesion.
The problem to be solved by the present invention is a photosensitive resin composition having a high optical density of the obtained cured product, excellent sensitivity, and excellent fine-line adhesion of the cured product after development, and curing the photosensitive resin composition. It is providing the hardened | cured material, the cured film, its manufacturing method, the resin pattern manufacturing method, and the liquid crystal display device, organic electroluminescent display device, and touchscreen display device which have the said cured film.

The above-described problems of the present invention have been solved by means described in the following <1>, <8> to <11>, or <13> to <15>. It describes below with <2>-<7> and <12> which are preferable embodiments.
<1> A polymer component that satisfies at least one of the following A1 to A5 as the component A, a photoacid generator as the component B, a solvent as the component C, and carbon black as the component S, A photosensitive resin composition, wherein the content of S is 35 to 60% by mass relative to the total solid content of the photosensitive resin composition;
A1: Polymer having structural unit a1 having an acid group protected by an acid-decomposable group, structural unit a2 having a crosslinkable group, and structural unit a3 having an acid group A2: acid group is an acid-decomposable group Polymer having structural unit a1 having protected group and structural unit a3 having acid group, and polymer having structural unit a2 having crosslinkable group and structural unit a3 having acid group A3: Acid group is acid A polymer having a structural unit a1 having a group protected by a decomposable group, and a polymer having a structural unit a2 having a crosslinkable group and a structural unit a3 having an acid group A4: the acid group is an acid-decomposable group Polymer having structural unit a1 having protected group and structural unit a3 having acid group, and polymer having structural unit a2 having crosslinkable group A5: Group in which acid group is protected by acid-decomposable group A structural unit a1 having A polymer having a structural unit a2 having a crosslinkable group, and a polymer having a structural unit a3 having an acid group

<2> The photosensitive resin composition according to <1>, wherein the crosslinkable group is at least one group selected from the group consisting of an epoxy group, an oxetanyl group, and —NH—CH ₂ —OR. ,
However, said R represents a C1-C20 alkyl group.
<3> The photosensitive resin composition according to <1> or <2>, wherein the acidic group equivalent of the photosensitive resin composition is 500 to 10,000 per 1 g of organic solid content,
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the crosslinkable group equivalent of the photosensitive resin composition is 200 to 1,500 per 1 g of organic solid content.
<5> The photosensitive resin composition according to any one of <1> to <4>, further containing a dispersant as component D,
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the component A is a polymer component that satisfies the above A1 and / or A2.
<7> The photosensitive resin composition according to any one of <1> to <6>, wherein the component A is a polymer component that satisfies the above A1.

<8> A method for producing a cured product comprising at least steps a to c in this order,
Step a: Application step of applying the photosensitive resin composition according to any one of <1> to <7> on a substrate Step b: Solvent removal step of removing the solvent from the applied resin composition Step c : A heat treatment step for heat-treating the resin composition from which the solvent has been removed, or an exposure step for irradiating the resin composition from which the solvent has been removed with actinic rays <9> including at least steps 1 to 4 in this order. Resin pattern manufacturing method,
Process 1: Application | coating process which apply | coats the photosensitive resin composition as described in any one of <1>-<7> on a board | substrate Process 2: The solvent removal process of removing a solvent from the apply | coated resin composition Process 3 : Exposure step of exposing the resin composition from which the solvent has been removed to form a pattern with actinic rays Step 4: development step of developing the exposed resin composition and the unexposed resin composition with an aqueous developer <10><8> Or a cured product obtained by the method for producing a cured product according to <9>,
<11> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <7>,
<12> The cured film according to <11>, which is a light-shielding color filter,
<13> A liquid crystal display device having the cured film according to <11> or <12>,
<14> An organic EL display device having the cured film according to <11> or <12>,
<15> A touch panel display device having the cured film according to <11> or <12>.

  According to the present invention, the obtained cured product has a high optical density, excellent sensitivity, and a photosensitive resin composition excellent in fine line adhesion of the cured product after development, a cured product obtained by curing the photosensitive resin composition, A cured film, a manufacturing method thereof, a resin pattern manufacturing method, and a liquid crystal display device, an organic EL display device, and a touch panel display device having the cured film could be provided.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present invention, the description of “lower limit to upper limit” representing a numerical range represents “lower limit or higher and lower limit or lower”, and the description of “upper limit to lower limit” represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit.
In the present invention, “a polymer component satisfying at least one of A1 to A5” or the like is also simply referred to as “component A” or the like, and “a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group”. "Is also simply referred to as" structural unit a1 ".
Furthermore, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention comprises a polymer component satisfying at least one of the following A1 to A5 as component A, a photoacid generator as component B, a solvent as component C, and carbon as component S. The content of component S is 35 to 60% by mass with respect to the total solid content of the photosensitive resin composition.
A1: Polymer having structural unit a1 having an acid group protected by an acid-decomposable group, structural unit a2 having a crosslinkable group, and structural unit a3 having an acid group A2: acid group is an acid-decomposable group Polymer having structural unit a1 having protected group and structural unit a3 having acid group, and polymer having structural unit a2 having crosslinkable group and structural unit a3 having acid group A3: Acid group is acid A polymer having a structural unit a1 having a group protected by a decomposable group, and a polymer having a structural unit a2 having a crosslinkable group and a structural unit a3 having an acid group A4: the acid group is an acid-decomposable group Polymer having structural unit a1 having protected group and structural unit a3 having acid group, and polymer having structural unit a2 having crosslinkable group A5: Group in which acid group is protected by acid-decomposable group A structural unit a1 having A polymer having a structural unit a2 having a crosslinkable group, and a polymer having a structural unit a3 having an acid group

In general, in a photosensitive resin composition that can be used as a resist, increasing the optical density of the resulting cured product by a method such as adding a large amount of black pigment is inversely proportional to it, and the sensitivity to actinic radiation such as light is naturally descend.
As a result of intensive studies, the inventors of the present invention have a specific amount of carbon black and the polymer contained therein has an unprotected acid group, so that the resulting cured product has high optical density and excellent sensitivity. Furthermore, it has been found that a photosensitive resin composition excellent in fine wire adhesion of a cured product after development can be obtained.
Although the mechanism of expression of the detailed effect is unknown, it is presumed that the polymer having an unprotected acid group and carbon black act in a concerted manner, have high optical density, and excellent sensitivity. In addition, since the optical density is high and the sensitivity is excellent, the cross-sectional shape of the fine line becomes a forward taper, and the pressure of the developer from the side of the fine line can be received, and the adhesion at the time of fine line formation becomes an advantageous shape. It is presumed that the cured product is excellent in thin wire adhesion.

The photosensitive resin composition of the present invention can be suitably used as a positive resist composition.
The photosensitive resin composition of the present invention is preferably a resin composition having a property of being cured by heat.
The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition, and is a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition). Is more preferable.
The photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as a photoacid generator sensitive to actinic rays. A 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less.
On the other hand, the photoacid generator used in the present invention acts as a catalyst for the deprotection of the protected acid group in Component A because the acid generated in response to actinic light acts as a catalyst. The acid generated by the action of a single photon contributes to a number of deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as a power of 10, which results in high sensitivity as a result of so-called chemical amplification. Is obtained.
Furthermore, the photosensitive resin composition of the present invention is preferably a photosensitive resin composition for a black matrix (light-shielding color filter) of a color filter.
Moreover, the cured film or hardened | cured material which hardened the photosensitive resin composition of this invention can be used suitably as a light shielding film or a light shielding member in various display apparatuses.
Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

Component S: Carbon Black The photosensitive resin composition of the present invention contains carbon black as component S.
As long as the dispersibility in the composition is stable, the carbon black used in the present invention is not limited to the classification by ASTM, regardless of the use (for example, for color, for rubber, for dry battery, etc.). Is possible.
Carbon black includes, for example, furnace black, thermal black, channel black, lamp black, acetylene black and the like. Carbon black can be used as a color chip or color paste that has been dispersed in nitrocellulose or a binder in advance, using a dispersing agent as necessary to facilitate dispersion. Is readily available as a commercial product. Carbon black may be surface-treated by a known method.
The carbon black used in the present invention can be exemplified by those described in paragraphs 0130 to 0134 of JP-A-2009-178869, and “Carbon Black Handbook” edited by Carbon Black Association can be referred to.

The shape of carbon black is not particularly limited, but is preferably particulate.
The particle size of carbon black is not particularly limited, but from the viewpoint of dispersibility and colorability, the average primary particle size is preferably in the range of 3 nm to 2,000 nm, and the average primary particle size is 10 nm or more. A range of 500 nm or less is more preferable, and an average primary particle size is more preferably in a range of 10 nm to 100 nm.
The particle size of carbon black can be measured by the following method.
The particle size can be measured by directly observing the particles using a transmission electron microscope, measuring the short axis diameter or the long axis diameter, or using a small-angle X-ray scattering method and a predetermined content contained in the object to be measured. It is known that it can be measured by a method of determining the particle content relative to the particle diameter.

  In addition, an extender pigment may be added to the carbon black in the present invention as necessary. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, saturn white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more. The amount of extender used is preferably 0 to 100 parts by mass, more preferably 5 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of carbon black. . In the present invention, the above-described carbon black and extender pigment can be used by modifying the surface with a polymer in some cases.

Carbon black may be used alone or in combination of two or more.
The content of carbon black in the photosensitive resin composition of the present invention is 35 to 60% by mass, preferably 40 to 60% by mass, based on the total solid content of the photosensitive resin composition of the present invention. More preferably, it is 41-58 mass%, and it is still more preferable that it is 45-55 mass%. When it is in the above range, the obtained cured product has a higher optical density and is excellent in sensitivity. In addition, solid content of the photosensitive resin composition represents the component except volatile components, such as a solvent.

Moreover, you may mix and use the pigment for light shielding other than carbon black for the photosensitive resin composition of this invention.
Such a light-shielding pigment that can be mixed is not particularly limited as long as it has an absorbance in the visible light region, and the above-mentioned extender pigment, titanium black, C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, C.I. I. Pigment Brown 25, 28, C.I. I. And organic pigments such as Pigment Black 1.
Examples of using a mixture of light-shielding pigments other than carbon black include a mixture of carbon black and titanium black 6: 1, a mixture of carbon black and titanium oxide 3: 1, and the like.
The light-shielding pigment other than carbon black used by mixing is preferably used in the range of 0 to 90 parts by mass, more preferably in the range of 0 to 50 parts by mass with respect to 100 parts by mass of carbon black.

