JP7188115B2 - Alkali-soluble resin, photosensitive resin composition, cured product, and image display device - Google Patents

Description

TECHNICAL FIELD The present invention relates to an alkali-soluble resin, a photosensitive resin composition, a cured product, and an image display device. In particular, an alkali-soluble resin, a photosensitive resin composition, a cured product obtained by curing thereof, and the cured product, which has good linearity and can suppress line width change during heat curing, and is suitable for forming a high-definition pattern. It relates to an image display device having The photosensitive resin composition of the present invention is particularly suitable as a photosensitive resin composition for forming a black matrix (hereinafter sometimes abbreviated as "BM") capable of forming fine fine lines.

A color filter is usually formed by forming a black matrix on the surface of a transparent substrate such as glass or plastic, and then sequentially forming pixels of three or more different colors such as red, green, and blue in a lattice or stripe pattern. It is formed in a pattern such as a shape or a mosaic shape. The pattern size varies depending on the application of the color filter and each color, but is usually about 5 to 700 μm.

A pigment dispersion method is currently known as a representative method for manufacturing color filters. When a color filter is produced by a pigment dispersion method, first, a photosensitive resin composition containing a black pigment such as carbon black is coated on a transparent substrate, dried, imagewise exposed and developed, and then heated to a high temperature of 200°C or higher. The BM is formed by thermally curing (curing and baking) by processing. Pixels are formed by repeating this for each color such as red, green, and blue, and a color filter having BM and pixels is formed.
BM is generally arranged in a grid, stripe, or mosaic pattern between red, green, and blue pixels, and serves to improve contrast or prevent light leakage by suppressing color mixture between pixels. be. Therefore, BM is required to have a high light shielding property.

In recent years, the output of backlights has tended to decrease in order to save energy and extend the life of mobile batteries. is in progress. Furthermore, in the liquid crystal display market, miniaturization such as tablets has become mainstream, and there is an increasing demand for high resolution in large-sized televisions. For these reasons as well, there is an increasing demand for higher definition of BM, and the line width of BM fine lines is now required to be around 6 μm from around 10 μm in the past.

On the other hand, in order to form a BM with a desired line width, it is necessary that the line width changes little during the heat curing process performed after exposure and development. For example, Patent Literature 1 describes that by using a heat-resistant resin having a softening point of 130° C. or higher together with an alkali-soluble resin, it is possible to form a BM that is less susceptible to shape change due to heating.

JP 2017-198918 A

As described above, there is a strong demand for thinning of BM in recent years, but in order to realize thinning, there is a problem that cannot be achieved simply by narrowing the exposure mask pattern.
In the line width management of BM, it is often managed so that it falls within the upper and lower limits (for example, 95% to 105%) with the design line width as the standard (100%). The effective control range is narrowed. Therefore, deterioration of linearity must be avoided from the viewpoint of manufacturing yield.

Further, the fine line pattern is heat-cured (cured and baked) by high-temperature treatment, but the resin component once softens and flows before the thermal cross-linking reaction begins, causing a phenomenon in which the line width increases. In this case, in order to obtain fine lines with a designed line width, it is necessary to form a fine line pattern that is thinner than the designed line width by the increase in line width during development. Therefore, the greater the increase in line width due to the flow, the more difficult it is to form fine lines, leading to a decrease in manufacturing yield.

Therefore, there is a demand for a photosensitive resin composition capable of suppressing line width change during heat curing (curing and baking) without deteriorating the linearity of fine lines.
When the present inventors examined the photosensitive resin composition described in Patent Document 1, although the increase in line width due to flow during heat curing was suppressed, the fine line pattern was accompanied by deterioration in linearity and was not satisfactory. It was found that formation of fine line patterns becomes difficult.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an alkali-soluble resin which has good linearity and can suppress line width change during heat curing (curing and baking).

As a result of intensive studies by the present inventors to solve the above problems, the above problems were solved by setting the softening point of the alkali-soluble resin and the storage elastic modulus G' obtained by dynamic viscoelasticity measurement to specific ranges. I found what I can do. That is, the gist of the present invention resides in the following.

[1] An alkali-soluble resin satisfying the following (I) and (II).
(I) Softening point of 100° C. or less (II) Minimum value of storage elastic modulus G′ obtained by dynamic viscoelasticity measurement of 2×10 ³ Pa or more

[2]
The alkali-soluble resin according to [1], which has a partial structure represented by the following general formula (1).

(In Formula (1), * represents a bond. The benzene ring in Formula (1) may be further substituted with any substituent.)

[3] The alkali-soluble resin according to [1] or [2], which has a partial structure represented by the following general formula (3).

(In Formula (3), R ¹ represents a hydrogen atom or a methyl group. * represents a bond.)

[4] A photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, and (c) a photopolymerization initiator,
A photosensitive resin composition, wherein (a) the alkali-soluble resin comprises the alkali-soluble resin according to any one of [1] to [3].

[5] The photosensitive resin composition according to [4], further comprising (d) a colorant.
[6] The photosensitive resin composition according to [5], wherein the (d) colorant contains a black pigment.
[7] A cured product obtained by curing the photosensitive resin composition according to any one of [4] to [6].
[8] An image display device comprising the cured product of [7].

According to the present invention, it is possible to provide an alkali-soluble resin that has good linearity and is capable of suppressing line width change during heat curing.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL (Electro Luminescence) element provided with the color filter of the present invention. FIG. 2 is a graph of dynamic viscoelasticity measurement of alkali-soluble resin (1) (vertical axis: storage elastic modulus G', horizontal axis: temperature).

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.
In the present invention, "(meth)acryl" means "acryl and/or methacryl", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

In the present invention, "total solid content" means all components other than the solvent contained in the photosensitive resin composition or the ink described later.
In the present invention, the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).
In the present invention, unless otherwise specified, the "amine value" represents the amine value in terms of effective solid content, and is a value represented by the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant. is. In addition, the measuring method will be described later.
Moreover, in the present invention, the term "carboxylic acid residue" means a group remaining after removing all carboxyl groups from a carboxylic acid compound. For example, the carboxylic acid residue in the carboxylic acid compound represented by A-COOH means a monovalent group represented by A. Similarly, "polyhydric alcohol residue" means a group remaining after removing all hydroxyl groups from a polyhydric alcohol compound. The term "polyvalent methylol residue" means a group remaining after removing all methylol groups ₍ --CH.sub.2--OH groups) from a polyvalent methylol compound.
Moreover, in this specification, a bond may be represented using "*". Numerical ranges are sometimes expressed using "-", which means a numerical range including upper and lower limits.

<Alkali-soluble resin (A)>
The alkali-soluble resin of the present invention (hereinafter sometimes referred to as "alkali-soluble resin (A)") satisfies the following (I) and (II).
(I) The softening point is 100° C. or lower (II) The minimum value of the storage elastic modulus G′ obtained by dynamic viscoelasticity measurement is 2×10 ³ Pa or higher

It is believed that the alkali-soluble resin (A) satisfies the above (I) so that the photocrosslinked film has appropriate flexibility and the linearity of the pattern after development is improved. In addition, it is believed that the movement of the main chain of the alkali-soluble resin (A) is large, photo-crosslinking between the alkali-soluble resins proceeds during exposure, and development adhesion is improved.
Further, when the alkali-soluble resin (A) satisfies the above (II), as the resin starts to soften, gelation due to thermal cross-linking between the alkali-soluble resins (A) begins to proceed predominantly, flow is suppressed, and heating It is thought that it is possible to suppress the change in line width during curing.

Among alkali-soluble resins, those having a structure in which the main chains are capable of interacting with each other at multiple points, and the polymerizable groups are close to each other so that cross-linking easily progresses tend to satisfy the above (I) and (II). There is For example, having a skeleton in which rings capable of π-π interaction are arranged close to each other, such as a fluorene ring, and polymerizable groups are arranged on both sides of the skeleton, the above (I) and ( II) tends to satisfy both.

The softening point of the alkali-soluble resin (A) is not particularly limited as long as it is 100° C. or lower, but is preferably 98° C. or lower, more preferably 96° C. or lower, and further preferably 95° C. or lower. The temperature is preferably 50°C or higher, more preferably 60°C or higher, even more preferably 70°C or higher, even more preferably 80°C or higher, and particularly preferably 90°C or higher. preferable. When it is equal to or less than the above upper limit, the linearity tends to be improved, and when it is equal to or more than the above lower limit, the adhesiveness of the coating film tends to decrease and the handleability tends to be improved.

Although the method for measuring the softening point is not particularly limited, it is preferably measured by dynamic viscoelasticity measurement. For example, using a rheometer, the storage elastic modulus G' is measured while increasing the temperature at 5°C/min in the temperature range of 70 to 230°C. The softening point is the first inflection point at which the temperature rises and the curve becomes downward convex. Specifically, the methods and conditions described in Examples can be employed.

On the other hand, the minimum value of the storage elastic modulus G′ of the alkali-soluble resin (A) obtained by dynamic viscoelasticity measurement is not particularly limited as long as it is 2×10 ³ Pa or more, and 2.3×10 ³ Pa. 2.6 × 10 ³ Pa or more is more preferable, 2.8 × 10 ³ Pa or more is more preferable, 1 × 10 ⁵ Pa or less is preferable, 5 × 10 ⁴ Pa or less is more preferable, 1 ×10 ⁴ Pa or less is more preferable. When it is at least the lower limit, deformation during curing tends to be suppressed, and when it is at most the upper limit, the linearity of the pattern after development tends to be improved.

Although the method for measuring the minimum value of the storage elastic modulus G' is not particularly limited, it is preferably measured by dynamic viscoelasticity measurement. For example, using a rheometer, the storage elastic modulus G' is measured while increasing the temperature at 5°C/min in the temperature range of 70 to 230°C, and the minimum value from the temperature change graph of the obtained storage elastic modulus G' can be obtained by reading Specifically, the methods and conditions described in Examples can be employed.

In addition, the alkali-soluble resin (A) has a storage modulus G′ at 220° C. of preferably 1×10 ⁴ Pa or more, more preferably 1×10 ⁵ Pa or more, further preferably 1×10 ⁶ Pa or more, and , preferably 1×10 ⁷ Pa or less, more preferably 5×10 ⁶ Pa or less. By setting it to the above lower limit or more, the strength of the thermoset film tends to increase, and by setting it to the above upper limit or less, it is possible to prevent the thermoset film from becoming too hard and brittle, resulting in patterning. Tend.

The weight average molecular weight of the alkali-soluble resin (A) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, still more preferably 3000 or more, particularly preferably 4000 or more, and preferably 20000 or less, more preferably 15000 or less. It is preferably 10,000 or less, more preferably 8,000 or less, and particularly preferably 6,000 or less. When it is at least the above lower limit, there is a tendency to suppress the insertion of patterns after development, and when it is at most the above upper limit, there is a tendency to suppress deterioration of resolubility.

The acid value of the alkali-soluble resin (A) is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 80 mgKOH/g or more, and preferably 200 mgKOH/g or less, and 150 mgKOH/g. The following is more preferable, and 120 mgKOH/g or less is even more preferable. When it is at least the lower limit, the solubility during development tends to be good, and when it is at most the upper limit, the storage stability tends to be good.

The double bond equivalent (g/mol) of the alkali-soluble resin (A) is not particularly limited, but is preferably 1000 or less, more preferably 900 or less, still more preferably 800 or less, and preferably 120 or more, more preferably 300 or more. Preferably, 400 or more is more preferable. The sensitivity tends to be improved by making it equal to or less than the above upper limit, and curing shrinkage tends to be suppressed by making it equal to or more than the above lower limit.
The double bond equivalent of the resin can be calculated from the following formula (x).

(double bond equivalent of resin) =
(Molecular weight of resin)/(Number of ethylenically unsaturated double bonds per resin molecule) (x)

The chemical structure of the alkali-soluble resin (A) is the solubility of the exposed area and the non-exposed area to alkali development after the coating film obtained by coating and drying the photosensitive resin composition containing the alkali-soluble resin (A) is exposed. is not particularly limited as long as it changes and satisfies the above (I) and (II), but it preferably has a carboxyl group. Moreover, from the viewpoint of photocrosslinking, it is preferable to have an ethylenically unsaturated group.
In particular, an epoxy (meth)acrylate resin having a carboxyl group is preferable from the viewpoint of satisfying both (I) and (II). In the epoxy (meth)acrylate resin having a carboxyl group, the main chains interact with each other at multiple points, so that the (meth)acrylate groups are also close to each other and the crosslinking reaction proceeds easily, so the above (I) and (II) ) tends to be satisfied.

An epoxy (meth)acrylate resin having a carboxyl group is produced by a reaction of a reaction product of an epoxy resin with an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group. It is a resin obtained by further reacting polybasic acid and/or its anhydride with the resulting hydroxyl group. Further, before reacting the polybasic acid and/or its anhydride with a hydroxyl group, after reacting a compound having two or more substituents capable of reacting with the hydroxyl group, the polybasic acid and/or its anhydride Resins obtained by reacting are also included in epoxy (meth)acrylate resins. The epoxy (meth)acrylate resin also includes a resin obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a reactive functional group.

Thus, the epoxy (meth)acrylate resin has substantially no epoxy group in terms of its chemical structure, and is not limited to "(meth)acrylate", but is made from an epoxy resin, and Since "(meth)acrylate" is a representative example, the name is used in this way according to common practice.

