JP7643133B2 - Method for preparing alkali-soluble resin, method for producing photosensitive resin composition, method for producing cured product, and method for producing image display device - Google Patents

Description

The present invention relates to a method for preparing an alkali-soluble resin, a method for producing a photosensitive resin composition containing the alkali-soluble resin prepared by this method, a method for producing a cured product obtained from the photosensitive resin composition, and a method for producing an image display device using the cured product.

Photosensitive resin compositions are widely used as photoresist materials to form the pixels and black matrices of color filters. Color filters are generally known to be made by forming a black matrix on the surface of a transparent substrate such as glass or plastic, followed by the formation of three or more different color pixels of red, green, blue, etc. in a lattice, stripe, mosaic, or other pattern.

The black matrix used in color filters is generally arranged in a grid, stripe or mosaic pattern between red, green, blue and other pixels, improving contrast by suppressing color mixing between pixels or preventing light leakage. Black matrices are generally formed by applying a photosensitive resin composition, which is a photoresist material, onto a substrate, exposing it to light and developing it.

Photosensitive resin compositions used as photoresist materials generally contain an alkali-soluble resin that is soluble in an alkaline developer. Photosensitive resin compositions used in black matrices are known to contain photopolymerizable monomers, photopolymerization initiators, colorants, and the like in addition to an alkali-soluble resin, as disclosed in Patent Document 1, for example.

Patent No. 6341351

In recent years, color filters have become more precise, and as a result, black matrices are becoming thinner. As black matrices become thinner, there is an increased demand for stabilizing quality, such as suppressing variations in line width, in actual production.

However, the properties of the alkali-soluble resin and other raw materials used in the photosensitive resin composition vary, for example, between lots, and the raw material variations affect various properties of the photosensitive resin composition, such as its photocurability and coatability, making it difficult to stabilize quality, such as suppressing line width variations, in actual production. In particular, photosensitive resin compositions for forming black matrices contain black colorants and have light-shielding properties, which results in low photocurability and a large impact on the properties caused by raw material variations, making it even more difficult to stabilize quality.

Therefore, the objective of the present invention is to stabilize the quality of cured products formed from photosensitive resin compositions, such as black matrices.

As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by using at least two types of alkali-soluble resins to be blended in a photosensitive resin composition for forming a cured product such as a black matrix and determining the mixing ratio of the at least two types of alkali-soluble resins by a predetermined method, and have completed the present invention as described below. That is, the present invention provides the following [1] to [7].
[1] A method for preparing an alkali-soluble resin for use in a photosensitive resin composition, comprising the steps of:
A step of preparing a plurality of photosensitive resin compositions for evaluation, each of which has a mixing ratio of an alkali-soluble resin (a-1) and an alkali-soluble resin (a-2) that is different from one another, in a mixing ratio of 0/100 to 100/0 (mass ratio);
evaluating the developability of each of the plurality of photosensitive resin compositions for evaluation;
determining a mixing ratio of the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) from the result of the positive evaluation of development, and mixing the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) in the determined mixing ratio to prepare an alkali-soluble resin;
A method for preparing an alkali-soluble resin for use in a photosensitive resin composition.
[2] A method for producing a photosensitive resin composition, comprising obtaining a photosensitive resin composition containing at least the alkali-soluble resin obtained by the preparation method according to the above [1], a photopolymerizable monomer, and a photopolymerizable initiator.
[3] The method for producing a photosensitive resin composition according to the above [2], further comprising blending a colorant into the photosensitive resin composition.
[4] The method for producing a photosensitive resin composition according to the above [3], wherein the colorant contains carbon black.
[5] A method for producing a cured product, comprising curing a photosensitive resin composition obtained by the method for producing a cured product according to any one of [2] to [4] above.
[6] A method for producing a black matrix, which is formed from the cured product obtained by the method for producing a black matrix according to the above [5].
[7] A method for producing an image display device, which uses a black matrix obtained by the method for producing the image display device according to the above [6].

The method for preparing an alkali-soluble resin of the present invention makes it possible to stabilize the quality of the cured product formed from the photosensitive resin composition.

Hereinafter, the embodiments of the present invention will be described in detail. However, the contents of the present invention are not limited to the embodiments described below.
In the following description, "(meth)acrylic" means "acrylic and/or methacrylic", and the same applies to other similar terms. Furthermore, the "total solid content" means all components other than the solvent contained in the photosensitive resin composition for evaluation or the photosensitive resin composition (F), or in the ink or dispersion liquid described below.
Furthermore, the weight average molecular weight refers to the weight average molecular weight (Mw) calculated in terms of polystyrene by GPC (gel permeation chromatography).

<Method for preparing alkali-soluble resin>
The method for preparing an alkali-soluble resin of the present invention comprises the following steps 1 to 3. The alkali-soluble resin prepared by this method (hereinafter, may be referred to as "alkali-soluble resin (f)") is a resin used in photosensitive resin compositions (hereinafter, may be referred to as "photosensitive resin composition (F)" or "resist") for forming various cured products such as black matrices in actual production, for example.

Step 1: A step of preparing a plurality of photosensitive resin compositions for evaluation in which an alkali-soluble resin (a-1) and an alkali-soluble resin (a-2) are blended at a mixing ratio of 0/100 to 100/0 (mass ratio) and the mixing ratios are different from each other. Step 2: A step of evaluating the developability of each of the plurality of photosensitive resin compositions for evaluation. Step 3: A step of determining the mixing ratio of the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) from the results of the developability evaluation, and mixing the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) at the determined mixing ratio to prepare an alkali-soluble resin (f).

In the present invention, the quality of the cured product formed from the photosensitive resin composition (F) can be stabilized by using the alkali-soluble resin (f) obtained by the preparation method including the above steps 1 to 3 in the photosensitive resin composition (F). Each of steps 1 to 3 will be described in detail below.

(Step 1)
In step 1, first, a plurality of photosensitive resin compositions for evaluation are prepared. Here, each photosensitive resin composition for evaluation is a mixture of at least an alkali-soluble resin (a-1) and an alkali-soluble resin (a-2) in a mass ratio (a-1/a-2) of 0/100 to 100/0. In addition, each photosensitive resin composition for evaluation has a different mixing ratio.

Details of the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) will be described later, but the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) are different from each other. And, because the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) are different from each other, they affect the developability evaluated in step 2. Therefore, the photosensitive resin compositions for evaluation have different mixing ratios of the resin (a-1) and the resin (a-2), and therefore the developability evaluations performed for each photosensitive resin composition for evaluation are different from each other.

Here, the above-mentioned mixing ratios in each photosensitive resin composition for evaluation are arbitrary as long as they are different from each other, but it is preferable that the mixing ratio of at least one photosensitive resin composition for evaluation is adjusted to be greater than the mixing ratio determined in step 3, and the mixing ratio of at least another photosensitive resin composition for evaluation is adjusted to be smaller than the mixing ratio determined in step 3. By adjusting the mixing ratios in this way, the quality of the cured product formed from the photosensitive resin composition (F) is less likely to deviate from the target quality, making it easier to stabilize the quality.

In addition, when the total amount of resin (a-1) and resin (a-2) in each photosensitive resin composition for evaluation is 100 parts by mass, the difference between the parts by mass of resin (a-1) in the photosensitive resin composition for evaluation with the least amount of resin (a-1) among the multiple photosensitive resin compositions for evaluation and the parts by mass of resin (a-1) in the photosensitive resin composition for evaluation with the most amount of resin (a-1) is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more. In this way, by increasing the difference in the content ratio of resin (a-1) between the photosensitive resin compositions for evaluation, the difference in the developability of each photosensitive resin composition for evaluation is also likely to increase. Therefore, the quality of the cured product formed from the photosensitive resin composition (F) is less likely to deviate from the target quality. The upper limit of the difference in the above parts by mass is not particularly limited, and it is sufficient that it is 100 parts by mass or less.

In the above mixing ratio, 0/100 means that no alkali-soluble resin (a-1) is blended, and 100/0 means that no alkali-soluble resin (a-2) is blended. Therefore, one of the multiple photosensitive resin compositions for evaluation may be a composition that does not contain the alkali-soluble resin (a-2). Also, one of the multiple photosensitive resin compositions for evaluation may be a composition that does not contain the alkali-soluble resin (a-1).
However, it is preferable that at least one of the multiple photosensitive resin compositions for evaluation contains both the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2). By containing both the resins (a-1) and (a-2) in at least one photosensitive resin composition for evaluation, the quality of the cured product formed from the photosensitive resin composition (F) is less likely to deviate from the target quality, and it is easier to stabilize the quality of the cured product.

The number of photosensitive resin compositions for evaluation prepared in step 1 may be 2 or more, but is preferably 3 or more. By using 3 or more, more evaluation data can be obtained in step 2, reducing errors and further stabilizing the quality of the cured product formed from the photosensitive resin composition (F). From the viewpoint of stabilizing the quality of the obtained cured product, the more the number of photosensitive resin compositions for evaluation, the better, but from the viewpoint of work efficiency, the fewer the number, for example 10 or less, preferably 5 or less.

(Step 2)
In step 2, the developability is evaluated for each of the multiple photosensitive resin compositions for evaluation prepared in step 1. The method for evaluating the developability in step 2 is not particularly limited as long as it can evaluate the developability of each of the photosensitive resin compositions for evaluation.
The evaluation of developability is preferably carried out by at least exposing and developing the photosensitive resin composition for evaluation to obtain a cured product for evaluation, and then evaluating the cured product for evaluation. Here, the exposure is preferably carried out using an exposure mask having a predetermined opening pattern.