In the present invention, carbon black can also be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill.
Examples of the solvent used for the preparation of the dispersion include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-propanol, in addition to the solvent described later as Component C. Examples include alcohols such as pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, and cyclohexanol. be able to.
These solvents can be used singly or in combination of two or more.

Carbon black that can be used in the present invention may be used as a carbon black dispersion in the production of a photosensitive resin composition.
The carbon black dispersion is preferably adjusted so that the carbon black content in the dispersion is 5 to 99% by mass, more preferably 40 to 92% by mass, and 40 to 80% by mass. More preferably.

Component A: Polymer component satisfying at least one of A1 to A5 The photosensitive resin composition of the present invention contains, as Component A, a polymer component satisfying at least one of the following A1 to A5.
A1: Polymer having structural unit a1 having an acid group protected by an acid-decomposable group, structural unit a2 having a crosslinkable group, and structural unit a3 having an acid group A2: acid group is an acid-decomposable group Polymer having structural unit a1 having protected group and structural unit a3 having acid group, and polymer having structural unit a2 having crosslinkable group and structural unit a3 having acid group A3: Acid group is acid A polymer having a structural unit a1 having a group protected by a decomposable group, and a polymer having a structural unit a2 having a crosslinkable group and a structural unit a3 having an acid group A4: the acid group is an acid-decomposable group Polymer having structural unit a1 having protected group and structural unit a3 having acid group, and polymer having structural unit a2 having crosslinkable group A5: Group in which acid group is protected by acid-decomposable group A structural unit a1 having A polymer having a structural unit a2 having a crosslinkable group, and a polymer having a structural unit a3 having an acid group

Component A is preferably a polymer component satisfying at least one of A1 to A3, more preferably a polymer component satisfying A1 and / or A2, and further being a polymer component satisfying A1. preferable.
Moreover, it is preferable that all the polymers contained in Component A are polymers each having at least a structural unit a3 having an acid group.
The photosensitive resin composition of the present invention may further contain a polymer other than these. Unless otherwise stated, component A in the present invention means those including other polymers added as necessary in addition to the above-described aspects of A1 to A5. In addition, even if it is a high molecular compound, the compound applicable to the crosslinking agent and dispersing agent mentioned later shall not be contained in the component A.

Component A is preferably an addition-polymerization type resin, and includes a structural unit derived from (meth) acrylic acid and / or an ester thereof, and / or a structural unit derived from hydroxystyrene and / or an ester thereof. More preferably, it is a coalescence. In addition, you may have structural units other than the above, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”. Further, “(meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.

<Structural unit a1 having an acid group protected by an acid-decomposable group>
Component A includes a polymer having at least a structural unit a1 having a group in which an acid group is protected with an acid-decomposable group. When component A contains a polymer having structural unit a1, an extremely sensitive photosensitive resin composition can be obtained.
As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited. Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group. The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal group such as an ester structure of a group represented by the formula a1-10 described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group). A functional group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl ester group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).

The structural unit a1 having a group in which an acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group in which a carboxyl group is protected with an acid-decomposable group (“protected carboxyl group protected with an acid-decomposable group” Or a structural unit having a protected phenolic hydroxyl group in which a phenolic hydroxyl group is protected by an acid-decomposable group (a structural unit having a protected phenolic hydroxyl group protected by an acid-decomposable group). Is also referred to as “.”
Hereinafter, the structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group and the structural unit a1-2 having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in this order.

<< Structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group >>
The structural unit a1-1 having a protected carboxyl group protected by the acid-decomposable group is a protective carboxyl group in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below. It is a structural unit.
There is no restriction | limiting in particular as a structural unit which has the said carboxyl group which can be used for the structural unit a1-1 which has the protected carboxyl group protected by the said acid-decomposable group, A well-known structural unit can be used. For example, the structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid, or ethylenic The structural unit a1-1-2 which has both an unsaturated group and the structure derived from an acid anhydride is mentioned.
Hereinafter, derived from the structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule used as the structural unit having the carboxyl group, derived from an ethylenically unsaturated group and an acid anhydride The structural unit a1-1-2 having both of the structures will be described in order.

<<< Structural Unit a1-1-1 Derived from Unsaturated Carboxylic Acid Having at least One Carboxyl Group in the Molecule >>>
Examples of the unsaturated carboxylic acid used in the present invention as the structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those listed below. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyl. Examples include loxyethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl phthalic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid. For example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both terminals, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among them, from the viewpoint of developability, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, anhydride of unsaturated polyvalent carboxylic acid, etc. It is preferable to use acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
The structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule may be composed of one kind alone, or may be composed of two or more kinds. Good.

<<< Structural unit a1-1-2 having both an ethylenically unsaturated group and a structure derived from an acid anhydride >>>
The structural unit a1-1-2 having both an ethylenically unsaturated group and a structure derived from an acid anhydride is obtained by reacting a hydroxyl group present in a structural unit having an ethylenically unsaturated group with an acid anhydride. The unit is preferably derived from a monomer.
As the acid anhydride, known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, from the viewpoint of developability.

-Acid-decomposable group that can be used for the structural unit a1-1-
As the acid-decomposable group that can be used for the structural unit a1-1 having a protected carboxyl group protected by the acid-decomposable group, the above-mentioned acid-decomposable group can be used.
Among these acid-decomposable groups, it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal. It is preferable from the viewpoint of the storage stability of the composition. Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula a1-10. In addition, when the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula a1-10, the entire protected carboxyl group is-(C = O) -O-CR ¹⁰¹ R ¹⁰² ( OR ¹⁰³ ).

In formula a1-10, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom, an alkyl group or an aryl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms. R ¹⁰³ represents an alkyl group or an aryl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.

In the formula a1-10, R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom, an alkyl group or an aryl group, R ¹⁰³ represents an alkyl group or an aryl group, and the alkyl group is linear or branched. Any of an annular shape may be used. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

In the above formula a1-10, when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be linear, branched or cyclic.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.

  The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become an aralkyl group.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are illustrated, Among these, a fluorine atom or a chlorine atom is preferable.
Moreover, as said aryl group, a C6-C20 aryl group is preferable and a C6-C12 aryl group is more preferable. Specifically, a phenyl group, an α-methylphenyl group, a naphthyl group and the like can be exemplified, and as an entire alkyl group substituted with an aryl group, that is, as an aralkyl group, a benzyl group, an α-methylbenzyl group, a phenethyl group, A naphthylmethyl group etc. can be illustrated.
As said alkoxy group, a C1-C6 alkoxy group is preferable, a C1-C4 alkoxy group is more preferable, and a methoxy group or an ethoxy group is still more preferable.
Further, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is linear Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.

In the above formula a1-10, when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ can be bonded together to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.

In the above formula a1-10, it is preferable that any one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

  As the radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the formula a1-10, a commercially available one may be used, or one synthesized by a known method may be used. You can also. For example, it can be synthesized by a synthesis method described in paragraphs 0037 to 0040 of JP2011-221494A.

  A first preferred embodiment of the structural unit a1-1 having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the following formula.

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or Represents an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group;

When R ¹ and R ² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferable.

  A second preferred embodiment of the structural unit a1-1 having a protected carboxyl group protected with the acid-decomposable group is a structural unit of the following formula.

In the formula, R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylenecarbonyl group, and R ^{122 to} R ¹²⁸ each independently represent a hydrogen atom or 1 to 4 carbon atoms. Represents an alkyl group.

R ¹²¹ is preferably a hydrogen atom or a methyl group.
L ¹ is preferably a carbonyl group.
R ^{122 to} R ¹²⁸ are preferably a hydrogen atom.

  Preferable specific examples of the structural unit a1-1 having a protected carboxyl group protected by the acid-decomposable group include the following structural units. R represents a hydrogen atom or a methyl group.

<< Structural unit a1-2 having a protected phenolic hydroxyl group protected with an acid-decomposable group >>
The structural unit a1-2 having a protected phenolic hydroxyl group protected with an acid-decomposable group is a structural unit having a phenolic hydroxyl group having a protected phenolic hydroxyl group protected by an acid-decomposable group described in detail below. It is a structural unit.

<<< constituent unit a1-2-1 having phenolic hydroxyl group >>>
Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene structural unit and a structural unit in a novolac resin. Among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene is sensitive. From the viewpoint of Moreover, as a structural unit having a phenolic hydroxyl group, a structural unit represented by the following formula a1-20 is also preferable from the viewpoint of sensitivity.

In formula a1-20, R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, and R ²²² represents a halogen atom or a linear or branched chain having 1 to 5 carbon atoms. Represents an alkyl group, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less. In addition, when two or more ^R222 exists, these ^R222 may mutually differ or may be the same.

In the above formula a1-20, R ²²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R ²²¹ represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved. Examples of the divalent linking group for R ²²¹ include an alkylene group, preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. . Specific examples in the case where R ²²¹ is an alkylene group include methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, tert-butylene group, pentylene group, isopentylene group, neopentylene group, hexylene. Groups and the like. Among them, R ²²¹ is preferably a single bond, a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, or a 2-hydroxy-1,3-propylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Moreover, although a represents the integer of 1-5, from the viewpoint of the effect of this invention, and the point that manufacture is easy, it is preferable that a is 1 or 2, and it is more preferable that a is 1. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R ²²¹ is defined as the reference (first position).
R ²²² each independently represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples include fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
B represents 0 or an integer of 1 to 4;

-Acid-decomposable group that can be used for the structural unit a1-2-
The acid-decomposable group that can be used for the structural unit a1-2 having a protected phenolic hydroxyl group protected with the acid-decomposable group includes a structural unit a1 having a protected carboxyl group protected with the acid-decomposable group. Similarly to the acid-decomposable group that can be used for -1, known ones can be used and are not particularly limited. Among the acid-decomposable groups, a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability. Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the above formula a1-10. When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the above formula a1-10, the whole protected phenolic hydroxyl group is -Ar-O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ). Ar represents an arylene group.