Examples of the epoxy (meth)acrylate resin having a carboxyl group include the following epoxy (meth)acrylate resin (A-1) and/or epoxy (meth)acrylate resin (A-2).

<Epoxy (meth)acrylate resin (A-1)>
Obtained by adding an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and/or its anhydride. alkali-soluble resin.
<Epoxy (meth)acrylate resin (A-2)>
An α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and a polyhydric alcohol and a polybasic acid and/or its anhydride are added. Alkali-soluble resin obtained by reacting.

Epoxy resins used as raw materials include, for example, epoxy resins having a fluorene ring in the molecule. Having a fluorene ring in the molecule tends to increase internal curability during exposure. In particular, it preferably has a fluorene ring linked by a hydrocarbon group having 6 or less carbon atoms in the molecule, more preferably has a fluorene ring linked by a hydrocarbon group having 4 or less carbon atoms, and has 2 or less carbon atoms. It is more preferable to have a fluorene ring linked by a hydrocarbon group. Having fluorene rings linked by short-chain hydrocarbon groups in this way tends to accelerate the cross-linking reaction between the main chains during heat curing. Specifically, one having a partial structure represented by the following formula (1) is preferable.

(In formula (1), n represents an integer of 1 to 6. * represents a bond. The benzene ring in formula (1) may be further substituted with any substituent.)

Although n in formula (1) is not particularly limited as long as it is an integer of 1 to 6, it is preferably 4 or less, more preferably 2 or less, from the viewpoint of increasing the number of π-π interactions.

Examples of optional substituents that the benzene ring in formula (1) may have include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group and the like. , is preferably unsubstituted from the viewpoint of strengthening the π-π interaction.

On the other hand, from the viewpoint of enhancing the π-π interaction by the fluorene ring, it may have a partial structure represented by the following formula (2).

(In formula (2), l and m each independently represent an integer of 1 to 6. * represents a bond. The benzene ring in formula (2) may be further substituted with an optional substituent. good.)

Although l and m in formula (2) are each independently an integer of 1 to 6, they are preferably 4 or less, more preferably 2 or less, from the viewpoint of increasing the number of π-π interactions.

Examples of optional substituents that the benzene ring in formula (2) may have include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a s-butyl group. , is preferably unsubstituted from the viewpoint of strengthening the π-π interaction.

Specific examples of epoxy resins include those having the following chemical structures.

α,β-unsaturated monocarboxylic acids and/or α,β-unsaturated monocarboxylic acid esters having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyladipic acid, 2 - (meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxyethyl maleate, 2-(meth) acryloyloxypropyl succinate, 2 - (meth) acryloyloxypropyl adipate, 2-(meth) acryloyloxypropyl tetrahydrophthalate, 2-(meth) acryloyloxypropyl phthalate, 2-(meth) acryloyloxypropyl maleate, 2- (Meth) acryloyloxybutyl succinate, 2-(meth) acryloyloxybutyl adipate, 2-(meth) acryloyloxybutyl hydrophthalate, 2-(meth) acryloyloxybutyl phthalate, 2-( As meth)acryloyloxybutyl maleate and (meth)acrylic acid esters, lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone are added to (meth)acrylic acid and the terminal A monomer having one hydroxyl group at the end, or a monomer having one hydroxyl group at the end such as hydroxyalkyl (meth) acrylate, or a terminal having one hydroxyl group such as pentaerythritol tri (meth) acrylate Acid (anhydride) such as (anhydride) succinic acid, (anhydride) phthalic acid, (anhydride) maleic acid is added to a compound having a hydroxyl group, and one or more ethylenically unsaturated groups and one carboxyl group at the end are added. (Meth)acrylic acid esters having (Meth)acrylic acid dimers and the like are also included.
Among these, (meth)acrylic acid is particularly preferable from the viewpoint of sensitivity.

As a method for adding an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known technique can be used. For example, an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group is reacted with an epoxy resin at a temperature of 50 to 150° C. in the presence of an esterification catalyst. be able to. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride can be used. .

The epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used singly or in combination of two. The above may be used in combination.
The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. , more preferably in the range of 0.7 to 1.1 equivalents.
By setting the amount of the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group to the above lower limit or more, the amount of the unsaturated group introduced becomes sufficient, and the amount of unsaturated groups continues to increase. Reaction with a basic acid and/or its anhydride becomes sufficient, and there is a tendency that a large amount of epoxy groups can be suppressed from remaining. On the other hand, by setting the amount to be equal to or less than the upper limit, it is possible to suppress the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group from remaining as an unreacted product. Tend.

Polybasic acids and/or their anhydrides include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid. One or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, anhydrides thereof, and the like.

Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof are preferred. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, and biphenyltetracarboxylic dianhydride.

A known method can also be used for the addition reaction of polybasic acids and/or their anhydrides. The desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of the carboxylic acid ester. The amount of polybasic acid and/or its anhydride component added is preferably such that the resulting carboxyl group-containing epoxy (meth)acrylate resin has an acid value in the range of 10 to 150 mgKOH/g. It is preferred to be in the range of ~140 mg KOH/g. Alkali developability tends to be improved by setting the content to the above lower limit or more, and curability tends to be improved by setting the content to be the above upper limit or less.

<Epoxy (meth)acrylate resin (A-2)>
A polyhydric alcohol such as trimethylolpropane, pentaerythritol, and dipentaerythritol may be added during the addition reaction of the polybasic acid and/or its anhydride for the resin (A-1) to introduce a multibranched structure. Well, by doing so an epoxy (meth)acrylate resin (A-2) is obtained.
Epoxy (meth)acrylate resin (A-2) is usually prepared by reacting an epoxy resin with an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group, After mixing the polybasic acid and / or its anhydride, or to the reaction product of the epoxy resin and α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group , a polybasic acid and/or its anhydride and a polyhydric alcohol are mixed and then heated. In this case, the order of mixing the polybasic acid and/or its anhydride and the polyhydric alcohol is not particularly limited. Any present in a mixture of a reaction product of an epoxy resin and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group and a polyhydric alcohol when heated A polybasic acid and/or its anhydride undergoes an addition reaction with the hydroxyl group of .

Epoxy (meth)acrylate resins having a carboxyl group may be used singly or as a mixture of two or more resins.
The amount of polyhydric alcohol used is, from the viewpoint of exhibiting effects while suppressing thickening and gelation, an epoxy resin and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated having a carboxyl group. It is usually about 0.01 to 0.5 times the weight, preferably about 0.02 to 0.2 times the weight of the reaction product with the monocarboxylic acid ester.

Although the chemical structure of the alkali-soluble resin (A) is not particularly limited, it preferably has a fluorene ring in the molecule from the viewpoint of enhancing internal curability upon exposure. From the viewpoint of strengthening the π-π interaction due to the fluorene ring by increasing the number of points, it is more preferable to have the partial structure represented by the above formula (1). Furthermore, from the viewpoint of enhancing the π-π interaction, it may have a partial structure represented by the above formula (2).

When the alkali-soluble resin (A) has a partial structure represented by the formula (1), the content is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass in the alkali-soluble resin (A). 40% by mass or more is more preferable, 80% by mass or less is preferable, 70% by mass or less is more preferable, and 60% by mass or less is even more preferable. When the content is at least the above lower limit, internal curability during exposure tends to increase, making it easier to form a fine line pattern.

When the alkali-soluble resin (A) has the partial structure represented by the formula (1) and/or the partial structure represented by the formula (2), from the viewpoint of photocrosslinkability, the following formula (3) It is preferable to have a partial structure represented by

(In Formula (3), R ¹ represents a hydrogen atom or a methyl group. * represents a bond.)

When the alkali-soluble resin (A) has a partial structure represented by the formula (3), the content is not particularly limited, but is preferably 10% by mass or more, and 12% by mass or more in the alkali-soluble resin (A). is more preferable, 14% by mass or more is more preferable, 30% by mass or less is preferable, 25% by mass or less is more preferable, and 20% by mass or less is even more preferable. When the thickness is set to the above lower limit or more, line width change during heat curing tends to be suppressed, and when the thickness is set to the above upper limit or less, cure shrinkage tends to decrease.
Further, when the alkali-soluble resin (A) has the partial structure represented by the formula (1) and the partial structure represented by the formula (3), 100 masses of the partial structure represented by the formula (1) The content ratio of the partial structure represented by the formula (3) to parts is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, further preferably 30 parts by mass or more, and preferably 60 parts by mass or less, 50 parts by mass or less is more preferable, and 40 parts by mass or less is even more preferable. When the thickness is set to the above lower limit or more, line width change during heat curing tends to be suppressed, and when the thickness is set to the above upper limit or less, cure shrinkage tends to decrease.

From the viewpoint of promoting the cross-linking reaction between the main chains, the alkali-soluble resin (A) has the following formula (4) as the partial structure represented by the above formula (1) and the partial structure represented by the above formula (3). It is preferable that the partial structure represented by is included.

(In formula (4), n has the same meaning as in formula (1) above. R ¹ has the same meaning as in formula (3) above. * represents a bond. The benzene ring in formula (4) further includes It may be substituted with any substituent.)

Examples of optional substituents that the benzene ring in formula (4) may have include the same groups as those listed in formula (1) above.

When the alkali-soluble resin (A) has a partial structure represented by the formula (4), the content is not particularly limited, but is preferably 40% by mass or more, 50% by mass or more in the alkali-soluble resin (A). is more preferably 60% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. When the thickness is set to the above lower limit or more, line width change during heat curing tends to be suppressed, and when the thickness is set to the above upper limit or less, cure shrinkage tends to decrease.

From the viewpoint of patterning properties during alkali development, the alkali-soluble resin (A) preferably further contains a partial structure represented by the following formula (5) and/or a partial structure represented by the following formula (6). .

(In formula (5), X is a divalent carboxylic acid residue. In formula (6), Z is a tetravalent carboxylic acid residue. * represents a bond.)

Examples of divalent carboxylic acid residues include divalent hydrocarbon groups which may have a substituent. Hydrocarbon groups include aliphatic or aromatic hydrocarbon groups. A combination of an aliphatic hydrocarbon and an aromatic hydrocarbon may also be used. Further, it may be a linear or branched chain hydrocarbon group, or a cyclic hydrocarbon group. The number of carbon atoms in the hydrocarbon group is not particularly limited, but from the viewpoint of solubility during development, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 15 or less. It is 10 or less, more preferably 8 or less. Examples of substituents include halogen atoms and hydroxyl groups, but unsubstituted groups are preferred.

Specifically, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride A divalent carboxylic acid residue such as is preferred, and a divalent carboxylic acid residue of tetrahydrophthalic anhydride or succinic anhydride is more preferred. The divalent carboxylic acid residues of these dibasic acid anhydrides may be used singly or in combination of two or more.

Specific examples of the partial structure represented by the formula (5) include the following.

On the other hand, since the alkali-soluble resin (A) contains the partial structure represented by the formula (6), that is, the alkali-soluble resin (A) has at least two carboxyl groups, the unexposed portion of the developer tend to have good solubility in Further, when the alkali-soluble resin (A) is used as the alkali-soluble resin in the photosensitive resin composition, the linearity tends to be good and the line width change during heat curing tends to be small.

Further, since the partial structure represented by the formula (6) has two bonds, when it contains two or more partial structures represented by the formula (4) having an ethylenically unsaturated group In addition, the molecular weight can be increased, the content of the ethylenically unsaturated groups can be increased, the cross-linking reaction can be increased during curing, and the sensitivity tends to be good.

Examples of the tetravalent carboxylic acid residue include a tetravalent hydrocarbon group optionally having a substituent. The hydrocarbon group may have a heteroatom such as an oxygen atom or a sulfur atom.

Hydrocarbon groups include aliphatic or aromatic hydrocarbons. A combination of an aliphatic hydrocarbon and an aromatic hydrocarbon may also be used. Further, it may be a linear or branched chain hydrocarbon group, or a cyclic hydrocarbon group. Although the number of carbon atoms in the hydrocarbon group is not particularly limited, it is usually 1 or more, preferably 5 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of solubility during development. Examples of substituents include halogen atoms and hydroxyl groups, but unsubstituted groups are preferred.

Specifically, for example, tetracarboxylic dianhydrides such as pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenylethertetracarboxylic dianhydride and the like. An acid residue is preferred, and a tetravalent carboxylic acid residue of biphenyltetracarboxylic anhydride is more preferred. The tetravalent carboxylic acid residues of these tetrabasic acid anhydrides may be used singly or in combination of two or more.

Specific examples of the partial structure represented by formula (6) include the following.

When the alkali-soluble resin (A) has a partial structure represented by the formula (5), the content is not particularly limited, but is preferably 1% by mass or more, 2% by mass or more in the alkali-soluble resin (A). is more preferable, 3% by mass or more is more preferable, 6% by mass or less is preferable, 5% by mass or less is more preferable, and 4% by mass or less is even more preferable. When it is equal to or higher than the above lower limit, there is a tendency to suppress footing of the pattern after development.

When the alkali-soluble resin (A) has a partial structure represented by the formula (6), the content is not particularly limited, but is preferably 6% by mass or more, 8% by mass or more in the alkali-soluble resin (A). is more preferably 10% by mass or more, preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 16% by mass or less. When the thickness is equal to or higher than the lower limit, there is a tendency to suppress the insertion of the pattern after development.

