Photosensitive resin composition, photosensitive resin laminate, and method for forming a resist pattern

Abstract

The present invention provides a photosensitive resin composition capable of improving various properties by controlling the type and ratio of at least the acid comonomer component among the comonomer components of an alkali-soluble polymer. The photosensitive resin composition comprises the following components: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, wherein the component (A) has a constituent unit derived from at least the following comonomer components: (a) methacrylic acid or acrylic acid, (b) a carboxylic acid different from the acid selected as the component (a), and (c) a compound having an aromatic structure or alicyclic structure, and the ratio (mass ratio (a1)) of the constituent unit derived from the component (a) and the mass ratio (b1) derived from the component (b) in the component (A) (mass ratio (a1) / mass ratio (b1)) is 1 / 10 to 10.

Description

Technology Field

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, and a method for forming a resist pattern. Background Technology

[0002] Conventionally, printed circuit boards mounted on electronic devices such as personal computers and mobile phones have been manufactured by photolithography. In photolithography, for example, a photosensitive resin laminate having a support and a photosensitive resin layer is laminated onto a substrate from the photosensitive resin layer side (opposite side to the support). By performing exposure and development on this photosensitive resin layer, a resist pattern can be formed on the substrate, and if necessary, etching can be performed on the substrate after undergoing plating treatment.

[0003] Here, various proposals have been made regarding photosensitive resin compositions for obtaining a photosensitive resin layer. For example, Patent Document 1 discloses a photosensitive resin composition comprising an alkali-soluble polymer having an inorganic value (I value) of less than or equal to a predetermined value. In this regard, photosensitive resin compositions with low hydrophobicity may have excellent solubility in a developer (excellent developability).

[0004] In addition, Patent Document 2 discloses a photosensitive resin composition comprising a carboxyl group-containing resin and an alkali-soluble polymer having an acid value of 50 to 200 as an addition product of an unsaturated compound having an α,β-unsaturated double bond and an epoxy group. In Synthesis Example 2 of Patent Document 2, the carboxyl group-containing resin is prepared from comonomer components such as 36 parts by mass of acrylic acid, 43 parts by mass of methacrylic acid, and 10 parts by mass of methyl methacrylate. Prior art literature

[0005] International Publication No. 2019 / 244724; Japanese Published Patent Application No. Hei 8-339081 The problem to be solved

[0006] However, the photosensitive resin compositions of Patent Documents 1 and 2 had room for improvement in terms of achieving compatibility between the developability of the photosensitive resin layer and the resolution of the obtained resist pattern. That is, while it is considered that improving the hydrophobicity of the photosensitive resin layer is a method for achieving high resolution, improving the hydrophobicity of the photosensitive resin layer tends to increase the development time because the solubility in the developer decreases.

[0007] In addition, due to the recent demand for high resolution, there has also been awaiting the provision of a photosensitive resin composition having a photosensitive resin layer capable of improving adhesion to a substrate.

[0008] The present invention is proposed in light of the above circumstances. Specifically, the objective of the present invention is to provide a photosensitive resin composition capable of improving various properties by controlling the type and ratio of at least the acid comonomer component among the comonomer components of an alkali-soluble polymer. Furthermore, the objective of the present invention is to provide a photosensitive resin laminate having a photosensitive resin layer obtained from such a photosensitive resin composition, and a method for forming a resist pattern realized using the same. means of solving the problem

[0009] [1]

[0010] The following ingredients:

[0011] (A) Alkali-soluble polymer,

[0012] (B) A compound having ethylenically unsaturated bonds, and

[0013] (C) A photosensitive resin composition comprising a photopolymerization initiator,

[0014] The above (A) component is at least the following comonomer component:

[0015] (a) methacrylic acid or acrylic acid,

[0016] (b) a carboxylic acid different from the acid selected as the component of (a) above, and

[0017] (c) Compounds having an aromatic or alicyclic structure

[0018] Having constituent units derived from,

[0019] In the above (A) component,

[0020] The mass ratio (a1) of constituent units derived from the above (a) component, and,

[0021] Mass ratio of constituent units derived from the above (b) component (b1)

[0022] A photosensitive resin composition in which the ratio (the mass ratio (a1) / the mass ratio (b1)) is 1 / 10 to 10.

[0023] [2]

[0024] A photosensitive resin composition described in Item 1, wherein the above ratio (the above mass ratio (a1) / the above mass ratio (b1)) is 1 / 8 to 8.

[0025] [3]

[0026] The above (A) component further comprises a constituent unit derived from (d) a hydroxyalkyl (meth)acrylic acid ester as a comonomer component, a photosensitive resin composition as described in Item 1 or 2.

[0027] [4]

[0028] The photosensitive resin composition described in Item 3, wherein the above (d) component is hydroxyethyl methacrylate.

[0029] [5]

[0030] A photosensitive resin composition described in any one of items 1 to 4, wherein the above (a) component is methacrylic acid.

[0031] [6]

[0032] A photosensitive resin composition described in any one of items 1 to 5, wherein the above (b) component is acrylic acid.

[0033] [7]

[0034] In the above (A) component,

[0035] The mass ratio (a1) of constituent units derived from the above (a) component, and,

[0036] A photosensitive resin composition described in any one of items 1 to 6, wherein the total mass ratio (b1) of constituent units derived from the above (b) component is 1 to 65 mass%.

[0037] [8]

[0038] The above (c) component comprises styrene and / or benzyl (meth)acrylate, a photosensitive resin composition as described in any one of items 1 to 7.

[0039] [9]

[0040] A photosensitive resin composition described in any one of items 1 to 8, wherein the proportion of constituent units derived from the above (c) component in the above (A) component is 10 to 95 mass%.

[0041]

[10]

[0042] The above (c) component is a photosensitive resin composition described in Item 8, comprising styrene.

[0043]

[11]

[0044] A photosensitive resin composition described in Item 10, wherein the proportion of constituent units derived from styrene in the above (A) component is 45 to 95 mass%.

[0045]

[12]

[0046] Based on the total amount of solids in the above photosensitive resin composition,

[0047] The above (A) component: 10 to 90 mass%,

[0048] The above (B) component: 5 to 70 mass%, and

[0049] Above (C) component: 0.01 to 20 mass%

[0050] A photosensitive resin composition comprising, as described in any one of items 1 to 11.

[0051]

[13]

[0052] The above (A) component comprises a plurality of alkali-soluble polymers, a photosensitive resin composition described in any one of items 1 to 12.

[0053]

[14]

[0054] A photosensitive resin composition described in Item 13, wherein the relationship between the mass average of the above mass ratio (a1) and the mass average of the above mass ratio (b1) (mass average of mass ratio (a1) / mass average of mass ratio (b1)) is 1 / 10 to 10.

[0055]

[15]

[0056] At least one of the alkali-soluble polymers included in the above (A) component is,

[0057] A photosensitive resin composition described in Item 13 or 14, having a constituent unit derived from the above components (a) to (c), and also satisfying the above ratio.

[0058]

[16]

[0059] Among the alkali-soluble polymers included in the above (A) component,

[0060] It has constituent units derived from the above components (a) to (c), and also,

[0061] A photosensitive resin composition described in any one of items 13 to 15, wherein the ratio of the alkali-soluble polymer satisfying the above ratio is 10 mass% or more.

[0062]

[17]

[0063] A photosensitive resin composition described in any one of items 1 to 16, wherein the acid value of the above (A) component is 50 to 600 mgKOH / g.

[0064]

[18]

[0065] The above (B) component comprises a compound having a bisphenol A structure and / or a hydrogenated bisphenol A structure, a photosensitive resin composition described in any one of items 1 to 17.

[0066]

[19]

[0067] The above (B) component comprises a compound having three or more of the above ethylenically unsaturated bonds in one molecule, a photosensitive resin composition described in any one of items 1 to 18.

[0068]

[20]

[0069] The above (C) component is a photosensitive resin composition described in any one of items 1 to 19, comprising a hexaarylbiimidazole (HABI) compound.

[0070]

[21]

[0071] (D) A photosensitive resin composition described in any one of items 1 to 20, further comprising a leuco dye as a component.