Preferred examples of the acetal ester structure of the phenolic hydroxyl group include R ¹⁰¹ = hydrogen atom, R ¹⁰² = R ¹⁰³ = methyl group combination, R ¹⁰¹ = hydrogen atom, R ¹⁰² = methyl group and R ¹⁰³ = benzyl group combination, R Examples include combinations of ¹⁰¹ = hydrogen atom, ^R102 = methyl group, and ^R103 = ethyl group.

Examples of the radical polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include, for example, paragraph 0042 of JP2011-215590A And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.

  Specific examples of the acetal protecting group for the phenolic hydroxyl group include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group. 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types.

  As the radical polymerizable monomer used for forming the structural unit a1-2 having a protected phenolic hydroxyl group protected by the acid-decomposable group, a commercially available one may be used, or a known method may be used. It is also possible to use what has been done. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.

  Preferable specific examples of the structural unit a1-2 having a protected phenolic hydroxyl group protected with the acid-decomposable group include the following structural units, but the present invention is not limited thereto. In the following specific examples, R represents a hydrogen atom or a methyl group.

-Preferred embodiment of structural unit a1-
When the polymer having the structural unit a1 does not substantially have the structural unit a2, the structural unit a1 is preferably 20 to 100 mol%, preferably 30 to 90 mol% in the polymer having the structural unit a1. Is more preferable.
When the polymer having the structural unit a1 has the following structural unit a2, the structural unit a1 is preferably 3 to 70 mol% from the viewpoint of sensitivity in the polymer having the structural unit a1 and the structural unit a2. 10-60 mol% is more preferable. In particular, when the structural unit a1 is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, 20 to 50 mol% is preferable.
In the present invention, when the content of the “structural unit” is defined in terms of molar ratio, the “structural unit” is synonymous with the “monomer unit”. In the present invention, the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

  The structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group is faster in development than the structural unit a1-2 having a protected phenolic hydroxyl group protected with the acid-decomposable group. There is. Therefore, when it is desired to develop quickly, the structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group is preferred. Conversely, when it is desired to delay the development, it is preferable to use the structural unit a1-2 having a protected phenolic hydroxyl group protected with an acid-decomposable group.

<Structural unit a2 having a crosslinkable group>
Component A contains a polymer having a structural unit a2 having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. As a mode of the constituent unit having a preferred crosslinking group, represented by an epoxy group, oxetanyl _{group, -NH-CH 2 -O-R} (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) And a structural unit containing at least one selected from the group consisting of a group, an ethylenically unsaturated group, and a blocked isocyanate group, an epoxy group, an oxetanyl group, —NH—CH ₂ —O—R (R is hydrogen It is preferably at least one selected from the group consisting of a group represented by an atom or an alkyl group having 1 to 20 carbon atoms), a (meth) acryloyl group, and a blocked isocyanate group, an epoxy group, oxetanyl group, and, -NH-CH ₂ -O-R of at least one (R is representing. a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) selected from the group consisting of groups represented by There it is more preferable. Among them, in the photosensitive resin composition of the present invention, it is more preferable that the component A includes a structural unit containing at least one of an epoxy group and an oxetanyl group. In more detail, the following are mentioned.

<< Structural Unit a2-1 Having Epoxy Group and / or Oxetanyl Group >>
Component A preferably contains a polymer having a structural unit a2-1 having an epoxy group and / or an oxetanyl group. A 3-membered cyclic ether group is also called an epoxy group, and a 4-membered cyclic ether group is also called an oxetanyl group.
The structural unit a2-1 having the epoxy group and / or oxetanyl group only needs to have at least one epoxy group or oxetanyl group in one structural unit, and one or more epoxy groups and one or more oxetanyl groups. Group, two or more epoxy groups, or two or more oxetanyl groups may be included, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups. It is more preferable to have one or two oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic epoch Such compounds may be mentioned containing shea skeleton, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Acid esters, and the like, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit a2-1 having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. A monomer is preferred.

  Among these, preferred are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid ( 3-ethyloxetane-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit a2-1 having an epoxy group and / or oxetanyl group include the following structural units. R represents a hydrogen atom or a methyl group.

<< Structural unit a2-2 having an ethylenically unsaturated group >>
As one of the structural unit a2 having the crosslinkable group, there may be mentioned a structural unit a2-2 having an ethylenically unsaturated group. The structural unit a2-2 having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms. The structural unit having

  In addition, regarding the structural unit a2-2 having an ethylenically unsaturated group, refer to the description of paragraphs 0072 to 0090 of JP2011-215580A and the description of paragraphs 0013 to 0031 of JP2008-256974A. The contents of which are incorporated herein by reference.

<<<-NH-CH ₂ —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) A group having a group represented by a2-3 >>
The copolymer used in the present invention is also preferably a structural unit a2-3 having a group represented by —NH—CH ₂ —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). . By having the structural unit a2-3, a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The structural unit a2-3 is more preferably a structural unit having a group represented by the following formula a2-30.

In Formula a2-30, R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents an alkyl group having 1 to 20 carbon atoms.

R ³² is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R ³² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, an i-butyl group, an n-butyl group, and a methyl group are preferable.

-Preferred embodiment of structural unit a2-
When the polymer having the structural unit a2 does not substantially have the structural unit a1, the structural unit a2 is preferably 5 to 90% by mole in the polymer having the structural unit a2, and is preferably 20 to 80% by mole. Is more preferable.
When the polymer having the structural unit a2 has the structural unit a1, the content of the structural unit a2 is 3 to 70 mol% in terms of chemical resistance in the polymer having the structural unit a1 and the structural unit a2. Preferably, 10 to 60 mol% is more preferable.
In this invention, it is preferable to contain 3-70 mol% of structural units a2 among all the structural units of the component A, and it is more preferable to contain 10-60 mol% irrespective of any aspect.
Within the above numerical range, the cured film obtained from the photosensitive resin composition has good transparency and chemical resistance.

<Structural Unit a3 Having Acid Group>
Component A contains a polymer having a structural unit a3 having an acid group.
When component A has an acid group, it is easily dissolved in an alkaline developer, not only the developability is improved, but also the sensitivity is excellent and the fine line adhesion of the cured product after development is also excellent.
The acid group in the present invention means a proton dissociable group having a pKa smaller than 11. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Examples of the acid group used in the present invention include a carboxylic acid group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonamide group, a sulfonylimide group, and acid anhydride groups of these acid groups, And the group etc. which neutralized these acid groups and made it into salt structure are illustrated, and a carboxylic acid group and / or a phenolic hydroxyl group are preferable. Although there is no restriction | limiting in particular as said salt, An alkali metal salt, alkaline-earth metal salt, and organic ammonium salt can illustrate preferably.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. . For example, the compounds described in JP2012-88459A, paragraphs 0021 to 0023 and paragraphs 0029 to 0044 can be used, the contents of which are incorporated herein. Among these, structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferable.

As the structural unit a3 having an acid group, from the viewpoint of sensitivity, a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group is preferable, and a structural unit having a carboxyl group is more preferable.
Specific examples of the structural unit a3 having an acid group include the structural unit a1-1-1, derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, an ethylenically unsaturated group, and an acid anhydride. Examples thereof include a structural unit a1-1-2 having a structure derived from a product and a structural unit a1-2-1 having a phenolic hydroxyl group, and preferred embodiments thereof are also the same.
Among these, as the structural unit a3 having an acid group, a structural unit derived from a compound selected from the group consisting of methacrylic acid, acrylic acid and p-hydroxystyrene (represented by any one of the following formulas a3-1 to a3-3): The structural unit derived from methacrylic acid (the structural unit represented by the following formula a3-1) or the structural unit derived from acrylic acid (the structural unit represented by the following formula a3-2). It is more preferable that it is a structural unit derived from methacrylic acid (a structural unit represented by the following formula a3-1).

-Preferred embodiment of structural unit a3-
The structural unit containing an acid group is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, still more preferably 5 to 40 mol%, and more preferably 5 to 30 mol%, based on the structural units of all polymer components. Particularly preferred is 5 to 20 mol%.
When the polymer having the structural unit a3 has the structural unit a1 and the structural unit a2, the content of the structural unit a3 is preferably 1 to 30 mol% with respect to all the structural units of the polymer, and 3 to 20 More preferably, mol% is more preferable, and 5-15 mol% is still more preferable.
When the polymer having the structural unit a3 has only either the structural unit a1 or the structural unit a2, the content of the structural unit a3 is preferably 1 to 50 mol% with respect to all the structural units of the polymer. 5-45 mol% is more preferable, and 10-40 mol% is still more preferable.

<Other structural unit a4>
In the present invention, the component A may have another structural unit a4 in addition to the structural unit a1 to the structural unit a3. These structural units may contain a polymer component that satisfies at least one of A1 to A5. Further, apart from the polymer component satisfying at least one of A1 to A5, the polymer component having other structural unit a4 substantially not including the structural unit a1 to structural unit a3 may be included. . In addition to the polymer component satisfying at least one of A1 to A5, when it contains a polymer component having another structural unit a4 substantially without the structural unit a1 to structural unit a3, the other structural unit The blending amount of the polymer component having a4 is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in all polymer components.

Other monomers that constitute the structural unit a4 are not particularly limited, and examples thereof include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, and unsaturated dicarboxylic acids. Examples include diesters, bicyclounsaturated compounds, maleimide compounds, and unsaturated aromatic compounds.
The monomer which forms the other structural unit a4 can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the other structural unit a4 include styrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4-hydroxybenzoic acid ( 3-methacryloyloxypropyl) ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth Examples of the structural unit include 2-hydroxypropyl acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, and ethylene glycol monoacetoacetate mono (meth) acrylate. In addition, compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  In addition, as the other structural unit a4, a structural unit derived from a monomer having a styrene or an aliphatic cyclic skeleton is preferable from the viewpoint of electrical characteristics. Specific examples include styrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.

  Furthermore, as the other structural unit a4, a structural unit derived from a (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable. In all the structural units constituting the polymer, the content of the structural unit a4 is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less. As a lower limit, although 0 mol% may be sufficient, it is preferable to set it as 1 mol% or more, for example, and it is more preferable to set it as 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.

In the present invention, a polymer having only the structural unit a3 may be included.
As such a polymer, a resin having a carboxyl group in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain. “Substantially free” means that the weight ratio in the polymer is 1% by mass or less.