[Photosensitive resin composition]
The alkali-soluble resin (A) is preferably used for forming members for image display devices such as liquid crystal displays and organic EL displays, such as color filters, black matrices, column spacers, colored spacers and partition walls. In particular, it can be preferably used as an alkali-soluble resin for a black matrix because it has good linearity and can suppress line width change during heat curing.

The photosensitive resin composition of the present invention contains (a) an alkali-soluble resin, (b) a photopolymerizable monomer, and (c) a photopolymerization initiator, and the (a) alkali-soluble resin is an alkali-soluble resin ( A). It is more preferable to further contain (d) a coloring material and (e) a dispersant. If necessary, it may further contain other compounding components such as thiols, adhesion improvers, applicability improvers, pigment derivatives and the like. Each compounding component is usually used in a state of being dissolved or dispersed in a solvent.

<(a) alkali-soluble resin>
The (a) alkali-soluble resin in the photosensitive resin composition of the present invention contains the alkali-soluble resin (A), but may further contain other alkali-soluble resins.

The softening point of the other alkali-soluble resin is not particularly limited, but is preferably 50° C. or higher, more preferably 60° C. or higher, further preferably 70° C. or higher, and 150° C. or lower. preferably 120° C. or lower, and even more preferably 100° C. or lower. When it is at least the above lower limit, the adhesiveness of the coating film tends to decrease and the handleability tends to be improved, and when it is at most the above upper limit, linearity tends to be good. The softening point of other alkali-soluble resins can be measured by the same measuring method as for the alkali-soluble resin (A).

The minimum value of the storage elastic modulus G′ obtained by dynamic viscoelasticity measurement of other alkali-soluble resins is not particularly limited, but is preferably 1×10 ¹ Pa or more, and 1×10 ² Pa or more. is more preferably 1×10 ³ Pa or more, preferably 1×10 ⁵ Pa or less, more preferably 5×10 ⁴ Pa or less, and 1×10 ⁴ Pa or less. It is even more preferable to have When it is at least the lower limit, deformation during curing tends to be suppressed, and when it is at most the upper limit, the linearity of the pattern after development tends to be improved. The minimum value of the storage elastic modulus G' obtained by dynamic viscoelasticity measurement of other alkali-soluble resins can be measured by the same measurement method as for the alkali-soluble resin (A).

In addition, the storage elastic modulus G′ at 220° C. of other alkali-soluble resins is preferably 1×10 ³ Pa or more, more preferably 1×10 ⁴ Pa or more, further preferably 1×10 ⁵ Pa or more. ×10 ⁷ Pa or less is preferable, and 5×10 ⁶ Pa or less is more preferable. When it is above the lower limit, the strength of the thermoset film tends to increase, and when it is below the upper limit, the thermoset film becomes too hard and brittle, and patterning is suppressed. Tend.

The weight average molecular weight of other alkali-soluble resins is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, and preferably 30,000 or less, more preferably 10,000 or less, and even more preferably 6,000 or less. When it is at least the above lower limit, there is a tendency to suppress the insertion of patterns after development, and when it is at most the above upper limit, there is a tendency for re-solubility to be good.

The acid value of the other alkali-soluble resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 80 mgKOH/g or more, preferably 200 mgKOH/g or less, and 150 mgKOH/g or less. is more preferred, and 120 mgKOH/g or less is even more preferred. When the amount is at least the lower limit, the solubility during development tends to be good, and when the amount is at most the upper limit, the stability during storage tends to be good.

The double bond equivalent (g/mol) of other alkali-soluble resins is not particularly limited, but is preferably 1000 or less, more preferably 900 or less, still more preferably 800 or less, preferably 120 or more, and more preferably 300 or more. , 400 or more is more preferable. The sensitivity tends to be improved by making it equal to or less than the above upper limit, and curing shrinkage tends to be suppressed by making it equal to or more than the above lower limit.

Other alkali-soluble resins are such that after exposure of the coating film obtained by applying and drying a photosensitive resin composition containing other alkali-soluble resins, the solubility in alkali development of the exposed area and the non-exposed area changes. Although it is not particularly limited as long as it is a substance, it is preferably an alkali-soluble resin having a carboxyl group. Moreover, those having an ethylenically unsaturated group are preferable, and alkali-soluble resins having an ethylenically unsaturated group and a carboxyl group are more preferable. Specifically, epoxy (meth)acrylate resins and acrylic copolymer resins having a carboxyl group can be mentioned. 1), (A2-2), (A2-3) and (A2-4), and these may be used alone or in combination of two or more. Among the above, epoxy (meth)acrylate resins having a carboxyl group are preferred, and (A1-1) and (A1-2) are particularly preferred.

An epoxy (meth)acrylate resin having a carboxyl group is produced by a reaction of a reaction product of an epoxy resin with an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group. It is a resin obtained by further reacting polybasic acid and/or its anhydride with the resulting hydroxyl group. Further, before reacting the polybasic acid and/or its anhydride with a hydroxyl group, after reacting a compound having two or more substituents capable of reacting with the hydroxyl group, the polybasic acid and/or its anhydride Resins obtained by reacting are also included in epoxy (meth)acrylate resins. The epoxy (meth)acrylate resin also includes a resin obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a reactive functional group.

Thus, the epoxy (meth)acrylate resin has substantially no epoxy group in terms of its chemical structure, and is not limited to "(meth)acrylate", but is made from an epoxy resin, and Since "(meth)acrylate" is a representative example, the name is used in this way according to common practice.

Examples of the epoxy (meth)acrylate resin having a carboxyl group include the following epoxy (meth)acrylate resin (A1-1) and/or epoxy (meth)acrylate resin (A1-2).

<Epoxy (meth)acrylate resin (A1-1)>
Obtained by adding an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and/or its anhydride. alkali-soluble resin.
<Epoxy (meth)acrylate resin (A1-2)>
An α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and a polyhydric alcohol and a polybasic acid and/or its anhydride are added. Alkali-soluble resin obtained by reacting.

<Epoxy (meth)acrylate resin (A1-1)>
Examples of epoxy resins used as raw materials include bisphenol A type epoxy resins (e.g., "jER (registered trademark; hereinafter the same) 828", "jER1001", "jER1002", "jER1004" manufactured by Mitsubishi Chemical Corporation, Nippon Kayaku "NER-1302" (epoxy equivalent 323, softening point 76 ° C.) manufactured by Mitsubishi Chemical Corporation, etc.), bisphenol F type resin (for example, Mitsubishi Chemical Corporation "jER807", "jER4004P", "jER4005P", "jER4007P", Japan Kayaku "NER-7406" (epoxy equivalent 350, softening point 66 ° C.), etc.), bisphenol S type epoxy resin, biphenyl glycidyl ether (e.g. Mitsubishi Chemical "jERYX-4000"), phenol novolak type Epoxy resin (e.g., Nippon Kayaku Co., Ltd. "EPPN (registered trademark) -201", Mitsubishi Chemical Co., Ltd. "jER-152", "jER-154", Dow Chemical Co., Ltd. "DEN- 438”), (o, m, p-) cresol novolak type epoxy resin (for example, Nippon Kayaku Co., Ltd. “EOCN (registered trademark; the same shall apply hereinafter)-102S”, “EOCN-1020”, “EOCN-104S ”), triglycidyl isocyanurate (e.g., “TEPIC (registered trademark)” manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane type epoxy resin (e.g., “EPPN-501”, “EPPN-502” manufactured by Nippon Kayaku Co., Ltd. , “EPPN-503”), alicyclic epoxy resin (“Celoxide (registered trademark) 2021P”, “Celoxide EHPE” manufactured by Daicel), glycidylation of phenolic resin by reaction of dicyclopentadiene and phenol Epoxy resins (for example, "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (a1) to (a5), etc. are preferably can be used. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (a1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (a2) NC-3000", and "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (a4).

In the above general formula (a1), b11 is an average value and represents a number from 0 to 10. R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. A plurality of R ¹¹ present in one molecule may be the same or different.

In the above general formula (a2), b12 is an average value and represents a number from 0 to 10. R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R ²¹ in one molecule may be the same or different.

In general formula (a3) above, X represents a linking group represented by general formula (a3-1) or (a3-2) below. However, it contains one or more adamantane structures in its molecular structure. b13 represents an integer of 2 or 3;

In general formulas (a3-1) and (a3-2) above, R ³¹ to R ³⁴ and R ³⁵ to R ³⁷ are each independently an optionally substituted adamantyl group, a hydrogen atom, a substituent or an optionally substituted phenyl group. Moreover, * in the formula represents a binding site in the general formula (a3).

In the above general formula (a4), p and q each independently represents an integer of 0-4. R ⁴¹ and R ⁴² each independently represent an alkyl group having 1 to 20 carbon atoms or a halogen atom. R ⁴³ and R ⁴⁴ each independently represent an alkylene group having 1 to 5 carbon atoms. x and y each independently represent an integer of 0 or more.

In general formula (a5) above, each of R ⁵¹ to R ⁵⁴ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. show. R ⁵⁵ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Each R ⁵⁶ independently represents an alkylene group having 1 to 5 carbon atoms. k represents an integer of 1 to 5, l represents an integer of 0 to 13, and m each independently represents an integer of 0 to 5.
Among these, epoxy resins represented by any one of general formulas (a1) to (a5) are preferably used.

α,β-unsaturated monocarboxylic acids and/or α,β-unsaturated monocarboxylic acid esters having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyladipic acid, 2 - (meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxyethyl maleate, 2-(meth) acryloyloxypropyl succinate, 2 - (meth) acryloyloxypropyl adipate, 2-(meth) acryloyloxypropyl tetrahydrophthalate, 2-(meth) acryloyloxypropyl phthalate, 2-(meth) acryloyloxypropyl maleate, 2- (Meth) acryloyloxybutyl succinate, 2-(meth) acryloyloxybutyl adipate, 2-(meth) acryloyloxybutyl hydrophthalate, 2-(meth) acryloyloxybutyl phthalate, 2-( As meth)acryloyloxybutyl maleate and (meth)acrylic acid esters, lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone are added to (meth)acrylic acid and the terminal A monomer having one hydroxyl group at the end, or a monomer having one hydroxyl group at the end such as hydroxyalkyl (meth) acrylate, or a terminal having one hydroxyl group such as pentaerythritol tri (meth) acrylate Acid (anhydride) such as (anhydride) succinic acid, (anhydride) phthalic acid, (anhydride) maleic acid is added to a compound having a hydroxyl group, and one or more ethylenically unsaturated groups and one carboxyl group at the end are added. (Meth)acrylic acid esters having (Meth)acrylic acid dimers and the like are also included.

Among these, (meth)acrylic acid is particularly preferable from the viewpoint of sensitivity.
As a method for adding an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known technique can be used. For example, an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group is reacted with an epoxy resin at a temperature of 50 to 150° C. in the presence of an esterification catalyst. be able to. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride can be used. .

The epoxy resin, the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used singly. You may use 2 or more types together.
The amount of the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group is in the range of 0.5 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. is preferred, more preferably in the range of 0.7 to 1.1 equivalents.
By setting the amount of the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group to the above lower limit or more, the amount of the unsaturated group introduced becomes sufficient, and the amount of unsaturated groups continues to increase. Reaction with a basic acid and/or its anhydride becomes sufficient, and there is a tendency that a large amount of epoxy groups can be suppressed from remaining. On the other hand, by setting the amount to be equal to or less than the upper limit, the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. tend to be suppressed.

Polybasic acids and/or their anhydrides include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid. One or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, anhydrides thereof, and the like.

Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof are preferred. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, and biphenyltetracarboxylic dianhydride.

A known method can also be used for the addition reaction of polybasic acids and/or their anhydrides. The desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of the carboxylic acid ester. The amount of polybasic acid and/or its anhydride component added is preferably such that the resulting carboxyl group-containing epoxy (meth)acrylate resin has an acid value in the range of 10 to 150 mgKOH/g. It is preferred to be in the range of ~140 mg KOH/g. Alkali developability tends to be improved by setting the content to the above lower limit or more, and curability tends to be improved by setting the content to be the above upper limit or less.

<Epoxy (meth)acrylate resin (A1-2)>
A polyhydric alcohol such as trimethylolpropane, pentaerythritol, and dipentaerythritol may be added during the addition reaction of the polybasic acid and/or its anhydride for the resin (A1-1) to introduce a multibranched structure. Well, by doing so an epoxy (meth)acrylate resin (A1-2) is obtained.
Epoxy (meth)acrylate resin (A1-2) is usually prepared by reacting an epoxy resin with an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group, After mixing the polybasic acid and / or its anhydride, or to the reaction product of the epoxy resin and α, β-unsaturated monocarboxylic acid and / or α, β-unsaturated monocarboxylic acid ester having a carboxyl group , a polybasic acid and/or its anhydride and a polyhydric alcohol are mixed and then heated. In this case, the order of mixing the polybasic acid and/or its anhydride and the polyhydric alcohol is not particularly limited. Any present in a mixture of a reaction product of an epoxy resin and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group and a polyhydric alcohol when heated A polybasic acid and/or its anhydride undergoes an addition reaction with the hydroxyl group of .