The evaluation of the cured product for evaluation obtained from the photosensitive resin composition for evaluation is preferably performed by measuring the size of the cured product for evaluation. The set size of the cured product is predetermined based on the size of the opening pattern of the exposure mask. Therefore, by measuring the size of the cured product for evaluation, the deviation from the set size can be known, and the accuracy of the developability can be confirmed and the developability can be evaluated.
Moreover, it is more preferable to evaluate the cured product for evaluation by measuring the line width of the linear cured product for evaluation obtained by exposure using an exposure mask having a linear opening and development. When the line width of the linear cured product for evaluation is measured to evaluate the developability, the variation in the line width of the linear cured product such as a black matrix can be effectively suppressed.
The set size is generally the same as the size of the opening pattern of the exposure mask. The set size is preferably the line width, and therefore, the set size is more preferably the same as the width of the linear opening.

In addition, in the evaluation of developability, the method for forming a cured product for evaluation from the photosensitive resin composition for evaluation may be the same as the method for forming a cured product from the photosensitive resin composition (F) using the alkali-soluble resin (f) prepared by this preparation method.
Specifically, the photosensitive resin composition for evaluation is applied to a substrate or the like, dried to form a coating film, exposed to light and developed, and then, if necessary, heated and cured to obtain a cured product for evaluation; details of this process will be described later.
In the evaluation of developability, the various conditions for forming a cured product for evaluation from the photosensitive resin composition for evaluation may be the same as the conditions for forming a cured product from the photosensitive resin composition (F), but they do not necessarily have to be the same. The conditions may be appropriately different as long as they are within the scope of the invention.

(Step 3)
In step 3, the mixing ratio of the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) is determined from the result of the developability evaluation in step 2, and the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) are mixed in the determined mixing ratio to prepare the alkali-soluble resin (f).

In step 3, the mixing ratio is preferably determined so that the cured product formed from the photosensitive resin composition (F) using the alkali-soluble resin (f) has the target quality. Specifically, it is preferable to determine the mixing ratio so that the size of the cured product formed by exposing the applied photosensitive resin composition (F) using an exposure mask having the above-mentioned predetermined opening pattern and then developing it, etc., is the target size. Note that the cured product is preferably a linear cured product as described above, and in this case, the size of the cured product referred to here means the line width of the linear cured product.

For example, in step 2, when the developability evaluation is performed by measuring the size of the cured product for evaluation, the size of the cured product for evaluation is measured for each photosensitive resin composition for evaluation in which the mixing ratios of resin (a-1) and resin (a-2) are different from each other. Therefore, data on multiple mixing ratios and size data on the cured product for evaluation corresponding to each mixing ratio are obtained in step 2. Then, based on the obtained data, the mixing ratio can be determined so that the size of the cured product obtained from photosensitive resin composition (F) is the target size.

More specifically, an approximation curve (calibration curve) represented by a function (y=f(x)) is created from the mixing ratio data (x) and size data (y) obtained in step 2. Then, in the calibration curve, a value of the mixing ratio that results in a target size (for example, the above-mentioned set size) is found, and the found value of the mixing ratio is preferably determined as the mixing ratio when obtaining the alkali-soluble resin (f).
The calibration curve is not particularly limited, and may be expressed by any function such as a linear function, a quadratic function, a cubic function, an exponential function, a logarithmic function, etc., but is preferably expressed by a linear function. The approximation method for creating the calibration curve is not particularly limited, and may be a known approximation method, for example, the least squares method.

In the above explanation, an example was given in which the developability was evaluated based on the size of the cured product for evaluation, but it may also be evaluated based on something other than the size of the cured product for evaluation, for example, it may be evaluated based on a parameter other than size, such as the time it takes for the coating film in the unexposed area to dissolve and be removed during development (the so-called break time (BT)). In that case, a calibration curve is created based on the data on the parameter other than size (y) and the data on the mixing ratio (x), and the value of the mixing ratio can be found from the target value of the parameter other than size on the created calibration curve.

Next, in step 3, the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) are mixed in the determined mixing ratio to obtain the alkali-soluble resin (f), and this preparation method is completed.
The mixing ratio (a-1/a-2) determined in step 3 is preferably determined between 0/100 and 100/0. Therefore, the alkali-soluble resin (f) may not contain either the alkali-soluble resin (a-1) or the alkali-soluble resin (a-2), but usually contains both the resin (a-1) and the resin (a-2).

According to the above preparation method, an alkali-soluble resin (f) is prepared based on the developability of multiple photosensitive resin compositions for evaluation, for example, so that the photosensitive resin composition (F) to be used in actual production has a target developability (e.g., developability such that the line width becomes a target size).
Therefore, for example, even if the production lots of the resins (a-1) and (a-2) and other raw materials constituting the photosensitive resin composition (F) are changed and the properties of the raw materials change, the mix ratio is changed in response to the change in the properties of the raw materials, and the developability of the resulting photosensitive resin composition (F) is optimized, so that the quality of the cured product of the photosensitive resin composition (F) can be stabilized.

Hereinafter, the photosensitive resin composition for evaluation and each component used in the photosensitive resin composition (F) will be described in detail.
[Alkali-soluble resin]
The alkali-soluble resins used in the alkali-soluble resin (a-1) and alkali-soluble resin (a-2) used in the photosensitive resin composition for evaluation and the photosensitive resin composition (F) are not particularly limited as long as they change the solubility of exposed and unexposed areas in an alkali developer after the coating film obtained by applying and drying the photosensitive resin composition is exposed to light. An alkali-soluble resin having an acidic functional group such as a hydroxyl group, a carboxyl group, a phosphoric acid group, or a sulfonic acid group is preferred, and an alkali-soluble resin having a carboxyl group is more preferred.
From the viewpoint of curability, those having an ethylenically unsaturated group are preferred, and from the viewpoint of curability and developability, alkali-soluble resins having an ethylenically unsaturated group and a carboxyl group are more preferred.
Specific examples include epoxy (meth)acrylate resins and acrylic copolymer resins having a carboxyl group, and more specific examples of preferred resins include those described below as (A1-1), (A1-2), (A2-1), (A2-2), (A2-3) and (A2-4), which may be used alone or in combination of two or more. Among the above, epoxy (meth)acrylate resins having a carboxyl group (A1-1) and (A1-2) are particularly preferred.

An epoxy (meth)acrylate resin having a carboxyl group is a resin obtained by further reacting a polybasic acid and/or anhydride thereof with the hydroxyl group generated by the 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 in the ester moiety. Also included in the epoxy (meth)acrylate resin is a resin obtained by reacting a compound having two or more substituents capable of reacting with the hydroxyl group before reacting the polybasic acid and/or anhydride thereof with the hydroxyl group, and then reacting the polybasic acid and/or anhydride thereof. Furthermore, a resin obtained by reacting a compound having a functional group capable of further reacting with the carboxyl group of the resin obtained by the above reaction is also included in the epoxy (meth)acrylate resin.
Thus, epoxy (meth)acrylate resins have substantially no epoxy groups in their chemical structure, and are not limited to "(meth)acrylate", but are named as such according to convention because epoxy resins are the raw material and "(meth)acrylate" is a representative example.

Examples of epoxy (meth)acrylate resins having a carboxyl group (carboxyl group-containing epoxy (meth)acrylate resins) include the following epoxy (meth)acrylate resin (A1-1) and/or epoxy (meth)acrylate resin (A1-2).
Epoxy (meth)acrylate resin (A1-1): An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting the resulting mixture with a polybasic acid and/or an anhydride thereof.
Epoxy (meth)acrylate resin (A1-2): An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting the resulting mixture with a polyhydric alcohol, and a polybasic acid and/or an anhydride thereof.
These resins (A1-1) and (A1-2) will be described in detail below.

<Epoxy (meth)acrylate resin (A1-1)>
The epoxy resin as a raw material includes the raw material compound before it is thermoset to form a resin, and the epoxy resin can be appropriately selected from known epoxy resins. The epoxy resin can be a compound obtained by reacting a phenolic compound with epihalohydrin. The phenolic compound is preferably a compound having a divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
As the type of epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenolmethane type epoxy resin, biphenyl novolac type epoxy resin, naphthalene novolac type epoxy resin, epoxy resin which is a reaction product of epihalohydrin with a polyaddition reaction product of dicyclopentadiene and phenol or cresol, adamantyl group-containing epoxy resin, fluorene type epoxy resin, etc. can be suitably used. In this way, those having an aromatic ring in the main chain can be suitably used.
Specific examples of epoxy resins include bisphenol A type epoxy resins (e.g., Mitsubishi Chemical Corporation's "jER (registered trademark; the same applies below) 828,""jER1001,""jER1002," and "jER1004"); epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (e.g., Nippon Kayaku Co., Ltd.'s "NER-1302" (epoxy equivalent: 323, softening point: 76° C.)); and bisphenol F type resins (e.g., Mitsubishi Chemical Corporation's "jER8 07, "EP-4001", "EP-4002", "EP-4004", etc.), epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin (for example, "NER-7406" (epoxy equivalent 350, softening point 66°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Co., Ltd.), phenol novolac type epoxy resin (for example, "EPPN- 201" manufactured by Mitsubishi Chemical Corporation, "EP-152" and "EP-154" manufactured by The Dow Chemical Company, "DEN-438" manufactured by The Dow Chemical Company), (o, m, p-)cresol novolac type epoxy resins (e.g., "EOCN (registered trademark; the same applies below)-102S", "EOCN-1020", and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (e.g., "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane type epoxy resins (e.g., "EPPN (registered trademark)" manufactured by Nippon Kayaku Co., Ltd. The epoxy resins preferably used include epoxy resins obtained by glycidylating phenolic resins obtained by reacting dicyclopentadiene with phenol (e.g., "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), and the like. Specifically, examples of the epoxy resin represented by the following general formula (a1) include "XD-1000" manufactured by Nippon Kayaku Co., Ltd., an epoxy resin represented by the following general formula (a1), "NC-3000" manufactured by Nippon Kayaku Co., Ltd., an epoxy resin represented by the following general formula (a2), and "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., an epoxy resin represented by the following general formula (a4), and the like.

