Resist resin composition, resist film manufacturing method, resist film and dry film

Abstract

A resist resin composition is provided that has good storage stability and can achieve improvements in heat resistance, flexibility, and resolution of a coating film. The resist resin composition contains an epoxy carboxylate (A), a novolac resin (B), and a quinone diazide group-containing compound (C). The epoxy carboxylate (A) is a reaction product of an epoxy resin (P) and a compound (Q) having a carboxy group.

Description

[Technical Field]

[0001] The present disclosure relates to a resist resin composition, a method for producing a resist film, a resist film, and a dry film. More specifically, the present disclosure relates to a positive resist resin composition, a method for producing a resist film from the resist resin composition, a resist film produced from the resist resin composition, and a dry film containing the resist resin composition. [Background technology]

[0002] Known image forming methods used for patterning semiconductor integrated circuits, liquid crystal display elements, circuit-forming substrates, etc. include etching a conductor layer using a resist film (hereinafter also referred to as a resist pattern) that protects the circuit pattern as a mask, and plating using the resist pattern as a plating mold.

[0003] Resin compositions for forming resist patterns are classified into negative and positive types. With a resin composition for a negative resist, a coating film is prepared from the resin composition, and the coating film is exposed to light and developed, thereby removing the portions of the coating film that are not irradiated with light, and the portions that are irradiated with light are cured and remain, thereby functioning as a resist film. On the other hand, with a resin composition for a positive resist, a coating film is prepared from the resin composition, and the coating film is exposed to light and developed, thereby removing the portions of the coating film that are irradiated with light, and the portions that are not irradiated with light remain, thereby functioning as a resist film.

[0004] Patent Document 1 discloses a positive-type photosensitive resin composition containing (A) an alkali-soluble novolak resin, (B) an alkali-soluble acrylic resin containing 5 to 40% by weight per repeating unit of a radically polymerizable unit having a carboxyl group and / or a phenolic hydroxyl group, and (C) a quinone diazide group-containing compound, in which the alkali-soluble acrylic resin (B) is contained in an amount of 5 to 50% by weight per 100 parts by weight of the alkali-soluble novolak resin (A). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-219536 Summary of the Invention [Problem to be solved by the invention]

[0006] From the viewpoint of improving the precision of resist patterns obtained from positive photosensitive resin compositions, high resolution of coating films is required.

[0007] Furthermore, the coating film may be heated during the process of forming a resist pattern. In this case, the shape of the resist pattern may be deformed or the edges of the resist pattern may become rounded. Therefore, in order to maintain the shape of the resist pattern, the coating film formed from the photosensitive resin composition is required to have heat resistance and flexibility.

[0008] Furthermore, if the compatibility of the components contained in the photosensitive resin composition is poor, the components may separate over time. A coating film made from a photosensitive resin composition in which the components have separated may have poor developability. Therefore, photosensitive resin compositions are required to have good storage stability.

[0009] An object of the present disclosure is to provide a resist resin composition that can achieve improved resolution, heat resistance, and flexibility of a coating film while maintaining good storage stability, a method for producing a resist film, a resist film, and a dry film. [Means for solving the problem]

[0010] A resist resin composition according to one embodiment of the present disclosure contains an epoxy carboxylate (A), a novolac resin (B), and a quinone diazide group-containing compound (C). The epoxy carboxylate (A) is a reaction product of an epoxy resin (P) and a compound (Q) having a carboxy group.

[0011] A method for producing a resist film according to one aspect of the present disclosure includes a disposing step of disposing a resin layer containing the resist resin composition on a substrate, an exposure step of partially exposing the resin layer to light, and a development step of removing the light-irradiated portions of the resin layer.

[0012] A resist film according to one embodiment of the present disclosure is made from the resist resin composition.

[0013] A dry film according to one aspect of the present disclosure contains the resist resin composition. [Effects of the Invention]

[0014] According to the present disclosure, it is possible to provide a resist resin composition that can achieve improved resolution, heat resistance, and flexibility of a coating film while maintaining good storage stability, a method for producing a resist film, a resist film, and a dry film. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of a coating film formed on a substrate from a resist resin composition according to the present disclosure. [Figure 2] FIG. 2 is a schematic cross-sectional view illustrating an example of a process for exposing a resin layer of a circuit-forming substrate using a coating film produced from a resist resin composition according to the present disclosure. [Figure 3] FIG. 3 is a schematic cross-sectional view showing an example of the state of the circuit-forming substrate after exposure, following FIG. [Figure 4] FIG. 4 is a schematic cross-sectional view showing an example of a developing step for the circuit-forming substrate, following FIG. [Figure 5] FIG. 5 is a cross-sectional view showing an example of a step of etching the circuit-forming board, following FIG. [Figure 6] FIG. 6 is a schematic cross-sectional view showing another example of a circuit-forming substrate using a coating film produced from a resist resin composition according to the present disclosure. [Figure 7]FIG. 7 is a schematic cross-sectional view of the circuit-forming substrate of FIG. 6 on which a protective film is formed. [Figure 8] 8A to 8C are schematic cross-sectional views showing an example of a process for etching the circuit-forming substrate of FIG. DETAILED DESCRIPTION OF THE INVENTION