Epoxy (meth)acrylate resins having a carboxyl group may be used singly or as a mixture of two or more resins.
The amount of polyhydric alcohol used is, from the viewpoint of exhibiting effects while suppressing thickening and gelation, an epoxy resin and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated having a carboxyl group. It is usually about 0.01 to 0.5 times the weight, preferably about 0.02 to 0.2 times the weight of the reaction product with the monocarboxylic acid ester.

<Acrylic copolymer resin (A2-1) (A2-2) (A2-3) (A2-4)>
As the acrylic copolymer resin, for example, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, Various polymer compounds described in publications such as JP-A-2000-56118, JP-A-2003-233179, and JP-A-2007-270147 can be used, but preferably the following ( Examples include resins A2-1) to (A2-4), among which resin (A2-1) is particularly preferred.

(A2-1): for a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, unsaturated monobasic acid is added to at least part of the epoxy groups of the copolymer; Resin obtained by addition, or resin obtained by adding polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction (A2-2): linear alkali-soluble containing carboxyl group in the main chain Resin (A2-3): resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of resin (A2-2) (A2-4): (meth)acrylic resin

Other alkali-soluble resins are at least any of (A1-1), (A1-2), (A2-1), and (A2-3) as alkali-soluble resins containing ethylenically unsaturated groups from the viewpoint of sensitivity. It is further preferred to include Further, from the viewpoint of surface curability, it is particularly preferable that at least one of epoxy (meth)acrylate resins (A1-1) and (A1-2) is included as the alkali-soluble resin containing an ethylenically unsaturated group. .

The content of (a) the alkali-soluble resin in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more in the total solid content. Preferably, 25% by mass or more is particularly preferable, 90% by mass or less is preferable, 70% by mass or less is more preferable, 50% by mass or less is more preferable, 40% by mass or less is even more preferable, and 30% by mass or less is particularly preferable. preferable. When it is at least the lower limit, the solubility of the unexposed portion in the developer tends to be good, and when it is at most the upper limit, excessive permeation of the developer into the exposed portion can be suppressed. This tends to improve pattern resolution and adhesion.

The content of the alkali-soluble resin (A) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and 2% by mass or more in the total solid content. is more preferably 90% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 30% by mass or less, particularly preferably 20% by mass or less, and 10% by mass or less is most preferred. When the lower limit value or more is used, the effect of suppressing line width change tends to be easily obtained. resolution and adhesion tend to be improved.

Further, when the (a) alkali-soluble resin contains other alkali-soluble resin, the content of the alkali-soluble resin (A) in the (a) alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, and 10% by mass. % or more, more preferably 15 mass % or more, preferably 100 mass % or less, more preferably 70 mass % or less, even more preferably 50 mass % or less, and particularly preferably 30 mass % or less. When it is at least the lower limit, the effect of suppressing line width change tends to be easily obtained, and when it is at most the upper limit, pattern linearity after heat curing tends to be improved.
In addition, the content ratio of the other alkali-soluble resin in (a) the alkali-soluble resin is not particularly limited, but is preferably 0% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, and 95% by mass or more. % by mass or less is preferable, 90% by mass or less is more preferable, and 85% by mass or less is even more preferable. When it is at least the lower limit, the pattern linearity after heat curing tends to be improved, and when it is at most the upper limit, the effect of suppressing line width change tends to be easily obtained.

<(b) Photopolymerizable Monomer>
The photosensitive resin composition of the present invention contains (b) a photopolymerizable monomer from the viewpoint of sensitivity and the like.
Examples of the (b) photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as "ethylenic monomer"). . Specific examples include (meth)acrylic acid, (meth)acrylic acid alkyl esters, acrylonitrile, styrene, carboxylic acids having one ethylenically unsaturated bond, and polyhydric or monohydric alcohol monoesters. be done.

In the present invention, it is particularly desirable to use polyfunctional ethylenic monomers having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is usually 2 or more, preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, particularly preferably 6 or more, and usually 10 or less, preferably 8 or less. The sensitivity of the photosensitive resin composition tends to be high when it is at least the above lower limit, and the cure shrinkage during polymerization tends to be small when it is at most the above upper limit.
Examples of polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic poly Esters obtained by an esterification reaction between a polyhydric hydroxy compound such as a hydroxy compound and an unsaturated carboxylic acid or a polybasic carboxylic acid are included.

Esters of the aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, and methacrylic acid esters obtained by replacing the acrylates of these exemplary compounds with methacrylates Similarly, itaconate instead of itaconate, crotonate instead of clonate, maleate instead of maleate, and the like.

Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. etc.
Polybasic carboxylic acid and unsaturated carboxylic acid, the ester obtained by the esterification reaction of the polyhydric hydroxy compound is not necessarily a single substance, but representative specific examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

Other examples of polyfunctional ethylenic monomers used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound, a polyol and a hydroxyl group-containing (meth)acrylic acid ester. Urethane (meth)acrylates such as those obtained; epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate are useful.
These may be used individually by 1 type, and may use 2 or more types together.

(b) The content of the photopolymerizable monomer is usually 1% by mass or more, preferably 5% by mass or more, and usually 90% by mass or less, preferably 70% by mass, based on the total solid content of the photosensitive resin composition. % by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less. By setting the content of the photopolymerizable monomer to the above lower limit or more, there is a tendency that photocuring by ultraviolet irradiation is improved and alkali developability is also improved. When the value is equal to or less than the above upper limit, there is a tendency that the permeability of the developing solution to the exposed area becomes appropriate, and good images can be obtained.

<(c) Photoinitiator>
The photosensitive resin composition of the present invention contains (c) a photopolymerization initiator. A photopolymerization initiator is a component that has the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating polymerization active radicals. If necessary, an additive such as a sensitizing dye may be added for use.

Examples of photopolymerization initiators include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; Imidazole derivatives; halomethylated oxadiazole derivatives described in JP-A-10-39503, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α- Amino acid salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP-A-2000-80068, JP-A-2006-36750, etc. and the like.

Specifically, for example, metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di( 2,6-difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl) titanium bis(2,3,4,5,6-pentafluorophenyl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl), dicyclopentadienyltitanium bis[2,6-difluoro-3-(1-pyrrolyl)phenyl] and the like.

Further, biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole. dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, (4′-methoxyphenyl )-4,5-diphenylimidazole dimer and the like.

Further, halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-(6″-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

Further, halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine and the like.

Further, α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate -, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4 -diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone and the like.

As the photopolymerization initiator, oxime derivatives (oxime ester compounds and ketoxime ester compounds) are particularly effective in terms of sensitivity. Among oxime derivatives, oxime ester compounds are particularly preferred from the viewpoint of adhesion to substrates.
Oxime ester compounds have a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals, so they are highly sensitive even in small amounts and are stable against thermal reactions. It is possible to design a photosensitive resin composition with a small amount and high sensitivity. In particular, in the case of an oxime ester compound containing an optionally substituted carbazolyl group (a group having an optionally substituted carbazole ring), from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source, This structural characteristic is well expressed, which is more preferable. At present, the market demands BM with a high degree of light shielding and a thin film, and the content of coloring materials is also increasing more and more. It is particularly effective in such circumstances.

Examples of the oxime ester-based compound include compounds containing a partial structure represented by the following general formula (22), preferably oxime ester-based compounds represented by the following general formula (23).

In the above formula (22), R ²² is an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and an alkenoyl group having 3 to 25 carbon atoms, each of which may be substituted. 3-8 cycloalkanoyl group, C3-20 alkoxycarbonylalkanoyl group, C8-20 phenoxycarbonylalkanoyl group, C3-20 heteroaryloxycarbonylalkanoyl group, C2-10 represents an aminoalkylcarbonyl group, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.

In formula (23), R ^21a is a hydrogen atom, or an optionally substituted alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 25 carbon atoms, or heteroarylalkyl group having 1 to 20 carbon atoms. , an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms. an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms; R ^21b represents an arbitrary substituent containing an aromatic ring; R ^22a represents the same group as R ²² in formula (22) above.

R ^21a may form a ring together with R ^21b , and the linking group may be an alkylene group having 1 to 10 carbon atoms each optionally having a substituent, or a polyethylene group (-(CH=CH) _r- ), a polyethylene group (-(C≡C) _r- ), or a group formed by combining these (where r is an integer of 0 to 3).
R ²² in the above general formula (22) and R ^22a in the above general formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or a heteroarylalkanoyl group having 1 to 20 carbon atoms. and a cycloalkanoyl group of.

R ^21a in the general formula (23) is preferably an unsubstituted methyl group, an ethyl group, a linear alkyl group such as a propyl group; a cycloalkylalkyl group; propyl group;
R ^21b in the general formula (23) preferably includes an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted phenylsulfide group.

As the oxime ester compound, those containing an optionally substituted carbazolyl group as R ^21b are more preferable for the reasons described above. Furthermore, optionally substituted aryl groups having 6 to 25 carbon atoms, optionally substituted arylcarbonyl groups having 7 to 25 carbon atoms, optionally substituted heteroaryl groups having 5 to 25 carbon atoms, substituted A carbazolyl group having at least one group selected from the group consisting of a heteroarylcarbonyl group having 6 to 25 carbon atoms which may be substituted and a nitro group is preferred. A carbazolyl group having at least one group selected from the group consisting of a benzoyl group, a toluoyl group, a naphthoyl group, a thienylcarbonyl group and a nitro group is particularly preferred. Moreover, it is desirable that these groups are bonded to the 3-position of the carbazolyl group.

Commercially available products of such oxime ester compounds include OXE-02 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Power Electronics New Materials.

Specific examples of the oxime ester compound suitable for the present invention include compounds as exemplified below, but the compounds are not limited to these compounds.

Examples of ketoxime ester compounds include compounds containing a partial structure represented by the following general formula (24), preferably oxime ester compounds represented by the following general formula (25).

In general formula (24) above, R ²⁴ has the same definition as R ²² in general formula (22) above.

In the above general formula (25), R ^23a is an optionally substituted phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroarylalkyl group having 1 to 20 carbon atoms. alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, alkylthioalkyl group having 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or heteroarylthio an alkyl group, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, It represents a heteroarylyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms.

R ^23b represents any substituent containing an aromatic ring.
R ^23a may form a ring together with R ^23b , and the linking group may be an alkylene group having 1 to 10 carbon atoms each optionally having a substituent, a polyethylene group (-(CH=CH) _r -), a polyethylene group (-(C≡C) _r -), or a group formed by combining these (where r is an integer of 0 to 3).

R ^24a is an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, and a carbon atom, each of which may be substituted. a heteroarylyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylamino group having 2 to 20 carbon atoms; represents a carbonyl group.
R ²⁴ in the above general formula (24) and R ^24a in the above general formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or a heteroarylalkanoyl group having 1 to 20 carbon atoms. and arylyl groups having 7 to 20 carbon atoms.

R ^23a in the general formula (25) preferably includes an unsubstituted ethyl group, a propyl group and a butyl group; and an ethyl group or a propyl group substituted with a methoxycarbonyl group.
R ^23b in the general formula (25) preferably includes an optionally substituted carbazolyl group and an optionally substituted phenylsulfide group.
Specific examples of the ketoxime ester compounds suitable for the present invention include compounds as exemplified below, but are not limited to these compounds.

Commercially available products of such ketoxime ester compounds include OXE-01 manufactured by BASF Corporation and TR-PBG-305 manufactured by Changzhou Power Electronics New Materials.

These oxime ester-based compounds and ketoxime ester-based compounds are themselves known compounds. is.
One of the above oxime derivatives may be used alone, or two or more thereof may be used in combination.

Other photopolymerization initiators include benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; anthraquinone derivatives such as chloroanthraquinone; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; -dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl ) ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4′-methylthiophenyl)-2-morpholino-1-propanone, 1,1,1-trichloromethyl-(p-butyl acetophenone derivatives such as phenyl)ketone; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; 9,10-dimethylbenz phenazine derivatives such as phenazine; and anthrone derivatives such as benzanthrone.
Among these photopolymerization initiators, oxime derivatives are particularly preferred for the reasons described above.

<Sensitizing dye>
If necessary, the photopolymerization initiator can be used in combination with a sensitizing dye corresponding to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and heterocycles described in JP-A-3-239703 and JP-A-5-289335. Coumarin dyes, 3-ketocoumarin compounds described in JP-A-3-239703 and JP-A-5-289335, pyrromethene dyes described in JP-A-6-19240, and others, JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005 Publications, JP-A-59-56403, JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, JP-A-4-288818 Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A-2003-200211.

Preferred among these sensitizing dyes are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone , benzophenone compounds such as 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5 ] benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl ) benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)- 1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine , p-dialkylaminophenyl group-containing compounds such as (p-diethylaminophenyl)pyrimidine.
Among these, the most preferred is 4,4'-dialkylaminobenzophenone.
The sensitizing dyes may be used singly or in combination of two or more.

(c) The content of the photopolymerization initiator is not particularly limited, but usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, in the total solid of the photosensitive resin composition of the present invention, More preferably 4% by mass or more, usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, particularly preferably 8% by mass or less. When it is at least the above lower limit, it tends to be possible to suppress a decrease in sensitivity, and when it is at most the above upper limit, it tends to be possible to improve the solubility of the unexposed portion in the developing solution.

Further, when a sensitizing dye is used, the content of the sensitizing dye is not particularly limited, but usually 0 to 20% by mass, preferably 0 to 15% by mass, more preferably 0 to 15% by mass, based on the total solid content of the photosensitive resin composition. is 0 to 10% by mass.

