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

Abstract

The present invention provides a photosensitive resin composition in which various properties can be improved by controlling the type and ratio of at least the acid comonomer component among the alkali-soluble polymer comonomer components. [Solution] The following components: A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, (A) Component is at least the following co-monomer component: (a) Having a constituent unit derived from methacrylic acid or acrylic acid, (b) a carboxylic acid different from the acid selected as component (a) above, and (c) a compound having an aromatic or alicyclic structure, A photosensitive resin composition is provided in which the ratio (mass ratio (a1) / mass ratio (b1)) of the mass ratio (a1) of constituent units derived from component (a) to the mass ratio (b1) of constituent units derived from component (b) in component (A) is 1 / 10 to 10.

Description

Technical Field

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

Background Art

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

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

[0004] Further, Patent Document 2 discloses a photosensitive resin composition that is an addition product of a carboxyl group-containing resin and an unsaturated compound having an α,β-unsaturated double bond and an epoxy group, and contains an alkali-soluble polymer having an acid value of 50 to 200. 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 Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

[0006] However, the photosensitive resin compositions described in Patent Documents 1 and 2 had room for improvement in terms of achieving both the developability of the photosensitive resin layer and the resolution of the resulting resist pattern. Specifically, one method for achieving high resolution is to improve the hydrophobicity of the photosensitive resin layer, but improving the hydrophobicity of the photosensitive resin layer tends to increase the development time because it reduces solubility in the developer. Furthermore, in response to the recent demand for higher resolution, there has been a need for a photosensitive resin composition that includes a photosensitive resin layer capable of improving adhesion to the substrate.

[0007] The present invention has been proposed in view of the above circumstances. Specifically, the object of the present invention is to provide a photosensitive resin composition that can improve various properties by controlling the type and ratio of at least the acid comonomer component among the comonomer components of an alkali-soluble polymer. Another object of the present invention is to provide a photosensitive resin laminate comprising a photosensitive resin layer obtained from such a photosensitive resin composition, and a method for forming a resist pattern using the same. [Means for solving the problem]

[0008] [1] The following ingredients: (A) Alkali-soluble polymer, (B) Compounds having ethylenically unsaturated bonds, and (C) A photosensitive resin composition comprising a photopolymerization initiator, The above component (A) comprises at least the following comonomer components: (a) Methacrylic acid or acrylic acid, (b) A carboxylic acid different from the acid selected as component (a), and (c) Compounds having an aromatic or alicyclic structure, It has constituent units derived from, In the above component (A), The mass ratio (a1) of the constituent units derived from the above component (a), The mass ratio (b1) of the constituent units derived from the above component (b), A photosensitive resin composition in which the ratio (mass ratio (a1) / mass ratio (b1)) is 1 / 10 to 10. [2] The photosensitive resin composition according to item 1, wherein the ratio (mass ratio (a1) / mass ratio (b1)) is 1 / 8 to 8. [3] The photosensitive resin composition according to item 1 or 2, wherein the (A) component further comprises (d) a structural unit derived from a hydroxyalkyl (meth)acrylic acid ester as a comonomer component. [4] The photosensitive resin composition according to item 3, wherein component (d) is hydroxyethyl methacrylate. [5] The photosensitive resin composition according to any one of items 1 to 4, wherein the component (a) is methacrylic acid. [6] The photosensitive resin composition according to any one of items 1 to 5, wherein the component (b) is acrylic acid. [7] In the above component (A), The mass ratio (a1) of the constituent units derived from the above component (a), The photosensitive resin composition according to any one of items 1 to 6, wherein the total mass percentage (b1) of constituent units derived from component (b) is 1 to 65% by mass. [8] The photosensitive resin composition according to any one of items 1 to 7, wherein the (c) component comprises styrene and / or benzyl (meth)acrylate. [9] The photosensitive resin composition according to any one of items 1 to 8, wherein the proportion of constituent units derived from component (c) in component (A) is 10 to 95% by mass.

[10] The component (c)is the photosensitive resin composition according to item 8, which contains styrene.

[11] The photosensitive resin composition according to item 10, wherein the proportion of the structural unit derived from styrene in the component (A) is 45 to 95% by mass.

[12] Based on the total solid content of the photosensitive resin composition, the component (A): 10 to 90% by mass, the component (B): 5 to 70% by mass, and the component (C): 0.01 to 20% by mass, The photosensitive resin composition according to any one of items 1 to 11, which contains them.

[13] The photosensitive resin composition according to any one of items 1 to 12, wherein the component (A) contains a plurality of alkali-soluble polymers.

[14] The photosensitive resin composition according to item 13, wherein the relationship (mass average of mass ratio (a1) / mass average of mass ratio (b1)) between the mass average of the mass ratio (a1) and the mass average of the mass ratio (b1) is 1 / 10 to 10.

[15] At least one of the alkali-soluble polymers contained in the component (A) has a structural unit derived from the component (a) to the component (c) and satisfies the ratio, and is the photosensitive resin composition according to item 13 or 14.

[16] Among the alkali-soluble polymers contained in the component (A), has a structural unit derived from the component (a) to the component (c), and The proportion of the alkali-soluble polymer that satisfies the ratio is 10% by mass or more, and is the photosensitive resin composition according to any one of items 13 to 15.

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

[18] The photosensitive resin composition according to any one of items 1 to 17, wherein the (B) component comprises a compound having a bisphenol A structure and / or a hydrogenated bisphenol A structure.

[19] The photosensitive resin composition according to any one of items 1 to 18, wherein the (B) component contains a compound having three or more ethylenically unsaturated bonds in one molecule.

[20] The (C) component is a photosensitive resin composition according to any one of items 1 to 19, comprising a hexaarylbiimidazole (HABI) compound. [twenty one] (D) A photosensitive resin composition according to any one of items 1 to 20, further comprising a leuco dye as component (D). [twenty two] In the above component (A), The mass ratio (a1) of the constituent units derived from the above component (a), The mass ratio (b1) of the constituent units derived from the above component (b), The mass ratio (c1) of the constituent units derived from the above component (c) is given by the following formulas (1) to (3): 10≦(a1)+(b1)≦50 (1) 0.5≦(a1) / (b1)≦8.0 (2) 30 ≤ (c1) ≤ 80 ··· (3) A photosensitive resin composition according to any one of items 1 to 21, which satisfies the following conditions. [twenty three] The aforementioned component (A) contains a plurality of alkali-soluble polymers, At least one of the alkali-soluble polymers contained in component (A) has a constituent unit derived from components (a) to (c), The photosensitive resin composition according to item 22, wherein the mass ratios (a1), (b1), and (c1) satisfy formulas (1) to (3). [twenty four] Of the alkali-soluble polymers contained in component (A) above, The photosensitive resin composition according to item 23, wherein the proportion of alkali-soluble polymers having constituent units derived from the components (a) to (c) and in which the mass ratios (a1), (b1), and (c1) satisfy the formulas (1) to (3) is 10% by mass or more. [twenty five] A photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from any one of the photosensitive resin compositions described in item 1 to 24.