[0072]

[22]

[0073] In the above (A) component,

[0074] The mass ratio (a1) of constituent units derived from the above (a) component, and,

[0075] The mass ratio (b1) of constituent units derived from the above (b) component, and,

[0076] The mass ratio (c1) of the constituent unit derived from the above (c) component is given by the following formulas (1) to (3):

[0077] 10 ≤ (a1)+(b1) ≤ 50 ··· (1)

[0078] 0.5 ≤ (a1) / (b1) ≤ 8.0 ··· (2)

[0079] 30 ≤ (c1) ≤ 80 ··· (3)

[0080] A photosensitive resin composition described in any one of items 1 to 21 that satisfies [the condition].

[0081]

[23]

[0082] The above component (A) comprises a plurality of alkali-soluble polymers, and

[0083] At least one of the alkali-soluble polymers included in the above component (A) has a constituent unit derived from the above components (a) to (c), and also,

[0084] A photosensitive resin composition described in Item 22, wherein the above mass ratios (a1), (b1) and (c1) satisfy the above formulas (1) to (3).

[0085]

[24]

[0086] Among the alkali-soluble polymers included in the above (A) component,

[0087] A photosensitive resin composition described in Item 23, having a constituent unit derived from the above components (a) to (c), and also having a mass ratio (a1), (b1) and (c1) of an alkali-soluble polymer satisfying the above formulas (1) to (3), wherein the ratio of the alkali-soluble polymer is 10 mass% or more.

[0088]

[25]

[0089] A photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from a photosensitive resin composition described in any one of items 1 to 24.

[0090]

[26]

[0091] A photosensitive resin laminate described in Item 25, having a protective film on the side opposite to the support of the photosensitive resin layer.

[0092]

[27]

[0093] A process of laminating a photosensitive resin laminate described in item 25 or 26 onto a substrate,

[0094] A process of exposing a photosensitive resin layer of the stacked photosensitive resin laminate, and

[0095] A process for developing the above-exposed photosensitive resin layer

[0096] A method for forming a resist pattern having

[0097]

[28]

[0098] A resist pattern forming method described in Item 27, wherein the above exposure is performed by direct imaging exposure. Effects of the invention

[0099] According to the photosensitive resin composition related to the present invention, the type and ratio of at least the acid comonomer component among the comonomer components of the alkali-soluble polymer can be controlled to improve the developability of the photosensitive resin layer. Furthermore, according to the photosensitive resin composition related to the present invention, the adhesion of the photosensitive resin layer to a substrate and the resolution of the resist pattern can also be improved. In addition, according to the present invention, a photosensitive resin laminate having a photosensitive resin layer obtained from such a photosensitive resin composition, and a method for forming a resist pattern realized using the same can be provided. Specific details for implementing the invention

[0100] Hereinafter, embodiments of the present invention (hereinafter abbreviated as “the present embodiment”) will be described. However, the present invention is not limited to the present embodiment and may be implemented with various modifications within the scope of its gist. In the present embodiment, a numerical range indicated using “~” includes the numerical values ​​indicated before and after the “~” within that range. Furthermore, in the present embodiment, in numerical ranges described in steps, an upper or lower limit value indicated in one numerical range may be substituted with an upper or lower limit value of another numerical range described in steps. Additionally, in the present embodiment, an upper or lower limit value indicated in one numerical range may be substituted with a value disclosed in the embodiment.

[0101] In this specification, “(meth)acryl” means acrylic or methacryl, “(meth)acryloyl” means acryloyl or methacryloyl, and “(meth)acrylate” means acrylate or methacrylate.

[0102] [Photosensitive resin composition]

[0103] [Outline]

[0104] The photosensitive resin composition related to the present embodiment is,

[0105] The following ingredients:

[0106] (A) Alkali-soluble polymer,

[0107] (B) A compound having ethylenically unsaturated bonds, and

[0108] (C) Photopolymerization initiator

[0109] Includes. In this specification, the above (A) to (C) are also simply referred to as “Component (A)” to “Component (C)”.

[0110] And, (A) component, at least the following comonomer component:

[0111] (a) methacrylic acid or acrylic acid,

[0112] (b) a carboxylic acid different from the acid selected as the component of (a) above, and

[0113] (c) Compounds having an aromatic or alicyclic structure

[0114] It has a constituent unit derived from. In this specification, (a) and (b) are also simply referred to as “(a) acid comonomer component” and “(b) acid comonomer component,” and (c) is also simply referred to as “(c) comonomer component.”

[0115] Here, regarding component (A),

[0116] (a) Mass ratio of constituent units derived from acid comonomer components (a1) and,

[0117] (b) Mass ratio of constituent units derived from acid comonomer components (b1)

[0118] The ratio of (mass ratio (a1) / mass ratio (b1)) is 1 / 10 to 10. Here, "1 / 10" is, for example, "0.1".

[0119] In such a photosensitive resin composition, a plurality of acid comonomer components are used in combination as comonomer components of an alkali-soluble polymer, and other comonomer components are also used in combination with the plurality of acid comonomer components. Furthermore, at least with respect to the acid comonomer components, their type and content ratio are controlled.

[0120] According to such a photosensitive resin composition, various properties (developability of the photosensitive resin layer, adhesion of the photosensitive resin layer to a substrate, and resolution of the resist pattern, etc.) can be improved.

[0121] In one preferred embodiment of the present invention, a plurality of acid comonomer components are used in combination as comonomer components of an alkali-soluble polymer, and additionally, comonomer components having other aromatic or alicyclic structures may also be used in combination with the plurality of acid comonomer components. Furthermore, the inventors have discovered that controlling the type and content ratio of at least the acid comonomer components leads to improvements in various performance characteristics, and the present invention is proposed based on this concept. In addition, in one preferred embodiment of the present invention, the ratio of comonomer components having other aromatic or alicyclic structures may also be controlled, and in this case, it is easy to improve various characteristics (e.g., adhesion of the photosensitive resin layer to the substrate and resolution of the resist pattern).

[0122] Below, each component constituting the photosensitive resin composition is described.

[0123] [(A) Component: Alkali-soluble polymer]

[0124] (Outline)

[0125] (A) The component is a polymer soluble in an alkaline solution. (A) The component preferably has a carboxyl group, and for the sake of improving developability, it is preferable to have an acid value of 50 to 600 mgKOH / g, and more preferable to have an acid value of 100 to 400 mgKOH / g. The acid value of (A) may be 60 mgKOH / g or higher, 80 mgKOH / g or higher, 100 mgKOH / g or higher, 500 mgKOH / g or lower, or 400 mgKOH / g or lower. (A) The component may be thermoplastic.

[0126] The above acid value refers to the number of milligrams of potassium hydroxide required to neutralize 1 g of component (A).

[0127] The weight average molecular weight of component (A) is preferably 5,000 to 500,000, more preferably 10,000 to 200,000, even more preferably 20,000 to 100,000, and particularly preferably 23,000 to 70,000. By having the weight average molecular weight of component (A) above the lower limit value, it becomes easier to maintain a uniform thickness of the photosensitive resin laminate and also easier to secure resistance to the developer of the exposure part. In addition, by having the weight average molecular weight of component (A) below the upper limit value, it becomes easier to maintain the developability of the photosensitive resin laminate.

[0128] In addition, the polydispersity (Mw / Mn), which is the ratio of the weight-average molecular weight (Mw) of component (A) to the number-average molecular weight (Mn) of component (A), is preferably 1.0 to 6.0.

[0129] The above weight-average molecular weight and polydispersity refer to the weight-average molecular weight and polydispersity measured using a calibration curve of polystyrene by gel permeation chromatography (GPC). The weight-average molecular weight can be measured, for example, under the following conditions.

[0130] (GPC conditions)

[0131] Pump: Hitachi L-6000 type (Manufactured by Hitachi, Ltd., Product name)

[0132] Columns: A total of 3 items below

[0133] Gelpack GL-R420

[0134] Gelpack GL-R430

[0135] Gelpack GL-R440 (Manufactured by Hitachi Kasei Corporation, Product Name)

[0136] Eluent: Tetrahydrofuran

[0137] Measured temperature: 40 ℃

[0138] Flow rate: 2.05 mL / min

[0139] Detector: Hitachi L-3300 type RI (Manufactured by Hitachi, Ltd., Trade Name)

[0140] The content of component (A) in the photosensitive resin composition (based on the total amount of solids in the photosensitive resin composition; hereinafter, unless specifically stated otherwise, it is the same for each contained component) is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and even more preferably 30 to 60 mass%. The content of component (A) is preferably greater than or equal to the lower limit value above from the perspective of maintaining the alkali developability of the photosensitive resin layer. On the other hand, it is preferable that the content be less than or equal to the upper limit value above from the perspective of ensuring that the resist pattern formed by exposure sufficiently exhibits performance as a resist material.

