CN116360210A

CN116360210A - Photoresist composition, cured product, substrate pattern, colored dispersion, and method for producing photoresist composition

Info

Publication number: CN116360210A
Application number: CN202211686645.6A
Authority: CN
Inventors: 小野悠树; 岩井航平
Original assignee: Nippon Steel and Sumikin Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2021-12-27
Filing date: 2022-12-26
Publication date: 2023-06-30
Also published as: TW202325753A; KR20230099669A

Abstract

The present invention relates to a resist composition, a cured product, a matrix pattern, a colored dispersion, and a method for producing a resist composition. The present invention provides a photoresist composition which is suitable for forming a hardened substance (hardened film) with excellent hardening property and patterning property even in the case of low-temperature hardening. The photoresist composition of the present invention comprises: (A) a partially (meth) acrylated epoxy resin in which a part of the epoxy resin is (meth) acrylated, (B) a solvent, (C) an alkali-soluble resin containing a polymerizable unsaturated group, and (D) a photopolymerization initiator.

Description

Photoresist composition, cured product, substrate pattern, colored dispersion, and method for producing photoresist composition

Technical Field

The present invention relates to a resist composition suitable for obtaining a substrate pattern excellent in low-temperature hardenability and patterning properties.

Background

In recent years, attention has been paid to conventional liquid crystal display devices, and organic EL display devices (OLEDs) which are advantageous in terms of thickness reduction and flexibility and have high light utilization efficiency have been put into practical use.

Such an OLED includes a circular polarizing plate as an antireflection film in order to prevent deterioration in visibility due to reflection of external light or the like. However, when the circularly polarizing plate is provided, not only the external light but also the light emitted from the organic EL is blocked, and therefore the light utilization efficiency is greatly reduced. Accordingly, it is desired to develop an OLED which has good visibility and can be used with low power consumption even without using a circularly polarizing plate.

Here, by utilizing the resonance effect of the Color Filter (CF) and light, not only the light emitted from the organic EL is not cut off, but also the spectrum is formed to be steep and high-intensity, and the brightness and color purity are improved, thereby contributing to the improvement of the transmittance of the OLED and the improvement of the power consumption. CF has a smaller film thickness than a circular polarizing plate, the device can be thinned, and a black matrix has a high light-shielding property, and when external light incident through CF is reflected, it has an antireflection function to absorb the reflected light, so that it has been attempted to replace the circular polarizing plate with CF. In this case, in CF, for example, in a resist (black resist), a transparent resist, or an RGB resist forming a black matrix to be used, in addition to a well-known function, it is necessary to form a pattern on an OLED element having low heat resistance as compared with a glass substrate, and thus, particularly, low-temperature curing performance is strongly demanded.

In order to form a resin film pattern on a plastic substrate or the like having a heat resistance of up to 140 ℃ in patent document 1, it has been proposed that a curing agent and/or a curing accelerator for an epoxy compound be blended into a photosensitive resin composition, and that the total amount of these epoxy compound and curing agent and/or curing accelerator be set to a specific range. However, even if such an epoxy compound or a hardening imparting component equivalent thereto is added, there is no ultraviolet curability, so that there is a concern that crosslinking that does not form covalent bonds with other components having ultraviolet curability in the composition, when cured, the crosslinking is uneven, and the low-temperature curability/film strength as a cured film is not improved.

[ Prior Art literature ]

[ patent literature ]

[ patent document 1] Japanese patent application laid-open No. 2019-070720

[ patent document 2] Japanese patent application laid-open No. 2019-52273.

Disclosure of Invention

[ problem to be solved by the invention ]

The present invention has been made in view of the above-described problems, and has found that a specific epoxy compound (epoxy resin) in which a part of the epoxy groups of an epoxy compound is acrylated and/or methacrylated (in some cases, these are collectively referred to as "(meth) acrylated" in the case of "(meth) acrylic acid" and the like) is blended in a resist composition such as a black resist, instead of or in combination with an epoxy compound conventionally used. It has been found that such a specific epoxy compound can impart thermosetting properties (low-temperature hardenability) due to epoxy groups and has ultraviolet hardenability to a component having a polymerizable unsaturated group which is blended not less than in a resist composition, so that even when cured at a low temperature, crosslinking becomes uniform, coating film strength and the like can be improved, and a cured product excellent in development adhesion can be obtained even when a pattern having a line width of less than 20 μm is formed, for example.

Although a partially esterified epoxy resin in which a part of the epoxy groups are (meth) acrylated is known (for example, see patent document 2), it is not known to blend the partially esterified epoxy resin in a resist composition for the purpose of imparting low-temperature curability. In addition, although such partially esterified epoxy resins have been evaluated as an example of a sealant for a liquid crystal display device, no studies have been made on the applicability to ink materials using solvents, patterning in development, and applicability to black matrices.

Accordingly, the present invention has been made in view of the above-described findings, and an object thereof is to provide a resist composition suitable for use in forming a cured product (cured film) excellent in curability and patterning properties even when low-temperature curing is performed.

Another object of the present application is to provide a cured product obtained by curing such a resist composition, and to provide a substrate pattern produced using the cured product.

Further, another object of the present application is to provide a colored dispersion that can be used for the production of such a photoresist composition, and to provide a method for producing a photoresist composition using the colored dispersion.

[ means for solving the problems ]

That is, the gist of the present invention is as follows.

[1] A photoresist composition comprising:

(A) A partially (meth) acrylated epoxy resin having a portion thereof (meth) acrylated,

(B) A solvent(s),

(C) Alkali-soluble resin containing polymerizable unsaturated group

(D) A photopolymerization initiator.

[2] The photoresist composition according to the item [1], wherein the component (A) is a compound represented by the following formula (1).

[ in formula (1), cy is an aromatic hydrocarbon group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms,

Y is a hydrocarbon group of 2 valences having 1 to 20 carbon atoms,

R ₁₁ independently a hydrocarbon group of 1 to 10 carbon atoms. R is R ₁₂ Independently represent a radical of the formula and/or a radical of the formula and comprise at least one of each of the radicals. R is R ₁₇ Is a hydrogen atom or a methyl group.

a. m and n each independently represents the number of repeating units, and a is 1 or more, m is 1 or 2, n is 0 to 7]

[3] The photoresist composition according to the item [1], wherein the component (A) is a compound represented by the following formula (2).

[ in formula (2), R ₁₄ Represents the residue of an organic compound having d active hydrogen groups. R is R ₁₂ Independently, the following formulae and/or formula (x) are represented, and at least one each is contained in a molecule. R is R ₁₇ Is a hydrogen atom or a methyl group.

d is an integer from 1 to 100. c are each independently an integer of 0 to 100, and the sum of each c is 2 to 100]

[4] The photoresist composition according to the item [1], wherein the component (A) is a compound represented by the following formula (3).

In formula (3), f, g, h, i is 0 or 1, respectively, and f+g+h+i=1 to 3.

R ₁₃ Independently, the following formulae (x) and/or formula (x) are represented, and at least one of each of the formulae (x) and (x) is included. R is R ₁₇ Is a hydrogen atom or a methyl group]

[5] The photoresist composition according to the item [1], wherein the component (A) is a compound represented by the following formula (4).

R ₁₃ -W-R ₁₃ (4)

[ in formula (4), W represents a single bond or a 2-valent organic group having 1 to 20 carbon atoms, which may contain a hetero element therein. R is R ₁₃ Independently, the following formulae (x) and/or (x) are represented, and at least comprises (x) and (x)) One each. R is R ₁₇ Is a hydrogen atom or a methyl group]

[6] The photoresist composition according to the item [1], wherein the component (A) is a compound represented by the following formula (5).

[ in formula (5), Z represents-CO-, -SO ] ₂ -、-C(CF ₃ ) ₂ -、-Si(CH ₃ ) ₂ -、-CH ₂ -、-C(CH ₃ ) ₂ -, -O-, 9-fluorenyl, or absent.

R ₁₂ Independently of each other, the following formulae and/or formula (x) are represented, and at least one each is included. R is R ₁₇ Is a hydrogen atom or a methyl group.

R ₁₅ R is R ₁₆ Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

p represents the number of repeating units and represents an integer of 0 to 10]

[7] The photoresist composition of [1], which further comprises (F) a dispersant and (G) a colorant.

[8] The photoresist composition according to the item [7], wherein the component (G) is a light shielding material.

[9] The photoresist composition according to the item [8], wherein the light shielding material as the component (G) is carbon black.

[10] The resist composition according to [8], wherein the light-shielding material as the component (G) is an organic black pigment and/or a mixed-color organic pigment.

[11] The photoresist composition according to the item [8], wherein the light-shielding material as the component (G) is carbon black or an organic black pigment.

[12] A cured product obtained by curing the photoresist composition of any one of [1] to [11 ].

[13] A matrix pattern produced by using the cured product of [12 ].

[14] A colored dispersion for use in the photoresist composition of any one of [7] to [11], the colored dispersion comprising:

a partially (meth) acrylated epoxy resin having a part of the (meth) acrylated epoxy resin (A),

A solvent(s),

The dispersant (F) described above

The colorant of the above (G).

[15] A method for producing a resist composition according to any one of [7] to [11], comprising the steps of I and II,

step I): a step of preparing a coloring dispersion by mixing in advance a (meth) acrylated epoxy resin partially (meth) acrylated with the (a) epoxy resin, a solvent, the (F) dispersant, and the (G) colorant;

step II): a step of producing a resist composition by adding at least the (C) alkali-soluble resin containing a polymerizable unsaturated group and the (D) photopolymerization initiator to the colored dispersion prepared in the step I).