[26] The photosensitive resin laminate according to item 25, wherein a protective film is provided on the side of the photosensitive resin layer opposite to the support.

[27] A step of laminating a photosensitive resin laminate described in item 25 or 26 onto a substrate, A step of exposing the photosensitive resin layer of the laminated photosensitive resin laminate, and A step of developing the exposed photosensitive resin layer, A method for forming a resist pattern, comprising the characteristics of a resist pattern.

[28] The resist pattern formation method according to item 27, wherein the exposure is performed by direct imaging exposure. [Effects of the Invention]

[0009] According to the photosensitive resin composition of the present invention, the developability of the photosensitive resin layer can be improved by controlling the type and ratio of at least the acid comonomer component among the alkali-soluble polymer comonomer components. In addition, according to the photosensitive resin composition of the present invention, the adhesion of the photosensitive resin layer to the substrate and the resolution of the resist pattern can also be improved. Furthermore, according to the present invention, it is possible to provide a photosensitive resin laminate comprising a photosensitive resin layer obtained from such a photosensitive resin composition, and a method for forming a resist pattern using the same. [Modes for carrying out the invention]

[0010] The embodiments of the present invention (hereinafter abbreviated as "these embodiments") will be described below. However, the present invention is not limited to these embodiments and can be implemented in various modifications within the scope of its gist. In these embodiments, numerical ranges indicated using "~" include the numerical values ​​indicated before and after "~" within that range. Furthermore, in these embodiments, in numerical ranges described in steps, the upper or lower limit indicated in one numerical range can be replaced with the upper or lower limit of another numerical range described in steps. Moreover, in these embodiments, the upper or lower limit indicated in one numerical range can also be replaced with the values ​​shown in the examples.

[0011] In this specification, "(meth)acrylic" means acrylic or methacrylic, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylate" means acrylate or methacrylate.

[0012] [Photosensitive resin composition] [Schematic configuration] The photosensitive resin composition according to this embodiment, The following ingredients: (A) Alkali-soluble polymer, (B) Compounds having ethylenically unsaturated bonds, and (C) Photopolymerization initiator, This includes (A) to (C) above, which are also referred to simply as "component (A)" to "component (C)".

[0013] And component (A) is at least the following comonomer component: (a) Methacrylic acid or acrylic acid, (b) A carboxylic acid different from the acid selected as component (a) above, and (c) Compounds having an aromatic or alicyclic structure It has constituent units derived from the above. In this specification, (a) and (b) above are also simply referred to as "(a) acid comonomer component" and "(b) acid comonomer component," and (c) above is also simply referred to as "(c) comonomer component."

[0014] Here, in component (A), (a) Mass ratio of constituent units derived from acid comonomer components (a1), (b) The mass percentage of constituent units derived from the acid comonomer component (b1), The ratio (mass ratio (a1) / mass ratio (b1)) is between 1 / 10 and 10. Here, "1 / 10" is, for example, "0.1".

[0015] In such a photosensitive resin composition, multiple acid comonomer components are used in combination as comonomer components of an alkali-soluble polymer, and these multiple acid comonomer components are also used in combination with other comonomer components. Furthermore, the type and content ratio of at least the acid comonomer components are controlled.

[0016] Such a photosensitive resin composition can improve various properties (such as the developability of the photosensitive resin layer, the adhesion of the photosensitive resin layer to the substrate, and the resolution of the resist pattern). In one preferred embodiment of this model, multiple acid comonomer components are used in combination as the comonomer component of the alkali-soluble polymer, and these multiple acid comonomer components can also be used in combination with other comonomer components having an aromatic or alicyclic structure. Furthermore, the inventors have found that controlling the type and content ratio of at least the acid comonomer components leads to improvements in various performance characteristics, and this embodiment was proposed based on this idea. In addition, in one preferred embodiment of this model, the ratio of other comonomer components having an aromatic or alicyclic structure can also be controlled, in which case it is easier to improve various properties (for example, the adhesion of the photosensitive resin layer to the substrate and the resolution of the resist pattern). The following describes each component that makes up the photosensitive resin composition.

[0017] [Component (A): Alkali-soluble polymer] (Schematic configuration) Component (A) is a polymer soluble in alkaline solutions. Component (A) preferably has a carboxyl group, and more preferably has an acid value of 50-600 mgKOH / g, and more preferably has an acid value of 100-400 mgKOH / g, from the viewpoint of improving developability. The acid value of component (A) may be 60 mgKOH / g or more, 80 mgKOH / g or more, 100 mgKOH / g or more, 500 mgKOH / g or less, or 400 mgKOH / g or less. Component (A) may be thermoplastic. The above acid value refers to the number of milligrams of potassium hydroxide required to neutralize 1 g of component (A).

[0018] 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. When the weight-average molecular weight of component (A) is above the lower limit of the above value, it becomes easier to maintain a uniform thickness of the photosensitive resin laminate and to ensure resistance of the exposed area to the developer. Furthermore, when the weight-average molecular weight of component (A) is below the upper limit of the above value, it becomes easier to maintain the developability of the photosensitive resin laminate. Furthermore, 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. The weight-average molecular weight and polydispersity mentioned above refer to the weight-average molecular weight and polydispersity measured using a polystyrene calibration curve by gel permeation chromatography (GPC). The weight-average molecular weight can be measured, for example, under the following conditions. (GPC conditions) Pump: Hitachi L-6000 model (manufactured by Hitachi, Ltd., product name) Columns: A total of 3 columns as follows Gelpack GL-R420 Gelpack GL-R430 Gelpack GL-R440 (manufactured by Hitachi Chemical Co., Ltd., product name) Eluent: Tetrahydrofuran Measurement temperature: 40℃ Flow rate: 2.05mL / min Detector: Hitachi L-3300 RI (manufactured by Hitachi, Ltd., product name)

[0019] The content of component (A) in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition; the same applies to each component unless otherwise specified) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 60% by mass. From the viewpoint of maintaining the alkali developability of the photosensitive resin layer, the content of component (A) is preferably above the lower limit. On the other hand, from the viewpoint of the resist pattern formed by exposure exhibiting sufficient performance as a resist material, it is preferably below the upper limit.

[0020] Here, component (A) is at least the following co-monomer component: (a) Methacrylic acid or acrylic acid, (b) A carboxylic acid different from the acid selected as the acid comonomer component in (a) above, and (c) Compounds having an aromatic or alicyclic structure, It is obtained by polymerizing the following. Therefore, component (A) has at least constituent units derived from each of (a) the acid comonomer component, (b) the acid comonomer component, and (c) the comonomer component.

[0021] ((a) Acid comonomer component) (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.