[0016] Embodiments of the present disclosure will be described. Note that the following embodiments are merely a portion of various embodiments of the present disclosure. Furthermore, the following embodiments can be modified in various ways depending on the design, etc., as long as the object of the present disclosure can be achieved. Although the mechanism of action in the embodiments may be described below, the description of the mechanism of action includes an explanation based on speculation, and the present disclosure is not bound by the description of the mechanism of action. In the following description, "(meth)acryl" is a generic term that is a higher-level concept of "acryl" and "methacryl", and refers to "acryl" or "methacryl", or "acryl" and "methacryl". For example, a "(meth)acryloyl group" refers to an acryloyl group or a methacryloyl group, or an acryloyl group and a methacryloyl group.

[0017] 1. Overview The resist resin composition according to the embodiment (hereinafter also referred to as composition (X)) contains an epoxy carboxylate (A), a novolac resin (B), and a quinone diazide group-containing compound (C). The epoxy carboxylate (A) is a reaction product of an epoxy resin (P) and a compound (Q) having a carboxy group.

[0018] Because composition (X) has the above-mentioned constitution, it can realize improvements in the resolution, heat resistance, and flexibility of the coating film while maintaining good storage stability. The reason why composition (X) can exhibit the above-mentioned effects is not precisely clear, but is presumed to be due to the following reasons.

[0019] Composition (X) contains three specific components: an epoxy carboxylate (A), a novolak resin (B), and a quinone diazide group-containing compound (C), which enhances the resolution of the coating film.

[0020] The epoxy carboxylate (A) is a reaction product of the epoxy resin (P) and the compound (Q) having a carboxy group, and therefore the epoxy carboxylate (A) can impart high flexibility to the coating film.

[0021] Furthermore, the epoxy carboxylate (A) and the novolac resin (B) can have high compatibility. Therefore, even if the composition (X) is stored for a long period of time, the epoxy carboxylate (A) and the novolac resin (B) are unlikely to separate. In other words, the storage stability of the composition (X) is improved.

[0022] The novolak resin (B) has an aromatic ring, which allows it to have high heat resistance, thereby improving the heat resistance of the coating film.

[0023] Due to this mechanism, composition (X) is able to exhibit the above-mentioned effects. Resolution refers to the absence of chips or cracks in the pattern formed when a coating film made from composition (X) is exposed and developed, or the absence of line chatter. Developability refers to the ability to dissolve in a developer. Heat resistance refers to the ability of a coating film made from composition (X) to maintain its shape before and after heating. Flexibility refers to the resistance of a coating film made from composition (X) to cracks or breaks when bent. Storage stability refers to the resistance of components contained in composition (X) to separation, resulting in the resistance of the developability of the light-irradiated portion of the coating film to deteriorate over time.

[0024] Composition (X) can be particularly suitably used for preparing a resist film. More specifically, composition (X) can be used to prepare a patterned resist film. Here, "patterned" means that a coating film prepared from composition (X) is exposed to light and then developed to form a predetermined resist pattern.

[0025] 2.Details 2.1 Ingredients (epoxycarboxylate) The epoxy carboxylate (A) is a reaction product (hereinafter also referred to as reaction product (a1)) between an epoxy resin (P) and a compound (Q) having a carboxy group (hereinafter also referred to as compound (Q)). The epoxy carboxylate (A) is formed by a modification reaction of the epoxy resin (P) with the compound (Q). More specifically, the epoxy resin (P) may have an epoxy group, and the reaction product (a1) may be formed by the reaction of the epoxy group with a carboxy group of the compound (Q). The reaction product (a1) formed by such a reaction may have a hydroxy group. The hydroxy group can increase the solubility of a coating film prepared from the composition (X) in alkaline solutions, particularly aqueous solutions. This can improve the developability of the coating film in the light-irradiated areas.

[0026] The epoxy resin (P) contains, for example, at least one selected from the group consisting of aliphatic epoxy resins and aromatic epoxy resins. The epoxy resin (P) preferably contains an aliphatic epoxy resin. In this case, the flexibility and resolution of the coating film can be further improved. The epoxy resin (P) contains, for example, at least one selected from the group consisting of bisphenol-type epoxy resins, biphenyl-type epoxy resins, glycidyl ether-type epoxy resins, glycidyl ester-type epoxy resins, cresol novolac-type epoxy resins, phenol novolac-type epoxy resins, alicyclic epoxy resins, and bisphenol fluorene-type epoxy resins. The epoxy resin (P) preferably contains a glycidyl ester-type epoxy resin. In this case, the effects of the embodiment can be more effectively exhibited.