For example, benzyl (meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid Copolymer and the like.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein.
These polymers may contain only 1 type and may contain 2 or more types.

  SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON are commercially available as these polymers. UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), JONCRYL 690, JONCRYL 678, JONCRYL 67, JONCRYL 586 (above, manufactured by BASF) are used. You can also.

-Molecular weight of polymer in component A-
The molecular weight of the polymer in Component A is a polystyrene-equivalent weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 10,000 to 20,000. is there. Various characteristics are favorable in the range of said numerical value. The ratio of the number average molecular weight Mn to the weight average molecular weight Mw (dispersity, Mw / Mn) is preferably 1.0 to 5.0, and more preferably 1.5 to 3.5.
In addition, it is preferable to measure the weight average molecular weight and the number average molecular weight in the present invention by a gel permeation chromatography (GPC) method. In the measurement by gel permeation chromatography in the present invention, HLC-8020GPC (manufactured by Tosoh Corporation) is used, and TSKgel Super HZ MH, TSK gel Super HZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) are used as columns. ), And THF (tetrahydrofuran) is preferably used as an eluent.

-Method for producing polymer in component A-
Also, various methods are known for the synthesis method of the polymer in component A. To give an example, a radical polymerizable monomer used to form at least the structural unit a1 to the structural unit a3. It can synthesize | combine by superposing | polymerizing the radically polymerizable monomer mixture containing this in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.

  The content of Component A in the photosensitive resin composition of the present invention is preferably 30 to 99% by mass, and 40 to 98% by mass with respect to the total solid content other than carbon black of the photosensitive resin composition. It is more preferable that it is 60-95 mass%. The effect of this invention is show | played more as content is this range.

-Crosslinkable group equivalent in the photosensitive resin composition-
The crosslinkable group equivalent in the solid content of the photosensitive resin composition will be described.
The crosslinkable group equivalent in the organic solid content is the mass (g) of the organic solid content when 1 mol of the crosslinkable group is present in the organic solid content of the composition. A certain amount of the organic solid content of the composition is weighed and can be determined by measuring the amount of the crosslinkable group contained in the organic solid content. In addition, the organic solid content here means the solid content of an organic substance obtained by removing a pigment component such as carbon black from the solid content of the composition.
Specifically, the above measurement is performed using a sample obtained by precipitating carbon black from the photosensitive resin composition of the present invention. Regarding the precipitation of carbon black, the photosensitive resin composition may be once diluted with a solvent.
When the crosslinkable group is an epoxy group, the crosslinkable group can be determined by the same method as the measurement of the epoxy equivalent specified in JIS K7236: 2001, for example, by the method described in Japanese Patent No. 4758647. In the case of other crosslinkable groups, it can be measured in the same manner.
From the viewpoint of the cured film strength, the crosslinkable group equivalent in the photosensitive resin composition of the present invention is preferably 1,500 or less, more preferably 700 or less, and more preferably 300 or less per 1 g of organic solid content of the photosensitive resin composition. Further preferred. The lower limit is not particularly limited, but is preferably 200 or more from the viewpoint of developability.

-Acidic group equivalent in the photosensitive resin composition-
The acidic group equivalent in the solid content of the photosensitive resin composition will be described.
The acidic group equivalent in organic solid content is the mass (g) of organic solid content when 1 mol of acidic groups are present in the organic solid content of the composition. It can be determined by weighing a certain amount of the organic solid content of the composition and measuring the amount of acidic groups contained in the organic solid content. In addition, the organic solid content here means the solid content of an organic substance obtained by removing a pigment component such as carbon black from the solid content of the composition.
Specifically, measurement is performed using a sample obtained by precipitating carbon black from the photosensitive resin composition of the present invention as a sample. Regarding the precipitation of carbon black, the photosensitive resin composition may be once diluted with a solvent. The measurement of the amount of acidic groups can be determined according to the test methods for acid value, saponification value, ester value, iodine value, hydroxyl value, and unsaponified product of chemical products specified in JIS K0070: 1992.
The acidic group equivalent in the photosensitive resin composition of the present invention is preferably 10,000 or less, more preferably 5,000 or less, and still more preferably 3,500 or less per 1 g of organic solid content of the photosensitive resin composition. The lower limit is preferably 500 or more from the viewpoint of developability.

Component B: Photoacid generator The photosensitive resin composition of the present invention contains a photoacid generator as Component B.
The photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less. Most preferred is a photoacid generator that generates an acid.

  Examples of photoacid generators include trichloromethyl-s-triazines, sulfonium salts and iodonium salts (onium salts), quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. . Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation and sensitivity. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP2011-221494A. It can be illustrated.

  As an oxime sulfonate compound, that is, a compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following formula B1 can be preferably exemplified, and the contents thereof are incorporated in the present specification.

In formula B1, R ²¹ represents an alkyl group or an aryl group, and the wavy line represents a bonding site with another group. )

Any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.
As the alkyl group for R ^21, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ²¹ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or other bridged type fat It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.

  The compound containing an oxime sulfonate structure represented by the formula B1 is also preferably an oxime sulfonate compound represented by the following formula B2.

When in the formula B2, R ⁴² represents an alkyl group or an aryl group, X is an alkyl group, an alkoxy group or a halogen atom, m4 represents an integer of 0 to 3, and m4 is 2 or 3, A plurality of X may be the same or different.

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1.
In the above formula B2, m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2 A compound that is an -oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

  The compound containing an oxime sulfonate structure represented by the formula B1 is also preferably an oxime sulfonate compound represented by the following formula B3.

In Formula B3, R ⁴³ represents an alkyl group or an aryl group, and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. , N4 represents an integer of 0-5.

R ⁴³ in the above formula B3 is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro. An -n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
As n4, the integer of 0-2 is preferable and 0 or 1 is especially preferable.

  As specific examples of the compound represented by the formula B3 and preferable examples of the oxime sulfonate compound, the description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to, and the contents thereof are incorporated in the present specification.

  The compound containing an oxime sulfonate structure represented by the formula B1 is preferably a compound represented by the following formula OS-1.

In formula OS-1, R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. Represents. ^R102 represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ₂ —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ^{105 to} R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ^{121 to} R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or Represents an aryl group. Two of R ^{121 to} R ¹²⁴ may be bonded to each other to form a ring.
R ^{121 to} R ¹²⁴ are each independently preferably a hydrogen atom, a halogen atom or an alkyl group, and an embodiment in which at least two of R ^{121 to} R ¹²⁴ are bonded to each other to form an aryl group is also preferable. Can be mentioned. Among these, an embodiment in which R ^{121 to} R ¹²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

  The compound represented by the formula OS-1 is preferably a compound represented by the formula OS-2 described in paragraphs 0087 to 0089 of JP2012-163937A, for example. Incorporated in the description.

  Specific examples of the compound represented by the formula OS-1 that can be suitably used in the present invention include compounds described in paragraphs 0128 to 0132 of JP2011-221494A (exemplary compounds b-1 to b-34). However, the present invention is not limited to this.

  In the present invention, the compound containing the oxime sulfonate structure represented by the formula B1 is preferably an oxime sulfonate compound represented by the following formula OS-3, the following formula OS-4, or the following formula OS-5. .

In formula OS-3 to formula OS-5, R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ each independently represent hydrogen. An atom, an alkyl group, an aryl group or a halogen atom, R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group; the X ¹ to X ³ each independently represent an oxygen atom or a sulfur atom, the n ¹ ~n ³ each independently represents a 1 or 2, in m ¹ ~m ³ are each independently an integer of 0 to 6 Represent.

  Moreover, the compound containing the oxime sulfonate structure represented by the formula B1 is represented by any one of the general formulas OS-6 to OS-11 described in paragraph 0117 of JP2012-163937A, for example. Are particularly preferred, the contents of which are incorporated herein.

  The preferred ranges for the general formulas OS-6 to OS-11 are the same as the preferred ranges for the general formulas OS-6 to OS-11 described in paragraphs 0110 to 0112 of JP2011-221494A.

  Specific examples of the oxime sulfonate compound represented by the above formula OS-3 to the above formula OS-5 include the compounds described in paragraphs 0114 to 0120 of JP2011-221494A. It is not limited to.

  The compound containing an oxime sulfonate structure represented by the formula B1 is also preferably an oxime sulfonate compound represented by the following formula B1-4.

In Formula B1-4, R ^b1 represents an alkyl group or an aryl group, and R ^b2 represents an alkyl group, an aryl group, or a heteroaryl group. R ^{b3 to} R ^b6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. However, R ^b3 and R ^b4 , R ^b4 and R ^b5 , or R ^b5 and ^{Re 6} may combine to form an alicyclic ring or an aromatic ring. X ^b represents —O— or —S—.

R ^b1 represents an alkyl group or an aryl group. The alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
The alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable, and when the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable. Examples of the alkyl group include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. , 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
Carbon number of an aryl group becomes like this. Preferably it is 6-12, More preferably, it is 6-8, More preferably, it is 6-7. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The alkyl group and aryl group represented by R ^b1 may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), linear, branched or cyclic alkyl group (eg, methyl group, ethyl group, propyl group), alkenyl group, alkynyl group. , Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group , A nitro group, a hydrazino group, a heterocyclic group, and the like. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.

In the photosensitive resin composition of the present invention, R ^b1 is preferably an alkyl group from the viewpoint of transparency, and R ^b1 has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity. An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. . By adopting such a bulky group (particularly a bulky alkyl group) as R ^b1 , it becomes possible to further improve the transparency.
Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.

R ^b2 represents an alkyl group, an aryl group, or a heteroaryl group. The alkyl group represented by R ^b2 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, and a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
The alkyl group, aryl group, and heteroaryl group represented by R ^b2 may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which ^Rb1 represents may have.
R ^b2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. As the substituent for the phenyl group, a methyl group is preferred.