In the above general formula (a1), b11 indicates an average value and is 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. Note that multiple R ¹¹ present in one molecule may be the same or different.

In the above general formula (a2), b12 represents an average value and is 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. Note that multiple R ²¹ present in one molecule may be the same or different.

In the above general formula (a3), X represents a linking group represented by the following general formula (a3-1) or (a3-2), provided that the molecular structure contains one or more adamantane structures. b13 represents an integer of 2 or 3.

In the above general formulae (a3-1) and (a3-2), R ³¹ to R ³⁴ and R ³⁵ to R ³⁷ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. Also, the * mark in the formula represents the binding site in (a3).

In the above general formula (a4), p and q each independently represent an integer of 0 to 4, ^R41 and ^R42 each independently represent an alkyl group having 1 to 20 carbon atoms or a halogen atom, ^R43 and ^R44 each independently represent an alkylene group having 1 to 5 carbon atoms, and x and y each independently represent an integer of 0 or more.

In the above general formula (a5), R ⁵¹ to R ⁵⁴ are each independently 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, R ⁵⁵ is 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, and R ⁵⁶ are each independently an alkylene group having 1 to 5 carbon atoms. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is each independently an integer of 0 to 5.
Among these, it is preferable to use an epoxy resin represented by any one of general formulas (a1) to (a5).

Examples of α,β-unsaturated monocarboxylic acids 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 (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic ... Examples of the acrylic acid ester include 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipic acid, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxybutyl succinic acid, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutyl hydrophthalic acid, 2-(meth)acryloyloxybutyl phthalic acid, 2-(meth)acryloyloxybutyl maleic acid, and (meth)acrylic acid esters.
Examples of (meth)acrylic acid esters include monomers having one terminal hydroxyl group obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth)acrylic acid, monomers having one terminal hydroxyl group such as hydroxyalkyl (meth)acrylate, and (meth)acrylic acid esters having one or more ethylenically unsaturated groups and one terminal carboxyl group obtained by adding acids (anhydrides) such as (succinic anhydride), (phthalic anhydride), and (maleic anhydride) to compounds having one terminal hydroxyl group such as pentaerythritol tri(meth)acrylate. Also included are (meth)acrylic acid dimers.
Among these, (meth)acrylic acid is particularly preferred from the viewpoint of sensitivity.

A known method can be used as a method for adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin. For example, an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be reacted with an epoxy resin in the presence of an esterification catalyst at a temperature of 50 to 150° C. Examples of the esterification catalyst used here include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride; and phosphorus compounds such as triphenylphosphine. A polymerization inhibitor such as paramethoxyphenol may also be used in combination.
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 each be used alone or in combination of two or more kinds.

The amount of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, per equivalent of the epoxy group of the epoxy resin.
When the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group used is equal to or more than the lower limit, the amount of unsaturated groups introduced is sufficient, the subsequent reaction with the polybasic acid and/or its anhydride is also sufficient, and the residual epoxy groups tend to be suppressed. On the other hand, when the amount is equal to or less than the upper limit, the α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group tends to be suppressed from remaining as unreacted substances, which deteriorates the curing properties.

The polybasic acid and/or its anhydride may be one or more selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and their anhydrides.

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

A known method can also be used for the addition reaction of a polybasic acid and/or its anhydride, and the target product can be obtained by continuing the reaction under conditions similar to those of the addition reaction of an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin. The amount of polybasic acid and/or its anhydride component added can be set so that the acid value of the resulting carboxyl group-containing epoxy (meth)acrylate resin falls within the range described below.

<Synthesis of (A1-1) resin and synthesis of (A1-2) resin obtained by adding polyhydric alcohol to (A1-1) resin to introduce a branched structure>
During the addition reaction synthesis of the polybasic acid and/or anhydride thereof to produce the resin (A1-1), a polyhydric alcohol such as trimethylolpropane, pentaerythritol, or dipentaerythritol may be added to introduce a hyperbranched structure (resin (A1-2)).
The carboxyl group-containing epoxy (meth)acrylate resin is usually obtained by mixing a polybasic acid and/or its anhydride with a reaction product of an epoxy resin and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group, or by mixing a polybasic acid and/or its anhydride and a polyhydric alcohol with a reaction product of an epoxy resin and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and then heating the mixture. In this case, there is no particular restriction on the order of mixing the polybasic acid and/or its anhydride and the polyhydric alcohol. By heating, the polybasic acid and/or its anhydride undergoes an addition reaction with any hydroxyl group present in the mixture of the reaction product of an epoxy resin and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyhydric alcohol.

The amount of polyhydric alcohol used is usually about 0.01 to 0.5 times by mass, and preferably about 0.02 to 0.2 times by mass, of the reaction product of the epoxy resin component with the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester component having a carboxyl group in the ester portion, from the viewpoint of exerting an effect while suppressing thickening and gelation.

The acid value of the epoxy (meth)acrylate resins (A1-1) and (A1-2) is usually 10 mgKOH/g or more, preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more, and even more preferably 90 mgKOH/g or more, and is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, and even more preferably 120 mgKOH/g or less. By making the acid value of the resin equal to or more than the lower limit, the developability tends to be improved, and by making it equal to or less than the upper limit, the alkali resistance tends to be improved.

The weight average molecular weight (Mw) of the epoxy (meth)acrylate resins (A1-1) and (A1-2) is preferably 1,000 or more, and more preferably 1,500 or more. It is also preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 6,000 or less. By setting the weight average molecular weight (Mw) to the lower limit or more, the sensitivity, coating strength, and alkali resistance tend to be improved, and by setting it to the upper limit or less, the developability and resolubility tend to be improved.

<Acrylic copolymer resin (A2-1), (A2-2), (A2-3), (A2-4)>
Examples of the acrylic copolymer resin that can be used include various polymer compounds described in JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and JP-A-2007-270147. Preferred examples include the following resins (A2-1) to (A2-4), and among these, resin (A2-1) is particularly preferred.

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

From the viewpoint of sensitivity, it is more preferable that the photosensitive resin composition (F) contains at least one of (A1-1), (A1-2), (A2-1), and (A2-3) as an alkali-soluble resin containing an ethylenically unsaturated group. From the viewpoint of surface curing, it is particularly preferable that the photosensitive resin composition (F) contains at least one of the epoxy (meth)acrylate resins (A1-1) and (A1-2) as an alkali-soluble resin containing an ethylenically unsaturated group.

As the alkali-soluble resin, resins other than the above-mentioned alkali-soluble resins (other alkali-soluble resins) may be used in combination. There are no restrictions on the other alkali-soluble resins, and they may be selected from resins that are typically used in photosensitive resin compositions. For example, alkali-soluble resins described in JP-A-2007-271727, JP-A-2007-316620, JP-A-2007-334290, etc. may be mentioned.

The alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) used in the photosensitive resin composition (F) and each photosensitive resin composition for evaluation are different from each other as described above. The alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) may be any resin that affects the developability evaluated in step 2 by being different from each other, and may be appropriately selected from the above-mentioned alkali-soluble resins.
The alkali-soluble resin (a-1) used in the photosensitive resin composition for evaluation is the same as the alkali-soluble resin (a-1) used in the photosensitive resin composition (F), and the same production lot, etc. may be used. Similarly, the alkali-soluble resin (a-2) used in the photosensitive resin composition for evaluation is the same as the alkali-soluble resin (a-2) used in the photosensitive resin composition (F), and the same production lot, etc. may be used.

Furthermore, it is advisable to make the total content ratio of the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) relative to the total solids content in each of the photosensitive resin composition for evaluation and the photosensitive resin composition (F) the same. In this way, if the total content ratio of the resin (a-1) and the resin (a-2) in each composition is the same, the development characteristics of the photosensitive resin composition for evaluation tend to reproduce those of the photosensitive resin composition (F), and the quality of the cured product formed from the photosensitive resin composition (F) can be further stabilized. However, the total content ratio of the resin (a-1) and the resin (a-2) in each composition does not necessarily need to be the same.

The alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) may differ from each other in at least one of the structure and the molecular weight (weight average molecular weight (Mw)), for example.
In a preferred embodiment, the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) have the same basic structure but different weight-average molecular weights (Mw). Such resins (a-1) and (a-2) have different solubilities in solvents, and thus tend to affect the curability and coatability of the photosensitive resin composition without affecting other properties, and the size (line width) of the resulting cured product can be easily changed by changing the mixing ratio.
Incidentally, here, having the same basic structure means that they have structural units derived from the same raw materials. For example, in the case of the epoxy (meth)acrylate resin (A1-2), it means that the raw materials used, that is, the epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, the polyhydric alcohol, and the polybasic acid and/or anhydride thereof, are all the same compound.
In addition, when the weight average molecular weight (Mw) of the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) is different, the difference is, for example, 300 or more, preferably 500 or more, and more preferably 1000 or more. When the weight average molecular weight (Mw) differs by a difference equal to or greater than the above lower limit, it becomes easier to differentiate the developability of each evaluation photosensitive resin composition evaluated in step 2 by changing the mixing ratio of the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2). The difference in weight average molecular weight (Mw) between the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) is not particularly limited, but is, for example, 10,000 or less, preferably 5,000 or less, and more preferably 2,000 or less.