[0022] ((b) Acid comonomer component) (b) The acid comonomer component is a carboxylic acid different from the acid comonomer component selected in (a) above. If (a) the acid comonomer component is methacrylic acid, then (b) the acid comonomer component may be a carboxylic acid different from methacrylic acid. Also, if (a) the acid comonomer component is acrylic acid, then (b) the acid comonomer component may be a carboxylic acid different from acrylic acid. Furthermore, regardless of the type of acid comonomer component (a), then (b) the acid comonomer component may be a carboxylic acid different from both methacrylic acid and acrylic acid. The acid comonomer component (b) may be a compound having an ethylenically unsaturated bond, and may be a compound having a (meth)acryloyl group. The acid comonomer component (b) may be a single type, or two or more types may be used in combination.

[0023] (b) The acid comonomer component may be acrylic acid if (a) the acid comonomer component is methacrylic acid, and may be methacrylic acid if (a) the acid comonomer component is acrylic acid. Furthermore, (b) the acid comonomer component may be a carboxylic acid other than, for example, methacrylic acid and acrylic acid. Examples of carboxylic acids other than methacrylic acid and acrylic acid include cinnamic acid, crotonic acid, succinic acid semi-ester, maleic acid semi-ester, fumaric acid semi-ester, 4-vinylbenzoic acid, succinic acid, maleic acid, fumaric acid, itaconic acid, and the like.

[0024] Here, in component (A), (a) Mass ratio of constituent units derived from acid comonomer components (a1), (b) The mass percentage of constituent units derived from the acid comonomer component (b1), The ratio (mass ratio (a1) / mass ratio (b1)) is between 1 / 10 and 10 (for example, 10.0).

[0025] (a) The acid comonomer component and (b) the carboxylic acid that can be selected as the acid comonomer component have different effects on the properties 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 alkali-soluble polymer comonomer components, it is possible to improve various properties of the photosensitive resin layer.

[0026] From the same viewpoint as above, the ratio (mass ratio (a1) / mass ratio (b1)) is preferably 1 / 8 to 8 (for example, 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.

[0027] (a) The acid comonomer component is preferably methacrylic acid. This makes it easier to realize a photosensitive resin layer with excellent properties due to the contribution of methacrylic acid.

[0028] Here, it is more preferable that (a) the acid comonomer component is methacrylic acid, and (b) the acid comonomer component is acrylic acid. Of methacrylic acid and acrylic acid, obtaining the contribution of methacrylic acid, which has relatively high hydrophobicity, makes it easier to improve the resolution of the resist pattern, and obtaining the contribution of acrylic acid, which has a relatively low glass transition temperature, makes it easier to improve developability. Therefore, the contributions of both acids can be suitably obtained, and as a result, various properties (developability of the photosensitive resin layer, resolution of the resist pattern, etc.) can be improved.

[0029] For example, acrylic acid, which can be used as component (b), has a lower glass transition temperature (Tg) than methacrylic acid, which can be used as component (a). Therefore, for example, when focusing on 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 in a way that is advantageous for improving resolution while ensuring the hydrophobicity of the entire component (A).

[0030] Furthermore, (a) the acid comonomer component may be methacrylic acid or acrylic acid, and (b) the acid comonomer component may contain a carboxylic acid different from either methacrylic acid or acrylic acid. This makes it easier to realize a photosensitive resin layer with excellent properties by obtaining the contribution of a carboxylic acid different from either methacrylic acid or acrylic acid.

[0031] In component (A), the sum of the mass percentage of constituent units derived from (a) acid comonomer component (a1) and the mass percentage of constituent units derived from (b) acid comonomer component (b1) is preferably 1 to 65% by mass. This ensures that there is room for other comonomer components, making it easier to broaden the range of compositional designs to suit various applications. The proportion of constituent units of the comonomer component in component (A) is approximately equivalent to the amount of that comonomer component added. From the same viewpoint as above, the above sum is more preferably 5 to 50% by mass, even more preferably 15 to 35% by mass, and particularly preferably 20 to 30% by mass.

[0032] ((c) Concomitant use of comonomer components) (c) The comonomer component is one of the comonomer components for obtaining component (A), and is a compound having an aromatic structure or an alicyclic structure. (c) Having such a structure in the comonomer component can improve the adhesion of the resist pattern. (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 used alone, or two or more may be used in combination.

[0033] Examples of compounds having an aromatic structure include styrene, styrene derivatives, benzyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, and the like. Examples of styrene derivatives include 4-methylstyrene, 4-hydroxystyrene, 4-methoxystyrene, 4-chlorostyrene, and 4-(chloromethyl)styrene.

[0034] Examples of compounds having an alicyclic structure include (meth)acrylic acid esters having a group consisting of one cyclic hydrocarbon group such as a cyclobutyl group, cyclopentyl group, cyclohexyl group, or cycloheptyl group, or a derivative thereof; and (meth)acrylic acid esters having a group consisting of two or more cyclic hydrocarbon groups such as a dicyclopentanyl group, dicyclopentenyl group, adamantyl group, or isobornyl group, or a derivative thereof.

[0035] (c) The comonomer component preferably contains styrene and / or benzyl (meth)acrylate, and more preferably contains styrene. This makes it easier to improve the adhesion of the resist pattern even when the development time is extended.

[0036] The content of component (c) comonomer in component (A) is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 90% by mass, even more preferably 45 to 80% by mass, and particularly preferably 65 to 80% by mass. Within this range, it is easy to maintain good alkali solubility and to improve the adhesion of the resist pattern.

[0037] (c) The comonomer component contains styrene, and it is preferable from the viewpoint of easily improving the adhesion of the resist pattern if the styrene content is 45% by mass or more, preferably 50% by mass or more, more preferably 55% by mass, even more preferably 60% by mass or more, and particularly preferably 65% ​​by mass or more. (c) If the comonomer component contains styrene, the styrene content may be 95% by mass or less.

[0038] In order to achieve both the developability of the photosensitive resin layer and the resolution of the resulting resist pattern, and to improve adhesion to the substrate, component (A) preferably contains (a) methacrylic acid, (b) acrylic acid, and (c) styrene as comonomer components, and using the mass ratio of constituent units derived from (a) methacrylic acid (a1), the mass ratio of constituent units derived from (b) acrylic acid (b1), and the mass ratio of constituent units derived from (c) styrene (c1), the following formulas (1) to (3): 10≦(a1)+(b1)≦50 (1) 0.5≦(a1) / (b1)≦8.0 (2) 30 ≤ (c1) ≤ 80 ··· (3) It is preferable that all of the following conditions be met. The following equations (4) to (6): 15≦(a1)+(b1)≦35 (4) 1.0≦(a1) / (b1)≦6.0 (5) 45 ≤ (c1) ≤ 75 ··· (6) It is more preferable that all of the following conditions be met: The following equations (7) to (9): 20≦(a1)+(b1)≦30 (7) 2.0≦(a1) / (b1)≦4.2 (8) 50 ≤ (c1) ≤ 70 ··· (9) It is even preferable if all conditions are met.