R ^{b3 to} R ^b6 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). The alkyl group represented by R ^{b3 to} R ^b6 has the same meaning as the alkyl group represented by R ^b2 , and the preferred range is also the same. The aryl group represented by R ^{b3 to} R ^b6 has the same meaning as the aryl group represented by R ^b1 , and the preferred range is also the same.
Among R ^{b3 to} R ^b6 , R ^b3 and R ^b4 , R ^b4 and R ^b5 , or R ^b5 and R ^b6 may combine to form a ring, and the ring forms an alicyclic ring or aromatic ring And a benzene ring is more preferable.
R ^{b3 to} R ^b6 are a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom), or R ^b3 and R ^b4 , R ^b4 and R ^b5 , or R ^b5 and R ^b6 are bonded. Benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, or R ^b3 and R ^b4 , R ^b4 and R ^b5 , or R ^b5 and R ^b6 are bonded It is more preferable that a benzene ring is formed.
Preferred embodiments of R ^{b3 to} R ^b6 are as follows.
Aspect 1: At least two are hydrogen atoms.
Aspect 2: The number of alkyl groups, aryl groups, or halogen atoms is one or less.
Aspect 3: R ^b3 and R ^b4 , R ^b4 and R ^b5 , or R ^b5 and R ^b6 combine to form a benzene ring.
Aspect 4: An aspect satisfying the above aspects 1 and 2 and / or an aspect satisfying the above aspects 1 and 3.

X ^b represents —O— or —S—.

  Specific examples of the formula B1-4 include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

Component B may be used alone or in combination of two or more.
In the photosensitive resin composition of the present invention, the photoacid generator is preferably used in an amount of 0.1 to 15 parts by mass, and 0.5 to 10 parts by mass with respect to 100 parts by mass of Component A in the photosensitive resin composition. It is more preferable to use a part.

Component C: Solvent The photosensitive resin composition of the present invention contains a solvent as Component C.
The photosensitive resin composition of the present invention is preferably prepared as a liquid obtained by dissolving or dispersing essential components and optional components described below in a solvent.
As the solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl. Ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like. Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A, and paragraphs 0167 to 0168 of JP2012-194290A. The solvents described are also included, the contents of which are incorporated herein.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents. , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added.
These solvents can be used alone or in combination of two or more. It is preferable that the solvent which can be used for this invention is single 1 type, or uses 2 types together.

Component C is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.
Among these, the solvent is preferably at least one solvent selected from the group consisting of propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers and esters, and includes propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether and / or Alternatively, ethyl 3-ethoxypropionate is more preferable, and propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, and ethyl 3-ethoxypropionate are particularly preferable.

  The content of the solvent in the photosensitive resin composition of the present invention is preferably 10 to 95% by mass, more preferably 50 to 95% by mass, and 60 to 90% by mass in the photosensitive resin composition. % Is more preferable.

Component D: Dispersant The photosensitive resin composition of the present invention preferably contains a dispersant as Component F. By containing the dispersant, the dispersibility of the carbon black in the resin composition can be further improved.
As the dispersant, a known dispersant can be used. For example, a known pigment dispersant can be appropriately selected and used.
As the dispersant, a polymer dispersant can be preferably used. The polymer dispersant is a dispersant having a molecular weight (weight average molecular weight) of 1,000 or more.

  As the dispersant, many types of compounds can be used. Specifically, for example, (meth) acrylic acid-based (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl Nonionic surfactants such as ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), DE Polymer dispersing agents such as Sparse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000 , 26000, 28000, etc. (AstraZeneca Co., Ltd.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103 , F108, L121, P-123 (manufactured by ADEKA Corporation) and Isonet S-20 (manufactured by Sanyo Chemical Industries), DISPERBYK 101, 103, 106, 108, 109, 111, 112, 116, 130, 140 142 , 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

In addition to the above, specific examples of the dispersant used in the photosensitive resin composition of the present invention include the following Exemplified Compound 1 to Exemplified Compound 26.
The dispersant is preferably a polymer dispersant having an acid group in the side chain, and more preferably a polymer dispersant having a carboxyl group in the side chain.
The dispersant is preferably a polymer dispersant having a graft chain in the side chain, and more preferably a polymer dispersant having an acid group and a graft chain in the side chain. The graft chain is a polymer chain different from the main chain in the side chain. As the graft chain, the number of atoms excluding hydrogen atoms per graft chain is preferably 40 to 10,000, and the number of atoms excluding hydrogen atoms per graft chain is 50 to 2,000. More preferably, the number of atoms excluding hydrogen atoms per graft chain is more preferably 60 to 1,000.

  The weight average molecular weight of Exemplified Compounds 1 to 26 in the present invention is preferably 10,000 or more and 300,000 or less, and preferably 15,000 or more and 200,000 or less, from the viewpoint of pattern peeling inhibition during development and developability. More preferably, it is 20,000 or more and 100,000 or less, more preferably 25,000 or more and 50,000 or less. In addition, the weight average molecular weight of a dispersing agent can be measured by GPC, for example.

  In the dispersion used in the photosensitive resin composition of the present invention, these Exemplified Compounds 1 to 26 are dispersion resins that impart dispersibility to carbon black, and have excellent dispersibility and affinity with a solvent due to graft chains. Therefore, the dispersibility of carbon black and the dispersion stability after aging are excellent. Moreover, when it is set as the photosensitive resin composition, since it has affinity with a solvent, a curing component, or other resin that can be used in combination, a residue is hardly generated by alkali development.

A dispersing agent may be used individually by 1 type, or may be used together 2 or more types.
The content of the dispersant in the photosensitive resin composition of the present invention is preferably in the range of 2 to 70% by mass and more preferably in the range of 5 to 50% by mass with respect to the total content of carbon black.
Moreover, a part of resin corresponding to the above-mentioned component A may function as a dispersant.

Component E: Basic Compound The photosensitive resin composition of the present invention may contain a basic compound as Component E.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraphs 0204 to 0207 of JP2011-221494A.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo [5.3.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
Among these, heterocyclic amines are preferable, and 2,4,5-triphenylimidazole and / or N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea is particularly preferable.

The basic compounds that can be used in the present invention may be used singly or in combination of two or more.
It is preferable that content of the basic compound in the photosensitive resin composition of this invention is 0.001-5 mass parts with respect to 100 mass parts of solid content other than carbon black in the photosensitive resin composition, 0 More preferably, the amount is 0.005 to 3 parts by mass.

Component F: Crosslinking agent The photosensitive resin composition of the present invention preferably contains a crosslinking agent as Component F, if necessary. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is not limited as long as it causes a crosslinking reaction by heat (except for component A). That is, a thermal crosslinking agent is preferably used as the crosslinking agent. For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated bond, a blocked isocyanate compound, or an alkoxysilane compound Etc. can be added. Especially, the compound which has 2 or more epoxy groups or oxetanyl groups in a molecule | numerator is preferable, and the compound which has 2 or more epoxy groups in a molecule | numerator is more preferable.
Further it, as the crosslinkable group in the crosslinking agent, an epoxy group, oxetanyl ^{_{group, -NH-CH 2 -OR 1,}} ( meth) acryloyl group, and at least one selected from the group consisting of blocked isocyanate groups Is preferred. R ¹ represents an alkyl group having 1 to 20 carbon atoms.

  The addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0 to 50 parts by mass with respect to 100 parts by mass of the solid content other than carbon black of the photosensitive resin composition. More preferably, it is 30 mass parts, and it is still more preferable that it is 0.5-10 mass parts. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.

<Compound having two or more epoxy groups or oxetanyl groups in the molecule>
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.

These are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) and the like are listed in JP01-221494A, paragraph 0189, etc. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN- 502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX- 313, EX-314, EX- 21, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC- 301, DLC-402 (above, manufactured by Nagase ChemteX Corporation), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, Nippon Steel Chemical Co., Ltd.) Manufactured).
These can be used alone or in combination of two or more.

  Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

<Alkoxymethyl group-containing crosslinking agent>
As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of outgas generation amount, A methyl group is particularly preferred.
Further, as the alkoxymethyl group, -NH-CH ₂ -OR 'are preferably exemplified. R ′ represents an alkyl group having 1 to 20 carbon atoms.
Among these crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferable crosslinkable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.
These alkoxymethyl group-containing crosslinking agents are available as commercial products. For example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicarax MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nicarac MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

<Block isocyanate compound>
In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably employed as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. Moreover, it is preferable that the said blocked isocyanate group is a group which can produce | generate an isocyanate group with the heat | fever of 90 to 250 degreeC.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic. Polyisocyanate may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1, 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, Isocyanate compounds such as hydrogenated 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate And prepolymer-type skeleton compounds derived from these compounds can be suitably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

Examples of the oxime compound include aldoxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

  The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (and above) , Manufactured by Asahi Kasei Chemicals Corporation, Death Module BL 100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) and the like are preferably used can do.

<Alkoxysilane compound>
The photosensitive resin composition of the present invention may contain an alkoxysilane compound as a crosslinking agent. Preferred examples of the alkoxysilane compound include trialkoxysilane compounds.
Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.

Moreover, the compound represented by the following formula can also be preferably employed.
_{^{(R 1) 4-n -Si-}} (OR 2) n
In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms having no reactive group, R ² is an alkyl group or a phenyl group having 1 to 3 carbon atoms, n represents an integer from 1 to 3 is there.
Specific examples include the following compounds. Ph represents a phenyl group.

The alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited, and known compounds can be used.
Moreover, when an alkoxysilane compound is used, the adhesiveness of the film | membrane formed with the photosensitive resin composition of this invention and a board | substrate can be improved besides the surface hardness improvement effect.

<Compound having at least one ethylenically unsaturated bond>
As the compound having at least one ethylenically unsaturated bond, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, a trifunctional or higher (meth) acrylate, or the like is preferably used. it can.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate.
Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
These compounds having at least one ethylenically unsaturated bond are used singly or in combination of two or more.
Moreover, when adding the compound which has at least 1 ethylenically unsaturated bond, it is preferable to add a radical polymerization initiator and it is more preferable to add a thermal radical polymerization initiator. Known radical polymerization initiators can be used.
Moreover, if it is a compound which has a (meth) acryl group, the bridge | crosslinking by Michael addition reaction is also possible.