The photosensitive resin composition (F) may contain, as the alkali-soluble resin, an alkali-soluble resin other than the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) (hereinafter, also referred to as "alkali-soluble resin (a-3)").
On the other hand, each photosensitive resin composition for evaluation may contain the same components as the photosensitive resin composition (F). Therefore, each photosensitive resin composition for evaluation may also contain an alkali-soluble resin (alkali-soluble resin (a-3)) other than the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) as the alkali-soluble resin.
The alkali-soluble resin (a-3) may be appropriately selected from the above-mentioned alkali-soluble resins.
The alkali-soluble resin (a-3) may be used alone or in combination of two or more kinds.

In each evaluation photosensitive resin composition and photosensitive resin composition (F), the total content of the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) is, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 55% by mass or more, and even more preferably 55% by mass or more, based on the total amount of the alkali-soluble resin contained in each composition. When the total amount of the resins (a-1) and (a-2) is increased, a significant difference occurs in the results of the developability evaluation in each evaluation photosensitive resin composition when the mixing ratio of the resins (a-1) and (a-2) is changed, and the quality of the cured product formed from the photosensitive resin composition (F) is less likely to deviate from the target quality.
The total content of the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) is not particularly limited as long as it is 100% by mass or less based on the total amount of the alkali-soluble resin contained in each composition, but may be, for example, 80% by mass or less. By making it 80% by mass or less, it is possible to contain a certain amount or more of the alkali-soluble resin (a-3), which makes it easier to impart various properties to the photosensitive resin composition (F).

In addition, in each evaluation photosensitive resin composition and photosensitive resin composition (F), the content of all alkali-soluble resins contained in each composition is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on the total solid content of the composition, and is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less. By setting the content of the alkali-soluble resin to the lower limit or more, the solubility of the unexposed part in the developer tends to be good, and by setting it to the upper limit or less, excessive penetration of the developer into the exposed part can be suppressed, and the sharpness and adhesion of the image tend to be good.

As described above, each of the photosensitive resin compositions for evaluation and the photosensitive resin composition (F) preferably contains at least one of the above-mentioned (A1-1), (A1-2), (A2-1), (A2-2), (A2-3) and (A2-4) as an alkali-soluble resin. If an alkali-soluble resin other than these is contained, the content is 20% by mass or less, preferably 10% by mass or less, based on the total amount of the alkali-soluble resin.

The photosensitive resin composition (F) of the present invention contains a photopolymerizable monomer and a photopolymerization initiator in addition to the above-mentioned alkali-soluble resin. On the other hand, each photosensitive resin composition for evaluation may contain the same components as the photosensitive resin composition (F). Therefore, each photosensitive resin composition for evaluation may also contain a photopolymerizable monomer and a photopolymerization initiator in addition to the alkali-soluble resin.

[Photopolymerizable monomer]
The photosensitive resin composition (F) contains a photopolymerizable monomer from the viewpoint of photosensitivity, etc. The photopolymerizable monomer used in the present invention can be a compound having at least one ethylenically unsaturated group in the molecule (hereinafter, sometimes referred to as an "ethylenic monomer"). Specifically, for example, (meth)acrylic acid, (meth)acrylic acid alkyl ester, acrylonitrile, styrene, and esters of a carboxylic acid having one ethylenically unsaturated bond and a polyhydric or monohydric alcohol can be mentioned.

As the photopolymerizable monomer, it is particularly desirable to use a polyfunctional ethylenic monomer 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, even more preferably 5 or more, particularly preferably 6 or more, and usually 10 or less, preferably 8 or less. By making the number of ethylenically unsaturated groups equal to or more than the lower limit, the photosensitive resin composition tends to have high sensitivity, and by making it equal to or less than the upper limit, the curing shrinkage during polymerization tends to be small.
Examples of polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification reactions of polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.

Examples of the esters of the aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylic acid esters in which the acrylate of these exemplary compounds is replaced with methacrylate, itaconic acid esters in which itaconate is replaced with itaconate, crotonic acid esters in which cronate is replaced with crotonate, or maleic acid esters in which maleate is replaced with crotonate, etc.

Examples of the 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, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single substance, but representative specific examples include a condensation product of acrylic acid, phthalic acid, and ethylene glycol, a condensation product of acrylic acid, maleic acid, and diethylene glycol, a condensation product of methacrylic acid, terephthalic acid, and pentaerythritol, and a condensation product of acrylic acid, adipic acid, butanediol, and glycerin.

Other useful examples of the polyfunctional ethylenic monomer that can be used in the present invention include urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester; epoxy acrylates such as the addition reaction product of a polyfunctional epoxy compound with a hydroxyl (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.
These may be used alone or in combination of two or more.

In each evaluation photosensitive resin composition and photosensitive resin composition (F), the content of the photopolymerizable monomer is usually 90% by mass or less, preferably 70% 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, based on the total solid content of each composition. When the content of the photopolymerizable monomer is equal to or less than the above upper limit, the permeability of the developer to the exposed area becomes moderate, and a good image tends to be obtained. The lower limit of the content of the photopolymerizable monomer is usually 1% by mass or more, preferably 5% by mass or more. When the content is equal to or more than the above lower limit, the photocuring by ultraviolet irradiation is improved and the alkaline developability tends to be good.

In each of the photosensitive resin compositions for evaluation and the photosensitive resin composition (F), the mass ratio of the content of the alkali-soluble resin to the content of the photopolymerizable monomer is usually 0.5 or more, preferably 1 or more, more preferably 2 or more, even more preferably 2.5 or more, and usually 15 or less, preferably 10 or less, more preferably 8 or less, even more preferably 5 or less. By making it equal to or more than the lower limit, the curing shrinkage during curing tends to be small, and by making it equal to or less than the upper limit, the hardness of the cured film tends to be high.

[Photopolymerization initiator]
Examples of the photopolymerization initiator include metallocene derivatives including titanocene derivatives described in JP-A-59-152396 and JP-A-61-151197; biimidazole derivatives such as hexaarylbiimidazole derivatives described in JP-A-2000-56118; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-aryl-α-amino derivatives such as N-phenylglycine described in JP-A-10-39503; Examples of such radical activators include acids, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, and α-aminoalkylphenone derivatives; and oxime ester derivatives described in JP-A-2000-80068, JP-A-2006-36750, JP-T-2004-534797, JP-T-2008-179611, JP-T-2012-526185, JP-T-2012-519191, and Japanese Patent No. 6341351. Among these, oxime ester derivatives are preferred from the viewpoints of high sensitivity and high fine line adhesion, and that the photosensitive resin composition (F) can be suitably used for black matrices.

Specific titanocene derivatives include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl-1-yl), dicyclopentadienyltitanium Examples include di(2,6-difluorophenyl-1-yl), dicyclopentadienyltitanium di(2,4-difluorophenyl-1-yl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl-1-yl), and dicyclopentadienyltitanium [2,6-difluoro-3-(pyrro-1-yl)-phenyl-1-yl].

Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 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, etc.

Examples of 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, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

Examples of 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, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

Examples of 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-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

Specific examples of suitable oxime ester derivatives include compounds having a carbazole skeleton, a diphenyl sulfide skeleton, and a fluorene skeleton. Specific compounds include those having the following structural formula. In the structural formula, n-Bu represents an n-butyl group.

Commercially available oxime ester derivatives include OXE-02 manufactured by BASF, and TR-PBG-304, TR-PBG-314, and TR-PBG-358 manufactured by Changzhou Strong Electronic New Materials Co., Ltd.
The photopolymerization initiator may be used alone or in combination of two or more kinds, for example, two kinds of oxime ester derivatives may be used in combination.

In each of the photosensitive resin compositions for evaluation and the photosensitive resin composition (F), the content of the photopolymerization initiator is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and particularly preferably 4% by mass or more, based on the total solid content of the composition, and is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 7.5% by mass or less. By setting the content of the photopolymerization initiator to the lower limit or more, the effect of oxygen inhibition tends to be suppressed, and by setting it to the upper limit or less, the substrate adhesion tends to be good.

[Coloring agent]
The photosensitive resin composition (F) of the present invention preferably further contains a colorant. Therefore, each photosensitive resin composition for evaluation preferably contains a colorant in addition to the alkali-soluble resin. Colorants and inks and dispersants containing colorants described later generally have unstable physical properties and often have large differences in properties between production lots. However, according to the preparation method of the present invention, even if a colorant with unstable physical properties is used, the mixing ratio can be adjusted to ensure constant quality in response to changes in the properties. Therefore, the quality of the cured product obtained from the photosensitive resin composition (F) can be stabilized.

The photosensitive resin composition (F) contains a colorant, and can be suitably used for forming pixels, black matrices, and colored spacers of color filters. The colorant is a material that colors the cured product obtained from the photosensitive resin composition (F). Dyes and pigments can be used, but pigments are preferred from the standpoint of heat resistance, light resistance, etc.

As the pigment, pigments of various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, black pigments, etc. In addition, in terms of the structure, organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments, as well as various inorganic pigments, etc. can be used.
Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
The colorant preferably contains at least a pigment, but when a pigment is used, a dye may be used in addition to the pigment.