[0039] (d) Optional co-use of comonomer components Component (A) may further contain a constituent unit derived from a hydroxyalkyl (meth)acrylic acid ester (also referred to as "(d) comonomer component") as a comonomer component. Such compounds have a hydroxyl (OH) group and are therefore more hydrophilic than, for example, methacrylic acid or acrylic acid. Thus, component (A) can be used in an optional combination with the (d) comonomer component to easily control the developability of the photosensitive resin layer. The (d) comonomer component may be used alone or in combination of two or more types.

[0040] Examples of hydroxyalkyl (meth)acrylic acid esters include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxypentyl (meth)acrylate.

[0041] (d) The comonomer component preferably contains hydroxyethyl methacrylate. This is because it is readily available and its developability is easily controlled. The content of component (d) comonomer in component (A) is preferably 1.0 to 50% by mass, more preferably 1.5 to 40% by mass, and even more preferably 2.0 to 20% by mass.

[0042] (Optional additional use of other comonomer components) Component (A) may further be used in combination with a comonomer component (also referred to as "other comonomer components") that is different from any of the above-mentioned (a) acid comonomer component and (b) acid comonomer component, as well as the comonomers that can be selected as (c) comonomer component and (d) comonomer component.

[0043] Other comonomer components include, for example, alkyl (meth)acrylates, conjugated diene compounds, polar monomers (excluding hydroxyalkyl (meth)acrylates), crosslinkable monomers, and acid anhydrides (e.g., maleic anhydride).

[0044] Alkyl (meth)acrylates are a concept that encompasses both linear alkyl esters and cyclic alkyl esters. 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, and cyclohexyl (meth)acrylate.

[0045] Examples of conjugated diene compounds include 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, and 3-butyl-1,3-octadiene.

[0046] Examples of polar monomers include amino group-containing monomers such as 2-aminoethyl methacrylate; amide group-containing monomers such as (meth)acrylamide and N-methylol(meth)acrylamide; cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-cyanoethyl acrylate; and epoxy group-containing monomers such as glycidyl(meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylic acid.

[0047] Examples of crosslinkable monomers include trimethylolpropane triacrylate and divinylbenzene.

[0048] ((A) Various aspects of component) Component (A) may contain multiple alkali-soluble polymers. For example, component (A) may be a combination of (A1) an alkali-soluble polymer containing methacrylic acid and styrene and (A2) an alkali-soluble polymer containing acrylic acid and styrene, or a combination of (A2) an alkali-soluble polymer containing acrylic acid and styrene and (A3) an alkali-soluble polymer containing methacrylic acid and hydroxyethyl methacrylate.

[0049] Furthermore, the mass average of the above mass ratios (a1), (b1), and (c1) is, for example, when component (A) contains N types of alkali-soluble polymers, with respect to the sum of those alkali-soluble polymers, Let X1 be the proportion of the first alkali-soluble polymer (polymer 1). Let X2 be the proportion of the second alkali-soluble polymer (polymer 2). Let XN be the proportion of the Nth alkali-soluble polymer (polymer N). When this is the case, the following formula: (a1)=(X1×a1-1)+(X2×a1-2)+··+(XN×a1-N) (b1)=(X1×b1-1)+(X2×b1-2)+··+(XN×b1-N) (c1)=(X1×c1-1)+(X2×c1-2)+··+(XN×c1-N) a1-1: Mass ratio of component (a) in polymer 1 a1-2: Mass ratio of component (a) in polymer 2 a1-N: Mass ratio of component (a) in polymer N b1-1: Mass ratio of component (b) in polymer 1 b1-2: Mass ratio of component (b) in polymer 2 b1-N: Mass ratio of component (b) in polymer N c1-1: Mass ratio of component (c) in polymer 1 c1-2: Mass ratio of component (c) in polymer 2 c1-N: Represented by the mass ratio of component (c) in polymer N.

[0050] In this case, the ratio ((a1) / (b1)) of the alkali-soluble polymer as a whole only needs to be within the above ratio range, and the ratio of the alkali-soluble polymer as a whole may not be within the above range. In this embodiment, it is preferable from the viewpoint of easily achieving the effects of this embodiment that the relationship between the mass average of mass ratio (a1) and the mass average of mass ratio (b1) (mass average of mass ratio (a1) / mass average of mass ratio (b1)) is 1 / 10 to 10.

[0051] On the other hand, at least one of the alkali-soluble polymers contained in component (A) has constituent units derived from the acid comonomer components (a) to (b) and the comonomer component (c), and can satisfy the above ratio. That is, if component (A) is composed of a single alkali-soluble polymer, that alkali-soluble polymer can satisfy the essential requirements for component (A) of the present invention, and if component (A) is composed of multiple alkali-soluble polymers, at least one of those multiple alkali-soluble polymers can satisfy the essential requirements for component (A) of the present invention on its own.

[0052] In one embodiment, the photosensitive resin composition preferably contains alkali-soluble polymers in component (A) that have constituent units derived from components (a) to (c), and the proportion of alkali-soluble polymers that satisfy the ratio is 10% by mass or more. Furthermore, if at least one of the alkali-soluble polymers contained in component (A) satisfies the essential requirements for component (A) of the present invention, it is preferable that the proportion of alkali-soluble polymers that satisfy those requirements among the alkali-soluble polymers contained in component (A) be 10% by mass or more. The proportion of such alkali-soluble polymers may be 30% by mass or more, 40% by mass or more, or 50% by mass or more. The proportion of such alkali-soluble polymers may be 100% by mass or less, or 60% by mass or less.

[0053] [(B) Component: Compound containing an ethylenically unsaturated bond] Component (B) is a compound having an ethylenically unsaturated bond in its structure. Preferably, component (B) contains a compound having a bisphenol A structure and / or a hydrogenated bisphenol A structure. This makes it easier to achieve the effects of the present invention. Of the total amount of component (B), compounds having a bisphenol A structure and / or a hydrogenated bisphenol A structure may be present in an amount of 30% by mass or more, 50% by mass or more, 80% by mass or more, or 90% by mass or more. Of component (B), the content of compounds having a bisphenol A structure and / or a hydrogenated bisphenol A structure may be the highest among the content of each of the other compounds in component (B). Examples of component (B) include compounds having one ethylenically unsaturated bond, compounds having two ethylenically unsaturated bonds, compounds having three ethylenically unsaturated bonds, compounds having four ethylenically unsaturated bonds, and compounds having five or more ethylenically unsaturated bonds. Different types of these compounds may be used in combination. In one embodiment, it is preferable that component (B) contains 30% by mass or more, 50% by mass or more, 80% by mass or more, or 90% by mass or more of a compound having two or more ethylenically unsaturated bonds. This makes it easier to achieve the effects of this embodiment.

[0054] As component (B), for example, a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds may be used in combination, and different compounds having three or more ethylenically unsaturated bonds may be used in combination. Examples of compounds having three or more ethylenically unsaturated bonds include compounds having four ethylenically unsaturated bonds, five ethylenically unsaturated bonds, or six ethylenically unsaturated bonds. In particular, component (B) preferably contains a compound having three or more ethylenically unsaturated bonds in one molecule, and also preferably contains a compound having four or more ethylenically unsaturated bonds in one molecule.