[0141] Here, component (A) is at least the following comonomer component:

[0142] (a) methacrylic acid or acrylic acid,

[0143] (b) a carboxylic acid different from the acid selected as the acid comonomer component of (a) above, and

[0144] (c) Compounds having an aromatic or alicyclic structure

[0145] It is obtained by polymerizing. Thus, component (A) has constituent units derived from each of at least (a) acid comonomer component, (b) acid comonomer component, and (c) comonomer component.

[0146] ((a) Acid comonomer component)

[0147] (a) The acid comonomer component is methacrylic acid or acrylic acid. In one embodiment, “methacrylic acid” refers to a compound represented by the chemical formula C4H6O2, and “acrylic acid” refers to a compound represented by the chemical formula C3H4O2.

[0148] ((b) Acid comonomer component)

[0149] (b) The acid comonomer component is a carboxylic acid different from the acid comonomer component selected from the acid comonomer component of (a) above. If the acid comonomer component of (a) is methacrylic acid, the acid comonomer component of (b) may be a carboxylic acid different from methacrylic acid. Also, if the acid comonomer component of (a) is acrylic acid, the acid comonomer component of (b) may be a carboxylic acid different from acrylic acid. Also, regardless of the type of acid comonomer component of (a), the acid comonomer component of (b) may be a carboxylic acid different from both methacrylic acid and acrylic acid. The acid comonomer component of (b) may be a compound having an ethylenically unsaturated bond or a compound having a (meth)acryloyl group. The acid comonomer component of (b) may be one type alone or two or more types may be used in combination.

[0150] (b) The acid comonomer component may be acrylic acid, for example, when (a) the acid comonomer component is methacrylic acid, and may be methacrylic acid, when (a) the acid comonomer component is acrylic acid.

[0151] Also, (b) the acid comonomer component may be a carboxylic acid different from both methacrylic acid and acrylic acid, for example. Examples of carboxylic acids different from both methacrylic acid and acrylic acid include cinnamic acid, crotonic acid, succinic acid half-ester, maleic acid half-ester, fumaric acid half-ester, 4-vinylbenzoic acid, succinic acid, maleic acid, fumaric acid, itaconic acid, etc.

[0152] Here, regarding component (A),

[0153] (a) Mass ratio of constituent units derived from acid comonomer components (a1) and,

[0154] (b) Mass ratio of constituent units derived from acid comonomer components (b1)

[0155] The ratio of (mass ratio (a1) / mass ratio (b1)) is 1 / 10 to 10 (e.g., 10.0).

[0156] (a) The acid comonomer component and (b) the carboxylic acid selectable as the acid comonomer component have different effects on the characteristics of the photosensitive resin composition and the photosensitive resin layer depending on their type. Therefore, by controlling the type and ratio of at least the acid comonomer component among the comonomer components of the alkali-soluble polymer, it is possible to improve various characteristics of the photosensitive resin layer.

[0157] In the same view as above, the ratio (mass ratio (a1) / mass ratio (b1)) is preferably 1 / 8 to 8 (e.g., 8.0), more preferably 1 / 7 to 7.0, even more preferably 1 / 5 to 5.0, and even more preferably 1 / 4.2 to 4.2.

[0158] (a) The acid comonomer component is preferably methacrylic acid. According to this, by obtaining the contribution of methacrylic acid, it becomes easier to realize a photosensitive resin layer with excellent various properties.

[0159] Here, it is more preferable that (a) the acid comonomer component is methacrylic acid, and (b) the acid comonomer component is acrylic acid. Among methacrylic acid and acrylic acid, by obtaining a contribution from methacrylic acid, which has relatively high hydrophobicity, it becomes easier to improve the resolution of the resist pattern, and by obtaining a contribution from acrylic acid, which has a relatively low glass transition temperature, it becomes easier to improve developability. Therefore, contributions from both acids can be obtained in a desirable manner, and as a result, various properties (developability of the photosensitive resin layer, resolution of the resist pattern, etc.) can be improved.

[0160] For example, compared to methacrylic acid which can be used as component (a), acrylic acid which can be used as component (b) has a smaller glass transition temperature (Tg). Therefore, for example, when considering the cases of methacrylic acid and acrylic acid, by controlling the type and content ratio of at least the acid comonomer component, it is possible to adjust the Tg to be advantageous for improving resolution while ensuring hydrophobicity as a whole component (A).

[0161] In addition, (a) the acid comonomer component is methacrylic acid or acrylic acid, and (b) the acid comonomer component may include a carboxylic acid different from both methacrylic acid and acrylic acid. According to this, by obtaining a contribution from a carboxylic acid different from both methacrylic acid and acrylic acid, it becomes easier to realize a photosensitive resin layer with excellent various properties.

[0162] In component (A), the sum of the mass ratio of constituent units derived from (a) the acid comonomer component (a1) and the mass ratio of constituent units derived from (b) the acid comonomer component (b1) is preferably 1 to 65 mass%. According to this, room can be secured for the inclusion of other comonomer components, and it becomes easier to broaden the range of composition design for various applications. Furthermore, in component (A), the ratio of constituent units of the comonomer component generally corresponds to the amount of the comonomer component injected. From the same perspective as above, the sum is more preferably 5 to 50 mass%, even more preferably 15 to 35 mass%, and particularly preferably 20 to 30 mass%.

[0163] ((c) Concurrent use of comonomer components)

[0164] (c) The comonomer component is one of the comonomer components for obtaining component (A) and is a compound having an aromatic structure or a dicyclic structure. By having (c) the comonomer component in this configuration, the adhesion of the resist pattern can be improved. (c) The comonomer component may be a compound having an ethylenically unsaturated bond or a compound having a (meth)acryloyl group. (c) The comonomer component may be one type alone or two or more types may be used in combination.

[0165] Examples of compounds having an aromatic structure include styrene, styrene derivatives, benzyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, etc. Examples of styrene derivatives include 4-methylstyrene, 4-hydroxystyrene, 4-methoxystyrene, 4-chlorostyrene, 4-(chloromethyl)styrene, etc.

[0166] Examples of compounds having a cyclocyclic structure include (meth)acrylic acid esters having a group having one cyclic hydrocarbon group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a derivative thereof, and (meth)acrylic acid esters having a group having two or more cyclic hydrocarbons such as a dicyclofentanyl group, a dicyclopentenyl group, an adamantyl group, or an isobornyl group, or a derivative thereof.

[0167] (c) The comonomer component preferably includes styrene and / or benzyl (meth)acrylate, and among them, it is preferable to include styrene. According to this, it is easier to improve the adhesion of the resist pattern even when the development time is prolonged.

[0168] The content ratio of (c) the comonomer component in (A) is preferably 10 to 95 mass%, more preferably 20 to 90 mass%, even more preferably 40 to 90 mass%, even more preferably 45 to 80 mass%, and particularly preferably 65 to 80 mass%. According to these ranges, it is easy to maintain good alkali solubility and also easy to improve the adhesion of the resist pattern.

[0169] (c) It is preferable that the comonomer component contains styrene, and that the styrene content is 45 mass% or more, preferably 50 mass% or more, more preferably 55 mass%, even more preferably 60 mass% or more, and particularly preferably 65 mass% or more, from the viewpoint that it is easy to improve the adhesion of the resist pattern. (c) When the comonomer component contains styrene, the styrene content may be 95 mass% or less.