[ Effect of the invention ]

According to the present invention, even when low-temperature curing is performed, a cured product (matrix pattern) excellent in curability and patterning can be formed.

Detailed Description

As described above, the resist composition of the present invention comprises at least (a) a partially (meth) acrylated epoxy resin in which a part of the epoxy resin is (meth) acrylated, (B) a solvent, (C) an alkali-soluble resin containing a polymerizable unsaturated group, and (D) a photopolymerization initiator as essential components.

In addition, the photoresist composition of the present invention may contain (E) a surfactant, or (H) a photopolymerizable monomer having no epoxy group and having at least 1 ethylenic unsaturated bond, as needed.

In addition, the colored photoresist composition may be formed by further containing (F) a dispersant and (G) a colorant, if at least the components (A) to (D) are necessary

The components used will be described below in detail mainly.

Part of (A) epoxy resin (meth) acrylated epoxy resin

The component (a) in the resist composition of the present invention is a partially (meth) acrylated epoxy resin in which a part of the epoxy resin is (meth) acrylated, and is obtained by reacting an epoxy resin (also referred to as an epoxy compound, hereinafter the same applies) as a raw material with acrylic acid and/or methacrylic acid to (meth) acrylate a part of the epoxy groups of the raw material epoxy resin.

Accordingly, component (a) has an epoxy group and a (meth) acrylic group (acryl group) in 1 molecule, and thus has thermosetting properties and ultraviolet ray hardening properties.

The relation between the amount of (meth) acrylic acid esterification and the number of (meth) acrylic acid groups after (meth) acrylic acid esterification can be determined from the relation determined by the number of epoxy groups (number of moles) in the raw material epoxy resin. More simply, the ratio of the respective raw materials to be charged may be determined in accordance with the condition of the number of functional groups (mole number) of (meth) acrylic acid reacting with the number (mole number) of epoxy groups of the raw material epoxy resin. The number of epoxy groups (mole number) of the raw material epoxy resin can be calculated from the weight average molecular weight and the epoxy group equivalent. The ratio of (meth) acrylic acid ester to the epoxy group as a raw material may be expressed as a modification ratio [% (mol%) ]. The modification ratio of the component (a) may be set and used in a wide range depending on the relation with other components of the composition, the use, and the like, but the lower limit is preferably 10%, more preferably 20%, still more preferably 30%, still more preferably 40%, and most preferably 50%. On the other hand, the upper limit of the modification ratio is more preferably 90%, still more preferably 80%, still more preferably 70%, still more preferably 60%, and most preferably 50%. (A) The components may be used by mixing a plurality of components having different modification ratios. When a plurality of components having different modification ratios are mixed and used, the average value is preferably in a range satisfying the modification ratio.

The component (A) can be synthesized by a method known from the publication described in Japanese patent application laid-open No. 2019-52273.

The epoxy groups of the raw epoxy resin are unmodified or all of the epoxy groups are modified, and are not included as separate components in the definition of the component (a), but these components may be included in the resist composition of the present invention. The mixture containing these components may be defined as, for example, component (a) having the above-mentioned characteristics such as a modification ratio.

The raw material epoxy resin used for the production of the component (a) may be any publicly known epoxy resin without limitation. For example, bisphenol a type epoxy compound, bisphenol F type epoxy compound, bisphenol fluorene type epoxy compound, diphenyl fluorene type epoxy compound, phenol novolac type epoxy compound, (o-, m-, p-) cresol novolac type epoxy compound, phenol aralkyl type epoxy compound, biphenyl type epoxy compound (for example, jER YX4000: a phenol novolac compound containing a naphthalene skeleton (for example, NC-7000L: manufactured by Mitsubishi chemical corporation, jER "is a registered trademark of Mitsubishi chemical corporation), a naphthol aralkyl type epoxy compound, a ginseng phenol methane type epoxy compound (for example, EPPN-501H: manufactured by Japan chemical corporation), a phenol ethane type epoxy compound, a glycidyl ether of a polyhydric alcohol, a glycidyl ester of a polyvalent carboxylic acid, a copolymer of a monomer having a (meth) acrylic group as a unit containing a glycidyl ester of a (meth) acrylic acid represented by a copolymer of methacrylic acid and a glycidyl ester of a methacrylic acid, a hydrogenated bisphenol A diglycidyl ether (for example, RIKARESIN HBE-100: manufactured by New Japan chemical corporation, a glycidyl group-containing epoxy compound such as" RIKARESIN "is a registered trademark of New Japan chemical corporation), a 1, 4-cyclohexanedimethanol-bis 3, 4-epoxycyclohexane carboxylate, a 2- (3, 4-epoxycyclohexyl-5, 3-dioxane-3, 4-dioxane), ARALDITE CY175: "ARALDITE" manufactured by HUNTSMAN Co., ltd.) bis (3, 4-epoxycyclohexylmethyl) adipate (e.g., CYRACURE UVR-6128: manufactured by DOW CHEMICAL company), an alicyclic epoxy compound represented by 3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexane carboxylate (for example, CELOXIDE 2021P: DAICEL Co., ltd., "CELOXIDE" is a registered trademark of DAICEL Co., ltd.), butane tetracarboxylic acid tetrakis (3, 4-epoxycyclohexylmethyl) modified epsilon-caprolactone (e.g., EPOLEAD GT401: "epolate" manufactured by DAICEL corporation is a registered trademark of DAICEL corporation), an epoxy compound having an epoxycyclohexyl group (for example, hiREM-1: manufactured by four-national chemical industry Co., ltd.), a polyfunctional epoxy compound having a dicyclopentadiene skeleton (for example, HP7200 series: DIC corporation), 1, 2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol (e.g., EHPE3150: alicyclic epoxy compounds, epoxidized polybutadienes (for example, NISSO-PB. JP-100: "NISSO-PB" manufactured by Nippon Caesada Co., ltd., registered trademark of Nissan Caesada Co., ltd.), an epoxy compound having a polysilicone skeleton, and the like. In addition, these raw material epoxy resins may be used alone in an amount of 1 kind or in an amount of 2 or more kinds. That is, the component (A) may be used by mixing not only components having different modification ratios as described above but also components having different raw materials and different molecular frameworks. The components having different molecular backbones and modification ratios may be mixed.

Among such raw material epoxy resins, in the case of (meth) acrylating and using as the component (a), it is preferable to use a polyfunctional epoxy compound having 3 or more functions as a raw material in the use of the epoxy resin in which the reaction point with other components is increased to achieve 3-dimensional crosslinking (curing). When a polyfunctional epoxy resin is used as a raw material, the epoxy resin having an epoxy group equivalent of 500 or less, more preferably 450 or less, still more preferably 80 to 400, and particularly preferably 80 to 300, is used as the raw material epoxy resin, from the viewpoint of improving the reaction probability with the light shielding material. In this case, from the viewpoint of both reactivity with the light shielding material and reactivity at the time of UV exposure, it is preferable to adjust the (meth) acrylation such that the epoxy equivalent of the (a) component after (meth) acrylation becomes 1.2 to 10 times the epoxy equivalent of the raw material. More preferably, the epoxy equivalent of the component (A) may be 1.4 to 8 times the epoxy equivalent of the raw material.

On the other hand, when the component (A) is used by (meth) acrylation, it is preferable to use a 2-functional epoxy compound as a raw material in an application where the adhesion to a substrate is high. The epoxy resin as a raw material is preferably appropriately selected depending on the application to be used. When a 2-functional epoxy resin is used as a raw material, for the above reasons, an epoxy resin having an epoxy group equivalent of 500 or less, more preferably 450 or less, still more preferably 80 or more and 200 or less, is preferably used as the raw material epoxy resin. In this case, from the viewpoint of both reactivity with the light shielding material and reactivity at the time of UV exposure, it is more preferable to adjust the (meth) acrylation such that the epoxy equivalent of the (a) component after (meth) acrylation becomes 1.5 to 8 times the epoxy equivalent of the raw material. More preferably, the epoxy equivalent of the component (A) may be 1.5 to 5 times, still more preferably 1.6 to 4.8 times the epoxy equivalent of the raw material.

The component (a) of the present invention is specifically exemplified by the following first to fifth embodiments. As described above, only 1 kind of embodiment may be used, or a plurality of embodiments may be used in combination.

< first embodiment >, first embodiment

(A) The first embodiment of the component (A) is represented by the following general formula (1).

Here, in formula (1), cy is an aromatic hydrocarbon group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms. More preferred Cy is a benzene ring, naphthalene ring, biphenyl ring, cyclopentane ring, cyclohexane ring, or a ring in which a part of these is substituted with an alkyl group having 1 to 6 carbon atoms or a halogen atom or the like, and more preferred Cy is a benzene ring, naphthalene ring, biphenyl ring.

Y is a hydrocarbon group of 2 valences having 1 to 20 carbon atoms, more preferably-R ₁₈ -the radical shown, or phi-R ₁₈ -Cy ₂ -R ₁₈ -phi (phi is the bond). Here, R is ₁₈ More preferably a group selected from methylene, vinyl and propylene groups. Cy (Cy) ₂ More preferably, the group is selected from the group consisting of phenylene group, naphthylene group, biphenylene group, dicyclopentanediyl group and dicyclopentenediyl group, and a group combining a plurality of these groups.