As the colorant, it is preferable to use a black colorant. By using a black colorant, it can be suitably used as a photosensitive resin composition (F) for a black matrix. The black colorant may be a single black colorant or a mixture of red, green, blue, etc. The colorant may be appropriately selected from inorganic or organic pigments and dyes. When the photosensitive resin composition (F) contains a black colorant, it has a light-shielding property, so that the photocurability is low and the influence of the variation in the raw material properties on the developability is large. However, by preparing the alkali-soluble resin (f) by the above-mentioned preparation method, the quality can be stabilized even if the raw material properties vary due to lot changes, etc.

Examples of black colorants 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. These black colorants may be used alone or in combination of two or more. When using a black colorant, a colorant other than these black colorants may be used in combination.
Among these colorants, carbon black is preferred from the viewpoints of light blocking rate and image characteristics.

In each of the photosensitive resin compositions for evaluation and the photosensitive resin composition (F), the content of the colorant can usually be selected in the range of 1 to 70 mass% based on the total solid content in the composition. Within this range, 20 mass% or more is more preferable, 30 mass% or more is even more preferable, 40 mass% or more is particularly preferable, and 60 mass% or less is more preferable. By setting the content of the colorant to be equal to or greater than the above lower limit, the cured product obtained from the photosensitive resin composition (F) can be appropriately colored. Furthermore, by setting it to be equal to or less than the upper limit, the curing characteristics of the photosensitive resin composition (F) can be improved.

[Other additives]
In addition to the above-mentioned components, the photosensitive resin composition (F) may appropriately contain dispersants, dispersion aids, sensitizing dyes, adhesion improvers, coatability improvers, thiols, development improvers, UV absorbers, antioxidants, etc. Therefore, the photosensitive resin composition for evaluation may also appropriately contain dispersants, dispersion aids, sensitizing dyes, adhesion improvers, coatability improvers, thiols, development improvers, UV absorbers, antioxidants, etc.

(Dispersant)
The photosensitive resin composition (F) of the present invention may further contain a dispersant. Therefore, each photosensitive resin composition for evaluation may also further contain a dispersant. The dispersant finely disperses the colorant and stabilizes the dispersed state, which makes it easier to stabilize the quality.
As the dispersant, a polymer dispersant having a functional group is preferred, and furthermore, from the viewpoint of dispersion stability, a polymer dispersant having a functional group such as 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 or pyrazine is preferred. Among them, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is particularly preferred. By using a polymer dispersant having these basic functional groups, it is possible to improve dispersibility and achieve high light-shielding properties.

Examples of polymeric dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of monomers and macromonomers having amino groups, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene diester-based dispersants, polyether phosphate-based dispersants, polyester phosphate-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified polyester-based dispersants. These polymeric dispersants may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less, and more preferably 30,000 or less. By setting the weight average molecular weight (Mw) to the upper limit or less, alkaline developability tends to be good even when the pigment concentration is high.

Specific examples of dispersants include, by trade name, EFKA (registered trademark, manufactured by EFKA Chemicals BV), Disperbyk (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Chemicals), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical), Polyflow or Florene (registered trademark, manufactured by Kyoeisha Chemical), and Ajisper (registered trademark, manufactured by Ajinomoto Fine-Techno Co., Ltd.).

Among these, from the viewpoints of adhesion and linearity, it is particularly preferable that the dispersant contains a urethane-based polymer dispersant and/or an acrylic-based polymer dispersant having a basic functional group. In particular, a urethane-based polymer dispersant is preferable from the viewpoint of adhesion. Also, from the viewpoints of dispersibility and storage stability, a polymer dispersant having a basic functional group and a polyester and/or polyether bond is preferable.
Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, etc. (all acrylic-based) (all manufactured by BYK-Chemie). Particularly preferred examples of the above-mentioned urethane-based polymer dispersants having a basic functional group and a polyester and/or polyether bond and a weight average molecular weight of 30,000 or less include DISPERBYK-167, 182, etc.
The dispersant may be used alone or in combination of two or more kinds.

In each evaluation photosensitive resin composition and photosensitive resin composition (F), the content of the dispersant is not particularly limited, but is usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less, and is usually 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more, relative to the total solid content of the composition. The content of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, usually 200 parts by mass or less, preferably 80 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, relative to 100 parts by mass of the colorant. By setting the content of the dispersant to the lower limit or more, sufficient dispersibility tends to be ensured, and by setting the content to the upper limit or less, the color density, sensitivity, film-forming properties, etc. tend to be sufficient without reducing the proportions of other components.

(Dispersing agent)
The dispersing aid is used in combination with a dispersing agent such as a polymer dispersing agent, and it is preferable to use a pigment derivative. Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and dioxazine-based derivatives, among which phthalocyanine-based and quinophthalone-based derivatives are preferred.
Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc., which are bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, etc., and are preferably a sulfonic acid group. A single pigment skeleton may be substituted with a plurality of these substituents. Specific examples of the pigment derivative include a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinophthalone, a sulfonic acid derivative of anthraquinone, a sulfonic acid derivative of quinacridone, a sulfonic acid derivative of diketopyrrolopyrrole, a sulfonic acid derivative of dioxazine, etc.
The pigment derivatives may be used alone or in combination of two or more kinds.

In each photosensitive resin composition for evaluation and photosensitive resin composition (F), the content of the dispersing aid is not particularly limited, but is usually 0.1 mass% or more, preferably 0.5 mass% or more, and usually 10 mass% or less, preferably 5 mass% or less, and more preferably 2 mass% or less, based on the total solid content of the composition.

(Adhesion improver)
Examples of the adhesion improver include silane coupling agents, titanium coupling agents, and phosphoric acid-based adhesion improvers such as (meth)acryloyloxy group-containing phosphates, among which silane coupling agents are preferred. By including the adhesion improver in the photosensitive resin composition (F), the adhesion to the substrate can be improved.
Examples of the silane coupling agent include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X12-1050 (manufactured by Shin-Etsu Silicones Co., Ltd.), Z-6040, Z-6043, and Z-6062 (manufactured by Dow Corning Toray Co., Ltd.).
The adhesion improver may be used alone or in combination of two or more kinds.

In each of the evaluation photosensitive resin compositions and photosensitive resin composition (F), the content of the adhesion improver is not particularly limited, but is preferably 0.1 mass% or more of the total solid content of the composition, more preferably 0.3 mass% or more, even more preferably 0.5 mass% or more, particularly preferably 1 mass% or more, and preferably 25 mass% or less, more preferably 20 mass% or less, even more preferably 10 mass% or less, particularly preferably 8 mass% or less, and most preferably 6 mass% or less. By making it equal to or more than the lower limit, adhesion to the substrate tends to be improved, and by making it equal to or less than the upper limit, residues during alkaline development tend to be suppressed.

(Coatability improver)
A surfactant can be used as the coating property improver. As the surfactant, various types of surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used. Among them, it is preferable to use a nonionic surfactant because it is less likely to adversely affect various properties, and among them, a fluorine-based or silicon-based surfactant is effective in terms of coating property.
Examples of 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 Silicones), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray Co., Ltd.), DS-401 (manufactured by Daikin Corporation), L-77 (manufactured by Nippon Unicar Co., Ltd.) and FC4430 (manufactured by 3M Japan Co., Ltd.). The surfactant may be used alone or in any combination and ratio of two or more kinds.
The surfactant may be used alone or in combination of two or more kinds.

In each of the photosensitive resin compositions for evaluation and the photosensitive resin composition (F), the content of the surfactant is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.05% by mass or more, and is preferably 1.0% by mass or less, more preferably 0.7% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less, based on the total solid content of the composition. By setting the surfactant content at or above the lower limit, the resist coating uniformity tends to improve, and by setting it at or below the upper limit, the resist sensitivity tends not to decrease.

(Sensitizing dye)
For the purpose of increasing sensitivity, a sensitizing dye according to the wavelength of the exposure light source can be used in combination with the photopolymerization initiator as necessary. Examples of the sensitizing dye include xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, pyrromethene dyes, and dyes having an aminobenzene skeleton such as a dialkylaminobenzene skeleton.
Among the sensitizing dyes, preferred are amino group-containing sensitizing dyes, more preferred are compounds having an amino group and a phenyl group in the same molecule, particularly preferred are, for example, benzophenone compounds and p-dialkylaminophenyl group-containing compounds, and most preferred is 4,4'-dialkylaminobenzophenone.
The sensitizing dyes may be used alone or in combination of two or more kinds.

[solvent]
The photosensitive resin composition (F) is usually used in a state in which the alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, and further the colorant and other additives that are optionally blended are dissolved or dispersed in an organic solvent. Therefore, the photosensitive resin composition for evaluation is also preferably used in a state in which the alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, and further the colorant and other additives that are optionally blended are dissolved or dispersed in an organic solvent.

It is preferable to select an organic solvent with a boiling point (under a pressure of 1013.25 [hPa]; the same applies to all boiling points below) in the range of 100 to 300°C. More preferably, it is a solvent with a boiling point of 120 to 280°C. Examples of such organic solvents include the following:

Glycol monoalkyl ethers such as 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, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and 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, and dipropylene glycol dimethyl ether;
glycol alkyl ether acetates such as 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 ether acetate, and 3-methyl-3-methoxybutyl acetate;

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 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, and dihexyl ether;
Ketones such as 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, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentanone;
monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
Chain or cyclic esters such as 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, butyl 3-methoxypropionate, and γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile.
Commercially available solvents that fall into this category include mineral spirits, 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 applies below), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diglyme (all trade names).
These organic solvents may be used alone or in combination of two or more kinds.

When forming pixels or black matrices of a color filter by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 250° C., more preferably 120 to 230° C.
Among the above organic solvents, glycol alkyl ether acetates are preferred because they have a good balance of coatability, surface tension, etc., and the solubility of the components in the composition is relatively high.