[0170] In order to achieve compatibility between the developability of the photosensitive resin layer and the resolution of the obtained resist pattern, and also to improve adhesion to the substrate, it is preferable that component (A) contains (a) methacrylic acid, (b) acrylic acid, and (c) styrene as comonomer components, and using (a) a mass ratio of constituent units derived from methacrylic acid (a1), (b) a mass ratio of constituent units derived from acrylic acid (b1), and (c) a mass ratio of constituent units derived from styrene (c1), the following formulas (1) to (3):

[0171] 10 ≤ (a1)+(b1) ≤ 50 ··· (1)

[0172] 0.5 ≤ (a1) / (b1) ≤ 8.0··· (2)

[0173] 30 ≤ (c1) ≤ 80 ··· (3)

[0174] It is desirable to satisfy all of the above, and

[0175] The following formulas (4) ~ (6):

[0176] 15 ≤ (a1)+(b1) ≤ 35 ··· (4)

[0177] 1.0 ≤ (a1) / (b1) ≤ 6.0 ··· (5)

[0178] 45 ≤ (c1) ≤ 75 ··· (6)

[0179] It is more desirable to satisfy all of them, and

[0180] The following formulas (7) ~ (9):

[0181] 20 ≤ (a1)+(b1) ≤ 30 ··· (7)

[0182] 2.0 ≤ (a1) / (b1) ≤ 4.2 ··· (8)

[0183] 50 ≤ (c1) ≤ 70 ··· (9)

[0184] It is more desirable to satisfy all of them.

[0185] ((d) Optional concomitant use of comonomer components)

[0186] (A) The component may additionally have a constituent unit derived from a hydroxyalkyl (meth)acrylic acid ester (also referred to as “(d) comonomer component”) as a comonomer component. This compound has a hydroxyl (OH) group and is therefore more hydrophilic compared to, for example, methacrylic acid or acrylic acid. Therefore, the (A) component makes it easier to control the developability of the photosensitive resin layer by optionally combining it with the (d) comonomer component. (d) The comonomer component may be used alone or in combination with two or more types.

[0187] Examples of hydroxyalkyl (meth)acrylic acid esters include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, etc.

[0188] (d) It is preferable that the comonomer component includes hydroxyethyl methacrylate. According to this, it is easy to obtain, and at the same time, it is easy to control the developability.

[0189] (A) The content ratio of (d) comonomer component in the component is preferably 1.0 to 50 mass%, more preferably 1.5 to 40 mass%, and even more preferably 2.0 to 20 mass%.

[0190] (Additional optional combination of other comonomer components)

[0191] (A) The component may additionally use a comonomer component different from all of the above-mentioned (a) acid comonomer component and (b) acid comonomer component, (c) comonomer component and (d) comonomer component selectable as comonomer component (also referred to as “another comonomer component”).

[0192] Other comonomer components include, for example, alkyl (meth)acrylate esters, conjugated diene compounds, polar monomers (excluding hydroxyalkyl (meth)acrylates), crosslinkable monomers, acid anhydrides (e.g., maleic anhydride), etc.

[0193] (Meth)acrylate alkyl esters are a concept that includes both chain-type alkyl esters and cyclic alkyl esters, and examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, etc.

[0194] Examples of conjugated diene compounds include, for instance, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, etc.

[0195] Examples of polar monomers include, for instance, amino group-containing monomers such as 2-aminoethyl methacrylate; amide group-containing monomers such as (meth)acrylamide, N-methylol(meth)acrylamide; cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-cyanoethylacrylate; epoxy group-containing monomers such as glycidyl(meth)acrylate, 3,4-epoxycyclohexyl(meth)acrylate; etc.

[0196] Examples of crosslinkable monomers include trimethylolpropane triacrylate and divinylbenzene.

[0197] ((A) Various aspects regarding the component)

[0198] (A) The component may include a plurality of alkali-soluble polymers. For example, the component (A) may be a combination of (A1) an alkali-soluble polymer comprising methacrylic acid and styrene and (A2) an alkali-soluble polymer comprising acrylic acid and styrene, or a combination of (A2) an alkali-soluble polymer comprising acrylic acid and styrene and (A3) an alkali-soluble polymer comprising methacrylic acid and hydroxyethyl methacrylate.

[0199] And, the mass average of each of the above mass ratio (a1), the above mass ratio (b1), and the above mass ratio (c1) is, for example, with respect to the total sum of the alkali-soluble polymers when component (A) includes N types of alkali-soluble polymers,

[0200] The ratio of the first alkali-soluble polymer (polymer 1) is X1,

[0201] The ratio of the second alkali-soluble polymer (polymer 2) is X2,

[0202] The ratio of the Nth alkali-soluble polymer (polymer N) to XN

[0203] When done as follows, the following formula:

[0204] (a1)=(X1×a1-1)+(X2×a1-2)+··+(XN×a1-N)

[0205] (b1)=(X1×b1-1)+(X2×b1-2)+··+(XN×b1-N)

[0206] (c1)=(X1×c1-1)+(X2×c1-2)+··+(XN×c1-N)

[0207] a1-1: Mass ratio of component (a) in polymer 1

[0208] a1-2: Mass ratio of component (a) in polymer 2

[0209] a1-N : Mass ratio of component (a) in polymer N

[0210] b1-1: Mass ratio of component (b) in polymer 1

[0211] b1-2: Mass ratio of component (b) in polymer 2

[0212] b1-N: Mass ratio of component (b) in polymer N

[0213] c1-1: Mass ratio of component (c) in polymer 1

[0214] c1-2: Mass ratio of component (c) in polymer 2

[0215] c1-N: Represents the mass ratio of component (c) in polymer N.

[0216] In this case, the ratio ((a1) / (b1)) of the total alkali-soluble polymer must be within the range of the above ratio, and there may be cases where the ratio of a single alkali-soluble polymer is not within the range of the above ratio.

[0217] In this embodiment, it is preferable that the relationship between the mass average of the mass ratio (a1) and the mass average of the mass ratio (b1) (mass average of the mass ratio (a1) / mass average of the mass ratio (b1)) is 1 / 10 to 10, from the perspective that it is easy to exhibit the effects of this embodiment.

[0218] Meanwhile, at least one of the alkali-soluble polymers included in component (A) has a constituent unit derived from the acid comonomer component (a) to (b) and the comonomer component (c), and can also satisfy the above ratio. That is, if component (A) is composed of any single alkali-soluble polymer, that alkali-soluble polymer, and if component (A) is composed of a plurality of alkali-soluble polymers, at least one of the plurality of alkali-soluble polymers can satisfy the essential requirements required as component (A) of the present invention alone.

[0219] In one embodiment, the photosensitive resin composition has a constituent unit derived from component (a) to component (c) among the alkali-soluble polymers included in component (A), and it is preferable that the ratio of alkali-soluble polymers satisfying the ratio is 10 mass% or more.

[0220] In addition, if at least one of the alkali-soluble polymers included in component (A) satisfies the essential requirements for component (A) of the present invention, it is preferable that the proportion of the alkali-soluble polymer satisfying the requirements among the alkali-soluble polymers included in component (A) be 10 mass% or more. The proportion of such alkali-soluble polymers may be 30 mass% or more, 40 mass% or more, or 50 mass% or more. The proportion of such alkali-soluble polymers may be 100 mass% or less, or 60 mass% or less.

[0221] [(B) Component: Compound having ethylenically unsaturated bonds]

[0222] (B) The component is a compound having an ethylenically unsaturated bond in its structure. (B) The component preferably includes a compound having a bisphenol A structure and / or a hydrogenated bisphenol A structure. Accordingly, it becomes easier to exert the effects of the present invention. Among the total amount of component (B), the compound having a bisphenol A structure and / or a hydrogenated bisphenol A structure may be included in an amount of 30 mass% or more, 50 mass% or more, 80 mass% or more, or 90 mass% or more. Among component (B), the content of the compound having a bisphenol A structure and / or a hydrogenated bisphenol A structure may be the highest among the contents of each compound of the other components (B). In addition, as component (B), examples include a compound having one ethylenically unsaturated bond, a compound having two ethylenically unsaturated bonds, a compound having three ethylenically unsaturated bonds, a compound having four ethylenically unsaturated bonds, and a compound having five or more ethylenically unsaturated bonds. Different types of these compounds may be used in combination.

[0223] In one embodiment, it is preferable that component (B) contains 30 mass% or more, 50 mass% or more, 80 mass% or more, or 90 mass% or more of a compound having two or more ethylenically unsaturated bonds. According to this, it becomes easier to exhibit the effects of the present embodiment.