R ₁₁ Is a substituent of the aforementioned Cy and is independently a hydrocarbon group of 1 to 10 carbon atoms, more preferably R ₁₁ Is methyl.

R ₁₂ Independently represents an epoxy group of the formula and/or a (meth) acrylated epoxy group of the formula. As described above, the component (a) is obtained by (meth) acrylating a part of the raw epoxy resin, and thus contains at least one of these groups and groups in one molecule.

In formula (1), a, m, and n each independently represent the number of repeating units, and a is 1 or more, preferably 1 to 50, and more preferably 2 to 45. When m is 1 or 2 and m is 1, a is preferably 2 or more. n is 0 to 7.

Specific examples of the first embodiment include, but are not limited to, compounds having the structures shown in the following (1-1) to (1-3).

In the formulae (1-1) and (1-2), a1 and b each independently represent the number of repeating units. a1 is usually 0 to 45 but more preferably 1 to 40, and b is usually 0 to 45 but more preferably 1 to 40. a1+b is 1 or more, and the bonding order of a1 and b may be arbitrary.

In the formula (1-3), q is also the number of repeating units, and q is usually 1 or more.

< second embodiment >

(A) A second embodiment of the component (A) is represented by the following general formula (2).

In the formula (2), R is ₁₄ Represents the residue of an organic compound having d active hydrogen groups. R is R ₁₂ As before, the epoxy groups represented by the formula (x) and/or (meth) acrylated epoxy groups represented by the formula (x). As in the case of formula (1), the resin of formula (2) can be obtained by (meth) acrylating the formula (x) of epoxy groups which are part of the raw material epoxy resin of formula (2). Thus, in formula (2), it also becomes a group containing at least one of the foregoing groups (x) and (x) in one molecule.

Further, c and d each independently represent the number of repeating units. d is an integer of 1 to 100, more preferably an integer of 2 to 10, and still more preferably an integer of 3 to 6.

In addition, c is an integer of 0 to 100, respectively and independently. More preferably, the number may be an integer of 2 to 10, and still more preferably, an integer of 3 to 6. In addition, from the viewpoint of the degree of crosslinking after curing, the workability such as solubility, and the like, the sum of c is 2 to 100, more preferably 3 to 30, and still more preferably 4 to 20.

Furthermore, regarding the aforementioned R ₁₄ Examples of the organic compound having an active hydrogen group which is a precursor thereof include alcohols, phenols, carboxylic acids, amines, thiols, and the like, and the compounds disclosed in Japanese patent No. 5744528 are known. Tool withWith the R ₁₄ Commercial products of the base raw material epoxy compound include, for example, EHPE3150[2, 2-bis (hydroxymethyl) -1-butanol 1, 2-epoxy-4- (2-oxiranyl) cyclohexane adduct of DAICEL Co., ltd]And the like, but is not limited thereto.

< third embodiment >

(A) A third embodiment of the component (A) is represented by the following general formula (3).

Here, in formula (3), f, g, h, i is 0 or 1, respectively, and f+g+h+i=1 to 3. R is independently R as for the compound represented by the formula (3) ₁₃ The radicals have the formula 3, 4-epoxycyclohexyl and a part thereof are (meth) acrylated radicals having the formula (i), and thus comprise at least one of these and (i) radicals. It is preferable to have a relatively large number of alicyclic skeletons because it is necessary to have excellent UV resistance.

Examples of commercial products of the raw material epoxy compound of the formula (3) include, but are not limited to, EPOLEAD GT401[ butane tetracarboxylic acid tetrakis (3, 4-epoxycyclohexylmethyl) modified epsilon-caprolactone ] of DAICEL corporation.

R ₁₇ Is a hydrogen atom or a methyl group.

< fourth embodiment >, a third embodiment

(A) A fourth embodiment of the component (A) is represented by the following general formula (4).

R ₁₃ -W-R ₁₃ (4)

In the formula (4), W represents a single bond or a 2-valent organic group having 1 to 20 carbon atoms, which may contain a hetero element therein. Specific W comprises a 2-valent hydrocarbon group, one or two 2-valent groups having a carboxyl group at the end of the hydrocarbon group, or the like, and may have thereinHaving an ether-linked oxygen atom or ester linkage. More specifically, compounds represented by formulas (14) to (20) described in Japanese patent application laid-open No. 2020-166254 can be used as a raw material. Regarding the compound represented by the formula (4), R ₁₃ The radicals have the formula 3, 4-epoxycyclohexyl radicals and a part thereof are (meth) acrylated radicals having the formula (x) indicated above, and thus comprise at least one of these and (x) radicals respectively. That is, in the formula (4), groups including the aforementioned formulas (x) and (x) are each one. Examples of commercially available products of the starting epoxy compound of the formula (4) include CELOXIDE2021P [3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexane carboxylate of DAICEL Co., ltd]And the like, but is not limited thereto.

< fifth embodiment >, a third embodiment

(A) A fifth embodiment of the component (A) is represented by the following general formula (5).

In the formula (5), Z represents-CO-, -SO ₂ -、-C(CF ₃ ) ₂ -、-Si(CH ₃ ) ₂ -、-CH ₂ -、-C(CH ₃ ) ₂ -, -O-, 9-fluorenyl or absent, but more preferably-CH ₂ -, 9-fluorenyl.

R ₁₂ Represents an epoxy group of the formula (x) and/or a (meth) acrylated epoxy group of the formula (x). Thus, the formula (5) is also defined as comprising one of each of these groups.

R ₁₅ R is R ₁₆ Each independently is a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, or represents a halogen atom, but is more preferably a hydrogen atom or a methyl group.

p represents the number of repeating units and an integer of 0 to 10, but more preferably 0 to 8]

The end point of the synthesis of component (A) can be confirmed by, for example, measurement of the acid value.

The component (a) exemplified in this embodiment is preferably a component having a weight average molecular weight of 200 to 20000, more preferably 250 to 15000.

The amount of the component (a) to be blended is preferably 0.2 to 80% by mass, more preferably 0.5 to 75% by mass, still more preferably 1 to 70% by mass, based on the solid content of the resist composition of the present invention.

The amount of the component (a) to be blended is preferably 1 to 800 parts by mass, more preferably 101 to 600 parts by mass, still more preferably 101 to 400 parts by mass, still more preferably 101 to 200 parts by mass, based on 100 parts by mass of the component (C) or 100 parts by mass of the total of the component (C) and the component (H) described later. In the applications where patterning is essential, 1 to 100 parts by mass is more preferable, 1 to 90 parts by mass is more preferable, and 1 to 80 parts by mass is still more preferable. The above-described amount of the component (C) or the total of the component (C) and the component (H) is preferable because good patterning characteristics can be obtained.

Solvent < (B) >

The solvent (E) in the resist composition of the present invention may be exemplified by, for example: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, diacetone alcohol, and the like; terpenes such as alpha-or beta-terpene alcohols; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone (Methyl pyrrolidone); aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate can be dissolved and mixed by using these, and a composition in a homogeneous solution can be formed.

(C) alkali-soluble resin containing polymerizable unsaturated group

The component (C) in the resist composition of the present invention is not particularly limited as long as it is a resin having a polymerizable unsaturated group and an acidic group in the molecule. The first example which can be preferably used is an epoxy (meth) acrylate acid adduct obtained by reacting a compound having 2 or more epoxy groups with (meth) acrylic acid (this means acrylic acid and/or methacrylic acid), and then reacting the obtained epoxy (meth) acrylate compound having a hydroxyl group with (a) a dicarboxylic acid or tricarboxylic acid or an acid monoanhydride thereof and/or (b) a tetracarboxylic acid or an acid dianhydride thereof. The compound having 2 or more epoxy groups derived as the (meth) acrylic acid adduct may be exemplified by bisphenol type epoxy compounds or novolak type epoxy compounds. Specifically, bisphenol-type epoxy compounds represented by the following general formula (I) are more preferably exemplified.

In the formula of the general formula (I), R ₁ 、R ₂ 、R ₃ R is R ₄ Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, A represents-CO-, -SO ₂ -、-C(CF ₃ ) ₂ -、-Si(CH ₃ ) ₂ -、-CH ₂ -、-C(CH ₃ ) ₂ -, -O-, fluorene-9, 9-diyl or direct bonding. l is an integer from 0 to 10. More preferred R ₁ 、R ₂ 、R ₃ 、R ₄ A is a hydrogen atom, and more preferably A is fluorene-9, 9-diyl. In addition, l is usually a mixture of a plurality of values, and thus becomes an average value of 0 to 10 (not limited to an integer), but it is more preferable that l be an average value of 0 to 3. Hereinafter, description will be made on the case where l=0.

The bisphenol type epoxy compound is an epoxy compound having 2 glycidyl ether groups obtained by reacting bisphenol with epichlorohydrin, and generally includes an epoxy compound having 2 or more bisphenol skeletons because the reaction is accompanied by oligomerization of the diglycidyl ether compound. The bisphenols used in this reaction may be exemplified by: bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3, 5-dimethylphenyl) ketone, bis (4-hydroxy-3, 5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3, 5-dimethylphenyl) sulfone, bis (4-hydroxy-3, 5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dichlorophenyl) methane, bis (4-hydroxy-3, 5-dibromophenyl) methane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-2, 2-chlorophenyl) propane, 2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3, 5-dimethylphenyl) ether, bis (4-hydroxy-3, 5-dichlorophenyl) ether, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9-bis (4-hydroxy-3-fluorophenyl) fluorene 9, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene 9, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, 4 '-biphenol, 3' -biphenol and the like. Among them, bisphenols having fluorene-9, 9-diyl groups are particularly preferably usable.