Glycol alkyl ether acetates may be used alone or in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferred as other organic solvents that may be used in combination. Among these, propylene glycol monomethyl ether is particularly preferred in terms of the solubility of the components in the composition. Glycol monoalkyl ethers have high polarity, and if too much is added, the pigments tend to aggregate, and the storage stability tends to decrease, such as the viscosity of the photosensitive resin composition obtained later increasing. Therefore, the proportion of glycol monoalkyl ethers in the solvent is preferably 5% to 30% by mass, and more preferably 5% 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"). By using such a high boiling point solvent, the photosensitive resin composition (F) becomes difficult to dry, but there is an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. In other words, there is an effect of preventing the occurrence of foreign matter defects due to precipitation and solidification of colorants, etc., at the tip of the slit nozzle, for example. In view of such a high effect, among the various solvents mentioned above, dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, triacetin, and 1,6-hexanediol diacetate are particularly preferable.

The content of the high boiling point solvent in the organic solvent is preferably 0 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass. By making the content of the high boiling point solvent equal to or greater than the lower limit, it tends to be possible to avoid, for example, the colorant precipitating and solidifying at the tip of the slit nozzle, which may cause foreign matter defects, and by making the content equal to or less than the upper limit, it tends to be possible to slow down the drying temperature of the composition, which may result in problems such as poor tact time in the reduced pressure drying process and pin marks in the pre-bake process.

In the photosensitive resin composition for evaluation and the photosensitive resin composition (F), the content ratio of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, it is preferable that the total solid content in the composition is adjusted to be preferably 5 mass% or more, more preferably 8 mass% or more, even more preferably 10 mass% or more, particularly preferably 12 mass% or more, and also preferably 40 mass% or less, more preferably 30 mass% or less, even more preferably 25 mass% or less, particularly preferably 20 mass% or less.

In the present invention, each photosensitive resin composition for evaluation preferably has the same composition as the photosensitive resin composition (F) with respect to the composition other than the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2), and the production lots of each component are preferably the same.
Therefore, the photosensitive resin composition for evaluation should contain a photopolymerizable monomer and a photopolymerization initiator as described above, and these should be the same as the photopolymerizable monomer and the photopolymerization initiator used in the photosensitive resin composition (F), and should be from the same production lot. Furthermore, the content of each of these components should also be the same.
In the present invention, each photosensitive resin composition for evaluation contains the same components as the photosensitive resin composition (F) in addition to the alkali-soluble resin (f), so that even if the production lot of the raw materials other than the alkali-soluble resin (f) is changed and the properties of each raw material are changed, the mixing ratio is adjusted to correspond to the change in properties so that the quality is constant according to the preparation method of the present invention. Therefore, the quality of the cured product obtained from the photosensitive resin composition (F) can be further stabilized.

From the same viewpoint, when the photosensitive resin composition (F) contains an alkali-soluble resin (a-3), the alkali-soluble resin (a-3) in the photosensitive resin composition for evaluation may be the same as the alkali-soluble resin (a-3) in the photosensitive resin composition (F), ... and may be the same in content.
In addition, even when the photosensitive resin composition (F) contains a colorant, the colorant contained in each photosensitive resin composition for evaluation may be the same as the colorant in the photosensitive resin composition (F) and may be from the same production lot. The content may also be the same. Note that colorants are generally often blended into the photosensitive resin composition (F) as ink (dispersion). Therefore, the photosensitive resin composition (F) and each photosensitive resin composition for evaluation may use the same ink (dispersion) and may use the same production lot, and may be the same in content.
The solvent used for each photosensitive resin composition for evaluation may be the same as that used for each photosensitive resin composition (F), and the total solid content in the composition may be the same.
Furthermore, even when the photosensitive resin composition (F) contains other additives as described above, the same components may be used, the same production lot may be used, and the contents may be the same.

However, the photosensitive resin composition for evaluation does not necessarily have to have the same composition as photosensitive resin composition (F) with respect to the composition other than resins (a-1) and (a-2), and the composition may be changed as appropriate as long as the results of the developability evaluation of the photosensitive resin composition for evaluation reproduce to a certain extent the exposure and development of photosensitive resin composition (F).

<Method for producing photosensitive resin composition (F)>
In the present invention, the photosensitive resin composition (F) can be produced by blending at least a photopolymerizable monomer and a photopolymerization initiator in addition to the alkali-soluble resin (f). The photosensitive resin composition (F) may preferably further contain a colorant, and may further contain the alkali-soluble resin (a-3) and the other additives described above.
As described above, the photosensitive resin composition (F) may be prepared by mixing and blending the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) in the mixing ratio determined in step 3 as the alkali-soluble resin (f), and the resin (a-1) and the resin (a-2) may be mixed together with other components to prepare the photosensitive resin composition (F).

A preferred embodiment of the method for producing the photosensitive resin composition (F) will be described in detail below. The following preferred embodiment is an example in which a colorant is blended into the photosensitive resin composition (F).
The colorant is preferably dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, etc. The colorant is finely divided by the dispersion treatment, which improves the coating properties of the photosensitive resin composition (F). In addition, when a black colorant such as carbon black is used as the colorant, it contributes to improving the light-shielding ability.

The dispersion treatment is usually preferably carried out in a system that uses a colorant, a solvent, and, if necessary, a part or all of a dispersant, a dispersion aid, and an alkali-soluble resin in combination. In the following description, the mixture to be subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as an "ink" or a "dispersion liquid".
In addition, when a dispersion treatment is performed on a liquid containing all the components to be blended in the photosensitive resin composition (F), the highly reactive components may be denatured due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment using a part of the components of the photosensitive resin composition (F), including a dispersant.

When dispersing the colorant with a sand grinder, glass beads or zirconia beads with a diameter of about 0.1 to 8 mm are preferably used. Dispersion conditions are generally a temperature of 0°C to 100°C, preferably in the range of room temperature to 80°C. The optimum dispersion time varies depending on the composition of the liquid and the size of the dispersion treatment device, and is adjusted accordingly. A guideline for dispersion is to control the gloss of the ink so that the 20 degree specular gloss (JIS Z8741) of the photosensitive resin composition (F) is in the range of 100 to 200.

Next, the dispersion obtained by the above dispersion treatment is mixed with other components contained in the photosensitive resin composition (F) to obtain a homogeneous solution. Since fine dust particles are often mixed in the liquid during the production process of the photosensitive resin composition (F), it is desirable to filter the obtained photosensitive resin composition (F) using a filter or the like.
Although the method for producing the photosensitive resin composition (F) has been described in detail above, the photosensitive resin composition for evaluation can be prepared in the same manner as the photosensitive resin composition (F), except that the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) are blended in an arbitrary mixing ratio instead of the mixing ratio determined in step 3.

<Method of producing the cured product>
In the present invention, a cured product can be produced by curing the photosensitive resin composition (F). The cured product can be suitably used as a component constituting a color filter such as a pixel, a black matrix, or a colored spacer, and can be suitably used as a component constituting a black matrix. When a black matrix is formed using the above preparation method, the variation in line width can be reduced, so that the quality can be stabilized even when the lines are thinned.

The method for producing the black matrix will now be described in detail.
(Support)
The black matrix is formed on a support. The material of the support for forming the black matrix is not particularly limited as long as it has a suitable strength. A transparent substrate is preferably used as the support. Examples of the material of the support include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly(meth)acrylic resins, and various glasses. In addition, a transparent electrode such as ITO or IZO may be formed on the surface of the substrate. In addition to the transparent substrate, it is also possible to form the substrate on a TFT array.

In order to improve surface properties such as adhesion, the support may be subjected to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, or thin film formation treatment with a silane coupling agent or various resins such as urethane resins, as necessary.
The thickness of the support is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When a thin film of various resins is formed on the surface of the support, the thickness of the thin film is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

<Method of forming black matrix>
The method for producing a black matrix according to the present invention involves forming a black matrix from a cured product obtained by curing the above-mentioned photosensitive resin composition (F).
Specifically, the photosensitive resin composition (F) is applied onto a support such as a transparent substrate and dried, and then an exposure mask is placed on the coating film, and the coating film is imagewise exposed through the exposure mask, developed, and optionally thermally or photocured to form a black matrix made of a cured product. Each step is described in detail below.

(1) Coating of Photosensitive Resin Composition Coating of the photosensitive resin composition (F) for a black matrix onto a transparent substrate can be carried out by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, etc. Among these, the die coating method is preferred from an overall viewpoint, since it significantly reduces the amount of coating solution used, there is no influence of mist or the like that adheres when the spin coating method is used, and the generation of foreign matter is suppressed.

The thickness of the coating film after drying is preferably in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and even more preferably in the range of 1 to 4 μm. By making the thickness below the upper limit, pattern development becomes easier, and gap adjustment during the liquid crystal cell formation process also tends to become easier. Also, by making the thickness above the lower limit, the desired color expression tends to become easier.

(2) Drying of the coating film After applying the photosensitive resin composition (F) to the substrate, the coating film is preferably dried 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 used, etc. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 200°C, and preferably in the range of 30 seconds to 3 minutes at a temperature of 50 to 130°C, depending on the type of the solvent component, the performance of the dryer used, etc.
By setting the drying temperature to the lower limit or more, the adhesion of the coating film to a support such as a transparent substrate is improved. By setting the drying temperature to the upper limit or less, the alkali-soluble resin is prevented from being decomposed, and development defects caused by thermal polymerization, etc. are suppressed. The drying process of the coating film may be a reduced pressure drying method in which the temperature is not increased and drying is performed in a reduced pressure chamber.