<(d) Colorant>
The photosensitive resin composition of the present invention preferably contains (d) a coloring material. A coloring material colors the photosensitive resin composition of the present invention. As the coloring material (d), pigments and dyes can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance, and the like.

Pigments of various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments and black pigments can be used. In addition to organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments, various inorganic pigments can also be used. is.

Specific examples of pigments that can be used in the present invention are shown below by pigment numbers. In addition, terms such as "C.I. Pigment Red 2" mentioned below mean a color index (C.I.).
As a red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among these, C.I. I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 may be mentioned.

As a blue pigment, C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, more preferably C.I. I. Pigment Blue 15:6 may be mentioned.
As a green pigment, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59 . Among these, C.I. I. Pigment Green 7, 36, 58, 59 can be mentioned.

As a yellow pigment, C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 can be mentioned. Among these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.

As an orange pigment, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned. Among these, C.I. I. Pigment Orange 38, 71 may be mentioned.

As a purple pigment, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned. Among these, C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.

Dyes may also be used in addition to these pigments. Examples of dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Examples of azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordan Tread 7, C.I. I. Mordant Yellow 5, C.I. I. mordant black 7 and the like.

Examples of anthraquinone dyes include C.I. I. bat blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like can be mentioned.
In addition, as a phthalocyanine dye, for example, C.I. I. Pad Blue 5 and the like are quinone imine dyes, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro-based dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Examples include Disperse Yellow 42 and the like.

Further, when the photosensitive resin composition of the present invention is used for a light-shielding application such as a resin black matrix of a color filter, a black colorant can be used as the (e) colorant. The black colorant may be a black colorant alone or a mixture of red, green, blue, and the like. These coloring materials can be appropriately selected from inorganic or organic pigments and dyes.
Colorants that can be mixed to prepare black colorants include Victoria Pure Blue (42595), Auramine O (41000), Catilone Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), and Rhodamine B (45170). , Safranin OK 70:100 (50240), Erioglaucine X (42080), No. 120/Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla Fast Red 4015 (12355), Lionol Red 7B4401 (15850), First Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15:6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (Note that the numbers in ( ) above mean the color index (C.I.).).

For other pigments that can be used in combination, C.I. I. When indicated by number, for example, C.I. I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment Blue 15, 15:1, 15:4, 22, 60, 64, C.I. I. Pigment Green 7, C.I. I. Pigment Brown 23, 25, 26 and the like can be mentioned.

Black pigments that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and lactam black.
Among these (d) colorants, when a black colorant is used, carbon black is preferable from the viewpoint of light shielding rate and image characteristics.

In addition, when carbon black is included, the hydrophobicity of the coating film increases, and the adhesion to the substrate tends to deteriorate. becomes insufficient, and the line width tends to change due to melting in the heat curing step. Therefore, by using the alkali-soluble resin (A), the linearity tends to be good and the change in line width during heat curing tends to be easily suppressed.

Examples of carbon black include the following.
Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350 , #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B
Degussa: Printex (registered trademark; hereinafter the same) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, PrintexPrintxL, PrintexPrintxL, PrintexPrintx Ｕ、Ｐｒｉｎｔｅｘ Ｖ、ＰｒｉｎｔｅｘＧ、ＳｐｅｃｉａｌＢｌａｃｋ５５０、ＳｐｅｃｉａｌＢｌａｃｋ３５０、ＳｐｅｃｉａｌＢｌａｃｋ２５０、ＳｐｅｃｉａｌＢｌａｃｋ１００、ＳｐｅｃｉａｌＢｌａｃｋ６、ＳｐｅｃｉａｌＢｌａｃｋ５、ＳｐｅｃｉａｌＢｌａｃｋ４、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２Ｖ、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１８、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１８、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２００、Ｃｏｌｏｒ Ｂｌａｃｋ Ｓ１６０、Ｃｏｌｏｒ Black S170
Cabot Corporation: Monarch (registered trademark; the same shall apply hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark; the same shall apply hereinafter) 99, REGAL45REGAL99 REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN® XC72R, ELFTEX®-8

ビルラー社製：ＲＡＶＥＮ１１、ＲＡＶＥＮ１４、ＲＡＶＥＮ１５、ＲＡＶＥＮ１６、ＲＡＶＥＮ２２ＲＡＶＥＮ３０、ＲＡＶＥＮ３５、ＲＡＶＥＮ４０、ＲＡＶＥＮ４１０、ＲＡＶＥＮ４２０、ＲＡＶＥＮ４５０、ＲＡＶＥＮ５００、ＲＡＶＥＮ７８０、ＲＡＶＥＮ８５０、ＲＡＶＥＮ８９０Ｈ、ＲＡＶＥＮ１０００、ＲＡＶＥＮ１０２０、ＲＡＶＥＮ１０４０、ＲＡＶＥＮ１０６０Ｕ、ＲＡＶＥＮ１０８０Ｕ、ＲＡＶＥＮ１１７０、ＲＡＶＥＮ１１９０Ｕ、ＲＡＶＥＮ１２５０、ＲＡＶＥＮ１５００、 RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black that is coated with a resin may be used. The use of resin-coated carbon black has the effect of improving the adhesion to the glass substrate and the volume resistivity. As the resin-coated carbon black, for example, carbon black described in JP-A-09-71733 can be preferably used.
The carbon black to be coated preferably has a total content of Na and Ca of 100 ppm or less. Carbon black usually contains Na, Ca, K, Mg, Al, Fe, etc. mixed from raw material oil, combustion oil (or gas), reaction stop water, granulation water, and furnace materials of reactors during normal production. The composition contains ash on the order of percent. Of these, Na and Ca are generally contained in amounts of several hundred ppm or more each. This is because there are cases where

As a method for reducing the content of ash containing these Na and Ca, carefully select those with as little content as possible as raw material oil, fuel oil (or gas) and reaction stop water when producing carbon black. and by minimizing the amount of the alkaline substance added to adjust the structure. Another method is to wash the carbon black produced from the furnace with water or hydrochloric acid to dissolve and remove Na and Ca.

(d) The content of the coloring material is not particularly limited, but is preferably 1% by mass or more, more preferably 20% by mass or more, more preferably 40% by mass or more, and 45% by mass in the total solid content of the photosensitive resin composition % or more is more preferable, 50% by mass or more is particularly preferable, 70% by mass or less is preferable, 60% by mass or less is more preferable, and 55% by mass or less is even more preferable. When the content is at least the above lower limit, the coloring property tends to be improved, and when the content is at most the above upper limit, the pattern formability and substrate adhesion tend to be improved.

Further, when the (d) colorant contains carbon black, the content of carbon black is not particularly limited, but is preferably 35% by mass or more, more preferably 45% by mass or more, in the total solid content in the photosensitive resin composition. It is preferably 50% by mass or more, more preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less. When the content is equal to or higher than the lower limit, the light-shielding property tends to be enhanced, and when the content is equal to or lower than the upper limit, pattern formability and substrate adhesion tend to be improved.

In the photosensitive resin composition, the content of (d) the coloring material is usually 20 to 500 parts by mass, preferably 30 to 300 parts by mass, more preferably 40 to 280 parts by mass, per 100 parts by mass of the alkali-soluble resin (a). It is in the range of parts by mass. When the content is equal to or higher than the lower limit, the light-shielding property tends to be improved, and when the content is equal to or lower than the upper limit, the image forming property tends to be improved.

<(e) Dispersant>
In the present invention, it is important to finely disperse (d) the coloring material and stabilize the dispersion state for ensuring the stability of the quality, so (e) dispersant is preferably included.
As the dispersant, a polymer dispersant having a functional group is preferable. Further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary or tertiary amino group. ; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine and pyrazine; Among them, polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are particularly preferred. By using a polymer dispersant having these basic functional groups, there is a tendency that dispersibility can be improved and high light-shielding properties can be achieved.

Examples of polymer dispersants include urethane-based dispersants, acrylic dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ether-based dispersants. Dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants and the like can be mentioned.

Specific examples of such dispersants include trade names of EFKA (registered trademark, manufactured by EFKA Chemicals B.V. (EFKA)), Disperbyk (registered trademark, manufactured by BYK-Chemie), and Disparon (registered trademark, Kusumoto Kasei). Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Floren (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Fine-Techno Co., Ltd.) ), etc. can be mentioned.
One of these polymer dispersants may be used alone, or two or more thereof may be used in combination.

Among these, it is particularly preferable that (e) the dispersant contains a urethane polymer dispersant and/or an acrylic polymer dispersant having a basic functional group, from the viewpoint of adhesion and linearity. In particular, a urethane-based polymer dispersant is preferable in terms of adhesion. From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and a polyester bond and/or a polyether bond is preferred.

The weight-average molecular weight (Mw) of the polymeric dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less, more preferably 30,000 or less. When the amount is equal to or less than the above upper limit, alkali developability tends to be good even when the content of the coloring material is high.
Examples of urethane-based and acrylic polymer dispersants include Disperbyk 160-167, 182 series (all of which are urethane-based), Disperbyk 2000, 2001, etc. (both of which are acrylic-based) (all of which are manufactured by BYK-Chemie). Disperbyk 167, 182 and the like are particularly preferred urethane polymer dispersants having a polyester and/or polyether bond and having a weight average molecular weight of 30,000 or less.

<Urethane Polymer Dispersant>
Specific examples of preferred chemical structures for urethane-based polymer dispersants include, for example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule, and Dispersion resins having a weight-average molecular weight of 1,000 to 200,000, which are obtained by reacting active hydrogen with a compound having a tertiary amino group, and the like.

Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), ω,ω 1 ,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanatophenylmethane), tris(isocyanatophenyl)thio Examples include triisocyanates such as phosphates, trimers thereof, water adducts, and polyol adducts thereof. Preferred polyisocyanates are trimers of organic diisocyanates, most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.

As a method for producing a trimer of isocyanate, the above-mentioned polyisocyanates are treated with a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. to convert the isocyanate group part After the trimerization is terminated by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Compounds having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and one terminal hydroxyl group of these compounds has 1 to 25 carbon atoms. and mixtures of two or more thereof.

Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more thereof. Examples of polyether diols include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and these. and mixtures of two or more of

Polyetherester diols include those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, e.g. oxytetramethylene) adipate and the like. The most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 ,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2 ,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol and other aliphatic glycols; bishydroxymethylcyclohexane and other aliphatic glycols; aromatic glycols such as lenglycol and bishydroxyethoxybenzene; N-alkyldialkanolamines such as N-methyldiethanolamine; , polyethylene/propylene adipate, etc., or polylactone diols or polylactone monools obtained by using the above diols or monohydric alcohols having 1 to 25 carbon atoms as initiators, such as polycaprolactone glycol, polymethylvalerolactone and these Mixtures of two or more are included. The most preferred polyester glycol is polycaprolactone glycol or polycaprolactone initiated by an alcohol having 1 to 25 carbon atoms.

Examples of polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate, and examples of polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. is mentioned.
These may be used individually by 1 type, and may use 2 or more types together.

The compound having one or two hydroxyl groups in the molecule generally has a number average molecular weight of 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000.
A compound having an active hydrogen and a tertiary amino group in the molecule used in the present invention will be explained. Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, includes hydrogen atoms in functional groups such as a hydroxyl group, an amino group, and a thiol group. A hydrogen atom of the amino group of is preferred.

The tertiary amino group is not particularly limited, but includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring.
Examples of such compounds having active hydrogen and a tertiary amino group in the molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N, N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N- dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1, 4-butanediamine and the like.

Further, when the tertiary amino group is a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocyclic ring includes a pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo N-containing hetero 5-membered rings such as triazole ring, benzoxazole ring, benzothiazole ring and benzothiadiazole ring; nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring ring. Preferred among these nitrogen-containing heterocycles are imidazole rings and triazole rings.

Specific examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl)imidazole and the like. Specific examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 ,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino-1,2,4-triazole preferable.

These may be used individually by 1 type, and may use 2 or more types together.
The preferable blending ratio of raw materials when producing a urethane polymer dispersant is 10 to 200 mass parts of a compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the molecule per 100 mass parts of a polyisocyanate compound. parts, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass of a compound having active hydrogen and a tertiary amino group in the molecule is.

The urethane polymer dispersant is produced according to a known method for producing polyurethane resins. Solvents used in the production generally include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters such as ethyl acetate, butyl acetate, and cellosolve acetate, benzene, toluene, xylene, and hexane. Some alcohols such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethylsulfoxide are used. These may be used individually by 1 type, and may use 2 or more types together.

A urethanization reaction catalyst is usually used for the above production. Examples of this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannus octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; One or two or more types such as class amines may be used.

<Method for measuring amine value>
The amine value of the dispersant is expressed by the mass of KOH equivalent to the amount of base per 1 g of the solid content excluding the solvent in the dispersant sample, and can be measured by the following method.
Accurately weigh 0.5 to 1.5 g of a dispersant sample in a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized and titrated with a 0.1 mol/L HClO ₄ (perchloric acid) acetic acid solution. The inflection point of the titration pH curve is defined as the end point of the titration, and the amine value is obtained by the following formula.