As the acid monoanhydride of the (a) dicarboxylic acid or tricarboxylic acid which is reacted with the epoxy (meth) acrylate, there may be used an acid monoanhydride of a chain hydrocarbon dicarboxylic acid or tricarboxylic acid or an acid monoanhydride of an alicyclic dicarboxylic acid or tricarboxylic acid, an acid monoanhydride of an aromatic dicarboxylic acid or tricarboxylic acid. Here, the acid monoanhydrides of the chain hydrocarbon dicarboxylic or tricarboxylic acids are, for example: succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citraconic acid, malonic acid, glutaric acid, citric acid, tartaric acid, ketoglutaric acid, heptanoic acid, sebacic acid, suberic acid, diglycolic acid, and other acid monoanhydrides, and dicarboxylic acid or tricarboxylic acid monoanhydrides to which an optional substituent is introduced may be used. In addition, acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include, for example: acid monoanhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylene tetrahydrophthalic acid (endomethylene tetrahydrophthalic anhydride), chlorobridge acid (chloric acid), hexahydrotrimellitic acid, and norbornane dicarboxylic acid, and acid monoanhydrides of dicarboxylic acid or tricarboxylic acid to which an optional substituent is introduced may be used. Further, the acid monoanhydrides of the aromatic dicarboxylic acid or tricarboxylic acid are, for example: acid monoanhydrides such as phthalic acid, isophthalic acid, trimellitic acid, 1, 8-naphthalene dicarboxylic acid, and 2, 3-naphthalene dicarboxylic acid, and dicarboxylic acid or tricarboxylic acid having an optional substituent may be used.

The acid dianhydride of (b) the tetracarboxylic acid that reacts with the epoxy (meth) acrylate may be an acid dianhydride of a chain hydrocarbon tetracarboxylic acid, an acid dianhydride of an alicyclic tetracarboxylic acid, or an acid dianhydride of an aromatic tetracarboxylic acid. Here, examples of the acid dianhydride of the chain hydrocarbon tetracarboxylic acid include: the acid dianhydride such as butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, etc., and may be a tetracarboxylic acid having an optional substituent introduced therein. In addition, examples of the acid dianhydride of the alicyclic tetracarboxylic acid include: acid dianhydrides such as cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norzhane tetracarboxylic acid, and acid dianhydrides of tetracarboxylic acids having optional substituents introduced therein may be used. Further, the acid dianhydride of an aromatic tetracarboxylic acid may be exemplified by, for example: acid dianhydrides such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid, naphthalene-2, 3,6, 7-tetracarboxylic acid, and the like, and acid dianhydrides of tetracarboxylic acids having any substituents introduced therein may be used.

The molar ratio (a)/(b) of the acid dianhydride of (a) dicarboxylic acid or tricarboxylic acid to (b) tetracarboxylic acid reacted with the epoxy (meth) acrylate may be 0.01 to 10.0, more preferably may be 0.02 or more and less than 3.0. The molar ratio (a)/(b) is in the above range, so that the most preferable molecular weight of the resist composition to be excellent in photo-patternability can be easily obtained, and the composition is more preferable because of no deterioration and alkali solubility.

The epoxy (meth) acrylate acid adduct can be produced by a known method, for example, the method described in Japanese patent application laid-open No. 8-278629 or Japanese patent application laid-open No. 2008-9401. First, the method of reacting an epoxy compound with (meth) acrylic acid is, for example, the following method: (meth) acrylic acid in an amount equal to the molar amount of the epoxy group of the epoxy compound is added to the solvent, and the mixture is heated to 90 to 120℃with blowing air in the presence of a catalyst (triethylbenzyl ammonium chloride, 2, 6-diisobutyl phenol, etc.), followed by stirring to react the mixture. Next, the method for reacting the hydroxyl group of the epoxy acrylate compound belonging to the reaction product with an acid anhydride includes the following methods: the epoxy acrylate compound is added with a predetermined amount of acid dianhydride and acid monoanhydride in a solvent, and heated and stirred at 90 to 130 ℃ in the presence of a catalyst (tetraethylammonium bromide, triphenylphosphine, etc.), so that they react. The epoxy acrylate acid adduct obtained by the method has a skeleton of a general formula (II).

[ in formula (II), R ₁ 、R ₂ 、R ₃ R is R ₄ Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, A represents-CO-, -SO ₂ -、-C(CF ₃ ) ₂ -、-Si(CH ₃ ) ₂ -、-CH ₂ -、-C(CH ₃ ) ₂ -, -O-, fluorene-9, 9-diyl or direct bond, X represents a carboxylic acid residue of valence 4, Y ₁ Y and Y ₂ Each independently represents a hydrogen atom or-OC-Z- (COOH) k (Z represents a 2-or 3-valent carboxylic acid residue, k represents a number of 1 to 2), and j represents an integer of 1 to 20. R is R ₅ Represents a hydrogen atom or a methyl group]

(C) Another example of the component (a) is a resin having a (meth) acrylic group and a carboxyl group in a copolymer of (meth) acrylic acid, a (meth) acrylic ester, and the like. For example, the first step is a copolymer obtained by copolymerizing (meth) acrylic esters containing glycidyl (meth) acrylate in a solvent, the second step is a copolymer obtained by reacting the copolymer with (meth) acrylic acid, and the third step is an alkali-soluble resin containing a polymerizable unsaturated group obtained by reacting the copolymer with an anhydride of a dicarboxylic acid or a tricarboxylic acid.

(C) Still another example of the components is as follows: a urethane compound obtained by reacting a polyol compound having an ethylenic unsaturated bond in a molecule as a first component, a diol compound having a carboxyl group in a molecule as a second component, and a diisocyanate compound as a third component. The resin of the system can be referred to as the resin shown in Japanese patent application laid-open No. 2017-76071.

(C) The component (c) is preferably 3 to 65 mass% and more preferably 5 to 60 mass% in the solid content of the resist composition of the present invention. Further, the composition may be appropriately adjusted in accordance with the relationship with other components to be blended or the balance of patterning properties. For example, in the case of using a black resist using a light-shielding material described later, the component (C) is preferably blended by adjusting it to about 3 to 40 mass%, and more preferably about 5 to 35 mass% in the resist composition.

In addition, the weight average molecular weight (Mw) thereof is usually between 2000 and 10000, more preferably between 3000 and 7000. When the weight average molecular weight (Mw) is less than 2000, the adhesiveness of the pattern at the time of development cannot be maintained, and pattern peeling occurs, and when the weight average molecular weight (Mw) exceeds 10000, development residues or residual films in unexposed portions tend to remain. In addition, the acid value of the component (B) is more preferably in the range of 30 to 200 KOHmg/g. If the value is less than 30KOHmg/g, alkali development may not be smoothly performed or special development conditions such as strong alkali may be necessary, and if it exceeds 200KOHmg/g, permeation of an alkali developer becomes too fast, and peeling development is likely to occur.

The component (B) may be used alone in 1 kind or in a mixture of 2 or more kinds.

(D) photopolymerization initiator

The component (D) in the resist composition of the present invention may be exemplified by, for example: acetophenones such as acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropionyl benzene, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzyl dimethyl ketal; benzophenone types such as benzophenone, 2-chlorobenzophenone, p '-bis-dimethylaminobenzophenone, 4' -bis-dimethylaminobenzophenone (michaelketone), 4-phenylbenzophenone, 4 '-dichlorobenzophenone, hydroxybenzophenone, and 4,4' -diethylaminobenzophenone; benzoin ethers such as benzyl, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; biimidazole compounds such as 2- (o-chlorophenyl) -4, 5-phenylbiimidazole, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4, 5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4, 5-diphenylbiimidazole, 2,4, 5-triarylbiimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl-1, 2-biimidazole; halomethyl oxadiazole compounds such as 2-trichloromethyl-5-styryl-1, 3, 4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3, 4-oxadiazole, and 2-trichloromethyl-5- (p-methoxystyryl) -1,3, 4-oxadiazole; halomethyl-s-triazine compounds such as 2,4, 6-ginseng (trichloromethyl) -1,3, 5-triazine, 2-methyl-4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-chlorophenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3, 4, 5-trimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methylsulfanyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine; 1, 2-octanedione, 1- [4- (phenylsulfanyl) phenyl ] -,2- (O-benzoyloxime), 1- (4-phenylsulfanyl) butane-1, 2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanyl) butane-1, 2-dione-2-oxime-O-acetate, 1- (4-methylsulfanyl) butane-1-ketoxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -bicycloheptyl-1-ketoxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -adamantyl methane-1-ketoxime-O-benzoate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -adamantyl methane-1-ketoxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -carbazolyl-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -tetrahydrofuranylmethan-1-one oxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -phenylthiomethane-1-one oxime-O-benzoate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -phenylthiomethane-1-one oxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -morpholinomethane-1-one oxime-O-benzoate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -formolinylmethan-1-one oxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-one oxime-O-carboxylate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-one oxime-O-tricyclodecane carboxylic acid ester, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-one oxime-O-adamantanecarboxylic acid ester, 1- [4- (phenylmercapto) phenyl ] octane-1, 2-dione = 2-O-benzoyl oxime, 1- [ 9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl ] ethanone-O-acetyl oxime, (2-methylphenyl) (7-nitro-9, 9-dipropyl-9H-fluoren-2-yl) -acetyl oxime, ethanone, 1- [7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] -1- (O-acetyl), ethanone, 1- (-9, 9-dibutyl-7-nitro-9H-fluoren-2-yl) -1-yl-O-ethanone, 1- [ 9-nitro-3-acetyl ] -ethanone, 1- [ 3-nitro-2-yl ] -ethanone, 1- [ 3-methyl-3-yl ] -ethanone, 3-methyl-2-yl ] -oxime, o-acyl oximes such as 1- (O-acetyl oxime); sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzanthraquinone, and 2, 3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumyl peroxide and the like; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, β -mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane ginseng (3-mercaptopropionate), ginseng- [ (3-mercaptopropionyloxy) -ethyl ] -triisocyanate, pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol tetrakis (3-mercaptopropionate), 3' -thiodipropionic acid, dithiodipropionic acid, and laurylthiopropionic acid, and the like. Among them, the use of O-acyl oxime compounds is preferred from the viewpoint of easy availability of high sensitivity. In addition, these photopolymerization initiators of 2 or more kinds may be used. The photopolymerization initiator used in the present invention is used in the sense of containing a sensitizer.