Component G: Surfactant The photosensitive resin composition of the present invention may contain Component G: a surfactant.
Component G: As the surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of the surfactant used in the composition of the present invention include those described in paragraphs 0201 to 0205 of JP2012-88459A and those described in paragraphs 0185 to 0188 of JP2011-215580A. And these descriptions are incorporated herein.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.), Mega Fuck (manufactured by DIC Corporation), Florard Novec FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-242 (manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox PF-6320 (manufactured by OMNOVA), SH-8400 (manufactured by Toray Dow Corning Silicone Co., Ltd.), and footgent FTX-218G (manufactured by Neos Co., Ltd.) You can list each series.
Moreover, the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography when tetrahydrofuran (THF) is used as a surfactant contains the structural unit A and the structural unit B represented by the following formula G-1. A preferred example is a copolymer having (Mw) of 1,000 or more and 10,000 or less.

In Formula G-1, R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or 1 carbon atom. Represents an alkyl group having 4 or less, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p represents a numerical value of 10% by mass to 80% by mass. Q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.

The L is preferably a branched alkylene group represented by the following formula G-2. R ⁴⁰⁵ in Formula G-2 represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. More preferred is an alkyl group of 3. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

  The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less with respect to 100 parts by mass of the solid content other than carbon black in the photosensitive resin composition. It is more preferable that it is a mass part, and it is still more preferable that it is 0.01-3 mass parts.

Component H: Antioxidant The photosensitive resin composition of the present invention preferably contains an antioxidant.
As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Of these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing film thickness, with phenol-based antioxidants being the most preferred. preferable. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraphs 0026 to 0031 of JP-A-2005-29515, the contents of which are incorporated herein.

  Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO. -50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 , ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS 90, ADK STAB ZS 90 -91 (above, manufactured by ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Company, Ltd.), Tinuvin 405 (manufactured by BASF), and the like. Among them, ADK STAB AO-60, ADK STAB AO-80, Irganox 1726, Irganox 1035, Irganox 1098, and Tinuvin 405 can be preferably used.

It is preferable that content of antioxidant is 0.1-10 mass% with respect to 100 mass parts of solid content other than carbon black of the photosensitive resin composition, and it is 0.2-5 mass%. More preferably, it is 0.5-4 mass% especially preferable. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
Further, as additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives” (Nikkan Kogyo Shimbun Co., Ltd.), metal deactivators, and the like are used in the present invention. You may add to a resin composition.

Component I: Sensitizer The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with a photoacid generator.
The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the photoacid generator undergoes a chemical change and decomposes to generate an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (For example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (for example, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (for example, thiacarbocyanine, oxacarbocyanine), merocyanines (Eg, merocyanine, carbomerocyanine), rhodocyanins, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridineo , Chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squariums (eg, squalium), styryls, base styryls ( For example, 2- {2- [4- (dimethylamino) phenyl] ethenyl} benzoxazole), coumarins (eg, 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2, 3, 6 , 7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolidine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

The addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition, and 10 to 500 parts. It is more preferable that it is a mass part, and it is still more preferable that it is 50-200 mass parts.
Moreover, a sensitizer may be used individually by 1 type and can also use 2 or more types together.

<Other ingredients>
In addition to the above components, the photosensitive resin composition of the present invention includes an ultraviolet absorber, a metal deactivator, an acid proliferator, a development accelerator, a plasticizer, a thermal radical generator, a heat as necessary. Known additives such as acid generators, thickeners, and organic or inorganic suspending agents can be added. Moreover, as these compounds, the description of paragraph 0201-0224 of Unexamined-Japanese-Patent No. 2012-88459 can also be considered, for example, The content of these is integrated in this-application specification.

[Acid multiplication agent]
The photosensitive resin composition of the present invention may use an acid proliferating agent for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
Specific examples of such an acid proliferating agent include the acid proliferating agents described in paragraphs 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.

  The content of the acid multiplier in the photosensitive resin composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator, in view of the dissolution contrast between the exposed part and the unexposed part. To 20 to 500 parts by mass.

[Development accelerator]
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, any compound having a development acceleration effect can be used, and the development accelerator may be a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group. Preferably, a compound having a carboxyl group or a phenolic hydroxyl group is more preferable, and a compound having a phenolic hydroxyl group is most preferable.
As the development accelerator, the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.

A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
The addition amount of the development accelerator in the photosensitive resin composition of the present invention is 0 to 30 parts by mass with respect to 100 parts by mass of the solid content other than carbon black of the photosensitive resin composition from the viewpoints of sensitivity and residual film ratio. Preferably, 0.1-20 mass parts is more preferable, and it is most preferable that it is 0.5-10 mass parts.
The molecular weight of the development accelerator is preferably from 100 to 2,000, more preferably from 150 to 1,500, still more preferably from 150 to 1,000.

[Plasticizer]
The resin composition of the present invention may contain a plasticizer.
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
The plasticizer content in the resin composition of the present invention is preferably 0.1 to 30 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of component A. .

  Further, as other additives, a thermal radical generator described in paragraphs 0120 to 0121 of JP2012-8223A, and a nitrogen-containing compound and a thermal acid generator described in International Publication No. 2011-136704 are also used. The contents of which are incorporated herein by reference.

<Method for preparing photosensitive resin composition>
Each component is mixed in a predetermined ratio and by any method, stirred and dissolved to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore size of 0.2 μm.
In the present invention, a carbon black dispersion containing carbon black, a solvent, and a dispersant is prepared in advance, and the carbon black dispersion, component A and component B, and an optional component are added to provide photosensitivity. It is particularly preferable to prepare a resin composition.

(Resin pattern manufacturing method)
Next, the resin pattern manufacturing method of the present invention will be described.
The resin pattern manufacturing method of the present invention preferably includes the following steps 1 to 4, and more preferably includes the following steps 1 to 5.
Step 1: a coating step of coating the photosensitive resin composition of the present invention on a substrate;
Step 2: Solvent removal step of removing the solvent from the applied resin composition;
Step 3: An exposure step of exposing the resin composition from which the solvent has been removed to a pattern with actinic rays;
Step 4: Development step of developing the exposed resin composition and the unexposed resin composition with an aqueous developer;
Step 5: a heat treatment step of heat-treating the developed resin composition.
Each step will be described below in order.

In the coating process, it is preferable to apply the photosensitive resin composition of the present invention on a substrate to form a wet film containing a solvent. It is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning before applying the photosensitive resin resin composition to the substrate, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesion of the photosensitive resin composition to the substrate is improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, resin composite materials, ITO, Cu substrates, polyethylene terephthalate, and plastic substrates such as cellulose triacetate (TAC).
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester resin, cyclic polyolefin, Is it a synthetic resin such as aromatic ether resin, maleimide-olefin resin, cellulose, episulfide resin, etc. A substrate made of, and the like.
These substrates are rarely used in the above-described form, and usually have a multilayer laminated structure such as a TFT element formed depending on the form of the final product.

Among these, in the present invention, it is preferable that all or part of the surface of the substrate is at least one selected from the group consisting of glass, SiO, ITO, IZO, a metal film, and a metal oxide film. It is particularly preferable that all or part of the surface of the substrate is ITO.
As a result of intensive studies by the present inventors, it has been found that when all or a part of the surface of the substrate is ITO (Indium Tin Oxide), the occurrence of development residue on the ITO is particularly remarkable. . The photosensitive resin composition of the present invention has a very remarkable effect that generation of development residues can be suppressed even when all or part of the surface of the substrate is ITO.

The coating method on the substrate is not particularly limited, and for example, a method such as an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
The coating film thickness is not particularly limited and can be applied with a film thickness according to the application, but it is preferably used in the range of 0.5 to 10 μm.

Ink jet method application, compared with conventional application methods such as spin coating method and slit coating method, the amount of coating liquid used is greatly reduced, and the influence of mist adhering to the spin coating method is reduced. This is preferable from a comprehensive point of view, for example, generation of foreign matter is suppressed.
For example, the application conditions by the ink jet method may be appropriately selected depending on the composition of the photosensitive resin composition, the type of coating film to be manufactured, and the like. In order to adjust the thickness of the coating film, the discharge amount of the liquid photosensitive resin composition and the number of discharges to the same portion may be adjusted. Moreover, what is necessary is just to select suitably the shape and position which apply | coat the photosensitive resin composition as desired. There is no restriction | limiting in particular as an apparatus used for the application | coating of an inkjet system, What is necessary is just to apply a well-known inkjet coating apparatus.
Specific examples include on-demand inkjet coating apparatuses IJ-DESK-S, IJ-DESK-H (manufactured by PMT Co., Ltd.), DIMADIX Material Printer DMP2831, DMP-3000 (manufactured by FUJIFILM Dimatix), and the like. It is done.

  There is no restriction | limiting in particular as an inkjet recording device which can be used for the said inkjet coating system, The well-known inkjet recording device which can achieve the target resolution can be selected arbitrarily and used. That is, if it is a well-known inkjet recording apparatus containing a commercial item, the application | coating by the inkjet application system of the photosensitive resin composition of this invention on the board | substrate in the said application | coating process can be implemented.

Examples of the ink jet recording apparatus that can be used in the present invention include an apparatus including a composition supply system and a temperature sensor.
The ink supply system includes, for example, an original tank containing the photosensitive resin composition of the present invention, a supply pipe, a composition supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The piezo-type inkjet head preferably has a multi-size dot of 1 to 100 pl, more preferably 8 to 30 pl, preferably 320 × 320 to 4,000 × 4,000 dpi (dot per inch), more preferably 400 × 400. ˜1,600 × 1,600 dpi, more preferably 720 × 720 dpi. In the present invention, dpi represents the number of dots per 2.54 cm.
The coating film thickness is not particularly limited and can be applied with a film thickness according to the application, but it is preferably used in the range of 0.5 to 10 μm.

In the solvent removal step, it is preferable to form a dry coating film on the substrate by removing the solvent from the applied film by vacuum (vacuum) and / or heating. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are within the above ranges, the pattern adhesion is good and the residue can be reduced.
Note that the coating step and the solvent removal step may be performed in this order, simultaneously, or alternately. For example, after all the inkjet application in the application process is completed, the solvent removal process may be performed, or the substrate is heated and the solvent is removed while discharging the photosensitive resin composition by the inkjet application method in the application process. You may go.
Especially, it is preferable to perform a solvent removal process, after all the inkjet application | coating in an application | coating process is complete | finished.

In the exposure step, it is preferable to irradiate the substrate on which the coating film is provided with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce an acid group, for example, a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used. Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment (Post Exposure Bake (hereinafter also referred to as “PEB”)) can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, the acid-decomposable group in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to produce an acid group, for example, a carboxyl group or a phenolic hydroxyl group. A positive image can be formed by development without performing PEB.