[0055] For example, component (B) may include polyalkylene glycol di(meth)acrylate obtained by adding an average of 1 to 15 moles of alkylene oxide to each end of bisphenol A; polyalkylen triol tri(meth)acrylate obtained by adding an average of 3 to 25 moles of alkylene oxide to trimethylolpropane; glycerin; trimethylolpropane; pentaerythritol; diglycerin; ditrimethylolpropane; isocyanurate rings, etc., to which polyalkylene oxide groups are added, or ε-capro Examples include compounds obtained by converting alcohols obtained by lactone modification into (meth)acrylates, or compounds obtained by directly reacting them with (meth)acrylic acid without modification with alkylene oxide groups or ε-caprolactone; tetra(meth)acrylates of polyols obtained by adding an average of 4 to 35 moles of alkylene oxide to pentaerythritol; hexa(meth)acrylates of polyols obtained by adding an average of 4 to 30 moles of alkylene oxide to dipentaerythritol; and so on. These can be used individually or in combination of two or more types. Specifically, the types of compounds that may be included in component (B) are: A polyethylene glycol dimethacrylate obtained by adding an average of 5 moles of EO (ethylene oxide) to each end of bisphenol A, Hexamethacrylate obtained by adding an average of 13 moles of EO (ethylene oxide) to dipentaerythritol. A polyethylene glycol dimethacrylate obtained by adding an average of 1 mole of EO (ethylene oxide) to each end of bisphenol A, EO (ethylene oxide) modified hydrogenated bisphenol A dimethacrylate, Polytetramethylene glycol dimethacrylate, Tetramethacrylate obtained by adding an average of 15 moles of EO (ethylene oxide) to pentaerythritol. Poly(propylene glycol) dimethacrylate, EO (ethylene oxide) modified bisphenol A dimethacrylate, and Examples include trimethacrylate, which is obtained by adding an average of 9 moles of EO (ethylene oxide) to glycerin.

[0056] The content of component (B) in the photosensitive resin composition is preferably 5 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass. From the viewpoint of suppressing poor curing of the photosensitive resin layer and delays in development time, the content of component (B) is preferably above the lower limit. Furthermore, from the viewpoint of improving the removeability of the cured photosensitive resin layer, it is preferably below the upper limit.

[0057] [(C) Component: Photopolymerization initiator] Component (C) is a compound that generates radicals when exposed to active light, thereby initiating the polymerization of component (B).

[0058] Examples of component (C) 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, dialkylketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-aryl amino acid ester compounds, and halogen compounds.

[0059] Examples of hexaarylbiimidazole compounds include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 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, and 2,4,5-tris-(o-chlorophenyl)-diphenyl Biimidazole, 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,Examples include 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',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, rofin dimers, etc.

[0060] Examples of rophine dimers, i.e., dimers of 2,4,5-triarylimidazole, include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. Among these, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred from the viewpoint of high sensitivity, resolution, and adhesion.

[0061] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred due to its high sensitizing effect.

[0062] 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-phenanthaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0063] Examples of aromatic ketone compounds include benzophenone, Michla's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. 4,4'-bis(diethylamino)benzophenone is also an example of an aromatic ketone compound, given its sensitizing effect and adhesion properties.

[0064] 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, and 1-chloroanthraquinone. From the viewpoint of sensitization effect and adhesion, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred, and 9,10-diphenylanthracene is particularly preferred.

[0065] 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-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Examples of commercially available acetophenone compounds include the Irgacure series (manufactured by Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0066] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. Examples of commercially available acylphosphine oxide compounds include Lucilin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).

[0067] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin. Examples of dialkylketal compounds include benzyldimethyl ketal and benzyldiethyl ketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorthioxanthone. Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0068] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).

[0069] As for the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine are preferred in terms of sensitivity, resolution, and availability.

[0070] As pyrazoline derivatives, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline are preferred from the viewpoint of adhesion and rectangularity of the resist pattern.

[0071] Examples of ester compounds of N-aryl amino acids include 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, and octyl ester of N-phenylglycine.

[0072] 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, and diallylodonium compounds. Among these, tribromomethylphenylsulfone is preferred.

[0073] The content of component (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, and more preferably 0.5 to 10% by mass. By adjusting the content of component (C) within the above range, sufficient sensitivity can be easily obtained, making it easier to transmit light sufficiently to the bottom of the photosensitive resin layer, and consequently, easier to achieve high resolution.

[0074] From the viewpoint of high sensitivity, resolution, and adhesion, it is preferable that the (C) component contains a rofin dimer. In this case, the content of the rofin dimer in the photosensitive resin composition is preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass.

[0075] It is preferable to use an anthracene derivative and a hexaarylbiimidazole compound in combination as component (C). In this case, the content of component (C) (e.g., anthracene derivative) in the photosensitive resin composition is preferably 0.5% by mass or less, more preferably 0.01% to 0.4% by mass, and the content of the hexaarylbiimidazole compound in the photosensitive resin composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

[0076] [(D) Component: Leuco dye] Component (D) can be incorporated into the photosensitive resin composition of this embodiment to provide color development in the unexposed areas and excellent peelability. Examples of component (D) include leucocrystal violet (tris[4-(dimethylamino)phenyl]methane) and 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide. Among these, leucocrystal violet is preferred.

[0077] The content of component (D) in the photosensitive resin composition is preferably 0.01 to 2% by mass, and more preferably 0.1 to 1.5% by mass, relative to the total mass of solids in the photosensitive resin composition. By adjusting the content of component (D) within this range, good color development and sensitivity can be achieved.

[0078] [Other ingredients] The photosensitive resin composition may optionally contain a base dye (a dye other than component (D)), an antioxidant, a stabilizer, a sensitizer, a plasticizer, etc. Other components are those other than those listed in (A) to (D) above.

[0079] 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 Co., Ltd.), Fuchsine [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 Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], and Basic Yellow 2 [2465-27-2]. Among these, Basic Green 1 is preferred from the viewpoint of improving colorability, hue stability, and exposure contrast. These can be used individually or in combination of two or more.

[0080] The base dye content in the photosensitive resin composition is preferably 0.001 to 3% by mass, more preferably 0.01 to 2% by mass, and even more preferably 0.04 to 1% by mass. From the viewpoint of obtaining good colorability, the base dye content is preferably above the lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably below the upper limit.

[0081] Examples of antioxidants include triphenyl phosphite (e.g., ADEKA Corporation, trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., ADEKA Corporation, trade name: 2112), tris(mononylphenyl) phosphite (e.g., ADEKA Corporation, trade name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., ADEKA Corporation, trade name: 329K). These can be used individually or in combination of two or more.