(3) Exposure Image exposure is performed by superposing an exposure mask having a negative mask pattern on the coating film of the photosensitive resin composition (F) and irradiating light having a wavelength ranging from the ultraviolet region to the visible region through this mask pattern. In this case, if necessary, in order to prevent a decrease in sensitivity due to oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the coating film of the photosensitive resin composition (F) before exposure. The light source used for the above 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. When using light of a specific wavelength, an optical filter can also be used.

(4) Development The black matrix can be prepared by imagewise exposing a coating of the photosensitive resin composition (F) to the above-mentioned light source, and then developing the coating with an organic solvent or an aqueous solution containing a surfactant and an alkaline compound to form an image on the substrate. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Examples of alkaline compounds include inorganic alkaline compounds such as 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, and ammonium hydroxide, as well as organic alkaline compounds such as 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), and choline. 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 alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate salts; and amphoteric surfactants such as alkyl betaines and amino acids.

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

(5) Heat curing treatment
After the development, the support is subjected to a heat curing treatment or a light curing treatment, preferably a heat curing treatment, in which the heat curing treatment conditions are selected from a temperature range of 100 to 280° C., preferably a range of 150 to 250° C., and a time range of 5 to 60 minutes.
The height of the black matrix thus formed is usually 0.5 to 5 μm, preferably 0.8 to 4 μm, and the line width of the black matrix is, for example, 3 to 80 μm, preferably 5 to 50 μm.

In the above explanation, an example of producing a black matrix as a cured product has been described, but cured products other than a black matrix, such as each pixel of a color filter and colored spacers, may also be produced from the photosensitive resin composition (F) by the same method. Specifically, the photosensitive resin composition (F) is applied to a support such as a transparent substrate in the same process as (1) to (5) above, and after drying, an exposure mask is placed on the coating film, and exposure is performed through the exposure mask, development is performed, and if necessary, heat curing or photocuring is performed to produce a cured product.

<Manufacturing Method of Image Display Device>
A method for manufacturing an image display device according to an embodiment of the present invention includes a method for manufacturing an image display device using the black matrix manufactured by the above-mentioned method. The image display device is not particularly limited as long as it is a device that displays images or videos, and examples of the image display device include a liquid crystal display device and an organic EL display.

A liquid crystal display device may be manufactured, for example, by forming an alignment film on a color filter, dispersing spacers on the alignment film, bonding it to an opposing substrate to form a liquid crystal cell, injecting liquid crystal into the formed liquid crystal cell, and connecting it to the opposing electrode. In this manufacturing method, it is preferable to use a color filter having a black matrix formed by the above-mentioned method from the photosensitive resin composition (F).

In addition, when an organic EL display is produced, a color filter having a pattern formed on a support such as a transparent substrate is first produced. Here, the pattern is made up of pixels and a black matrix provided between adjacent pixels, and the black matrix may be produced by the above-mentioned method.
Next, an organic light-emitting body is laminated on the color filter via an organic protective layer and an inorganic oxide film, thereby producing an organic EL element. Examples of a method for laminating an organic light-emitting body include a method for sequentially forming a transparent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer, and a cathode on the upper surface of a color filter, and a method for laminating an organic light-emitting body formed on a separate substrate on an inorganic oxide film. Using the organic EL element produced in this way, an organic EL display can be produced by, for example, a method described in "Organic EL Display" (Ohmsha, August 20, 2004, Light Emitting, by Shizuo Tokito, Chinaya Adachi, and Hideyuki Murata).
The organic EL display may be a passive drive organic EL display or an active drive organic EL display.

In addition, in the above-mentioned manufacturing method of the image display device, the embodiment in which the black matrix is formed from the photosensitive resin composition (F) has been shown, but components other than the black matrix, such as pixels and colored spacers, may also be formed from the photosensitive resin composition (F).

Next, the present invention will be described in more detail with reference to Synthesis Examples, Examples, and Comparative Examples. However, the present invention is not limited to the following Examples as long as it does not depart from the gist of the present invention.
The components of the photosensitive resin composition used in the following Examples and Comparative Examples are as follows.

<Synthesis of Polymer A>
Nippon Kayaku Co., Ltd. "XD1000" (polyglycidyl ether of dicyclopentadiene-phenol polymer, epoxy equivalent 252) 600 parts by mass, methacrylic acid 121 parts by mass, p-methoxyphenol 0.2 parts by mass, triphenylphosphine 5 parts by mass, propylene glycol monomethyl ether acetate 255 parts by mass were charged into a reaction vessel and stirred at 100 ° C. until the acid value reached 3.0 mg KOH / g. It took 9 hours for the acid value to reach the target (acid value 2.5 mg KOH / g). Next, 181 parts of tetrahydrophthalic anhydride was added and reacted at 120 ° C. for 4 hours to obtain a solution of polymer A with an acid value of 100 mg KOH / g and a weight average molecular weight (Mw) of 2600 in terms of polystyrene measured by GPC.

<Synthesis of Polymer B>

240 parts by mass of an epoxy compound (epoxy equivalent: 264) having the structure of the above formula (A), 81.6 parts by mass of methacrylic acid, 263.1 parts by mass of methoxybutyl acetate, 6.4 parts by mass of triphenylphosphine, and 0.16 parts by mass of paramethoxyphenol were placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and reacted with stirring at 90° C. for 12 hours until the acid value became 5 mgKOH/g or less.
Next, 199.1 parts by mass of methoxybutyl acetate, 8.3 parts by mass of trimethylolpropane (TMP), 80.7 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 51.6 parts by mass of tetrahydrophthalic anhydride (THPA) were added to the reaction liquid obtained by the above reaction in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105° C. with stirring to react, thereby obtaining a solution of Polymer B having a solids acid value of 104 mg KOH/g and a polystyrene-equivalent weight average molecular weight (Mw) of 2,500 measured by GPC.

<Synthesis of Polymer C>
240 parts by mass of an epoxy compound (epoxy equivalent: 264) having the structure of the above formula (A), 81.6 parts by mass of methacrylic acid, 263.1 parts by mass of methoxybutyl acetate, 6.4 parts by mass of triphenylphosphine, and 0.16 parts by mass of paramethoxyphenol were placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and reacted with stirring at 90° C. for 12 hours until the acid value became 5 mgKOH/g or less.
Next, 207.2 parts by mass of methoxybutyl acetate, 8.3 parts by mass of trimethylolpropane (TMP), 129.2 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 11.2 parts by mass of tetrahydrophthalic anhydride (THPA) were added to the reaction liquid obtained by the above reaction in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105° C. with stirring to react, thereby obtaining a solution of Polymer C having a solid content acid value of 107 mgKOH/g and a polystyrene-equivalent weight average molecular weight (Mw) of 6,000 measured by GPC.

<Synthesis of Polymer D>
240 parts by mass of an epoxy compound (epoxy equivalent: 264) having the structure of the above formula (A), 68.3 parts by mass of acrylic acid, 252.3 parts by mass of methoxybutyl acetate, 6.2 parts by mass of triphenylphosphine, and 0.16 parts by mass of paramethoxyphenol were placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and reacted with stirring at 90° C. for 12 hours until the acid value became 5 mgKOH/g or less.
Next, 237.9 parts by mass of methoxybutyl acetate, 18.4 parts by mass of trimethylolpropane (TMP), 96.8 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 66.7 parts by mass of tetrahydrophthalic anhydride (THPA) were added to the reaction liquid obtained by the above reaction in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105° C. with stirring to react, thereby obtaining a solution of Polymer D having a solid acid value of 112 mg KOH/g and a polystyrene-equivalent weight average molecular weight (Mw) of 4,000 as measured by GPC.

<Synthesis of Polymer E>
240 parts by mass of an epoxy compound (epoxy equivalent: 264) having the structure of formula (A) above, 68.3 parts by mass of acrylic acid, 263.1 parts by mass of methoxybutyl acetate, 6.4 parts by mass of triphenylphosphine, and 0.16 parts by mass of paramethoxyphenol were placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and reacted with stirring at 90° C. for 12 hours until the acid value became 5 mgKOH/g or less.
Next, 238.9 parts by mass of methoxybutyl acetate, 18.4 parts by mass of trimethylolpropane (TMP), 75.0 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 89.4 parts by mass of tetrahydrophthalic anhydride (THPA) were added to the reaction liquid obtained by the above reaction in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105° C. with stirring to react, thereby obtaining a solution of Polymer E having a solid acid value of 112 mg KOH/g and a polystyrene-equivalent weight average molecular weight (Mw) of 2,800 measured by GPC.
The polymers A to E were mixed in the form of a solution when the photosensitive resin composition was prepared. The polymers A to E are alkali-soluble resins.