[0224] (B) As a component, for example, a compound having two ethylene unsaturated bonds and a compound having three or more ethylene unsaturated bonds may be used in combination, and different compounds having three or more ethylene unsaturated bonds may also be used in combination. Examples of compounds having three or more ethylene unsaturated bonds include compounds having four ethylene unsaturated bonds, five ethylene unsaturated bonds, or six ethylene unsaturated bonds. Among these, it is preferable that component (B) includes a compound having three or more ethylene unsaturated bonds in one molecule, and it is also preferable that it includes a compound having four or more ethylene unsaturated bonds in one molecule.

[0225] For example, as component (B), a di(meth)acrylate of a polyalkylene glycol obtained by adding an average of 1 mol to 15 mol of alkylene oxide to each end of bisphenol A; a tri(meth)acrylate of a polyalkylentriol obtained by adding an average of 3 mol to 25 mol of alkylene oxide to trimethylolpropane; glycerin; trimethylolpropane; pentaerythritol; diglycerin; ditrimethylolpropane; a compound obtained by converting an alcohol obtained by adding a polyalkylene oxide group to an isocyanurate ring, etc., or by denaturing it with ε-caprolactone, into a (meth)acrylate, or a compound obtained by reacting (meth)acrylic acid directly with such alcohol without denaturing it with an alkylene oxide group or ε-caprolactone; a tetra(meth)acrylate of a polyol obtained by adding an average of 4 mol to 35 mol of alkylene oxide to pentaerythritol; Examples include hexa(meth)acrylates of polyols to which an average of 4 to 30 moles of alkylene oxide are added to dipentaerythritol; etc. These can be used as a single type or in combination of two or more types.

[0226] Specifically, the types of compounds that may be included in component (B) are,

[0227] Dimethacrylate of polyethylene glycol obtained by adding an average of 5 moles of EO (ethylene oxide) to each end of bisphenol A,

[0228] Hexamethacrylate with an average of 13 moles of EO (ethylene oxide) added to dipentaerythritol,

[0229] Dimethacrylate of polyethylene glycol obtained by adding an average of 1 mole of EO (ethylene oxide) to each end of bisphenol A,

[0230] EO (ethylene oxide) modified hydrogenated bisphenol A dimethacrylate,

[0231] Polytetramethylene glycol dimethacrylate,

[0232] Tetramethacrylate with an average of 15 moles of EO (ethylene oxide) added to pentaerythritol,

[0233] Poly(propylene glycol) dimethacrylate,

[0234] EO (ethylene oxide) modified bisphenol A dimethacrylate, and

[0235] Examples include trimethacrylate, which has an average of 9 moles of EO (ethylene oxide) added to glycerin.

[0236] The content of component (B) in the photosensitive resin composition is preferably 5 to 70 mass%, more preferably 20 to 60 mass%, and even more preferably 30 to 50 mass%. The content of component (B) is preferably greater than or equal to the lower limit value above in order to suppress poor curing of the photosensitive resin layer and delay of the development time. In addition, it is preferably less than or equal to the upper limit value above in order to improve the removeability of the cured photosensitive resin layer.

[0237] [(C) Component: Photopolymerization Initiator]

[0238] Component (C) is a compound that generates radicals by active light and, accordingly, can initiate the polymerization of component (B).

[0239] (C) Examples of components include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxantone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazolin derivatives, N-aryl amino acid ester compounds, and halogen compounds.

[0240] As hexaarylbiimidazole compounds, for example, 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (alias: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-Bis-(2-fluorophenyl)-4,4',5,5'-Tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,3-difluoromethylphenyl)-4,4',5,5'-Tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,4-difluorophenyl)-4,4',5,5'-Tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,5-difluorophenyl)-4,4',5,5'-Tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,6-difluorophenyl)-4,4',5,5'-Tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,Examples include 5'-tetrakis-(3-methoxyphenyl)-biimidazole, lopin dimer, etc.

[0241] Examples of lopin dimers, that is, dimers of 2,4,5-triarylimidazole, include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, etc. Among these, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred in terms of high sensitivity, resolution, and adhesion.

[0242] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, etc. Among these, N-phenylglycine is preferred because it has a high saturation-to-decrease effect.

[0243] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, etc.

[0244] Examples of aromatic ketone compounds include benzophenone, mihiller ketone [4,4'-bis(dimethylamino)benzophenone], 4-methoxy-4'-dimethylaminobenzophenone, etc. As for aromatic ketone compounds, 4,4'-bis(diethylamino)benzophenone can also be cited in terms of saturation effect and adhesion.

[0245] In this specification, the term "anthracene derivative" includes both anthracene and compounds derived therefrom. Examples of anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, etc. From the perspective of stimulating / degrading effects and adhesion, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred, and 9,10-diphenylanthracene is particularly preferred.

[0246] Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, etc. Examples of commercially available acetophenone compounds include the Yirgacure series (manufactured by Ciba Specialty Chemicals: Yirgacure-907, Yirgacure-369, and Yirgacure-379, etc.).

[0247] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. Examples of commercially available acylphosphine oxide compounds include Lucyrin TPO (manufactured by BASF) and Yirgacure-819 (manufactured by Ciba Specialty Chemicals).

[0248] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, etc.

[0249] Examples of dialkyl ketal compounds include benzyldimethyl ketal and benzyldiethyl ketal.

[0250] Examples of thioxantone compounds include 2,4-diethylthioxantone, 2,4-diisopropylthioxantone, 2-chlorothioxantone, etc.

[0251] Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, 2-ethylhexyl-4-(dimethylamino)benzoate, etc.

[0252] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Examples of commercially available oxime ester compounds include CGI-325, Yirgacure-OXE01, and Yirgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).

[0253] As for the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred in terms of sensitivity, resolution, and availability.

[0254] As pyrazolin derivatives, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazolin, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazolin, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazolin are preferred in terms of adhesion and the rectangularity of the resist pattern.

[0255] Examples of ester compounds of N-aryl amino acids include, for instance, methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, octyl ester of N-phenylglycine, etc.

[0256] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, diallyl iodine compounds, etc. Among these, tribromomethylphenylsulfone is preferred.

[0257] The content of component (C) in the photosensitive resin composition is preferably 0.01 to 20 mass%, and more preferably 0.5 to 10 mass%. By adjusting the content of component (C) to within the above range, it becomes easier to obtain sufficient sensitivity, so it becomes easier to transmit light sufficiently to the bottom of the photosensitive resin layer, and furthermore, it becomes easier to realize high resolution.

[0258] It is preferable to include a lofin dimer as component (C) for high sensitivity, resolution, and adhesion. In this case, the content of the lofin dimer in the photosensitive resin composition is preferably 0.1 to 15 mass%, and more preferably 0.5 to 10 mass%.

[0259] As for component (C), it is preferable to use an anthracene derivative and a hexaarylbiimidazole compound in combination. In this case, the content of component (C) (e.g., anthracene derivative) in the photosensitive resin composition is preferably 0.5 mass% or less, and more preferably 0.01 mass% to 0.4 mass%, and the content of the hexaarylbiimidazole compound in the photosensitive resin composition is preferably 0.1 to 10 mass%, and more preferably 0.5 to 5 mass%.

[0260] [(D) Component: Leuco dye]

[0261] (D) The component can be incorporated into the photosensitive resin composition of the present embodiment to impart color development and excellent peeling characteristics to the unexposed area.

[0262] (D) Examples of components include leucocrystalline violet (tris[4-(dimethylamino)phenyl]methane), 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, etc. Among these, leucocrystalline violet is preferred.

[0263] The content of component (D) in the photosensitive resin composition is preferably 0.01 to 2 mass% with respect to the total mass of the solids of the photosensitive resin composition, and more preferably 0.1 to 1.5 mass%. By controlling the content of component (D) within this range, good color development and sensitivity can be achieved.

[0264] [Other ingredients]

[0265] The photosensitive resin composition may, as desired, include a base dye (a dye other than component (D)), an antioxidant, a stabilizer, a sensitizer, a plasticizer, etc. Other components are components other than (A) to (D).

[0266] Examples of base dyes include Basic Green 1 [CAS number (hereinafter the same): 633-03-4] (e.g., Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Industry), Fuchsin [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, trade name, manufactured by Hodogaya Chemical Industry), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2], etc. Among these, Basic Green 1 is preferred from the perspective of improving tintability, color stability, and exposure contrast. These can be used as a single type or in combination of two or more types.