[0082] The antioxidant content in the photosensitive resin composition is preferably 0.01 to 0.8% by mass, and more preferably 0.01 to 0.3% by mass. From the viewpoint of exhibiting good hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer, the antioxidant content is preferably above the lower limit. On the other hand, from the viewpoint of exhibiting good hue stability while suppressing the color development of the resist pattern and improving adhesion, it is preferably below the upper limit.

[0083] Stabilizers 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 radical polymerization inhibitors and alkylene oxide compounds having a glycidyl group. These can be used individually or in combination of two or more.

[0084] 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), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salts (e.g., aluminum salts to which 3 moles of nitrosophenylhydroxylamine are added), and diphenylnitrosamines. Among these, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or aluminum salts to which 3 moles of nitrosophenylhydroxylamine are added are preferred. These can be used individually or in combination of two or more.

[0085] 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.), and 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.). These can be used individually or in combination of two or more.

[0086] The total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably 0.001 to 3% by mass, and more preferably 0.05 to 1% by mass. From the viewpoint of providing good storage stability to the photosensitive resin composition, the total content is preferably above the lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably below the upper limit.

[0087] [Photosensitive resin composition solution] A photosensitive resin composition solution can be prepared by adding a solvent to the photosensitive resin composition. Suitable 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 the solvent to the photosensitive resin composition solution so that its viscosity is 500 to 4000 mPa·sec at 25°C.

[0088] [Photosensitive resin laminates, dry film resists, and transfer films] A photosensitive resin layer, and subsequently a photosensitive resin laminate, can be obtained using a photosensitive resin composition or a solution of a photosensitive resin composition. The photosensitive resin laminate, for example, comprises a support (support film) and a photosensitive resin layer laminated on the support. The photosensitive resin laminate may optionally have a protective film on the side opposite to the support. From the viewpoint of significantly enhancing the effects of the present invention, the photosensitive resin laminate is preferably a dry film resist or a transfer film, and more preferably a dry film resist.

[0089] The support is preferably transparent and transmits light emitted from the exposure light source. Such a support is preferably a plastic film, specifically, examples of which 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, and cellulose derivative film. These films may be used in stretched form as needed.

[0090] The haze of the support is preferably 5 or less. While a thinner support is advantageous in terms of image formation and cost-effectiveness, a thickness of 10 to 30 μm is preferable when considering the function of maintaining strength.

[0091] The photosensitive resin layer described above may contain or consist 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. The closer the thickness of the photosensitive resin layer is to 3 μm, the better the resolution, and the closer it is to 100 μm, the better the film strength, so it can be appropriately selected depending on the application.

[0092] An important characteristic of the protective film used in a photosensitive resin laminate is that it has appropriate adhesion. In other words, it is preferable 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 the photosensitive resin laminate. Examples of protective films that can be used include polyethylene film, polypropylene film, polyethylene terephthalate film, and polyester film. The film thickness of the protective film is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

[0093] A release layer can be applied to the surface of the protective film to allow for easy peeling of the protective film from the photosensitive resin layer. Release layers are classified, for example, into silicone compounds and non-silicone compounds.

[0094] Examples of silicone compounds include condensation reaction type silicone resins obtained by reacting terminally silanol polydimethylsiloxane with polymethylhydrogen siloxane or polymethylmethoxysiloxane; addition reaction type silicone resins obtained by reacting dimethylsiloxane-methylvinylsiloxane copolymer or dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogen siloxane; UV-curable or electron-beam-curable silicone resins obtained by curing acrylic silicone and epoxy group-containing silicone with ultraviolet light or electron beams; and modified silicone resins such as epoxy-modified silicone resin (silicone epoxy), polyester-modified silicone resin (silicone polyester), acrylic-modified silicone resin (silicone acrylic), phenol-modified silicone resin (silicone phenol), alkyd-modified silicone resin (silicone alkyd), and melamine-modified silicone resin (silicone melamine).

[0095] Examples of non-silicone compounds include alkyd resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.

[0096] The 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 thickness is below the above upper limit, the appearance of the coating film tends to be good, and the coating film is easier to cure sufficiently. On the other hand, if the thickness is above the above lower limit, it is easier to ensure sufficient release properties.

[0097] [Method for fabricating photosensitive resin laminates] A photosensitive resin laminate can be manufactured by sequentially laminating a photosensitive resin layer and, if necessary, a protective film onto a support. For example, in the manufacturing method, a photosensitive resin composition to be used for the photosensitive resin layer is mixed with a solvent to dissolve it, thereby creating a photosensitive resin composition solution (coating solution). Next, the coating solution is applied to the support using a bar coater or roll coater, dried, and the photosensitive resin layer is laminated onto the support. Then, if necessary, a protective film is laminated onto the photosensitive resin layer to produce the photosensitive resin laminate.

[0098] [Method for forming a resist pattern] The method for forming a resist pattern using the photosensitive resin laminate according to this embodiment involves the following steps: A process of laminating a photosensitive resin laminate onto a substrate; A step of exposing the photosensitive resin layer of a laminated photosensitive resin structure; and A developing process for developing an exposed photosensitive resin layer; The following are preferably included in this order:

[0099] [Lamination process] 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, laminating 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 using a laminator equipped with rolls, or by repeatedly passing the laminate of the substrate and photosensitive resin layer through the rolls several times. Heat pressing can be performed under reduced pressure if desired.

[0100] [Exposure process] In the exposure process, the photosensitive resin layer is exposed to active light using an exposure machine. Exposure can be performed after peeling off the support, if desired. When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and may be measured using a light meter. Direct imaging exposure may also be performed in the exposure process. In direct imaging exposure, exposure is performed directly on the substrate using a drawing device without using a photomask. A semiconductor laser with a wavelength of 350 to 410 nm or an ultra-high pressure mercury lamp is used as the light source. 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.

[0101] The light irradiation method used in the exposure process is preferably at least one method selected from projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct writing, and is more preferably performed by projection exposure or direct imaging exposure.

[0102] [Development process] In the development process, after peeling off the support, the unexposed areas (non-patterned areas) of the photosensitive resin layer are dissolved in a developer solution and removed. The developer solution contains an alkaline aqueous solution. When a negative-type photosensitive resin composition is used, the resist pattern is obtained by removing the unexposed areas in the development process. When a positive-type photosensitive resin composition is used, the resist pattern is obtained by removing the exposed areas.

[0103] 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% by mass. A surfactant, an antifoaming agent, and a small amount of organic solvent to promote development can be mixed into the alkaline aqueous solution. It is preferable to maintain the temperature of the developer solution in the development process at a constant temperature in the range of 18 to 40°C.

[0104] If necessary, a heating step can be performed after the development process, in which the obtained resist pattern is heated to 100-300°C. This heating step makes it easier to improve the chemical resistance and resolution of the resist pattern. Heating can be performed using methods such as hot air, infrared radiation, or far-infrared radiation.