In the development step, it is preferable to develop a copolymer having a liberated acid group, such as a carboxyl group or a phenolic hydroxyl group, using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having an acid group that easily dissolves in an alkaline developer, such as a carboxyl group or a phenolic hydroxyl group.
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
Preferred examples of the developer include a 0.4% by mass aqueous solution, a 0.5% by mass aqueous solution, a 0.7% by mass aqueous solution, or a 2.38% by mass aqueous solution of tetraethylammonium hydroxide.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be either a liquid piling method or a dipping method. After the development, washing with running water can be performed for 30 to 300 seconds to form a desired pattern.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, a shower rinse, a dip rinse, etc. can be mentioned.

In the heat treatment step (post-bake), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate an acid group, for example, a carboxyl group or a phenolic hydroxyl group, and a crosslinkable group, a crosslinking agent, etc. A cured film can be formed by crosslinking. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 ° C. to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to process. By proceeding with the crosslinking reaction, it is possible to form a protective film or an interlayer insulating film excellent in heat resistance, hardness and the like. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere. When using a plastic substrate, it is preferable to heat-process at 80 to 140 degreeC for 5 to 120 minutes.
Prior to the heat treatment step (post-bake), the heat treatment step can be performed after baking at a relatively low temperature (addition of a middle bake step). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Further, middle baking and post baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. As a preferable exposure amount when the post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

  Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. In the case where a cured film obtained by thermal curing in a heat treatment step is used as a dry etching resist, dry etching processing such as ashing, plasma etching, ozone etching, or the like can be performed as the etching processing.

(Cured film)
The cured film of the present invention is a film obtained by curing the photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as a light-shielding color filter. The cured film of the present invention is preferably a film obtained by the method for producing a cured product of the present invention or the resin pattern production method of the present invention, and is a film obtained by the resin pattern production method of the present invention. It is more preferable.

(Hardened product and manufacturing method thereof)
The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. As described above, the shape does not have to be a film, and may be any shape.
In addition, the cured product of the present invention may be a cured product in which the hardness is increased by removing at least a part of the solvent from the photosensitive resin composition of the present invention, but from the photosensitive resin composition of the present invention. A cured product obtained by removing the solvent and thermosetting is preferable.
Although the manufacturing method of the hardened | cured material of this invention does not have a restriction | limiting in particular, It is preferable that the following process a-process c are included at least in this order.
Step a: Application step of applying the photosensitive resin composition of the present invention on a substrate;
Step b: Solvent removal step of removing the solvent from the applied resin composition;
Step c: a heat treatment step for heat-treating the resin composition from which the solvent has been removed, or an exposure step for irradiating the resin composition from which the solvent has been removed with actinic rays.

Step a and step b are synonymous with the coating step and the solvent removal step, respectively, and the preferred embodiments are also the same.
The heat treatment step in step c is the same step as the heat treatment step except that the heat treatment target is a resin composition from which the solvent obtained in step b has been removed. The heating temperature and heating time in the heat treatment step The preferred embodiments such as heating means are also preferred.
Moreover, the exposure process in the process c is the same process as the said exposure process except that it is not necessary to perform exposure in a pattern form. In the exposure step in step c, it is preferable to expose the entire surface of one side of the resin composition from which the solvent has been removed.
Moreover, it is preferable that the hardened | cured material of this invention is the hardened | cured material obtained by the resin pattern manufacturing method of this invention.

  The cured product of the present invention includes a color filter in a liquid crystal display device or an organic EL device, an insulating film in the liquid crystal display device, a spacer for keeping the thickness of the liquid crystal layer constant, and a structural member of a MEMS (Micro Electro Mechanical Systems) device. It can be suitably used for electronic materials such as antireflection films for various substrates and wirings.

<Light-shielding color filter>
The light-shielding color filter of the present invention is a light-shielding color filter obtained by curing the photosensitive resin composition of the present invention, and is a light-shielding color filter manufactured by the resin pattern manufacturing method of the present invention. preferable.
The light-shielding color filter of the present invention is formed using the cured film of the present invention. The light-shielding color filter formed using the cured film of the present invention is excellent in light-shielding properties.
The optical density per 1 μm thickness of the light-shielding color filter obtained by curing the photosensitive resin composition of the present invention is preferably 2.0 or more and 6.0 or less from the viewpoint of sensitivity and fine wire adhesion. 0 or more and 5.0 are more preferable.

The light-shielding color filter of the present invention is suitably used as a black matrix. The film thickness of the black matrix is not particularly limited, but from the viewpoint of obtaining the effect of the present invention more effectively, the film thickness after drying is preferably 0.2 μm or more and 10 μm or less, and 0.4 μm or more and 5 μm or less. More preferably, it is 0.6 μm or more and 5 μm or less.
The line width of the black matrix is not particularly limited, but is preferably from 0.5 μm to 500 μm, more preferably from 0.7 μm to 20 μm, and even more preferably from 1.0 μm to 5 μm.

Since the light-shielding color filter of the present invention uses the photosensitive resin composition of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition is excellent in development resistance. Therefore, it is possible to form a high-resolution pattern that has excellent exposure sensitivity, good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape.
Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a smartphone having a resolution higher than FHD, a high-resolution CCD device exceeding 5 million pixels, a CMOS, or the like. That is, the light-shielding color filter of the present invention is preferably applied to a liquid crystal display device, an organic EL display device, and a solid-state image sensor.

(Liquid crystal display device)
The liquid crystal display device of the present invention comprises the cured product of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a light-shielding color filter or an insulating film formed using the photosensitive resin composition of the present invention, and is a known liquid crystal display device having various structures. Can be mentioned.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
The liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtical Alignment) method, IPS (In-Place-Switching) method, FFS (Fringe Field Switching) method, OCB (OCB). Optically Compensated Bend) method.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) described in JP-A-2005-284291, It can be used as the organic insulating film (212) described in Japanese Unexamined Patent Application Publication No. 2005-346054.
Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer alignment may be supported by the PSA (Polymer Sustained Alignment) technique described in JP2003-149647A or JP2011-257734A.

(Organic EL display device)
The organic EL display device of the present invention comprises the cured product of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic materials having various structures. An EL display device and a liquid crystal display device can be given.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

(Touch panel and touch panel display device)
The touch panel of the present invention is a touch panel having at least a cured film obtained by curing the photosensitive resin composition of the present invention, and all or part of the insulating layer and / or the protective layer cures the photosensitive resin composition of the present invention. It is preferable that the touch panel is a cured film. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an electrode, an insulating layer, and / or a protective layer at least.
The touch panel display device of the present invention is a touch panel display device having at least a cured film obtained by curing the photosensitive resin composition of the present invention, and is preferably a touch panel display device having the touch panel of the present invention.
As the touch panel of the present invention, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, and an electromagnetic induction method may be used. Among these, the electrostatic capacity method is preferable.
Examples of the capacitive touch panel include those disclosed in JP 2010-28115 A and those disclosed in International Publication No. 2012/057165. As another touch panel, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7 and FIG. 8 of JP-T-2012-517051), a so-called on-cell type (for example, JP-A-2012-43394). FIG. 14, FIG. 2 (b) of International Publication No. 2012/141148, OGS type, TOL type, and other configurations (for example, FIG. 6 of JP 2013-164871 A).

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
MATHF: tetrahydrofuran-2-yl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MACHOE: 1- (cyclohexyloxy) ethyl methacrylate (synthetic product)
MATHP: tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
PHSEVE: 1-ethoxyethyl ether of p-hydroxystyrene (synthetic product)
PHSTHF: tetrahydrofuranyl ether of p-hydroxystyrene (synthetic product)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
NBMA: n-butoxymethylacrylamide (manufactured by Mitsubishi Rayon Co., Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
PHS: p-hydroxystyrene (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate (Methoxypropyl acetate manufactured by Showa Denko KK)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

MATHF was synthesized according to the synthesis example described in paragraph 0187 of JP2013-80203A.
MACHOE was synthesized in the same manner as MATH, except that 2-dihydrofuran was changed to the corresponding compound.
PHSEVE was synthesized by changing methacrylic acid in the MAEVE synthesis method to 4-hydroxystyrene.
PHSTHF was synthesized by changing methacrylic acid in the MATHF synthesis method to 4-hydroxystyrene.

<Synthesis of Polymer P-1>
PGMEA was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. In the solution, 40 molar equivalents of MATHF, 50 molar equivalents of GMA, 10 molar equivalents of MAA, and V-65 (corresponding to 4 mol% with respect to 100 mol% in total of all monomer components) were dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 2 hours. Thereby, polymer P-1 was obtained. The ratio of PGMEA to the total amount of other components was 60:40. That is, a polymer solution having a solid content concentration of 40% was prepared.

<Synthesis of Polymers P-2 to P-15>
Other polymers were synthesized in the same manner as the synthesis of polymer P-1, except that the types of monomers used were changed as shown in Table 1 below.

<Carbon black dispersion>
A carbon black dispersion having the following composition was used.
・ Carbon black (Nexex 35, manufactured by Degussa): 50%
・ The following dispersant 1: 5%
Propylene glycol monomethyl ether acetate: 45%

Example 1
<Preparation of photosensitive resin composition>
The composition shown in Table 2 was mixed and mixed to obtain a uniform solution, and then filtered using a polyethylene filter having a pore size of 0.2 μm to prepare a photosensitive resin composition of Example 1. . The solvent was added so that the solid content concentration of the photosensitive resin composition was 20% by mass.
Various evaluations described later were performed using the obtained photosensitive resin composition. The evaluation results are shown in Table 2 described later. In addition, the numerical value of each compounding quantity of Table 2 represents the mass part of solid content, and content of carbon black is content with respect to the total solid content of the photosensitive resin composition.

(Examples 2-14 and Comparative Examples 1-4)
The photosensitive resin compositions of Examples 2 to 14 and Comparative Examples 1 to 4 were prepared by the same method as in Example 1 except that the composition in Example 1 was changed to the composition described in Table 2 below. .

<Evaluation>
The following evaluation was performed using each obtained photosensitive resin composition of Examples 1-14 and Comparative Examples 1-4. The evaluation results are shown in Table 3.