In addition, a compound that does not function as a photopolymerization initiator or sensitizer itself may be added, but the ability of the photopolymerization initiator or sensitizer may be increased by using the above-described compound in combination. Examples of such compounds include amine compounds having effects when used in combination with benzophenone. Examples of the amine compound include: triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4' -bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4' -bis (ethylmethylamino) benzophenone, and the like.

The amount of component (D) to be blended is preferably 2 to 95 parts by mass, more preferably 2 to 40 parts by mass, still more preferably 3 to 30 parts by mass, per 100 parts by mass of the component (C) or 100 parts by mass of the total of the component (C) and the component (H) described later.

< other Components >)

Surfactant (E)

In addition, the present invention may contain (E) a surfactant as required. Examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate, cationic surfactants such as stearyl amine acetate and lauryl trimethylammonium chloride, amphoteric surfactants such as lauryl dimethylamine oxide and lauryl carboxymethyl hydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and sorbitan monostearate, and silicone surfactants having polydimethylsiloxane as a main skeleton, fluorine surfactants, and the like.

The component (E) may be a polymer containing a side chain having an ethylenically unsaturated group and a side chain having a perfluoroalkyl group or a perfluoroether group, and for example, a polymer described in japanese patent application laid-open No. 2010-164965 or japanese patent application laid-open No. 2010-250256 may be used without particular limitation. Specific surfactants can be exemplified by: MEGAFAC RS-56, RS-72-A, RS-72-K, RS-75, RS-76-E, RS-76-NS, RS-78, RS-90 (manufactured by DIC Co., ltd.), etc.

The component (E) is usually preferably 0.01 to 10% by mass based on the solid content of the composition.

Dispersing agent (F) colorant (G)

The resist composition of the present invention may contain (F) a dispersant and (G) a colorant in addition to other components, and may be used as a colored resist composition. The following components can be used as the component (F) and the component (G).

(F) As the dispersant, publicly known dispersants such as various polymer dispersants can be used. Examples of the dispersant include, but are not particularly limited to, publicly known compounds (commercially available compounds called dispersants, dispersion wetting agents, dispersion accelerators, and the like) conventionally used for pigment dispersion, but examples thereof include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative type dispersants (dispersion aids), and the like. In particular, the cationic polymer-based dispersant having a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amine group, and having an amine value of 1 to 100mgKOH/g and a number average molecular weight of 1 to 10 thousands is suitable as the adsorption point of the pigment. The blending amount of the dispersant is preferably 1 to 30% by mass relative to the colorant (G).

On the other hand, the colorant (G) is not particularly limited, and publicly known colorants usable in the field can be used, but an organic pigment or an inorganic pigment is more preferable, and when a light-shielding film (black matrix) is formed, a light-shielding material is more preferable. The light-shielding material is more preferably a light-shielding material composed of an organic black pigment, a mixed-color organic pigment, or an inorganic black pigment. Here, examples of the organic black pigment include: perylene black, nigrosine, cyanine black, lactam black, and the like. Examples of the mixed-color organic pigment include pigments which are pseudo-blackened by mixing 2 or more pigments selected from red, cyan, chlorine, violet, yellow, cyanine, magenta, and the like. Examples of the inorganic black pigment include carbon black, chromium oxide, iron oxide, and titanium black. These coloring components may be used alone in an amount of 1 or 2 or more. The photoresist composition of the present invention can be appropriately selected for use according to the purpose.

Among these light-shielding materials, carbon black is more preferable from the viewpoints of light-shielding properties, surface smoothness, dispersion stability, and affinity with resins. In addition, when low dielectric characteristics of the coating film are required, the light-shielding material may be an organic black pigment and/or a mixed-color organic pigment. On the other hand, in applications where both the light-shielding property of visible light and the infrared ray-transmitting property are important, for example, as in the case of the combination of carbon black and an organic black pigment, the combination of carbon black and lactam black may be suitably used.

Carbon black is more preferably untreated or oxidized carbon black. Here, the untreated means that no special surface treatment such as oxidation treatment or resin coating treatment is applied, and the oxidation treatment is to treat the surface of carbon black with a certain oxidizing agent before the dispersion step. Such untreated or oxidized carbon blacks have many acidic functional groups on the surface, so in the case of using this, it is more preferable to use untreated or oxidized carbon blacks. In addition, when carbon black is used to further increase the resistance value of the cured film, a surface-coated carbon black obtained by coating the surface of carbon black with a dye, pigment, resin or the like may be used.

When the component (G) is used, it can be appropriately set in accordance with the purpose or use of the present invention, and for example, it can be arbitrarily determined so as to have a desired light shielding degree, but it is more preferably 5 to 70 mass% and still more preferably 7 to 65 mass% with respect to the solid content in the resist composition.

< Dispersion, coloring Dispersion >

In the case of using these components (F) and (G), it is more preferable that the components (F) and (G) are dispersed in advance with a solvent to form a dispersion, and then blended in the composition. The solvent to be dispersed in the component (B) may be part or all of the solvents listed for the component (B), but propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and the like may be suitably used. Products or commercial products in which some or all of these (F) components, (G) components and solvents are mixed may be used in advance.

Still more preferably, the dispersion is a colored dispersion in which a part or all of the (meth) acrylated epoxy resin which is a part of the component (a) is further co-dispersed in the dispersion. Accordingly, the coloring dispersion liquid also containing the component (a) is preferably formed of the solvent which is a part or all of the component (B), the dispersant which is the component (F) and the colorant which is the component (G), so that the interaction between the colorant and the component (a) can be improved, and the effects such as the dispersibility of the colorant and the optimization of patterning characteristics can be obtained. In this case, the amount of the component (a) to be blended is preferably 2 to 20 mass% in the colored dispersion, more preferably 5 to 15 mass% in order to obtain the aforementioned effects, or to obtain the non-destructive viscosity/dispersibility.

That is, when the component (F) and the component (G) are blended in the resist composition of the present invention to obtain a colored resist composition, it is preferable to have a step of previously mixing the component (A), the solvent, the component (F) and the component (G) to prepare a colored dispersion. Here, a composition in which a part or all of the component (F) and the component (G) is mixed in advance may be used. Then, it is more preferable to prepare a composition by adding at least the component (C) and the component (D) to the colored dispersion after the colored dispersion is obtained, and adding components other than the components as necessary. In order to obtain a colored dispersion, it is particularly preferable to mix the colorant so as not to coagulate.

[ (H) photopolymerizable monomer having no epoxy group and having at least 1 ethylenic unsaturated bond ]

The resist composition of the present invention may contain the component (H) as required. The component (H) is a component which can exert a role of crosslinking molecules of the alkali-soluble resin belonging to the component (C) with each other. Examples of the component (H) include: (meth) acrylic esters having a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxyhexyl (meth) acrylate; or ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide hexa (meth) acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dendritic polymers having a modified (meth) acryloyl group, and the like, may be used. Examples of the dendritic polymer having a (meth) acryloyl group include publicly known dendritic polymers obtained by adding a thiol group in a polyvalent mercapto compound to a part of a carbon-carbon double bond in a (meth) acryloyl group of a polyfunctional (meth) acrylate compound.

Since the component (H) plays the role described above, it is more preferable to use a component having 2 or more ethylenically unsaturated bonds in order to perform its function. In addition, the acrylic equivalent of dividing the molecular weight of the monomer by the number of (meth) acryloyl groups in 1 molecule may be 50 to 300.

(H) The amount of the component (C) to be blended is 50/50 to 90/10, preferably 60/40 to 80/20 in terms of the mass ratio (C)/(H). (C) When the blending ratio of the components is less than 50/50, the cured product after photo-curing becomes brittle, and in the unexposed portion, the acid value of the coating film is low, so that the solubility in an alkali developer is lowered, and there is a concern that the edges of the pattern are not sharp. If the blending ratio of component (C) is more than 90/10, the proportion of photoreactive functional groups occupied by the resin is small, the formation of crosslinked structures is insufficient, and the acid value in the resin component is too high, and the solubility in an alkali developer in an exposed portion is high, so that there is a concern that the formed pattern is thinner than the target line width, or a problem that pattern defects are likely to occur.