Amine value [mgKOH/g] = (561 x V)/(W x S)
[However, W: Amount of weighed dispersant sample [g], V: Amount of titration [mL] at the end point of titration, S: Solid content concentration [% by mass] of dispersant sample. ]
The introduction amount of the compound having active hydrogen and tertiary amino group in the molecule is preferably controlled in the range of 1 to 100 mgKOH/g in terms of amine value after the reaction. More preferably, it is in the range of 5-95 mgKOH/g. The amine value is a value expressed in mg of KOH corresponding to the acid value obtained by neutralizing and titrating the basic amino group with an acid. When the amine value is above the lower limit, the dispersibility tends to be good, and when the amine value is below the upper limit, the developability tends to be good.

When the isocyanate group remains in the polymer dispersant after the reaction described above, it is preferable to crush the isocyanate group with an alcohol or an amino compound, since the stability of the product over time increases.
The weight-average molecular weight (Mw) of the urethane polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. 30000 or less is especially preferable. The dispersibility and dispersion stability tend to be improved by setting the amount to the lower limit or more, and the solubility tends to be improved by setting the amount to the upper limit or less. When the molecular weight is 30,000 or less, the alkali developability tends to be good even when the coloring material content is particularly high. Examples of such particularly preferred commercially available urethane dispersants include Disperbyk 167 and 182 (Byk-Chemie).

When the photosensitive resin composition of the present invention contains (e) a dispersant, the content of (e) dispersant is usually 50% by mass or less, preferably 30% by mass, in the total solid content of the photosensitive resin composition. %, more preferably 20% by mass or less, usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, particularly preferably 10% by mass or more. By setting it to the above lower limit or more, there is a tendency to easily secure sufficient dispersibility, and by setting it to the above upper limit or less, color density, sensitivity, film formation properties, etc. can be improved without reducing the proportion of other components. It tends to be good enough.

The content of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and usually 200 parts by mass or less, relative to 100 parts by mass of the (d) coloring material. , preferably 80 parts by mass or less, more preferably 50 parts by mass or less.
By setting it to the above lower limit or more, there is a tendency to easily secure sufficient dispersibility, and by setting it to the above upper limit or less, color density, sensitivity, film formation properties, etc. can be improved without reducing the proportion of other components. It tends to be good enough.

<Thiols>
The photosensitive resin composition of the present invention preferably contains thiols in order to increase sensitivity and improve adhesion to substrates. Examples of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate. , butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, Ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) (PGMB for short), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy ) Butane (trade name: Karenz MT BD1, manufactured by Showa Denko), butanediol trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) (trade name: Karenz MT PE1, Showa Denko company), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate) ), trimethylolpropane tris(3-mercaptobutyrate) (TPMB for short), trimethylolpropane tris(2-mercaptoisobutyrate) (TPMIB for short), 1,3,5-tris(3-mercaptobutyloxy ethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trade name: Karenz MT NR1, manufactured by Showa Denko Co., Ltd.), and the like. A seed|species can be used individually or in mixture of 2 or more types. Preferably, polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are preferred. Especially preferred.

When a thiol compound is used, the content of the thiol compound is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, more preferably 0.3% by mass or more, in the total solid content of the photosensitive resin composition of the present invention. It is 0.5% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less. When it is at least the above lower limit, it tends to be possible to suppress a decrease in sensitivity, and when it is at most the above upper limit, there tends to be a tendency to improve the storage stability.

<Solvent>
The photosensitive resin composition of the present invention is generally composed of (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator and optionally various components dissolved in an organic solvent. Or used in a distributed state.
As the organic solvent, it is preferable to select one having a boiling point (under a pressure of 1013.25 [hPa]; hereinafter, the same applies to all boiling points) in the range of 100 to 300°C. A solvent having a boiling point of 120 to 280° C. is more preferred.
Examples of such organic solvents include the following.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl glycol monoalkyl ethers such as ethers, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;

glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl glycol alkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone, methoxymethyl pentanone ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

Halogenated hydrocarbons such as butyl chloride, amyl chloride;
ether ketones such as methoxymethylpentanone;
Acetonitrile, nitriles such as benzonitrile, etc.:
Commercially available solvents corresponding to the above include Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2, Solvesso #150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“cellosolve” is a registered trademark. The same shall apply hereinafter.), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any are also trade names).

These organic solvents may be used alone or in combination of two or more.
When forming pixels of a color filter or a black matrix by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 250°C. More preferably, it has a boiling point of 120-230°C.
Among the above organic solvents, glycol alkyl ether acetates are preferable because they have a good balance of applicability, surface tension, etc., and relatively high solubility of constituent components in the composition.

Also, the glycol alkyl ether acetates may be used alone, or may be used in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferred as other organic solvents that may be used in combination. Among them, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituents in the composition. Glycol monoalkyl ethers have a high polarity, and if the amount added is too large, the pigment tends to aggregate, and the viscosity of the subsequently obtained photosensitive resin composition tends to decrease, resulting in a decrease in storage stability. , the ratio of the glycol monoalkyl ether in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

It is also preferable to use an organic solvent having a boiling point of 200° C. or higher (hereinafter sometimes referred to as a “high boiling point solvent”). The combined use of such a high boiling point solvent makes the photosensitive resin composition difficult to dry, but has the effect of preventing the uniformly dispersed state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of foreign matter defects due to deposition and solidification of the coloring material at the tip of the slit nozzle. From the point that such an effect is high, among the above-mentioned various solvents, dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1, 3-butylene glycol diacetate, triacetin, 1,6-hexanediol diacetate are preferred.

When a high boiling point solvent is used in combination, the content of the high boiling point solvent in the organic solvent is preferably 0% by mass to 50% by mass, more preferably 0.5% by mass to 40% by mass, and 1% by mass to 30% by mass. is particularly preferred. By making it equal to or higher than the above lower limit, there is a tendency to suppress, for example, the deposition and solidification of a coloring material at the tip of a slit nozzle and causing foreign matter defects. can be suppressed from becoming too slow, and it tends to be easy to avoid the occurrence of problems such as takt failure in the reduced pressure drying process and pre-baking pin marks in the color filter manufacturing process.

In the photosensitive resin composition of the present invention, the content of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more, More preferably 8% by mass or more, still more preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, particularly preferably 20% by mass or less. It is prepared as follows.

<Other compounding components of the photosensitive resin composition>
In the photosensitive resin composition of the present invention, in addition to the components described above, an adhesion improver, a coatability improver, a pigment derivative, a development improver, an ultraviolet absorber, an antioxidant, and the like can be appropriately blended.

<Adhesion improver>
In order to improve the adhesion to the substrate, an adhesion improver may be included, such as a silane coupling agent, a titanium coupling agent, etc., but a silane coupling agent is particularly preferred.
Examples of such silane coupling agents include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shin-Etsu Silicone Co., Ltd.), Z-6040, Z-6043, Z-6062 (manufactured by Dow Corning Toray Co., Ltd.) and the like. In addition, 1 type may be used for a silane coupling agent, and 2 or more types may be used together by arbitrary combinations and ratios.
Further, an adhesion improver other than the silane coupling agent may be contained in the photosensitive resin composition of the present invention, and examples thereof include a phosphoric acid-based adhesion improver and other adhesion improvers.

As the phosphoric acid-based adhesion improver, (meth)acryloyloxy group-containing phosphates are preferable, and among them, those represented by the following general formulas (g1), (g2), and (g3) are preferable.

In general formulas (g1), (g2) and (g3) above, each R ⁵¹ independently represents a hydrogen atom or a methyl group. l and l' each independently represent an integer of 1 to 10; m each independently represents 1, 2 or 3;
Other adhesion improvers include TEGO (registered trademark) Add Bond LTH (manufactured by Evonik). These phosphoric acid group-containing compounds and other adhesion agents may be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention contains an adhesion improver, the content of the adhesion improver is not particularly limited, but it is preferably 0.01% by mass or more in the total solid content, and 0.10% by mass. % or more, more preferably 0.50% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and 2 0% by mass or less, and particularly preferably 1.5% by mass or less. Adhesion strength tends to improve when the content is equal to or higher than the lower limit, and developability tends to be improved when the content is equal to or lower than the upper limit.

<Applicability improver>
The photosensitive resin composition of the present invention may contain a surfactant as a coatability improver in order to improve coatability. Various surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used as surfactants. Among them, it is preferable to use nonionic surfactants because they are less likely to adversely affect various properties. Among them, fluorine-based or silicone-based surfactants are effective in terms of coatability.

Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340. (manufactured by Shin-Etsu Silicone Co., Ltd.), Megafac F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray), DS-401 (Daikin) ), L-77 (manufactured by Nippon Unicar) and FC4430 (manufactured by 3M Japan). In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.
When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is not particularly limited. It is preferably 0.05% by mass or more, more preferably 1.0% by mass or less, more preferably 0.7% by mass or less, and 0.5% by mass or less. is more preferable, and 0.3% by mass or less is particularly preferable. When the concentration is equal to or higher than the above lower limit, coating uniformity tends to be improved.

<Pigment derivative>
The photosensitive resin composition of the present invention may contain a pigment derivative in order to improve dispersibility and storage stability. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine. Among them, phthalocyanine-based and quinophthalone-based derivatives are preferred.

Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, and the like, which may be directly attached to the pigment skeleton or may be attached to the skeleton of the pigment. Examples thereof include those bonded via a ring group or the like, preferably a sulfonic acid group. A single pigment skeleton may be substituted with a plurality of these substituents. Specific examples of pigment derivatives include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used individually by 1 type, and may use 2 or more types together.
The pigment derivative is preferably used together with a dispersant.

When the photosensitive resin composition of the present invention contains a pigment derivative, the content of the pigment derivative in the photosensitive resin composition is not particularly limited, but the total solid content of the photosensitive resin composition is 0.1% by mass. 0.5% by mass or more is more preferable, 1.0% by mass or more is even more preferable, and 10% by mass or less is preferable, and 5% by mass or less is more preferable. When the content is equal to or higher than the lower limit, the dispersion stability tends to be improved, and when the content is equal to or lower than the upper limit, the developability tends to be improved.

<Physical properties of the photosensitive resin composition>
The photosensitive resin composition of the present invention can be suitably used for forming a black matrix, and from such a viewpoint, it preferably exhibits a black color. Further, the optical density (OD) per 1 μm of film thickness of the cured film is preferably 1.0 or more, more preferably 2.0 or more, further preferably 2.5 or more, and 3 It is more preferably 0.0 or more, particularly preferably 4.0 or more, most preferably 4.5 or more, and usually 6.0 or less. By making it equal to or higher than the lower limit, there is a tendency that sufficient light shielding properties can be ensured.

<Method for producing a photosensitive resin composition>
The photosensitive resin composition of the present invention is produced according to a conventional method.
When (d) a colorant is included, it is usually preferred that the (d) colorant is previously dispersed using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. Since the coloring material (d) is finely divided by the dispersion treatment, the coating properties of the photosensitive resin composition tend to be improved. In addition, when a black colorant is used as the colorant (d), it contributes to the improvement of the light shielding ability.

Dispersion treatment is usually preferably carried out in a system in which (d) a coloring material, an organic solvent, and optionally (e) a dispersant and (a) a part or all of an alkali-soluble resin are used in combination (hereinafter referred to as The mixture subjected to the dispersion treatment and the composition obtained by the treatment are sometimes referred to as "ink" or "pigment dispersion"). In particular, it is preferable to use a polymer dispersant as the dispersant, since the resulting ink and photosensitive resin composition are prevented from thickening over time (excellent in dispersion stability).
When dispersion treatment is performed on a liquid containing all the components to be blended in the photosensitive resin composition, highly reactive components may be denatured due to heat generated during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymer dispersant.

When dispersing (d) the coloring material with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is usually from 0°C to 100°C, preferably from room temperature to 80°C. The appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, etc., and is therefore adjusted as appropriate. The index of dispersion is to control the glossiness of the ink so that the 20 degree specular glossiness (JIS Z8741) of the photosensitive resin composition is in the range of 100-200. When the glossiness of the photosensitive resin composition is low, dispersion processing is often insufficient and rough pigment (coloring material) particles remain, resulting in insufficient developability, adhesion, resolution, etc. there is a possibility. Further, if the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment is crushed to produce a large number of ultrafine particles, which tends to impair the dispersion stability.

Next, the ink obtained by the dispersion treatment and the other components contained in the photosensitive resin composition are mixed to form a uniform solution. In the production process of the photosensitive resin composition, fine dust is often mixed in the liquid, so it is desirable to filter the obtained photosensitive resin composition with a filter or the like.

[Cured product]
The cured product of the invention is obtained by curing the photosensitive resin composition of the invention. A cured product obtained by curing the photosensitive resin composition can be suitably used as a member constituting a color filter such as a pixel, a black matrix, and a colored spacer.

[Black Matrix]
The black matrix of the present invention comprising the cured product of the present invention and the color filter containing the black matrix of the present invention will be described according to the production method thereof.

(1) Support The material of the support for forming the black matrix is not particularly limited as long as it has an appropriate strength. Transparent substrates are mainly used, and the materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy resins. , unsaturated polyester resin, thermosetting resin sheet such as poly(meth)acrylic resin, or various glasses. Among these, glass and heat-resistant resin are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Besides the transparent substrate, it can also be formed on a TFT array.