[0267] The content of the base dye in the photosensitive resin composition is preferably 0.001 to 3 mass%, more preferably 0.01 to 2 mass%, and even more preferably 0.04 to 1 mass%. The content of the base dye is preferably greater than or equal to the lower limit value above from the viewpoint of obtaining good colorability, while on the other hand, it is preferably less than or equal to the upper limit value above from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

[0268] Examples of antioxidants include triphenylphosphite (e.g., manufactured by ADEKA, trade name: TPP), tris(2,4-di-tert-butylphenyl)phosphite (e.g., manufactured by ADEKA, trade name: 2112), tris(monononylphenyl)phosphite (e.g., manufactured by ADEKA, trade name: 1178), bis(monononylphenyl)-dinonylphenylphosphite (e.g., manufactured by ADEKA, trade name: 329K), etc. These can be used individually or in combination of two or more types.

[0269] The content of the antioxidant in the photosensitive resin composition is preferably 0.01 to 0.8 mass%, and more preferably 0.01 to 0.3 mass%. The content of the antioxidant is preferably greater than or equal to the lower limit value above from the perspective of expressing good color stability of the resist pattern and also improving the sensitivity of the photosensitive resin layer. On the other hand, it is preferably less than or equal to the upper limit value above from the perspective of suppressing the color development of the resist pattern while expressing good color stability and also improving adhesion.

[0270] A stabilizer can be used to improve the thermal stability and / or storage stability of the photosensitive resin composition. Examples of stabilizers include at least one of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group. These can be used individually or in combination of two or more.

[0271] Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salt (e.g., aluminum salt to which 3 moles of nitrosophenylhydroxyamine are added), diphenylnitrosamine, etc. Among these, an aluminum salt to which 3 moles of triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or nitrosophenylhydroxylamine are added is preferred. These can be used alone or in combination of two or more types.

[0272] Examples of alkylene oxide compounds having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2 molar adduct diglycidyl ether (e.g., Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.), etc. These can be used individually or in combination of two or more types.

[0273] In the photosensitive resin composition, the total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group is preferably 0.001 to 3 mass%, and more preferably 0.05 to 1 mass%. The total content is preferably greater than or equal to the lower limit value from the viewpoint of providing good storage stability to the photosensitive resin composition, and on the other hand, is preferably less than or equal to the upper limit value from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

[0274] [Photosensitive resin composition combination liquid]

[0275] A photosensitive resin composition solution can be prepared by adding a solvent to a photosensitive resin composition. Preferred solvents include, for example, ketones such as acetone and methyl ethyl ketone (MEK); and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition solution is 500 to 4000 mPa·sec at 25°C.

[0276] [Photosensitive resin laminate, dry film resist and transfer film]

[0277] By using a photosensitive resin composition or a combination of photosensitive resin compositions, a photosensitive resin layer, and furthermore, a photosensitive resin laminate, can be obtained. The photosensitive resin laminate has, for example, a support (support film) and a photosensitive resin layer laminated on the support. The photosensitive resin laminate may have a protective film on a side opposite to the support as needed. From the viewpoint that the photosensitive resin laminate is more likely to be a dry film resist or a transfer film, and more preferably a dry film resist, as this makes it easier to significantly exhibit the effects of the present invention.

[0278] It is preferable that the support be transparent and transmit light emitted from an exposure light source. Such a support is preferably a plastic film, and specifically, examples include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. If necessary, these films may be used in a stretched form.

[0279] It is preferable that the haze of the support be 5 or less. Although a thinner thickness of the support is advantageous in terms of image formation and cost-effectiveness, it is preferable that the thickness be 10 to 30 μm when considering the function of maintaining strength.

[0280] The photosensitive resin layer described above may include a photosensitive resin composition or be composed of a photosensitive resin composition. The film thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 3 to 100 μm, more preferably 10 to 50 μm, and even more preferably 15 to 50 μm. As the thickness of the photosensitive resin layer approaches 3 μm, the resolution improves, and as it approaches 100 μm, the film strength improves, so it can be appropriately selected according to the application.

[0281] An important characteristic of the protective film used in the photosensitive resin laminate is that it has appropriate adhesion. In short, it is desirable that the adhesion of the protective film to the photosensitive resin layer is sufficiently smaller than the adhesion of the support to the photosensitive resin layer so that the protective film can be easily peeled off from the photosensitive resin laminate. As the protective film, for example, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a polyester film, etc., may be used. The film thickness of the protective film is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

[0282] A release layer can be applied to the surface of a protective film so that the protective film can be preferably peeled off from a photosensitive resin layer. The release layer is classified, for example, into silicon compounds and non-silicon compounds.

[0283] Examples of silicone compounds include, for instance, a condensation reaction type silicone resin obtained by reacting a silanol polydimethylsiloxane with polymethylhydrosiloxane or polymethylmethoxysiloxane; an addition reaction type silicone resin obtained by reacting a dimethylsiloxane-methylvinylsiloxane copolymer or a dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrosiloxane; an ultraviolet curing type or electron beam curing type silicone resin obtained by curing acrylic silicone and epoxy group-containing silicone with ultraviolet rays or electron beams; and modified silicone resins such as epoxy-modified silicone resin (silicon epoxy), polyester-modified silicone resin (silicon polyester), acrylic-modified silicone resin (silicon acrylic), phenol-modified silicone resin (silicon phenol), alkyd-modified silicone resin (silicon alkyd), and melamine-modified silicone resin (silicon melamine).

[0284] Examples of non-silicon compounds include alkyd (or alkyd) resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.

[0285] The film thickness of the release layer is preferably 0.001 to 2 μm, more preferably 0.005 to 1 μm, and even more preferably 0.01 to 0.5 μm. If the film thickness is below the upper limit value, the appearance of the coating film is likely to be good, and the coating film is also likely to be sufficiently cured. On the other hand, if the film thickness is above the lower limit value, it is easier to ensure sufficient release properties.

[0286] [Method for manufacturing a photosensitive resin laminate]

[0287] A photosensitive resin laminate can be manufactured by sequentially laminating a photosensitive resin layer and, if necessary, a protective film onto a support. As a manufacturing method, for example, a photosensitive resin composition used in the photosensitive resin layer is mixed with a solvent that dissolves them to prepare a photosensitive resin composition mixture solution (coating solution). Subsequently, the coating solution is applied to a support using a bar coater or a roll coater, dried, and a photosensitive resin layer is laminated onto the support. Then, if necessary, a protective film is laminated onto the photosensitive resin layer to manufacture the photosensitive resin laminate.

[0288] [Method for forming a resist pattern]

[0289] A method for forming a resist pattern using a photosensitive resin laminate related to the present embodiment comprises the following process:

[0290] Process of laminating a photosensitive resin laminate onto a substrate;

[0291] A process for exposing a photosensitive resin layer of a laminated photosensitive resin structure; and

[0292] Development process for developing an exposed photosensitive resin layer;

[0293] It includes, preferably, this in order.

[0294] [Lamination Process]

[0295] In the lamination process, specifically, if the photosensitive resin laminate has a protective film, the protective film is peeled off from the photosensitive resin laminate, and then the photosensitive resin layer is heat-pressed onto the substrate surface using a laminator and laminated once or multiple times. Examples of substrate materials include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). The heating temperature during lamination is generally 40 to 160°C. Heat-pressing can be performed by using a laminator equipped with rolls, or by passing the laminate of the substrate and the photosensitive resin layer through the rolls repeatedly several times. Heat-pressing can be performed under a reduced pressure environment as desired.

[0296] [Photolithography Process]

[0297] In the photolithography process, a photosensitive resin layer is exposed to active light using an exposure machine. Exposure may be performed after peeling off the support as desired. When exposure is performed through a photomask, the exposure amount is determined by the light source illuminance and exposure time, and may be measured using a photometer. Direct imaging exposure may be performed in the photolithography process. In direct imaging exposure, exposure is performed directly on the substrate by a drawing device without using a photomask. As a light source, a semiconductor laser with a wavelength of 350 to 410 nm or an ultra-high pressure mercury lamp is used. When the drawing pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0298] The light irradiation method used in the photolithography process is preferably at least one type selected from projection lithography, proximity lithography, contact lithography, direct imaging lithography, and electron beam direct projection, and it is more preferable to perform the process using projection lithography or direct imaging lithography.