The components of the photosensitive resin composition used in the following Examples and Comparative Examples are as follows.
<Coloring agent (pigment)>
R1060: BIRLA CARBON "RAVEN1060U" (carbon black)
R1080: BIRLA CARBON "RAVEN1080U" (carbon black)
<Dispersant>
BYK167: BYK-Chemie "DISPERBYK-167" (urethane polymer dispersant)
<Dispersion Aid>
S12000: Lubrizol's "S12000" (phthalocyanine acid derivative)
<Alkali-soluble resin>
Alkali-soluble resin-I: Epoxy acrylate resin "WR-301" manufactured by ADEKA Corporation (weight average molecular weight (Mw) = 5700, solid acid value = 100 mgKOH/g)
<Photopolymerizable Monomer>
PE-4A: "Light Acrylate PE-4A" (multifunctional acrylate) manufactured by Kyoeisha Chemical Co., Ltd.
DPCA-20: "KAYARAD DPCA-20" (multifunctional acrylate) manufactured by Nippon Kayaku Co., Ltd.
<Photopolymerization initiator>
TR-PBG-314: "TR-PBG-314" (oxime ester) manufactured by Changzhou Strong Electronic New Materials Co., Ltd.
<Adhesion improver>
X-12-1048: "X-12-1048" (polyfunctional acrylic silane) manufactured by Shin-Etsu Chemical Co., Ltd.
<Surfactant>
F-554: "Megafac F554" manufactured by DIC Corporation (fluorine-based surfactant)
<Solvent>
PGMEA: Propylene glycol monomethyl ether acetate MBA: 3-methoxybutyl acetate

<Preparation of Dispersion-I and Dispersion-II>
A mixed liquid was obtained by mixing the pigment, dispersant, dispersion aid, alkali-soluble resin, and solvent shown in Table 1 in the mass ratio shown in Table 1. The blending ratio of the solvent in Table 1 also includes the amounts of the dispersant, dispersion aid, and solvent derived from the alkali-soluble resin.
This mixture was subjected to a dispersion treatment for 3 hours at a temperature range of 25 to 45° C. using a paint shaker. Zirconia beads with a diameter of 0.5 mm were used as the beads, and 2.5 times the mass of the dispersion liquid was added. After dispersion was completed, the beads and the dispersion liquid were separated using a filter to prepare Dispersion Liquid-I and Dispersion Liquid-II.

[Example 1]
<Preparation of Photosensitive Resin Compositions 1 to 3 for Evaluation>
Using the dispersion I and dispersion II prepared above, each component was added so that the ratio of the solid content of each component in the total solid content was the blending ratio in Table 2 below, and PGMEA was added so that the solvent ratio in the photosensitive resin composition was the ratio shown in Table 2 and the content ratio of the total solid content was 13 mass%, and the mixture was stirred and dissolved to prepare photosensitive resin compositions 1 to 3 for evaluation. In photosensitive resin compositions 1 to 3 for evaluation, the total contents of polymer D and polymer E were the same, and the mixing ratio (mass ratio) of polymer D:polymer E was changed to 6:56, 21:41, and 36:26, respectively.

(Evaluation of Resist)
<Line width evaluation of 25 μm pattern (developability evaluation)>
Each of the prepared photosensitive resin compositions 1 to 3 (resist) for evaluation was applied with a spin coater so that the film thickness after post-baking was 1.36 μm, and after drying under reduced pressure, it was dried on a hot plate at 100 ° C. for 135 seconds. Subsequently, the obtained dried coating film was subjected to pattern exposure at 30 mJ with a high-pressure mercury lamp under the condition of an exposure gap of 300 μm through an exposure mask having a line width opening of 25 μm, and then spray development was performed for 58 seconds with an alkaline developer adjusted to a 0.04 mass% KOH aqueous solution with ultrapure water at room temperature (23 ° C.), and after removing the photosensitive layer, spray cleaning was performed with ultrapure water. Subsequently, post-baking was performed for 30 minutes in an oven at 230 ° C., and a linear cured product was formed on the substrate, and a sample for line width evaluation was prepared.
The resulting linear pattern on the substrate was observed with an optical microscope (Nikon Eclipse L200ND), and the line width was measured with image analysis software (NIS-Elements).

Table 3 shows the line width evaluation results for each sample prepared from the evaluation photosensitive resin compositions 1 to 3. A calibration curve was prepared by plotting the line width data against the blend ratio of polymer D from the line width evaluation results for the evaluation photosensitive resin compositions 1 to 3. The calibration curve was prepared as a linear function by the least squares method.
The mixing ratio at which the set line width (25.0 μm) was obtained in the created calibration curve was determined, and the mixing ratio (mass ratio) of polymer D:polymer E in photosensitive resin composition (F) was determined to be 18:44.
Photosensitive resin composition (F) was prepared by mixing the polymer D:polymer E at a determined ratio of 18:44, and the line width was evaluated to be 24.9 μm, which was very close to the set line width. Photosensitive resin composition (F) was the same as evaluation photosensitive resin composition 1 shown in Table 1, except that the parts by mass (solid content equivalent) of polymer D and polymer E were changed to 4.38 parts by mass and 10.70 parts by mass (solid content equivalent).

[Comparative Example 1]
If the comparative photosensitive resin composition were prepared without carrying out the preparation method using the evaluation photosensitive resin compositions 1 to 3, and with a mixing ratio (mass ratio) of polymer D:polymer E of 15:47, the line width would be estimated to be 24.8 μm. The comparative photosensitive resin composition is the same as evaluation photosensitive resin composition 1 shown in Table 1, except that the parts by mass (solid content equivalent) of polymer D and polymer E were changed to 3.65 parts by mass and 11.43 parts by mass (solid content equivalent).

[Example 2]
Photosensitive resin compositions for evaluation 4 to 6 were prepared in the same manner as photosensitive resin compositions for evaluation 1 to 3 in Example 1, except that the production lots of the pigment, dispersant, dispersion aid, and alkali-soluble resin contained in the dispersion, and the photopolymerizable monomer, photopolymerization initiator, adhesion improver, and surfactant contained in the photosensitive resin composition were changed.

The line width evaluation results for each sample prepared from the evaluation photosensitive resin compositions 4 to 6 are shown in Table 4. A calibration curve was prepared from the line width evaluation results for the photosensitive resin compositions 4 to 6 in the same manner as in Example 1. The mixing ratio resulting in the set line width (25.0 μm) in the prepared calibration curve was determined, and the mixing ratio (mass ratio) of polymer D:polymer E in the photosensitive resin composition (F) was determined to be 22:40.
Photosensitive resin composition (F) was prepared by setting the mixing ratio (mass ratio) of polymer D:polymer E to the determined ratio of 22:40, and the line width evaluation was performed, resulting in 24.9 μm, which was very close to the set line width. The blending amounts (parts by mass) of each component of photosensitive resin composition (F) were the same as those of evaluation photosensitive resin composition 1 shown in Table 1, except that the parts by mass (solid content equivalent) of polymer D and polymer E were changed to 5.35 parts by mass and 9.73 parts by mass (solid content equivalent).

[Comparative Example 2]
If the comparative photosensitive resin composition were prepared without carrying out the preparation method using the evaluation photosensitive resin compositions 4 to 6, and with a mixing ratio (mass ratio) of polymer D:polymer E of 15:47, the line width would be estimated to be 24.3 μm, which is estimated to be a result significantly different from the set line width. The comparative photosensitive resin composition is the same as the evaluation photosensitive resin composition 4, except that the parts by mass (solid content equivalent) of polymer D and polymer E were changed to 3.65 parts by mass and 11.43 parts by mass (solid content equivalent).

As described above, in Examples 1 and 2, the mixing ratio of resins (a-1) and (a-2) in photosensitive resin composition (F) was determined so as to obtain a set line width based on the line width evaluation results using the photosensitive resin composition for evaluation, and photosensitive resin composition (F) was prepared at the determined mixing ratio. Therefore, even if the production lot of the raw materials changed, the line width of the cured product obtained from photosensitive resin composition (F) was almost the same as the set line width, with little variation, and the quality of the cured product was stable.
In contrast, in Comparative Examples 1 and 2, the mixing ratio of the resins (a-1) and (a-2) in the photosensitive resin composition for obtaining a cured product was constant. Therefore, when the production lot of the raw materials changed, the line width of the cured product obtained from the photosensitive resin composition fluctuated significantly, and the quality of the cured product was not stable.

Claims (7)

A method for preparing an alkali-soluble resin for use in a photosensitive resin composition, comprising the steps of:
A step of preparing a plurality of photosensitive resin compositions for evaluation, each of which has a mixing ratio of an alkali-soluble resin (a-1) and an alkali-soluble resin (a-2) that is different from one another, in a mixing ratio of 0/100 to 100/0 (mass ratio);
evaluating the developability of each of the plurality of photosensitive resin compositions for evaluation;
determining a mixing ratio of the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) from the results of the evaluation of the developability , and mixing the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) in the determined mixing ratio to prepare an alkali-soluble resin;
In the step of preparing the plurality of photosensitive resin compositions for evaluation, when the total amount of the alkali-soluble resin (a-1) and the alkali-soluble resin (a-2) in the photosensitive resin compositions for evaluation is 100 parts by mass, the difference between the parts by mass of the resin (a-1) in the photosensitive resin composition for evaluation having the least amount of the alkali-soluble resin (a-1) and the parts by mass of the alkali-soluble resin (a-1) in the photosensitive resin composition for evaluation having the most amount of the alkali-soluble resin (a-1) is prepared to be 20 parts by mass or more.
A method for preparing an alkali-soluble resin for use in a photosensitive resin composition. A method for producing a photosensitive resin composition, which produces a photosensitive resin composition containing at least an alkali-soluble resin obtained by the preparation method according to claim 1, a photopolymerizable monomer, and a photopolymerizable initiator. The method for producing a photosensitive resin composition according to claim 2, further comprising blending a colorant into the photosensitive resin composition. The method for producing a photosensitive resin composition according to claim 3, wherein the colorant comprises carbon black. A method for producing a cured product, comprising curing a photosensitive resin composition obtained by the method according to any one of claims 2 to 4. A method for producing a black matrix formed from a cured product obtained by the method of claim 5. A method for manufacturing an image display device using a black matrix obtained by the manufacturing method described in claim 6.