In order to improve surface physical properties such as adhesiveness, if necessary, the support may be subjected to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, silane coupling agent, or thin film formation treatment using various resins such as urethane resins. may be performed.
The thickness of the transparent substrate is usually in the range of 0.05-10 mm, preferably 0.1-7 mm. When thin films of various resins are formed, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2) Black Matrix In order to form the black matrix of the present invention from the above-described photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention is coated on a transparent substrate, dried, and then the sample. A photomask is placed thereon, and a black matrix is formed by imagewise exposure through the photomask, development, and heat curing or photocuring as required.

(3) Formation of black matrix (3-1) Application of photosensitive resin composition The photosensitive resin composition for the black matrix can be applied onto the transparent substrate by spinner method, wire bar method, flow coat method or die coat method. , a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating liquid used is greatly reduced, and there is no effect of mist that adheres when using the spin coating method, and the generation of foreign matter is suppressed. preferred from

The thickness of the coating film after drying is usually preferably in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and still more preferably in the range of 1 to 4 μm. be. By making it below the said upper limit, there exists a tendency for pattern development to become easy and to become easy to adjust the gap in a liquid-crystal cell-forming process. By making it more than the said lower limit, there exists a tendency for desired color expression to become easy.

(3-2) Drying of Coating Film Drying of the coating film after applying the photosensitive resin composition to the substrate is preferably by a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions can be appropriately selected depending on the type of the solvent component, the performance of the dryer to be used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably at a temperature of 50 to 130 ° C., depending on the type of solvent component, the performance of the dryer used, etc. It is selected in the range of 30 seconds to 3 minutes.

The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. In addition, the drying process of this coating film may be a reduced pressure drying method in which the drying is performed in a reduced pressure chamber without increasing the temperature.

(3-3) Exposure Imagewise exposure is carried out by overlaying a negative mask pattern on the coating film of the photosensitive resin composition and irradiating light of wavelengths from the ultraviolet region to the visible region through this mask pattern. In this case, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, the exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film. The light source used for the above image exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and carbon arcs. An optical filter can also be used when using it by irradiating the light of a specific wavelength.

(3-4) Development The black matrix according to the present invention is prepared by subjecting a coating film made of a photosensitive resin composition to imagewise exposure with the light source described above, followed by an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. can be produced by forming an image on the substrate by development with This aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate. , sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, inorganic alkaline compounds such as ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine , mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. compound. These alkaline compounds may be a mixture of two or more.

Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; Anionic surfactants such as salts, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinate ester salts, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of organic solvents include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution.
The conditions for the development treatment are not particularly limited, and the development temperature is usually in the range of 10 to 50°C, especially 15 to 45°C, particularly preferably 20 to 40°C. Any method such as a development method or an ultrasonic development method can be used.

(3-5) Heat Curing Treatment The substrate after development is subjected to heat curing treatment or photocuring treatment, preferably heat curing treatment. At this time, the heat curing treatment conditions are selected within a temperature range of 100 to 280° C., preferably 150 to 250° C., and a time range of 5 to 60 minutes.
The height of the black matrix formed as described above is usually 0.5 to 5 μm, preferably 0.8 to 4 μm.
Furthermore, the optical density (OD) per 1 μm of thickness is 2.0 or more, preferably 2.5 or more, more preferably 3.0 or more, and particularly preferably 3.2 or more.

On a transparent substrate provided with a black matrix, a photosensitive resin composition containing a coloring material of one of red, green, and blue is applied in the same process as (3-1) to (3-5) above, and dried. After that, a photomask is overlaid on the coating film, imagewise exposure through the photomask, development, and if necessary, thermal curing or photocuring are performed to form a pixel image, thereby forming a colored layer. A color filter image can be formed by performing this operation for each of the three photosensitive resin compositions of red, green, and blue. These orders are not limited to the above.

The photosensitive resin composition of the present invention can also be used as a photosensitive resin composition for colored spacers in addition to the black matrix. When spacers are used in a TFT-type LCD, light incident on the TFTs may cause the TFTs to malfunction as switching elements. Colored spacers are used to prevent this. describes that the spacer is light-shielding. The colored spacers can be formed in the same manner as the black matrix described above, except that a colored spacer mask is used.

(3-6) Formation of transparent electrodes The color filter is used as a part of parts such as color displays and liquid crystal display devices by forming transparent electrodes such as ITO on the image in this state. A topcoat layer of polyamide, polyimide, or the like may be provided on the image, if necessary, in order to improve the properties and durability. In addition, in some applications such as planar alignment driving system (IPS mode), the transparent electrode may not be formed.

[Image display device]
The image display device of the present invention has the cured product of the present invention, and includes, for example, the black matrix of the present invention. The image display device is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display, which will be described later.

[Liquid crystal display device]
The liquid crystal display device of the present invention has the above-described black matrix of the present invention, and the formation order and formation position of the color pixels and the black matrix are not particularly limited.

In a liquid crystal display device, an alignment film is usually formed on a color filter, spacers are dispersed on the alignment film, and then bonded to a counter substrate to form a liquid crystal cell. Liquid crystal is injected into the formed liquid crystal cell, It is completed by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. A gravure printing method and/or a flexographic printing method is usually employed for forming the alignment film, and the thickness of the alignment film is set to several tens of nanometers. After hardening the alignment film by heat baking, the surface is treated by irradiation with ultraviolet rays or treatment with a rubbing cloth, so that the surface state is processed so that the tilt of the liquid crystal can be adjusted.

As the spacer, a spacer having a size corresponding to the gap (clearance) with the counter substrate is used, and a spacer of 2 to 8 μm is usually suitable. A photospacer (PS) made of a transparent resin film can be formed on the color filter substrate by photolithography and used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly suitable.

The gap between the opposing substrate and the bonding substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the opposing substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and/or heating to seal the periphery of the liquid crystal cell.
After the liquid crystal cell with its periphery sealed is cut into panels, the pressure is reduced in a vacuum chamber, the liquid crystal inlet is immersed in the liquid crystal, and then the chamber is leaked to inject the liquid crystal into the liquid crystal cell. . The degree of pressure reduction in the liquid crystal cell is usually 1×10 ^-2 to 1×10 ^-7 Pa, preferably 1×10 ^-3 to 1×10 ^-6 Pa. Moreover, it is preferable to heat the liquid crystal cell when the pressure is reduced, and the heating temperature is usually 30 to 100.degree. Heating and holding at reduced pressure is usually in the range of 10 to 60 minutes, and then immersed in liquid crystal. A liquid crystal display device (panel) is completed by sealing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected by curing the UV curing resin.

There are no particular restrictions on the type of liquid crystal, and any known liquid crystal such as aromatic, aliphatic, polycyclic compounds, lyotropic liquid crystal, thermotropic liquid crystal, or the like may be used. Thermotropic liquid crystals include nematic liquid crystals, smestic liquid crystals, cholesteric liquid crystals, and the like, and any of them may be used.

[Organic EL display]
The organic EL display of the invention is produced using the color filter of the invention.

When producing an organic EL display using the color filter of the present invention, for example, as shown in FIG. A color filter is prepared by forming a resin black matrix (not shown) provided between the pixels 20, and an organic light emitter 500 is formed on the color filter with an organic protective layer 30 and an inorganic oxide film 40 interposed therebetween. The organic EL element 100 can be produced by laminating the . At least one of the pixels 20 and the resin black matrix is manufactured using the photosensitive resin composition of the present invention. As a method of stacking the organic light emitter 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter, or , a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40, and the like. Using the organic EL element 100 produced in this way, for example, the method described in "Organic EL Display" (Ohmsha, August 20, 2004, Shizuo Tokito, Chihaya Adachi, Hideyuki Murata), etc. , an organic EL display can be produced.

The color filter of the present invention can be applied to both a passive drive type organic EL display and an active drive type organic EL display.

EXAMPLES Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

<Synthesis of alkali-soluble resin>
Alkali-soluble resins (1) to (5) were prepared according to the following procedure.

(Alkali-soluble resin (1))

6 g of the epoxy compound (epoxy equivalent weight: 228) having the above chemical structure, 1.92 g of acrylic acid, 8.02 g of propylene glycol monomethyl ether acetate, 0.0995 g of triphenylphosphine, and 0.006 g of p-methoxyphenol were mixed with a thermometer, a stirrer, and a cooler. The mixture was placed in a flask fitted with a tube, heated with stirring at 90°C for 7 hours, and then reacted at 110°C until the liquid acid value reached 5 mgKOH/g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
13.2 g of the resulting epoxy acrylate solution, 0.3 g of trimethylolpropane (TMP), 1.99 g of biphenyltetracarboxylic dianhydride (BPDA), 0.51 g of tetrahydrophthalic anhydride (THPA), and propylene glycol monomethyl Put 5.49 g of ether acetate (PGMEA) in a flask equipped with a thermometer, a stirrer and a cooling tube, slowly raise the temperature to 105 ° C. while stirring to react, solid content acid value 102 mg KOH / g, weight average molecular weight 5400 An alkali-soluble resin (1) was obtained.

(Alkali-soluble resin (2))
A mixed liquid of 210.1 parts by mass of propylene glycol monomethyl ether acetate and 52.5 parts by mass of propylene glycol monomethyl ether was stirred under nitrogen substitution and heated to 120°C. Here, 3.52 parts by mass of benzyl methacrylate, 68.8 parts by mass of methacrylic acid, 39.7 parts by mass of monomethacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton and 2,2'-azobis-2- A mixed solution of 3.3 parts by mass of methylbutyronitrile was added dropwise over 3 hours, and the mixture was further stirred at 90° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 38.4 parts by mass of glycidyl methacrylate, 0.8 parts by mass of trisdimethylaminomethylphenol and 0.1 part by mass of hydroquinone were added, and the reaction was continued at 100°C for 12 hours. Thus, an alkali-soluble resin (2) having a weight average molecular weight of 19,100 and a solid content acid value of 198 mgKOH/g was obtained.

(Alkali-soluble resin (3))

50 g of the epoxy compound (epoxy equivalent weight: 264) having the above chemical structure, 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of p-methoxyphenol were mixed with a thermometer, a stirrer, and a condenser. was placed in a flask equipped with , and the mixture was reacted at 90° C. with stirring until the liquid acid value became 5 mgKOH/g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.

25 g of the epoxy acrylate solution, 0.74 g of trimethylolpropane (TMP), 4.0 g of biphenyltetracarboxylic dianhydride (BPDA), and 2.7 g of tetrahydrophthalic anhydride (THPA) were mixed with a thermometer, a stirrer, and a cooling The mixture was placed in a flask fitted with a tube and slowly heated to 105° C. with stirring to react to obtain an alkali-soluble resin (3) having a solid content acid value of 110 mgKOH/g and a weight average molecular weight of 4,000.

(Synthesis of alkali-soluble resin (4))

42 g of the epoxy compound (epoxy equivalent weight: 246) having the above chemical structure, 12.7 g of acrylic acid, 47.8 g of PGMEA, 1 g of triphenylphosphine, and 0.025 g of p-methoxyphenol were placed in a flask equipped with a thermometer, a stirrer and a cooling tube. , while stirring, the mixture was reacted at 90° C. until the liquid acid value became 5 mgKOH/g or less. The reaction took 15 hours to obtain an epoxy acrylate solution.
25 g of the resulting epoxy acrylate solution, 0.76 g of trimethylolpropane (TMP), 3.7 g of biphenyltetracarboxylic dianhydride (BPDA), and 3.9 g of tetrahydrophthalic anhydride (THPA) were measured with a thermometer, a stirrer, and a cooling The mixture was placed in a flask equipped with a tube and slowly heated to 105° C. with stirring to react, thereby obtaining an alkali-soluble resin (4) having a solid content acid value of 131 mgKOH/g and a weight average molecular weight of 3,000.

(Synthesis of alkali-soluble resin (5))

6 g of the epoxy compound (epoxy equivalent weight: 240) having the above chemical structure, 1.82 g of acrylic acid, 7.915 g of propylene glycol monomethyl ether acetate, 0.094 g of triphenylphosphine, and 0.0056 g of p-methoxyphenol were mixed with a thermometer, a stirrer, and a cooler. The mixture was placed in a flask equipped with a tube and reacted at 100° C. with stirring until the liquid acid value became 5 mgKOH/g or less. The reaction took 9 hours to obtain an epoxy acrylate solution.
7.28 g of the resulting epoxy acrylate solution, 0.047 g of trimethylolpropane (TMP), 1.57 g of biphenyltetracarboxylic dianhydride (BPDA), 0.29 g of tetrahydrophthalic anhydride (THPA), and propylene glycol monomethyl Put 6.11 g of ether acetate (PGMEA) in a flask equipped with a thermometer, a stirrer and a cooling tube, slowly raise the temperature to 105 ° C. while stirring to react, solid content acid value 101 mg KOH / g, weight average molecular weight 10200 An alkali-soluble resin (5) was obtained.