[0105] [Etching process] By forming a resist pattern using the resist pattern formation method described above, and then performing a plating treatment as necessary, a wiring pattern corresponding to the resist pattern can be formed on the substrate by etching the substrate.

[0106] The etching process can employ, for example, a method of spraying an etching solution onto the resist pattern. Etching methods include acid etching and alkaline etching. Examples of etching solutions include aqueous hydrochloric acid solution, aqueous ferric chloride solution, or mixtures thereof.

[0107] Plating can be performed by applying metallic plating (e.g., metallic plating with copper sulfate solution) or solder plating to the parts exposed by development, according to known plating methods.

[0108] If plating is performed, the resist pattern can be removed after the plating process; if plating is omitted, the resist pattern can be removed after the etching process using an aqueous solution (stripping solution) that is more alkaline than the developer. The stripping solution is preferably an aqueous solution of NaOH or KOH, or an aqueous solution of an organic amine compound, with a concentration of about 2 to 5% by mass and a temperature of about 40°C to 70°C.

[0109] The various parameters mentioned above are measured according to the measurement methods described in the examples below, unless otherwise specified. The present invention will be described in more detail below based on the examples, but the present invention is not limited to these examples. [Examples]

[0110] [Examples 1-18 and Comparative Examples 1-10] <1. Preparation of photosensitive resin composition> The components shown in the table below were mixed, and then acetone, the solvent, was added until the solid content reached 60% by mass. The mixture was then thoroughly stirred and mixed to prepare a photosensitive resin composition solution. The values ​​in the table represent the solid content.

[0111] <2. Manufacturing of photosensitive resin laminates> The resulting 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 (GF-18, manufactured by Tamapoly Co., Ltd.) was laminated as a protective film to the side of the photosensitive resin layer that did not have the PET film laminated on it to obtain a photosensitive resin laminate.

[0112] <3. Surface preparation of the circuit board> The surface of the copper-clad laminate was smoothed by sequentially performing surface treatment using a polishing machine and cleaning with a 10% by mass H2SO4 aqueous solution. This resulted in a copper-clad laminate (substrate) with a thickness of 0.4 mm, on which 18 μm thick copper foil was laminated.

[0113] <4. Fabrication of evaluation boards> laminate: While peeling off the polyethylene film (protective film) of the photosensitive resin laminate, the photosensitive resin laminate was laminated to a substrate preheated to 50°C using a hot roll laminator (Asahi Kasei Electronics Corporation, AL-700) after surface preparation as described above, at a roll temperature of 105°C. This obtained an evaluation substrate. The air pressure was 0.35 MPa and the lamination speed was 1.5 m / min.

[0114] exposure: Examples 1-18 and Comparative Examples 1-10 involved exposing evaluation substrates using a direct imaging (DI) exposure pattern with a predetermined pattern, employing a direct imaging exposure machine (FDi-3, manufactured by Oak Seisakusho, with a main wavelength of 400 nm). Exposure was performed at a dose such that the line width of the cured resist pattern after exposure and development of the L (line) / S (space) = 10 μm / 10 μm portion of the pattern was 10 μm. Examples 19 and 20 involved exposure with i-line monochromatic light using a segmented projection exposure apparatus (UX2003 SM-MS04, manufactured by Ushio Inc., using an i-line bandpass filter) with a predetermined mask pattern. Exposure was performed at a point where the line width of the cured resist pattern after exposure and development was 10 μm, specifically at the L (line) / S (space) = 10 μm / 10 μm section of the mask pattern.

[0115] heating: The evaluation substrates, one minute after exposure, were heated using a hot roll laminator (Asahi Kasei Corporation, AL-700). The roll temperature was 105°C, the air pressure was 0.30 MPa, and the lamination speed was 1 m / min.

[0116] developing: After peeling off the PET film (support film), an alkaline developer (manufactured by Fuji Kiko Co., Ltd., for dry film) was used to spray a 1% by mass Na2CO3 aqueous solution at 30°C from a full-cone type nozzle at a spray pressure of 0.15 MPa for a time twice the minimum development time. This dissolved and removed the unexposed portions of the photosensitive resin layer (development). After development, the substrate was washed with pure water for 1.5 times the development time, dewatered with an air knife, and then dried with hot air to obtain a substrate with a cured film for evaluation.

[0117] <5. Evaluation Method> Minimum development time: The shortest development time was defined as the time required for the photosensitive resin layer in the unexposed areas to completely dissolve after development using the method described above. A shorter minimum development time (in seconds) indicates better developability. The minimum development time was evaluated according to the following criteria. A: 25 seconds or less B: Over 25 seconds and under 30 seconds C: Over 30 seconds and under 40 seconds D: Over 40 seconds

[0118] Resolution evaluation: For this evaluation, a photosensitive resin laminate was laminated using the method described in <Lamination> above, and an evaluation substrate was used after 15 minutes. Positive or negative patterns with line / space = 1 / 1 of various sizes were exposed to the evaluation substrate. Subsequently, the substrate was developed using the method described in <Development> above. The smallest pattern width formed in the resulting patterns was observed with an optical microscope, and the resolution was evaluated according to the following criteria. A: Minimum pattern width is 5 μm or less B: Minimum pattern width exceeds 5 μm and is 6 μm or less. C: Minimum pattern width exceeds 6 μm and is 7 μm or less. D: Minimum pattern width exceeds 7 μm

[0119] Adhesion evaluation: For this evaluation, a photosensitive resin laminate was laminated using the method described in <Lamination> above, and an evaluation substrate was used after 15 minutes. Independent line patterns of various sizes were directly exposed to the evaluation substrate. Subsequently, the substrate was developed using the method described in <Development> above. The obtained patterns were observed with an optical microscope at 100x magnification, and adhesion was evaluated according to the following criteria. Normal formation refers to the absence of meandering and chipping in the resist. A: The smallest pattern formed normally is 8 μm or less. B: The smallest normally formed pattern is greater than 8 μm and less than or equal to 9 μm. C: The smallest normally formed pattern is greater than 9 μm and less than or equal to 10 μm. D: The smallest pattern formed normally exceeds 10 μm.

[0120] Press flow evaluation: A photosensitive resin laminate was cut into 2.5 cm squares, the cover film (protective film) was removed, and it was sandwiched between 10 cm squares of PET film. A hydraulic press heated to 40°C applied a force of 100 kg for 5 minutes. Afterwards, the width of the photosensitive resin layer overhang was measured in four directions (8 points in total), and the average value was calculated. This test was performed twice, and the average value was used as the press flow test value. The press flow was evaluated according to the following criteria. A: 100μm or less B: Exceeding 100 μm and 150 μm or less C: Exceeds 150 μm and 200 μm or less D: Exceeding 200 μm

[0121] Support material peel strength (tackiness): For this evaluation, an evaluation substrate was prepared by laminating a photosensitive resin laminate to one side using the method described in <Lamination> above, and left at 23°C and 50% relative humidity for 24 hours. Subsequently, a 1-inch wide support (PET film in this example) was peeled off at a speed of 100 mm / min at a 180° angle, and the strength at that time was measured using a Tensilon RTM-500 (manufactured by Toyo Seiki), and the peel strength was evaluated according to the following criteria. A: Peel strength is less than 3.0 gf D: Peel strength of 3.0 gf or higher

[0122] Peel test: In this evaluation, a 1.6 mm thick copper-clad laminate, constructed by laminating 35 μm rolled copper foil, was used as the evaluation substrate. The surface was smoothed by wet buffing. Polishing was performed twice using Scotch-Brite® HD #600 manufactured by 3M Ltd.