[0299] [Development Process]

[0300] In the development process, after peeling off the support, the unexposed portion (non-pattern portion) of the photosensitive resin layer is dissolved in a developer solution and removed. The developer solution includes an alkaline aqueous solution. When a negative-type photosensitive resin composition is used, a resist pattern is obtained in the development process by removing the unexposed portion. When a positive-type photosensitive resin composition is used, a resist pattern is obtained by removing the exposed portion.

[0301] As the alkaline aqueous solution, it is preferable to use an inorganic alkaline aqueous solution such as Na2CO3 or K2CO3. The alkaline aqueous solution can be selected according to the characteristics of the photosensitive resin layer, and is preferably a Na2CO3 aqueous solution with a concentration of 0.2 to 2 mass%. A surfactant, an antifoaming agent, and a small amount of an organic solvent to promote development may be incorporated into the alkaline aqueous solution. During the development process, it is preferable to maintain the temperature of the developer solution at a constant temperature within the range of 18 to 40°C.

[0302] If necessary, a heating process can be performed after the development process to heat the obtained resist pattern at 100 to 300°C. By performing the heating process, it becomes easier to improve the chemical resistance and resolution of the resist pattern. The heating here can be performed using methods such as hot air, infrared rays, or far-infrared rays.

[0303] [Etching Process]

[0304] By forming a resist pattern using the above method for forming a resist pattern, and then, if necessary, performing plating treatment, and then performing etching on the substrate, a wiring pattern corresponding to the resist pattern can be formed on the substrate.

[0305] The etching process may employ, for example, a method of spraying an etching solution over a resist pattern. Examples of etching methods include acid etching and alkaline etching. Examples of etching solutions include an aqueous hydrochloric acid solution, an aqueous ferric chloride solution, or a mixture thereof.

[0306] The plating treatment can be carried out by metal plating (e.g., metal plating with a copper sulfate plating solution) or solder plating on the parts exposed by the phenomenon according to a known plating method.

[0307] In the case where plating treatment is performed, the resist pattern can be stripped using an aqueous solution (stripping solution) having stronger alkalinity than the developer after the plating treatment; in the case where plating treatment is omitted, it can be stripped using an aqueous solution (stripping solution) having stronger alkalinity than the developer. The stripping solution is preferably, for example, an aqueous solution of NaOH or KOH having a concentration of about 2 to 5 mass% and a temperature of about 40°C to 70°C, or an aqueous solution of an organic amine-based compound.

[0308] The various parameters described above are measured in accordance with the measurement methods in the embodiments described below, unless otherwise specifically stated. The present invention will be explained in more detail below based on embodiments, but the present invention is not limited by these embodiments.

[0309] Examples

[0310] [Examples 1 to 18 and Comparative Examples 1 to 10]

[0311] <1. Preparation of Photosensitive Resin Composition>

[0312] Subsequently, each component shown in the table published thereafter was mixed, and additionally, acetone, a solvent, was added until the solid content reached 60 mass%, and the mixture was thoroughly stirred and mixed to prepare a photosensitive resin composition solution. The values ​​in the table represent the solid content.

[0313] <2. Manufacture of Photosensitive Resin Laminate>

[0314] The obtained mixture was uniformly applied to a 16 μm thick polyethylene terephthalate (PET) film (support) using a bar coater, and dried in a 95°C dryer for 3 minutes to form a photosensitive resin layer (dry film). The thickness of the photosensitive resin layer was 25 μm. Subsequently, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-18) was laminated as a protective film to the side of the photosensitive resin layer that was not laminated with the PET film, thereby obtaining a photosensitive resin laminate.

[0315] <3. Surface Preparation of the Substrate>

[0316] The surface of the copper-clad laminated substrate was polished by sequentially performing surface treatment using a polishing machine and cleaning with a 10 mass% aqueous solution of H2SO4, and thereby obtained a copper-clad laminated substrate (substrate) with a thickness of 0.4 mm, on which a copper foil with a thickness of 18 μm was laminated.

[0317] <4. Fabrication of Evaluation Boards>

[0318] Laminate :

[0319] While peeling off the polyethylene film (protective film) of the photosensitive resin laminate, the surface was prepared as described above using a hot roll laminator (manufactured by Asahi Kasei Electronics Co., Ltd., AL-700), and then the photosensitive resin laminate was laminated onto a substrate preheated to 50°C at a roll temperature of 105°C. Accordingly, an evaluation substrate was obtained. The air pressure was set to 0.35 MPa and the lamination speed to 1.5 m / min.

[0320] Exposure:

[0321] Examples 1 to 18 and Comparative Examples 1 to 10 exposed an evaluation substrate using a direct imaging (DI) exposure pattern with a predetermined pattern for direct imaging (DI) exposure by a direct imaging exposure machine (FDi-3 manufactured by Oak Manufacturing, frequency 400 nm). The exposure was performed with an exposure amount such that the line width of the cured resist pattern becomes 10 μm when exposed and developed at a location of L (line) / S (space) = 10 μm / 10 μm of the exposure pattern.

[0322] Examples 19 and 20 were exposed using i-line monochromatic light with a predetermined mask pattern by a segmented projection exposure device (UX2003 SM-MS04 manufactured by Ushio Electric Inc., using an i-line bandpass filter). The exposure was performed with an exposure amount such that the line width of the cured resist pattern becomes 10 μm when exposed and developed at a location of L (line) / S (space) = 10 μm / 10 μm of the mask pattern.

[0323] Heating:

[0324] An evaluation substrate, 1 minute after exposure, was heated using a hot roll laminator (manufactured by Asahi Kasei Co., Ltd., AL-700). The roll temperature was 105 ℃, the air pressure was 0.30 MPa, and the lamination speed was 1 m / min.

[0325] phenomenon :

[0326] After peeling off the PET film (support film), an alkaline developer (manufactured by Fujikiko Inc., a developing device for dry films) was used to spray a 1 mass% Na2CO3 aqueous solution at 30°C from a full-cone type nozzle at a spray pressure of 0.15 MPa for a period twice the minimum development time. Accordingly, the unexposed portion of the photosensitive resin layer was dissolved and removed (developed). After development, the substrate was washed with pure water for a period 1.5 times the development time, dehydrated with an air knife, and then dried with hot air to obtain a substrate having a cured film for evaluation.

[0327] <5. Evaluation Method>

[0328] Minimum development time:

[0329] The development was carried out using the above method, and the shortest time required for the photosensitive resin layer of the unexposed portion to completely dissolve was set as the shortest development time.

[0330] A shorter minimum development time (unit: seconds) indicates better development quality. The minimum development time was evaluated according to the following criteria.

[0331] A: 25 seconds or less

[0332] B: Exceeds 25 seconds and is also 30 seconds or less

[0333] C: Exceeds 30 seconds and is also 40 seconds or less

[0334] D : Exceeds 40 seconds

[0335] Resolution Evaluation :

[0336] For this evaluation, an evaluation substrate was used after 15 minutes had elapsed following lamination of a photosensitive resin laminate using the method described in <Laminate> above. Positive or negative patterns with line / space = 1 / 1 of various sizes were exposed to the evaluation substrate. Subsequently, the pattern was developed using the method described in <Develop> above. For the obtained pattern, the minimum pattern width formed was observed using an optical microscope, and the resolution was evaluated according to the following criteria.

[0337] A: Minimum pattern width is 5 µm or less

[0338] B: The minimum pattern width exceeds 5 µm and is also 6 µm or less.

[0339] C: The minimum pattern width exceeds 6 µm and is also 7 µm or less.

[0340] D: Minimum pattern width exceeds 7 µm

[0341] Adhesion Evaluation :

[0342] For this evaluation, an evaluation substrate was used after 15 minutes had elapsed following lamination of a photosensitive resin laminate using the method described in <Laminate> above. On the evaluation substrate, independent line patterns of various sizes were directly drawn and exposed. Afterward, the substrate was developed using the method described in <Develop> above. The obtained patterns were observed under an optical microscope at a magnification of 100x, and the adhesion was evaluated according to the following criteria. Normal formation refers to the absence of meandering or defects in the resist.

[0343] A: The minimum pattern formed normally is 8 µm or less

[0344] B: The minimum pattern formed normally exceeds 8 µm and is also 9 µm or less.