<Dynamic viscoelasticity measurement>
After vacuum drying the alkali-soluble resins (1) to (5) at 85 ° C. for 3 hours, press machine (Mini Test Press 10 (manufactured by Toyo Seiki Seisakusho), 70 ° C. press, pressure 15 MPa, preheating time before pressurization 5 A film with a thickness of 0.3 mm was prepared at 3 minutes, pressurization time 3 minutes), dynamic viscoelasticity was measured with a rheometer (ARES-G2 (manufactured by TA Instruments)), and the softening point was calculated. . The measurement conditions and the method of calculating the softening point are as follows. Table 1 shows the results. FIG. 2 shows a graph of the dynamic viscoelasticity measurement of the alkali-soluble resin (1) (vertical axis: storage elastic modulus G', horizontal axis: temperature).
Frequency: 1Hz
Strain amount: 1%
Plate diameter: 25mm
Plate type: Al disposable parallel plate Automatic tension adjustment: Axial Force 200g
Measurement object: temperature change of storage modulus G' Measurement temperature: 70 to 230 ° C. (temperature increase, 5 ° C./min)
Calculation method of softening point: In the curve of the obtained graph (vertical axis: storage elastic modulus G ', horizontal axis: temperature), the temperature rises from 70 ° C. and the first inflection point that turns convex downward The temperature was taken as the softening point (°C), and the point where G' showed the minimum value was taken as the minimum point (°C). In addition, when it is already convex downward at 70°C, the softening point is set to less than 70°C. In addition, when the inflection point that becomes a downward convexity does not appear even when the temperature is raised to 230°C, the softening point is defined as exceeding 230°C.

<Preparation of carbon black ink>
A carbon black ink was prepared by blending a pigment, a dispersant, a dispersing aid, and a solvent according to the following composition and method. Specifically, first, the solid content of the pigment, the dispersant, and the dispersing aid and the solvent were mixed so as to have the following mass ratio.
・ Pigment: RAVEN1060U (R1060) (carbon black manufactured by Birler); 100.0 parts by mass ・ Dispersant: DISPERBYK-167 (basic urethane-based dispersant manufactured by BYK-Chemie); 11.63 parts by mass (solid content conversion)
Dispersing aid (pigment derivative): Solsperse 12000 (manufactured by Lubrizol, phthalocyanine pigment derivative having an acidic group); 1.98 parts by mass Solvent: propylene glycol monomethyl ether acetate (PGMEA); 215.5 parts by mass They were sufficiently stirred and mixed to obtain a dispersion liquid.

Next, this dispersion was subjected to dispersion treatment for 6 hours at a temperature of 25 to 45° C. using a paint shaker. As the beads, zirconia beads with a diameter of 0.5 mm were used, and 180 parts by mass of the beads were added to 60 parts by mass of the dispersion. After completion of the dispersion treatment, the beads and the dispersion liquid were separated by a filter to prepare a carbon black ink having a total solid content of 34.5% by mass.

<Preparation of photosensitive resin composition>
(Preparation of black resist 1)
Using the carbon black ink prepared in <Preparation of Carbon Black Ink>, each component was added in the ratio shown in Table 2, and the mixture was stirred and dissolved with a stirrer to prepare Black Resist 1. The content ratio of the total solid content in the black resist 1 is 15% by mass.

The details of each component in the table are as follows.
Photopolymerizable monomer (1): Dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator (1): TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.)
Surfactant (1): Megafac F-554 (manufactured by DIC, fluorine-based surfactant)
PGMEA: propylene glycol monomethyl ether acetate MBA: 3-methoxybutyl acetate

(Preparation of black resist 2)
Black resist 2 was prepared in the same manner as black resist 1, except that alkali-soluble resin (1) in black resist 1 was changed to alkali-soluble resin (2).

(Preparation of black resist 3)
Black resist 3 was prepared in the same manner as black resist 1, except that alkali-soluble resin (1) in black resist 1 was changed to alkali-soluble resin (3).

(Preparation of black resist 4)
Black resist 4 was prepared in the same manner as black resist 1, except that alkali-soluble resin (1) in black resist 1 was changed to alkali-soluble resin (4).

(Preparation of black resist 5)
Black resist 5 was prepared in the same manner as for black resist 1, except that alkali-soluble resin (1) in black resist 1 was changed to alkali-soluble resin (5).

(Preparation of black resist 6)
Black resist 1 is the same as black resist 1 except that alkali-soluble resin (1) in black resist 1 is changed to a mixture of alkali-soluble resin (1) and alkali-soluble resin (3) (mixing ratio is 20:80 (mass ratio)). A black resist 6 was similarly prepared.

(Preparation of black resist 7)
Black resist 7 was prepared in the same manner as black resist 6, except that alkali-soluble resin (1) in black resist 6 was changed to alkali-soluble resin (2).

<Evaluation of black resist>
(1) Production of Black Matrix (BM) Cured Film The prepared black resist was applied to a glass substrate using a spin coater, dried under reduced pressure, and dried on a hot plate at 100° C. for 120 seconds. The coating conditions were adjusted so that each coating film thickness was about 1.2 μm.

Subsequently, the resulting dried coating film was exposed using an exposure machine (EXF-2829-F-00 manufactured by Oak Manufacturing Co., Ltd.) with a high-pressure mercury lamp (ADH-3000M-FN manufactured by Oak Manufacturing Co., without an optical filter). Pattern exposure (proximity gap 180 μm) was performed at 40 mJ/cm ² through an exposure mask having linear openings with a pattern width of 1 to 20 μm (1 to 10 μm: increments of 1 μm, 10 to 20 μm: increments of 5 μm). After that, using a KOH aqueous solution adjusted to 0.04% by mass with ultrapure water as an alkaline developer, at room temperature (23 ° C.), spray development for 1.9 times the dissolution time (spray pressure: 0.1 MPa ), and further spray-cleaned with ultrapure water (spray pressure: 0.1 MPa) to obtain a BM film. Then, it was cured and baked in an oven at 230° C. for 30 minutes to prepare a BM cured film. The dissolution time is the time during which the unexposed portion of the photosensitive layer dissolves and the entire substrate begins to be visible during development, and the dissolution time of each black resist was between 12 and 81 seconds.

(2) Evaluation of BM Line Width and Line Width Variation The line width of the BM line pattern in the BM film and the BM cured film was measured with an optical microscope, and the line width variation before and after curing and baking was measured. Table 3 shows the measurement results of the line width and line width variation of the BM film of the pattern corresponding to the 15 μm opening.
In the BM film corresponding to the opening of 1 μm to 10 μm, the width of the opening of the exposure mask corresponding to the pattern with the thinnest line width among those left on the glass substrate without chipping or surface roughness. was evaluated as development adhesion. The smaller the development adhesion value, the better the adhesion to the substrate and the higher the resolution. Table 3 shows the results.

(3) Linearity A BM film having a pattern corresponding to a 15 μm opening was observed with an optical microscope (magnification: 500), and the line shape was evaluated according to the following criteria. Table 3 shows the results.
◯: The line is straight without rattling or chipping.
Δ: The line has several defects, but is almost straight.
x: Lines are rickety, and line width variations of 2 μm or more occur. Or the pattern is peeled off.

As shown in Table 3, in the photosensitive resin compositions of Examples 2 and 3 using the alkali-soluble resin of the present invention, the linearity is good, the development adhesion is as small as 7 μm, and the line width change due to curing. was suppressed, and good fine lines could be obtained.
Furthermore, when the results of Example 3 and Comparative Example 6 are compared, the effect of suppressing the line width change is sufficient even when the content of the alkali-soluble resin of the present invention in the alkali-soluble resin is about 20% by mass. I understand.

The alkali-soluble resin of the present invention has a softening point of 100° C. or lower and a minimum value of storage elastic modulus G′ of 2×10 ³ Pa or higher. This is probably because the thermal cross-linking reaction between the alkali-soluble resins proceeded efficiently.

On the other hand, the pattern of the photosensitive resin composition of Comparative Example 5 was peeled off by development, leaving no fine lines. This is because the alkali-soluble resin (2) contained in the photosensitive resin composition has a minimum storage elastic modulus G′ of 2×10 ³ Pa or more, but a softening point of more than 100°C. This is probably because the movement of the main chain of the alkali-soluble resin is small, and the photocrosslinking reaction between the alkali-soluble resins does not progress easily.

The photosensitive resin compositions of Comparative Examples 6 to 8 have good linearity, but the line width after curing and baking is greatly increased. This is because the alkali-soluble resins (3) to (5) contained in the photosensitive resin composition have a softening point of 100° C. or lower, but a minimum storage elastic modulus G′ of less than 2×10 ³ Pa. It is considered that this is because the flow progresses more favorably than the thermal cross-linking reaction between the alkali-soluble resins.

On the other hand, in Comparative Example 9, 20% by mass of the alkali-soluble resin (3) in Comparative Example 6 was replaced with the alkali-soluble resin (2). A deterioration in the properties was confirmed, and a good fine line could not be obtained. This is probably because the softening point of the alkali-soluble resin (2) is as high as 145° C., making it hard and brittle, and chipping easily during spray development and spray washing.

Based on the above results, by giving the alkali-soluble resin the function of suppressing the line width change, the mixing ratio can be changed in a wide range, and compositions having various performances can be selected.
Although the details of the action of the alkali-soluble resin in the present invention are not clear, it is believed to be as follows.

In general, when heat resistance is required for resins, those with high glass transition points and softening points are oriented. A heat-resistant resin having a softening point of 130° C. or higher is used to provide the In addition, in the case of a curable resin composition, it is considered sufficient if the heat resistance after curing is high.

However, if an alkali-soluble resin with a high softening point is used, although deformation during curing and baking can be suppressed, a hard and brittle film is formed, which reduces the linearity of the pattern after development. Poor linearity remains). Also, with alkali-soluble resins with a high softening point, the motion of the main chain is restricted to local vibrations, making photocrosslinking between alkali-soluble resins difficult to proceed during exposure, leading to a decrease in development adhesion (pattern peeling, etc.). Seem. From the above, it is considered that a resin having a high softening point is not suitable for thin line formation because it involves problems such as a decrease in linearity and a decrease in developability such as development adhesion. High softening point settings should be avoided to maintain linearity.

On the other hand, in the case of an alkali-soluble resin having a softening point of 100° C. or lower and a minimum value of G' of less than 2×10 ³ Pa, there is no problem in linearity after development, but softening and viscosity reduction occur at the initial stage of curing and baking. occurs, the line width increases, and then gelation due to thermal cross-linking (solidification due to the formation of a network structure) proceeds, so the increase in line width cannot be suppressed.
During the temperature rise of the cure bake, the softening and viscosity reduction of the resin progresses, while the thermal cross-linking reaction (which leads to the viscosity increase) occurs competitively. This thermal cross-linking reaction can occur between alkali-soluble resins, between an alkali-soluble resin and a photopolymerizable monomer, or between photopolymerizable monomers. It is considered important to proceed. In the case of an alkali-soluble resin with a minimum value of G' of less than 2×10 ³ Pa, the thermal cross-linking reaction between the alkali-soluble resin and the photopolymerizable monomer or between the photopolymerizable monomers proceeds predominantly, and flow due to a decrease in viscosity can be suppressed. not

In the case of an alkali-soluble resin having a softening point of 100° C. or less and a minimum value of G' of 2×10 ³ Pa or more, it is assumed that the interaction between the main chains of the alkali-soluble resin acts to develop structural viscosity. Conceivable. The proximity of the main chains of the alkali-soluble resins works favorably to the progress of the thermal cross-linking reaction between the alkali-soluble resins. It is considered that in the alkali-soluble resin having a G' of 2×10 ³ Pa or more, gelation due to thermal cross-linking between the alkali-soluble resins begins to proceed predominantly as the resin begins to soften, thereby suppressing the flow. Moreover, even in a resin mixed system such as that of Example 3, it is considered that the effect of suppressing the flow is maintained due to the interaction between the main chains of the resins.
In particular, the alkali-soluble resin (1) has a skeleton in which two fluorene rings are linked by a methylene group, and the main chains can be adsorbed to each other through multipoint π-π interactions through the fluorene rings. Furthermore, polymerizable groups (acryloyl groups) are arranged on both sides of this skeleton, and since they are present at a short distance from each other, the resin is such that cross-linking between the main chains easily proceeds.

As described above, by using the alkali-soluble resin of the present invention, it is possible to control the line width change during heat curing while avoiding the deterioration of the linearity. goods can be provided.

REFERENCE SIGNS LIST 10 transparent support substrate 100 organic EL element 20 pixel 30 organic protective layer 40 inorganic oxide film 50 transparent anode 500 organic light emitter 51 hole injection layer 52 hole transport layer 53 light emitting layer 54 electron injection layer 55 cathode

Claims (4)

(a) an alkali-soluble resin, (b) a photopolymerizable monomer, and (c) a photopolymerization initiator
A photosensitive resin composition that
The (a) alkali-soluble resin satisfies the following (I) and (II) and has the following general formula (
1) containing an alkali-soluble resin having a partial structure represented by
Further (d) contains a coloring material,
The photosensitive resin composition, wherein the (d) colorant contains carbon black .
(I) Softening point of 100° C. or less (II) Minimum value of storage elastic modulus G′ obtained by dynamic viscoelasticity measurement of 2×10 ³ Pa or more

(In Formula (1), * represents a bond. The benzene ring in Formula (1) may be further substituted with any substituent.) Al satisfies the above (I) and (II) and has a partial structure represented by the general formula (1)
2. The sensor according to claim 1, wherein the potash-soluble resin has a partial structure represented by the following general formula (3):
Optical resin composition .

(In Formula (3), R ¹ represents a hydrogen atom or a methyl group. * represents a bond.) A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2 . An image display device comprising the cured product according to claim 3 .

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