[ (E) to (H) components other than

In addition, in the resist composition of the present invention, additives such as epoxy resins other than the above-mentioned component (a) and a curing agent and/or curing accelerator thereof, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, and a viscosity adjuster may be blended as necessary in addition to the above-mentioned components (E) to (H). The epoxy resin other than the component (a) may be any publicly known epoxy resin which is a raw material of the component (a), and the publicly known component may be used as a curing agent and/or a curing accelerator thereof without limitation. Examples of the thermal polymerization inhibitor and the antioxidant include: hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine, hindered phenol compounds, and the like, and examples of plasticizers include: examples of the filler include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like: glass fibers, silica, mica, alumina, and the like. In particular, by containing silica particles, the reflectance of the cured product (cured film) can be adjusted to impart low reflectance. The silica particles are suitably selected and used within the scope of the object of the present invention, for example, from the embodiments described in Japanese patent application laid-open No. 2020-166254. Further, as the defoaming agent or leveling agent, there may be mentioned: silicone-based, fluorine-based, and acrylic-based compounds. The coupling agent may be exemplified by: silane coupling agents such as 3- (glycidoxy) propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

< solids >

The resist composition of the present invention contains the above-mentioned components (A) to (D) as main components. In the case where the colorant of the component (G) is not contained in the solid (the solid contains the monomer that becomes a solid after hardening) from which the solvent is removed, the total of the components (a), (C) and (D) is more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more. When the colorant contains the component (G), the total of the components including the component (F) and the component (G) is more preferably 70 mass% or more, still more preferably 80 mass% or more, still more preferably 90 mass% or more, in addition to the components (a), (C) and (D). The amount of the solvent belonging to the component (B) varies depending on the viscosity to be aimed, but may be set to be contained in the range of 60 to 90 mass% in the resist composition of the present invention.

Method for forming cured product (cured film, matrix pattern)

The resist composition of the present invention is excellent, for example, as a composition for forming a cured film (protective film, light shielding film) of a color filter, and the following photolithographic etching method is used as a method for forming the cured film. There may be mentioned: first, a resist composition is applied onto a transparent substrate, then a solvent is dried (prebaked), a mask is covered on the film obtained in this manner, an exposed portion is cured by irradiation with ultraviolet light, development is performed by eluting an unexposed portion with an aqueous alkali solution to form a pattern, and further post baking (heat firing) is performed as a post-drying method.

The transparent substrate coated with the composition may be exemplified by a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.), a transparent electrode of ITO, gold, etc. deposited or patterned, in addition to a glass substrate. In addition, a substrate or the like having an organic device formed with an OLED or an organic Thin Film Transistor (TFT) is also included, and a protective film, or the like is also included after the organic device is formed.

The method of applying the solution of the composition on the transparent substrate may be any method such as a method using a roll coater, a reverse roll coater, a slit coater or a spin coater, in addition to the publicly known solution dipping method and spraying method. By these methods, after coating to a desired thickness, a coating film is formed by removing a solvent (prebaking). The prebaking may be performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time in the pre-baking are appropriately selected depending on the solvent used, and are carried out at a temperature of 60 to 110 ℃ for 1 to 3 minutes, for example.

The exposure after the pre-baking is performed by an ultraviolet exposure device and is performed through a photomask, whereby only the portion of the photoresist corresponding to the pattern is sensitized. The exposure apparatus and the exposure irradiation conditions thereof can be appropriately selected, and the composition in the coating film is light-cured by exposure using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halogen lamp, or a far ultraviolet lamp.

The alkali development after exposure is performed for the purpose of removing the photoresist in the unexposed portion, and a desired pattern is formed by the development. Examples of the developer suitable for the alkali development include an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of a hydroxide of an alkali metal, etc., but particularly, a weakly alkaline aqueous solution containing 0.05 to 3% by mass of a carbonate such as sodium carbonate, potassium carbonate, lithium carbonate, etc., is used, and development is performed at a temperature of 23 to 28 ℃.

After development, it is more preferable to perform heat treatment (post baking) at a temperature of 80 to 150℃and under a condition of 20 to 60 minutes. The post baking is performed for the purpose of improving adhesion between the patterned cured film and the substrate, and the like. This is performed by heating in an oven, a hot plate, or the like, as in the case of the prebaking. The patterned cured film of the present invention is formed by the steps performed by the photolithography etching method described above. The resulting cured film may then be used to obtain the desired matrix pattern.

The resist composition of the present invention is suitable for forming a fine pattern by an operation such as exposure to light or alkali development as described above. The resist composition of the present invention is suitable for use as a coating material, and in particular, as an ink for color filters used in liquid crystal display devices or image pickup devices, and the cured film formed by the composition can be used as a color filter, a black matrix for liquid crystal projection, a light shielding film for touch panels, and the like.

The cured film (light-shielding film) obtained by the present invention is excellent in low-temperature curability, does not deteriorate solvent resistance even when heated at 80 ℃ for 60 minutes (post baking), has no rough coating film surface after immersion in a solvent, and has little change in optical concentration (OD) when a colorant is used. In addition, the resist composition of the present invention is suitable for forming a pattern excellent in, for example, development adhesion in the case of forming a pattern having a line width of less than 20 μm even after the same low-temperature curing conditions.

Examples (example)

Embodiments of the present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.

First, a synthetic example (synthetic example 1) of an alkali-soluble resin containing a polymerizable unsaturated group corresponding to the component (C) of the present invention is presented. The resin in synthesis example 1 was evaluated as follows.

[ solid concentration ]

1g of the resin solution obtained in Synthesis example 1 was impregnated into a glass filter [ mass: w (W) ₀ (g)]And weigh [ W ] ₁ (g)]From mass [ W ] after heating at 160℃for 2 hours ₂ (g)]The result is obtained by the following equation.

Solid concentration (mass%) =100× (W ₂ -W ₀ )/(W ₁ -W ₀ )

[ acid value ]

The resin solution was dissolved in dioxane, and titrated with a 1/10N-KOH aqueous solution using a potential difference titration apparatus [ trade name COM-1600 manufactured by Ping biogas Co., ltd. ], thereby obtaining the resin solution

[ molecular weight ]

The Gel Permeation Chromatography (GPC) [ product name HLC-8220GPC, manufactured by TOSOH Co., ltd., solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) +TSKgelSuperH-3000 (1) +TSKgelSuperH-4000 (1) +TSKgelSuper-H5000 (1) [ TOSOH Co., ltd. ] temperature: 40 ℃ and speed: the weight average molecular weight (Mw) was determined by measuring 0.6ml/min as a standard polystyrene (PS-oligomer kit, manufactured by TOSOH Co., ltd.).

[ epoxy equivalent weight ]

After dissolving an epoxy compound to be measured in dioxane, an acetic acid solution of tetraethylammonium bromide was added, and the resulting mixture was titrated with a 1/10N-perchloric acid solution using a potential difference titration apparatus "COM-1600" (manufactured by Ping Zhu Shi industry Co., ltd.).

The following is a short term for use in synthesis examples and the like.

AA: acrylic acid

BPFE: reactants of 9, 9-bis (4-hydroxyphenyl) fluorene and chloromethyl ethylene oxide. In the compounds of the general formula (I), A is fluoren-9, 9-diyl and R ₁ To R ₄ A compound which is a hydrogen atom.

BPDA:3,3', 4' -biphenyltetracarboxylic dianhydride

THPA:1,2,3, 6-tetrahydrophthalic anhydride

TPP: triphenylphosphine and process for preparing same

PGMEA: propylene glycol monomethyl ether acetate

Tea b: tetraethylammonium bromide

PTMA: pentaerythritol tetrakis (Hydrogen thioglycolate)

DPHA: mixtures of dipentaerythritol pentaacrylate and hexaacrylate

HQ: hydroquinone

BzDMA: benzyl dimethyl amine

Synthesis example 1

A500 ml four-necked flask equipped with a reflux condenser was charged with 114.4g (0.23 mol), 33.2g (0.46 mol) of AA, 157g of PGMEA and 0.48g of TEAB, and the mixture was stirred for 20 hours under heating at 100 to 105℃to react. Then, 35.3g (0.12 mol) of BPDA and 18.3g (0.12 mol) of THPA were charged into the flask, and the mixture was stirred at 120 to 125℃for 6 hours under heating to obtain an alkali-soluble resin solution containing a polymerizable unsaturated group. The solid concentration of the obtained resin solution was 56.5% by mass, the acid value (in terms of solid content) was 103mgKOH/g, and the Mw by GPC analysis was 3600.

Further, synthesis examples (synthesis example 2) of the (H) -3 component described below are shown.

Synthesis example 2

In a 1 liter four-necked flask, PTMA (20 g, 0.19 mol of mercapto group), DPHA (212 g (2.12 mol of acrylic group)), PGMEA (58 g), HQ (0.1 g), and BzDMA (0.01 g) were added, and the mixture was reacted at 60℃for 12 hours to obtain a dendrimer solution (H) -3. The solid concentration of the dendrimer solution was 80 mass%, and the Mw obtained by GPC analysis was 10000. Further, disappearance of the mercapto group was confirmed by iodine measurement for the obtained dendrimer.

Further, synthesis examples (synthesis examples 3 to 10) of the component (a) of the present invention are shown.