-Sensitivity evaluation-
The obtained photosensitive resin composition is spin-coated on a glass substrate at a rotational speed of 1.4 μm after removal of the solvent, and after removal of the solvent, it is exposed with an L & S pattern mask of 3 μm line, 3 μm space, and alkali development. The exposure amount that can be developed with a liquid and can form an L & S pattern of 3 μm line and 3 μm space with a mask bias of 1: 1 was evaluated as sensitivity. The ranks of the evaluation values are as follows.
A ··· 100mJ / cm ² or less B ··· 100mJ / cm ^2, greater 150 mJ / cm ² or less C ··· 150mJ / cm ^2, greater 200 mJ / cm ² or less (more is a practical level)
D: More than 200 mJ / cm ² and 500 mJ / cm ² or less E: Resolution could not be achieved even when the exposure amount was increased from 500 mJ

-Evaluation of fine wire adhesion after development-
About the board | substrate which performed the said sensitivity evaluation, arbitrary five places were observed with the optical microscope, and it evaluated by the number of the defects (location where the matrix pattern is disconnected) in a visual field. The ranks of the evaluation values are as follows.
A: No defects at all B: Defects from 1 to 5 (practical level)
C: 6 to 19 defects D: 20 or more defects

-Optical density (OD) evaluation-
The obtained photosensitive resin composition was spin-coated on a glass substrate at an arbitrary number of revolutions, and after removing the solvent, baked at 250 ° C. for 1 hour to prepare a baked film (solid film) having a thickness of 1 μm. The OD (Optical Density) value and the actual film thickness of the fired film were measured, and the OD value at a film thickness of 1 μm was calculated. The OP value was measured with a transmission densitometer (BMT-1 (manufactured by Sakata Inx Engineering)).

Details of the abbreviations described in Table 2 other than those described above are described below.
B-1: DTS-105 (triarylsulfonium salt, manufactured by Midori Chemical Co., Ltd.)
B-2: CGI1397 (manufactured by BASF Japan Ltd., the following compound)
B-3: PAI-101 (manufactured by Midori Chemical Co., Ltd., the following compound)
B-4: The following compound B-5: The following compound

<Synthesis of Compound B-4>
The compound was synthesized according to the method described in paragraph 0239 of JP2013-182077A.

<Synthesis of Compound B-5>
4.0 g of 1-amino-2-naphthol hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) is suspended in 16 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) and sodium hydrogen carbonate (Wako Pure Chemical Industries, Ltd.). After adding 3.4 g, 4.9 g of methyl 4,4-dimethyl-3-oxovalerate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise and heated at 120 ° C. for 2 hours in a nitrogen atmosphere did. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-5- 2A. Crude B-5-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-5-2A.
B-5-2A (1.7 g) and p-xylene (6 mL) were mixed, and 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added at 140 ° C. Heated for 2 hours. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated, and the organic phase was dried over magnesium sulfate, filtered and concentrated to give crude B-5-2B.
Tetrahydrofuran (THF) (2 mL) and the whole amount of crude B-5-2B were mixed, and 2 mL hydrochloric acid / THF solution 6.0 mL under ice-cooling, then isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g) Was added dropwise and the mixture was heated to room temperature (25 ° C.) and stirred for 2 hours. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic layer was washed with water, dried over magnesium sulfate, filtered, and concentrated to obtain intermediate crude B-5- 2C.
The total amount of intermediate crude B-5-2C was mixed with acetone (10 mL), and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (1.2 g) and p-toluenesulfonyl chloride (Tokyo Chemical Industry Co., Ltd.) under ice cooling. )) (1.4 g) was added, and the mixture was warmed to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-5. Crude B-5 was reslurried with cold methanol, filtered and dried to obtain B-5 (1.2 g).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-5 is δ = 8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7. -7.6 (m, 2H), 7.6-7.5 (m, 1H), 7.4 (d.2H), 2.4 (s, 3H), 1.4 (s, 9H) there were.

C-1: PGMEA (propylene glycol monomethyl ether acetate)
S-1: The above carbon black dispersion E-1: Diazabicyclononene (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-2: N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea (CMTU, the following compound, manufactured by Toyo Kasei Kogyo Co., Ltd.)

F-1: γ-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)
F-2: Bis (triethoxysilylpropyl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.)
F-3: jER157S65 (phenol novolac type epoxy resin, manufactured by Mitsubishi Chemical Holdings Corporation)
F-4: Celoxide 2021P (3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation)
F-5: Duranate 17B-60P (block isocyanate compound, manufactured by Asahi Kasei Chemicals Corporation)
W-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC Corporation)

(Example 15)
<Production of color filter>
-Formation of black matrix-
The photosensitive resin composition produced in Example 1 was applied to the washed glass substrate using a slit coater at a coating speed of 120 mm / second.
Next, after heating (prebaking treatment) at 80 ° C. for 120 seconds using a hot plate, exposure is performed at 50 mJ / cm ² using a proximity type exposure machine (model number LE5565A, manufactured by Hitachi High-Technologies Corporation). did.
Then, it was shower-developed with a 1.0% developer of potassium hydroxide developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.) for 50 seconds and washed with pure water.
Next, a post-baking process is performed in a 220 ° C. clean oven for 40 minutes, the color pixel formation region opening is 15 μm × 45 μm, the black matrix thickness is 1.2 μm, and the black matrix line width is about 5 μm. Formed.

-Preparation of coloring composition-
In accordance with the method described in paragraphs 0173 to 0185 of JP2009-199066, the photosensitive coloring composition coating liquid CR-1 for red, the photosensitive coloring composition coating liquid CG-1 for green, and for blue Photosensitive coloring composition coating liquid CB-1 was prepared.

-Formation of colored pixels-
The obtained photosensitive coloring composition coating solution CR-1 for red was applied to the black matrix forming surface side of the black matrix substrate. Specifically, as in the case of black matrix formation, the spacing between the slit and the black matrix substrate and the discharge amount are adjusted so that the layer thickness of the photosensitive coloring composition layer after post-baking is about 2.1 μm. Then, coating was performed at a coating speed of 100 mm / second.

-Colored layer pre-baking step, colored layer exposure step-
Next, after heating at 100 ° C. for 120 seconds using a hot plate, exposure was performed at 90 mJ / cm ² using a proximity type exposure machine.
Then, the shower pressure was set to 0.2 MPa with 1.0% developer of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials), developed for 45 seconds, and washed with pure water did.
Next, post baking was performed for 30 minutes in a 220 ° C. clean oven to form heat-treated red pixels.

A green pixel and a blue pixel were formed in the same manner to obtain a color filter.
The black matrix in the obtained color filter was thin but excellent in light shielding properties and high in surface hardness.

(Examples 16 to 28)
A color filter was produced in the same manner as in Example 15 except that the photosensitive resin composition produced in Example 1 was changed to the photosensitive resin composition produced in Examples 2-14, respectively.
Each black matrix in the obtained color filter was a thin film but excellent in light shielding properties and high in surface hardness.

Claims (15)

As component A, a polymer component satisfying at least one of the following A1 to A5,
As component B, a photoacid generator,
As component C, a solvent, and
Carbon black as component S,
Content of component S is 35-60 mass% with respect to the total solid content of the photosensitive resin composition, The photosensitive resin composition characterized by the above-mentioned.
A1: Polymer having structural unit a1 having an acid group protected by an acid-decomposable group, structural unit a2 having a crosslinkable group, and structural unit a3 having an acid group A2: acid group is an acid-decomposable group Polymer having structural unit a1 having protected group and structural unit a3 having acid group, and polymer having structural unit a2 having crosslinkable group and structural unit a3 having acid group A3: Acid group is acid A polymer having a structural unit a1 having a group protected by a decomposable group, and a polymer having a structural unit a2 having a crosslinkable group and a structural unit a3 having an acid group A4: the acid group is an acid-decomposable group Polymer having structural unit a1 having protected group and structural unit a3 having acid group, and polymer having structural unit a2 having crosslinkable group A5: Group in which acid group is protected by acid-decomposable group A structural unit a1 having A polymer having a structural unit a2 having a crosslinkable group, and a polymer having a structural unit a3 having an acid group The photosensitive resin composition according to claim 1, wherein the crosslinkable group is at least one group selected from the group consisting of an epoxy group, an oxetanyl group, and —NH—CH ₂ —OR.
However, said R represents a C1-C20 alkyl group.   The photosensitive resin composition of Claim 1 or 2 whose acidic group equivalent of the photosensitive resin composition is 500-10,000 per 1g of organic solid content.   The photosensitive resin composition of any one of Claims 1-3 whose crosslinkable group equivalent of the photosensitive resin composition is 200-1,500 per g of organic solid content.   The photosensitive resin composition of any one of Claims 1-4 which further contains a dispersing agent as component D.   The photosensitive resin composition of any one of Claims 1-5 whose component A is a polymer component which satisfy | fills said A1 and / or A2.   The photosensitive resin composition of any one of Claims 1-6 whose component A is a polymer component which satisfy | fills said A1. The manufacturing method of the hardened | cured material characterized by including at least process a-process c in this order.
Step a: Application step of applying the photosensitive resin composition according to any one of claims 1 to 7 on a substrate Step b: Solvent removal step of removing the solvent from the applied resin composition Step c: Solvent Heat treatment step of heat-treating the resin composition from which the solvent has been removed, or exposure step of irradiating the resin composition from which the solvent has been removed with actinic rays A resin pattern manufacturing method comprising at least steps 1 to 4 in this order.
Process 1: Application | coating process of apply | coating the photosensitive resin composition of any one of Claims 1-7 on a board | substrate Process 2: The solvent removal process of removing a solvent from the apply | coated resin composition Process 3: Solvent Step of exposing the resin composition from which the resin has been removed to form a pattern with actinic rays Step 4: Development step of developing the exposed resin composition and the unexposed resin composition with an aqueous developer   The hardened | cured material obtained by the manufacturing method of the hardened | cured material of Claim 8, or the resin pattern manufacturing method of Claim 9.   The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-7.   The cured film according to claim 11, which is a light-shielding color filter.   A liquid crystal display device having the cured film according to claim 11.   An organic EL display device having the cured film according to claim 11.   A touch panel display device comprising the cured film according to claim 11.