[0345] C: The minimum pattern formed normally exceeds 9 µm and is also 10 µm or less.

[0346] D: The minimum pattern formed normally exceeds 10 µm

[0347] Press Flow Evaluation :

[0348] A photosensitive resin laminate was cut into a 2.5 cm by 2.5 cm section, the cover film (protective film) was peeled off, and the section was placed in the center of a PET film 10 cm by 10 cm. A force of 100 kg was applied for 5 minutes using a hydraulic press heated to 40 ℃. Afterward, the protrusion width of the photosensitive resin layer was measured in 4 directions (a total of 8 points), and the average value was calculated. This test was performed twice, the average value was taken as the press flow test value, and the press flow was evaluated according to the following criteria.

[0349] A: 100 µm or less

[0350] B: Exceeding 100 µm and also 150 µm or less

[0351] C: Exceeding 150 µm and also 200 µm or less

[0352] D: Exceeds 200 µm

[0353] Peel strength (tackiness) of the support:

[0354] For this evaluation, an evaluation substrate was prepared by laminating a photosensitive resin laminate on one side using the method described in <Laminate> above, and was left at 23°C and 50% relative humidity for 24 hours. Afterwards, a 1-inch wide support (a PET film in this example) was peeled 180° at a speed of 100 mm / min, and the strength at that time was measured using Tensilon RTM-500 (manufactured by Toyo Seiki), and the peel strength was evaluated according to the following criteria.

[0355] A: Peel strength less than 3.0 gf

[0356] D: Peel strength of 3.0 gf or higher

[0357] Peel-off test:

[0358] In this evaluation, a 1.6 mm thick copper-clad laminate with a 35 μm rolled copper foil was prepared by wet buff roll polishing, and this was used as the evaluation substrate. Polishing was performed twice using Scotch-Brite HD#600 manufactured by 3M Inc. (registered trademark).

[0359] While peeling off a polyethylene film from a photosensitive resin laminate with a photosensitive resin layer thickness of 25 μm, a hot roll laminator (manufactured by Asahi Kasei Co., Ltd., AL-700) was used on an evaluation substrate after surface preparation under conditions of a roll temperature of 105 ℃, an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min.

[0360] An evaluation substrate was used after 15 minutes had elapsed since lamination, and a rectangular pattern of 4 cm × 6 cm was exposed to the evaluation substrate by the method described in <Exposure> above, and then developed by the method described in <Development> above. The obtained evaluation substrate was cut into 4 cm × 6 cm pieces and immersed in a stripping solution of R-101 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) at 50°C. The time until the photosensitive resin layer was completely peeled off from the evaluation substrate was measured, and this was used as the peeling time to evaluate the peelability according to the following criteria.

[0361] A: Peeling time is 20 seconds or less

[0362] B: Peeling time exceeds 20 s and is also 25 s or less

[0363] D: Peeling time exceeds 25 s

[0364]

[0365]

[0366]

[0367]

[0368]

[0369] From the results shown in the table, it was confirmed that in the example, all items of [minimum development time], [resolution], and [adhesion] were "B" or higher.

Claims

Claim 1 A photosensitive resin composition for forming a wiring pattern on a substrate, comprising the following components: (A) an alkali-soluble polymer, (B) a compound having ethylenically unsaturated bonds, and (C) a photopolymerization initiator, wherein the component (A) has a constituent unit derived from at least the following comonomer components: (a) methacrylic acid, (b) acrylic acid, and (c) a compound having an aromatic structure or alicyclic structure, and the component (c) comprises styrene, wherein the ratio (mass ratio (a1) / mass ratio (b1)) of the mass ratio of the constituent unit derived from the component (a) and the mass ratio of the constituent unit derived from the component (b) in at least one of the alkali-soluble polymers included in the component (A) is 2.0 to 10, and furthermore, the ratio of the constituent unit derived from the styrene is 45 to 95 mass%. Claim 2 A photosensitive resin composition according to claim 1, wherein the ratio (the mass ratio (a1) / the mass ratio (b1)) is 2.0 to 8. Claim 3 A photosensitive resin composition according to claim 1, wherein the (A) component further comprises a constituent unit derived from (d) a hydroxyalkyl (meth)acrylic acid ester as a comonomer component. Claim 4 A photosensitive resin composition according to claim 3, wherein the component (d) is hydroxyethyl methacrylate. Claim 5 A photosensitive resin composition according to claim 1, wherein the sum of the mass ratio (a1) of a constituent unit derived from component (a) and the mass ratio (b1) of a constituent unit derived from component (b) in component (A) is 1 to 65 mass%. Claim 6 A photosensitive resin composition according to claim 1, comprising, based on the total amount of solids of the photosensitive resin composition, 10 to 90 mass% of component (A), 5 to 70 mass% of component (B), and 0.01 to 20 mass% of component (C). Claim 7 In claim 1, the above (A) component is a photosensitive resin composition comprising a plurality of alkali-soluble polymers. Claim 8 A photosensitive resin composition according to claim 7, wherein the relationship between the mass average of the mass ratio (a1) and the mass average of the mass ratio (b1) (mass average of mass ratio (a1) / mass average of mass ratio (b1)) is 1 / 10 to 10. Claim 9 A photosensitive resin composition according to claim 1, wherein among the alkali-soluble polymers included in the above (A) component, the composition has constituent units derived from the above (a) to (c) components, and furthermore, the ratio of the alkali-soluble polymer satisfying the above ratio is 10 mass% or more. Claim 10 A photosensitive resin composition according to claim 1, wherein the acid value of component (A) is 50 to 600 mgKOH / g. Claim 11 A photosensitive resin composition according to claim 1, wherein the (B) component comprises a compound having a bisphenol A structure and / or a hydrogenated bisphenol A structure. Claim 12 A photosensitive resin composition according to claim 1, wherein the component (B) comprises a compound having three or more ethylenically unsaturated bonds in one molecule. Claim 13 A photosensitive resin composition according to claim 1, wherein the (C) component comprises a hexaarylbiimidazole (HABI) compound. Claim 14 A photosensitive resin composition according to claim 1, further comprising (D) a leuco dye as a component. Claim 15 A photosensitive resin composition according to claim 1, wherein the mass ratio (a1) of a constituent unit derived from component (a), the mass ratio (b1) of a constituent unit derived from component (b), and the mass ratio (c1) of a constituent unit derived from component (c) in component (A) satisfy the following formulas (1) ~ (3): 10 ≤ (a1)+(b1) ≤ 50 ··· (1) 0.5 ≤ (a1) / (b1) ≤ 8.0 ··· (2) 30 ≤ (c1) ≤ 80 ··· (3). Claim 16 A photosensitive resin composition according to claim 1, wherein the component (A) comprises a plurality of alkali-soluble polymers, and at least one of the alkali-soluble polymers included in the component (A) has a constituent unit derived from the components (a) to (c), and further, the mass ratio (a1) of the constituent unit derived from the component (a), the mass ratio (b1) of the constituent unit derived from the component (b), and the mass ratio (c1) of the constituent unit derived from the component (c) satisfy the following formulas (1) to (3): 10 ≤ (a1)+(b1) ≤ 50 ··· (1) 2.0 ≤ (a1) / (b1) ≤ 8.0 ··· (2) 45 ≤ (c1) ≤ 80 ··· (3). Claim 17 A photosensitive resin composition according to claim 16, wherein among the alkali-soluble polymers included in the above (A) component, the alkali-soluble polymers have constituent units derived from the above (a) component to (c) component, and furthermore, the proportion of the alkali-soluble polymers whose mass ratios (a1), (b1), and (c1) satisfy the above formulas (1) to (3) is 10 mass% or more. Claim 18 A photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from a photosensitive resin composition described in any one of claims 1 to 17. Claim 19 In claim 18, a photosensitive resin laminate having a protective film on the side opposite to the support of the photosensitive resin layer. Claim 20 A method for forming a resist pattern, comprising: a process of laminating a photosensitive resin laminate described in claim 18 onto a substrate; a process of exposing a photosensitive resin layer of the laminated photosensitive resin laminate to light; and a process of developing the exposed photosensitive resin layer. Claim 21 A method for forming a resist pattern according to claim 20, wherein the exposure is performed by direct imaging exposure. Claim 22 delete Claim 23 delete Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete Claim 28 delete

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