Synthesis example 3

Used in the structure shown in the formula (1), cy is a benzene ring, R ₁₂ All radicals of formula (x), Y is methylene, R ₁₁ Methyl, m=1, n=1, a.about.7.8, mw=1574, epoxy equivalent=203 g/eq. To 282 parts by mass (1.389 equivalents) of the raw resin, 50 parts by mass (0.694 equivalents) of acrylic acid, 111 parts by mass of PGMEA, 1 part by mass of triphenylphosphine, 0.1 part by mass of hydroquinone monomethyl ether, and 1 part by mass of phenolsulfonic acid were added, and the mixture was reacted at 80 to 90 ℃ for 10 hours. Accordingly, R of the raw material resin is obtained ₁₂ A part of the functional groups (equivalent ratio 50%) of the acrylated partially acrylated epoxy resin (A) -1-1.

Synthesis example 4

The same procedure as in Synthesis example 3 was repeated except that the cresol novolak type epoxy resin in Synthesis example 3 was changed to 157 parts by mass (0.773 equivalent) and PGMEA was changed to 70 parts by mass. Accordingly, R of the raw material resin is obtained ₁₂ A part of the functional groups (equivalent ratio 90%) of the acrylated partially acrylated epoxy resin (A) -1-2.

Synthesis example 5

The same procedure as in Synthesis example 3 was repeated except that the cresol novolak type epoxy resin in Synthesis example 3 was changed to 1410 parts by mass (6.946 equivalents) and PGMEA was changed to 487 parts by mass. Accordingly, R of the raw material resin is obtained ₁₂ A part of the functional groups (equivalent ratio 10%) of the acrylated partially acrylated epoxy resin (A) -1-3.

Synthesis example 6

Used in the structure shown in the formula (1), cy is a benzene ring, R ₁₂ All groups are methylene, m=1, n=0, a.about.2.9, mw=684, epoxy equivalent=177 g/eq. To 246 parts by mass (1.390 equivalents) of this raw resin, 50 parts by mass (0.694 equivalents) of acrylic acid, 99 parts by mass of PGMEA, 1 part by mass of triphenylphosphine, 0.1 part by mass of hydroquinone monomethyl ether, and 1 part by mass of phenolsulfonic acid were added, and reacted at 80 to 90 ℃ for 10 hours. Accordingly, R of the raw material resin is obtained ₁₂ A part of the functional groups (equivalent ratio 50%) of the acrylated partially acrylated epoxy resin (a) -2.

Synthesis example 7

Used in the structure shown in formula (5), p=0, r ₁₅ R is R ₁₆ Is a hydrogen atom, Z is-C (CH) ₃ ) ₂ -，R ₁₂ Bisphenol a epoxy resins with all (x) groups, mw=370, epoxy equivalent=190 g/eq are used as base resins. To 246 parts by mass (1.389 equivalents) of this raw material resin, 50 parts by mass (0.694 equivalents) of acrylic acid, 1 part by mass of triphenylphosphine, 0.1 part by mass of hydroquinone monomethyl ether, and 1 part by mass of phenolsulfonic acid were added, and the mixture was reacted at 80℃to 90℃for 10 hours. Accordingly, R of the raw material resin is obtained ₁₂ A part of the functional groups (equivalent ratio 50%) of the acrylated partially acrylated epoxy resin (A) -3.

Synthesis example 8

3',4' -epoxycyclohexylmethyl 3',4' -epoxycyclohexane carboxylate (CELOXIDE 2021P, mw =260, epoxy equivalent 130g/eq, manufactured by DAICEL corporation) was used as the base resin. To 181 parts by mass (1.392 equivalents) of this raw material resin, 50 parts by mass (0.694 equivalents) of acrylic acid, 1 part by mass of triphenylphosphine, 0.1 part by mass of hydroquinone monomethyl ether, and 1 part by mass of phenolsulfonic acid were added, and the mixture was reacted at 80℃to 90℃for 10 hours. Hereby, a partially acrylated epoxy resin (A) -4 was obtained in which a part (equivalent ratio 50%) of the 3, 4-epoxycyclohexyl group of the raw resin was acrylated.

Synthesis example 9

Tetrakis (3, 4-epoxycyclohexylmethyl) butane-tetracarboxylic acid modified ε -caprolactone (EPOLEAD GT401, mw=900, epoxy equivalent 217g/eq, manufactured by DAICEL Co., ltd.) was used as the base resin. To 301 parts by mass (1.387 equivalent) of this raw resin, 50 parts by mass (0.694 equivalent) of acrylic acid, 118 parts by mass of PGMEA, 1 part by mass of triphenylphosphine, 0.1 part by mass of hydroquinone monomethyl ether, and 1 part by mass of phenolsulfonic acid were added, and reacted at 80 to 90 ℃ for 10 hours. Hereby, a partially acrylated epoxy resin (A) -5 was obtained in which a part (equivalent ratio 50%) of the 3, 4-epoxycyclohexyl group of the raw resin was acrylated.

Synthesis example 10

1, 2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol (EHPE 3150, mw=1800, epoxy equivalent 180g/eq, manufactured by DAICEL corporation) was used as a base resin. To 250 parts by mass (1.389 equivalents) of the raw resin, 50 parts by mass (0.694 equivalents) of acrylic acid, 101 parts by mass of PGMEA, 1 part by mass of triphenylphosphine, 0.1 part by mass of hydroquinone monomethyl ether, and 1 part by mass of phenolsulfonic acid were added, and reacted at 80 to 90 ℃ for 10 hours. Hereby, a partially acrylated epoxy resin (A) -6 was obtained in which a part (equivalent ratio 50%) of the 3, 4-epoxycyclohexyl group of the raw resin was acrylated.

[ preparation of resist composition ]

Formulations were prepared according to the compositions shown in tables 1 to 7. The components used for the formulation are as follows. All the values in the table are mass%, and the values other than the component (B) are expressed as solids. The solids content was adjusted to 20 mass%.

First, examples 1 to 17 and comparative examples 1 to 3, which are examples in which the (F) component (dispersant) and the (G) component (colorant) were not used, are shown in tables 1 to 2.

As embodiments using the component (F) and the component (G), the embodiments in which the component (G) is (G) -1 (carbon black) are shown in tables 3 to 4 as examples 18 to 38 and comparative examples 4 to 6. Further, examples 39 to 63 and comparative examples 7 to 9 were shown in tables 5 to 7 as examples in which the component (G) was (G) -2 (lactam black) or (G) -2 and (G) -1 were used in combination.

In addition, as shown in the compositions of tables 8 to 9, coloring dispersions (examples 64 to 78) in which the (a) component, (B) component, (F) component and (G) component were mixed and dispersed in advance were prepared. Then, example 64 and example 76 were used so as to be 30 mass% of the respective compositions in the colored dispersion, and the solids were adjusted to 20 mass% by adding other components to the respective compositions. The same PGMEA was used for the solvent. Table 10 shows embodiments (examples 79 and 80) of the respective coloring dispersions using examples 64 and 76.

Component (A)

(A) -1-1: the partially acrylated epoxy resin obtained in Synthesis example 3 above

(A) -1-2: the partially acrylated epoxy resin obtained in Synthesis example 4 above

(A) -1-3: the partially acrylated epoxy resin obtained in Synthesis example 5 above

(A) -2: the partially acrylated epoxy resin obtained in Synthesis example 6 above

(A) -3: the partially acrylated epoxy resin obtained in Synthesis example 7 above

(A) -4: the partially acrylated epoxy resin obtained in Synthesis example 8 above

(A) -5: the partially acrylated epoxy resin obtained in Synthesis example 9 above

(A) -6: the partially acrylated epoxy resin obtained in Synthesis example 10 above

Component (B)

PGMEA

Component (C)

The alkali-soluble resin solution containing a polymerizable unsaturated group obtained in Synthesis example 1

Component (D)

(D) -1: oxime ester photopolymerization initiator (Irgacure OXE01, manufactured by BASF JAPAN Co., ltd.)

(D) -2: oxime ester-based photopolymerization initiator [ NCI-831E of ADEKA Co., ltd. ]

Component (E)

MEGAFAC RS-72-A (DIC)

Component (F) and component (G)

Dispersion of 25.0% by mass of carbon black as component (G) -1 and 6.25% by mass of PGMEA solvent as polymer dispersant as component (F)

15.0% by mass of lactam black as component (G) -2 and 3.75% by mass of PGMEA solvent as polymer dispersant as component (F)

Component (H)

(H) -1: mixtures of pentaerythritol triacrylate and pentaerythritol tetraacrylate (ARONIX M-450, manufactured by east Asia Synthesis Co., ltd.)

(H) -2: mixtures of dipentaerythritol pentaacrylate and hexaacrylate [ DPHA, acrylic acid equivalent 96 to 115, manufactured by Japanese chemical Co., ltd.)

(H) -3: the resinous polymer obtained in Synthesis example 2

(I) Epoxy resin: CELOXIDE 2021P (manufactured by DAICEL Co., ltd.)

(J) Hardening agent: TMA (Mitsubishi GAS chemical Co., ltd.)

(K) Silica PGMEA dispersion "YA010C" (manufactured by ADMATECH Co., ltd., solid content 20% by mass, average particle diameter 10 nm)

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

TABLE 6

TABLE 7

TABLE 8

TABLE 9

TABLE 10

Blending components	Example 79	Example 80
			The coloring dispersion used	Example 64	Example 76
(A)-1-1	3.0	3.0
			(A)-1-2
(A)-1-3
			(A)-2
(A)-3
			(B)	80.00	80.00
(C)	5.13	5.13
			(H)-1	1.71	1.71
(H)-2
			(H)-3
(D)-2	0.80	0.80
			(I)	1.00	100
(J)	0.76	076
			(E)	0.10	010
(G)-1	6.0
			(G)-2		6.0
(F)	1.5	1.5
			(K)

[ evaluation ]

The following evaluations were performed using the photoresist compositions of examples 1 to 63, 79 to 80, and comparative examples 1 to 9. These evaluation results are shown in tables 11 to 18.