[0123] A polyethylene film was peeled off a photosensitive resin laminate with a photosensitive resin layer thickness of 25 μm, and then laminated onto a surface-prepared evaluation substrate using a hot roll laminator (Asahi Kasei Corporation, AL-700) under the conditions of a roll temperature of 105°C, an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min. Using an evaluation substrate that had been laminated for 15 minutes, a 4cm x 6cm rectangular pattern was exposed to the evaluation substrate using the method described in <Exposure> above, and then developed using the method described in <Development> above. The resulting evaluation substrate was cut to 4cm x 6cm, immersed in a stripping solution of R-101 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) at 50°C, and the time until the photosensitive resin layer was completely peeled off the evaluation substrate was measured. This was defined as the peeling time, and the peelability was evaluated according to the following criteria. A: Peeling time is 20 seconds or less. B: Peeling time is more than 20 seconds and 25 seconds or less. D: Peeling time exceeds 25 seconds.

[0124] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5]

[0125] The results shown in the table confirm that in this example, all items, including [minimum development time], [resolution], and [adhesion], were rated "B" or higher.

Claims

1. The following ingredients: (A) Alkali-soluble polymer, (B) Compounds having ethylenically unsaturated bonds, and (C) A photosensitive resin composition comprising a photopolymerization initiator, The above component (A) comprises at least the following comonomer components: (a) Methacrylic acid or acrylic acid, (b) A carboxylic acid different from the acid selected as component (a), and (c) Compounds having an aromatic structure or an alicyclic structure, It has constituent units derived from, In the above component (A), The mass ratio (a1) of the constituent units derived from the above component (a), The mass ratio (b1) of the constituent units derived from the above component (b), A photosensitive resin composition in which the ratio (mass ratio (a1) / mass ratio (b1)) is 1 / 10 to 10.

2. The photosensitive resin composition according to claim 1, wherein the ratio (mass ratio (a1) / mass ratio (b1)) is 1 / 8 to 8.

3. The photosensitive resin composition according to claim 1, wherein the (A) component further comprises (d) a structural unit derived from a hydroxyalkyl (meth)acrylic acid ester as a comonomer component.

4. The photosensitive resin composition according to claim 3, wherein the (d) component is hydroxyethyl methacrylate.

5. The photosensitive resin composition according to claim 1, wherein the component (a) is methacrylic acid.

6. The photosensitive resin composition according to claim 1, wherein component (b) is acrylic acid.

7. In the above component (A), The mass ratio (a1) of the constituent units derived from the above component (a), The photosensitive resin composition according to claim 1, wherein the total mass percentage (b1) of the constituent units derived from component (b) is 1 to 65% by mass.

8. The photosensitive resin composition according to claim 1, wherein the (c) component comprises styrene and / or benzyl (meth)acrylate.

9. The photosensitive resin composition according to claim 1, wherein the proportion of constituent units derived from component (c) in component (A) is 10 to 95% by mass.

10. The photosensitive resin composition according to claim 8, wherein the (c) component comprises styrene.

11. The photosensitive resin composition according to claim 10, wherein the proportion of constituent units derived from styrene in component (A) is 45 to 95% by mass.

12. Based on the total amount of solids in the aforementioned photosensitive resin composition, The above-mentioned component (A): 10 to 90% by mass, The above-mentioned component (B): 5 to 70% by mass, and Component (C): 0.01 to 20% by mass, A photosensitive resin composition according to claim 1, comprising the above.

13. The photosensitive resin composition according to claim 1, wherein component (A) comprises a plurality of alkali-soluble polymers.

14. The photosensitive resin composition according to claim 13, 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.

15. At least one of the alkali-soluble polymers contained in component (A) is The photosensitive resin composition according to claim 13, having constituent units derived from the above components (a) to (c), and satisfying the above ratio.

16. Among the alkali-soluble polymers contained in component (A) above, It has constituent units derived from the aforementioned components (a) to (c), The photosensitive resin composition according to claim 15, wherein the proportion of alkali-soluble polymer that satisfies the above ratio is 10% by mass or more.

17. The photosensitive resin composition according to claim 1, wherein the acid value of component (A) is 50 to 600 mg KOH / g.

18. The photosensitive resin composition according to claim 1, wherein component (B) comprises a compound having a bisphenol A structure and / or a hydrogenated bisphenol A structure.

19. The photosensitive resin composition according to claim 1, wherein component (B) contains a compound having three or more ethylenically unsaturated bonds in one molecule.

20. The photosensitive resin composition according to claim 1, wherein the (C) component comprises a hexaarylbiimidazole (HABI) compound.

21. The photosensitive resin composition according to claim 1, further comprising a leuco dye as component (D).

22. In the above component (A), The mass ratio (a1) of the constituent units derived from the above component (a), The mass ratio (b1) of the constituent units derived from the above component (b), The mass ratio (c1) of the constituent units derived from component (c) is given by the following formulas (1) to (3): 10≦(a1)+(b1)≦50... (1) 0.5≦(a1) / (b1)≦8.0... (2) 30≦(c1)≦80... (3) A photosensitive resin composition according to claim 1, satisfying the following conditions.

23. The aforementioned component (A) contains a plurality of alkali-soluble polymers, At least one of the alkali-soluble polymers contained in component (A) has a constituent unit derived from components (a) to (c), The photosensitive resin composition according to claim 22, wherein the mass ratios (a1), (b1), and (c1) satisfy formulas (1) to (3).

24. Among the alkali-soluble polymers contained in component (A) above, The photosensitive resin composition according to claim 23, wherein the proportion of alkali-soluble polymers having constituent units derived from the above components (a) to (c), and in which the mass ratios (a1), (b1), and (c1) satisfy the above formulas (1) to (3), is 10% by mass or more.

25. A photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from a photosensitive resin composition according to any one of claims 1 to 24.

26. The photosensitive resin laminate according to claim 25, wherein a protective film is provided on the side of the photosensitive resin layer opposite to the support.

27. A step of laminating the photosensitive resin laminate according to claim 25 or 26 onto a substrate, A step of exposing the photosensitive resin layer of the laminated photosensitive resin laminate, and A step of developing the exposed photosensitive resin layer, A method for forming a resist pattern, comprising the characteristics of a resist pattern.

28. The resist pattern formation method according to claim 27, wherein the exposure is performed by direct imaging exposure.

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