< Low temperature hardenability (solvent resistance) >)

The compositions obtained above were applied to a 125mm×125mm glass substrate (CORNING 1737) by a spin coater so that the film thickness after post baking became 1.5 μm, and pre-baked at 80 ℃ for 1 minute. Thereafter, the irradiation with i-ray was performed at an irradiation intensity of 30mW/cm ² Is irradiated by an ultra-high pressure mercury lamp of 50mJ/cm ² Ultraviolet rays of (2) and carrying out a photo-hardening reaction.

Next, a 0.04% aqueous potassium hydroxide solution at 23℃was used at 1kgf/cm ² After the exposed coated plate was developed for 80 seconds under the shower pressure of 5kgf/cm ² The pressed spray water was washed, and then, heat post-baked at 80 ℃ for 60 minutes using a hot air dryer.

Thereafter, the transmittance of the coated plate was evaluated by a spectrophotometer, and the OD value was evaluated by a penetrometer. That is, when the colorant belonging to the component (G) was not used, the coated sheet was immersed in PGMEA for 100 seconds, and the change in the transmittance before and after immersion (transmittance after immersion—transmittance before immersion) was represented by a difference, and was determined based on the following criteria. On the other hand, when a colorant belonging to the component (G) was used, the change in OD value before and after impregnation (OD after impregnation-OD before impregnation) was represented by a difference, and the determination was made based on the following criteria.

< when no colorant is used >

And (2) the following steps: the penetration rate variation is less than 3 percent

Delta: the difference of the penetration rate change is more than 3% and less than 5%

X: the change difference of the penetration rate is more than 5 percent

< use of colorant >

And (2) the following steps: the OD variation difference is less than 0.2

Delta: the OD change difference is more than 0.2 and less than 0.3

X: the OD change difference is more than 0.3

< evaluation of patterning >)

The compositions obtained above were applied to a 125mm×125mm glass substrate (CORNING 1737) by a spin coater so that the film thickness after post baking became 1.5 μm, and pre-baked at 80 ℃ for 1 minute. Thereafter, a negative mask having a line pattern with an opening width of 1 to 20 μm was adhered on the dried coating film at an i-ray illuminance of 30mW/cm ² Is irradiated by an ultra-high pressure mercury lamp of 50mJ/cm ² The ultraviolet ray of the photosensitive part is used for photo-hardening reaction.

Next, the exposed coated plate was subjected to a temperature of 23℃and a 0.04% aqueous potassium hydroxide solution at a rate of 1kgf/cm ² After a development Time (Break time=bt) from the beginning of the pattern, +60 seconds of development, 5kgf/cm was performed ² After the non-exposed portion of the coating film was removed by washing with water under pressure to form a line pattern on the glass substrate, the line pattern was baked at 80 ℃ for 60 minutes using a hot air dryer, and the smallest opening line that did not cause pattern peeling was used as the smallest analysis line width.

And (3) the following materials: less than 10 mu m

The method comprises the following steps: more than 10 μm and less than 13 μm

And (2) the following steps: 13 μm or more and less than 17 μm

Delta: 17 μm or more and less than 20 μm

X: 20 μm or more

< evaluation of OD/. Mu.m >

The compositions obtained above were applied to a 125mm×125mm glass substrate (CORNING 1737) by a spin coater so that the film thickness after post baking became 1.0 μm, and pre-baked at 90 ℃ for 1 minute. Then, the negative mask was not covered, but the i-ray illuminance was 30mW/cm ² 40mJ/cm of ultra-high pressure mercury lamp irradiation ² Ultraviolet rays of (2) and carrying out a photo-hardening reaction.

Next, the exposed coated plate was subjected to a temperature of 23℃to a pressure of 1kgf/cm using a 0.04% aqueous potassium hydroxide solution ² After 80 seconds of shower pressure development of 5kgf/cm ² The pressed spray water was washed, after which it was baked for 30 minutes after heating at 230 ℃ using a hot air dryer. The OD value of the coated plate was evaluated using a penetrometer. The film thickness of the light shielding film formed on the coated plate was measured so that the OD value was divided by the film thickness to obtain OD/. Mu.m.

< reflectivity evaluation >)

Next, the exposed coated plate was subjected to a temperature of 23℃to a pressure of 1kgf/cm using a 0.04% aqueous potassium hydroxide solution ² After 80 seconds of shower pressure development of 5kgf/cm ² The pressed spray water was washed, and then, heat post-baked at 80 ℃ for 60 minutes using a hot air dryer. The reflectance of the coated sheet on the film surface side was measured at an incident angle of 2 ° using an ultraviolet visible near infrared spectrophotometer "UH4150" (manufactured by hitachi High Tech Science corporation), and was determined based on the following criteria.

And (3) the following materials: the reflectivity is below 5%

O: reflectance exceeds 5% and is less than 7%

TABLE 11

TABLE 12

TABLE 13

TABLE 14

TABLE 15

TABLE 16

TABLE 17

TABLE 18

From the results of examples 1 to 63 and 79 to 80, and comparative examples 1 to 9, it is apparent that the addition of the partially (meth) acrylated epoxy resin belonging to the component (a) to the photoresist composition makes it possible to impart the low-temperature curability at the same time, as compared with the case of adding the epoxy resin and the curing agent, and therefore, the addition of the partially (meth) acrylated epoxy resin having an unsaturated group and an epoxy group in the molecule makes it possible to uniformly cure the coating film even if the curing reaction is performed by either UV or heat. Further, it is found that the colorant dispersion containing the partially (meth) acrylated epoxy resin having an epoxy group is prepared in advance, and thus good patterning properties can be obtained, and dispersion stability of the colorant is preferable.

Claims

1. A photoresist composition comprising:

(B) A solvent(s),

(C) Alkali-soluble resin containing polymerizable unsaturated group

(D) A photopolymerization initiator.

2. The photoresist composition according to claim 1, wherein the component (A) is a compound represented by the following formula (1),

in the formula (1), cy is an aromatic hydrocarbon group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms,

y is a hydrocarbon group of 2 valences having 1 to 20 carbon atoms,

R ₁₁ independently a hydrocarbon group of 1 to 10 carbon atoms, R ₁₂ Independently represents a group of the formula and/or a group of the formula, and comprises at least one of each of R ₁₇ Is a hydrogen atom or a methyl group,

a. m and n each independently represent the number of repeating units, a is 1 or more, m is 1 or 2, and n is 0 to 7;

3. the photoresist composition according to claim 1, wherein the component (A) is a compound represented by the following formula (2),

in the formula (2), R ₁₄ Represents the residue of an organic compound having d active hydrogen groups, R ₁₂ Independently of the other, the formulae and/or formula (I) each comprising at least one of the following and R in a molecule ₁₇ Is a hydrogen atom or a methyl group,

d1 to 100, c are each independently an integer from 0 to 100, and the sum of each c is from 2 to 100;

4. The photoresist composition according to claim 1, wherein the component (A) is a compound represented by the following formula (3),

in formula (3), f, g, h, i are each independently 0 or 1, and f+g+h+i=1 to 3,

R ₁₃ independently of each other, are of the formula (x) and/or formula (x) at least comprising (x) and (x) each of the following (x) and (x) is ₁₇ Is a hydrogen atom or a methyl group;

5. the photoresist composition according to claim 1, wherein the component (A) is a compound represented by the following formula (4),

R ₁₃ -W-R ₁₃ (4)

in formula (4), W represents a single bond or a C1-20 organic group which may contain a hetero element therein, R ₁₃ Independently of each other, are of the formula (x) and/or (x) and at least comprises (x) and (x) each of the following (x) and (x) is ₁₇ Is a hydrogen atom or a methyl group,

6. the photoresist composition according to claim 1, wherein the component (A) is a compound represented by the following formula (5),

in formula (5), Z represents-CO-, -SO ₂ -、-C(CF ₃ ) ₂ -、-Si(CH ₃ ) ₂ -、-CH ₂ -、-C(CH ₃ ) ₂ -, -O-, 9-fluorenyl or absent,

R ₁₂ independently of each other, are of the formula (x) and/or (x) and comprise at least one of each of (x) and (x), R ₁₇ Is a hydrogen atom or a methyl group,

R ₁₅ r is R ₁₆ Are respectively independentRepresents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom,

p represents the number of repeating units and an integer of 0 to 10,

7. The photoresist composition of claim 1, further comprising (F) a dispersant and (G) a colorant.

8. The resist composition according to claim 7, wherein the component (G) is a light shielding material.

9. The resist composition according to claim 8, wherein the light-shielding material as the component (G) is carbon black.

10. The resist composition according to claim 8, wherein the light-shielding material as the component (G) is an organic black pigment and/or a mixed-color organic pigment.

11. The resist composition according to claim 8, wherein the light-shielding material as the component (G) is carbon black or an organic black pigment.

12. A cured product of the photoresist composition of any one of claims 1 to 11.

13. A matrix pattern produced using the cured product according to claim 12.

14. A colored dispersion for use in the photoresist composition of any one of claims 7 to 11, the colored dispersion comprising:

A solvent(s),

The dispersant (F) described above

The colorant of the above (G).

15. A method for producing a resist composition according to any one of claims 7 to 11, comprising the steps of I and II,