[0027] The epoxy resin (P) preferably contains a copolymer (hereinafter also referred to as copolymer (P1)) of a monomer (M1) having an epoxy group and an ethylenically unsaturated group (hereinafter also referred to as monomer (M1)) and a monomer (M2) having an ethylenically unsaturated group different from the monomer (M1) (hereinafter also referred to as monomer (M2)). In this case, the compatibility between the epoxy carboxylate (A) and the novolac resin (B) can be further improved. The ratio of copolymer (P1) to the epoxy resin (P) is preferably 25% by mass or more, more preferably 50% by mass or more, and even more preferably 100% by mass.

[0028] The copolymer (P1) can be produced by radical polymerization of the monomer (M1) and the monomer (M2). A radical polymerization initiator may be used during radical polymerization. The radical polymerization initiator is a compound capable of generating radicals when exposed to heat or light. The radical polymerization initiator includes at least one selected from the group consisting of azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis(2-cyclopropylpropionitrile), 2,2-azobis(2,4-dimethyldimethylvaleronitrile), and dimethyl 2,2-azobisisobutyrate; and organic peroxide polymerization initiators such as benzoyl peroxide, di-tert-butyl peroxide, and cumene hydroperoxide. A chain transfer agent may be used during radical polymerization to adjust the degree of polymerization of the copolymer (P1). The chain transfer agent includes at least one selected from the group consisting of unsaturated hydrocarbon compounds such as α-methylstyrene dimer, α-terpinene, dipentene, and terpinolene; mercaptan compounds such as n-butyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, and 2-ethylhexyl thioglycolate; and halogen compounds such as carbon tetrachloride, methylene chloride, and bromoform.

[0029] The monomer (M1) includes at least one selected from the group consisting of, for example, glycidyl (meth)acrylate, epoxybutyl (meth)acrylate, and epoxycyclohexyl (meth)acrylate. It is particularly preferable that the monomer (M1) includes glycidyl (meth)acrylate. In this case, the flexibility and resolution of the coating film can be further improved.

[0030] Monomer (M2) includes at least one selected from the group consisting of radically polymerizable compounds, monofunctional (meth)acrylates, and polyfunctional (meth)acrylates. Examples of the radically polymerizable compound include at least one selected from the group consisting of styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylnaphthalene, propene, butene, vinylcyclohexane, (meth)acrylonitrile, α-chloro(meth)acrylonitrile, α-ethyl(meth)acrylonitrile, vinylidene cyanide, maleimide, N-alkylmaleimide, and N-phenylmaleimide. The monofunctional (meth)acrylate includes at least one selected from the group consisting of, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, isoamyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and isobornyl (meth)acrylate.The polyfunctional (meth)acrylate includes at least one selected from the group consisting of, for example, ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate.

[0031] Copolymer (P1) may have a structural unit derived from monomer (M1) (hereinafter also referred to as structural unit (U1)) and a structural unit derived from monomer (M2) (hereinafter also referred to as structural unit (U2)). The proportion of structural unit (U1) in copolymer (P1) is preferably 30% by mass or more and 90% by mass or less of all structural units constituting copolymer (P1). In this case, the flexibility and resolution of the coating film can be further improved. This proportion is more preferably 40% by mass or more, and even more preferably 50% by mass or more. This proportion is more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0032] The compound (Q) includes, for example, an aliphatic carboxylic acid compound. The number of carbon atoms in the aliphatic carboxylic acid compound excluding the carboxy group is preferably 1 or more and 6 or less. In this case, the effects of the embodiment can be more effectively exhibited. The compound (Q) may also have an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a (meth)acryloyl group, an allyl group, and a vinyl group. Among these, a (meth)acryloyl group is preferred. In this case, the effects of the embodiment can be more effectively exhibited. A coating film made of the composition (X) can be used as a mask for protecting a conductor layer when etching a conductor layer provided on a circuit-forming substrate or the like. For example, when the compound (Q) has a (meth)acryloyl group, the resistance of the coating film made of the composition (X) to an etching solution can be improved.

[0033] Compound (Q) includes a compound (Q1) having an ethylenically unsaturated group (hereinafter also referred to as compound (Q1)). Compound (Q1) includes at least one selected from the group consisting of, for example, (meth)acrylic acid, crotonic acid, cinnamic acid, carboxymethyl (meth)acrylate, carboxyethyl (meth)acrylate, carboxycyclohexyl (meth)acrylate, carboxyphenyl (meth)acrylate, carboxybenzyl (meth)acrylate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl tetrahydrophthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxyethyl succinate, and ω-carboxy-polycaprolactone mono(meth)acrylate. Compound (Q1) preferably includes (meth)acrylic acid. In this case, the effects of the embodiment can be particularly well exhibited. Compound (Q) may contain a compound (hereinafter also referred to as compound (Q2)) having a carboxy group different from that of compound (Q1) instead of or in addition to compound (Q1). Compound (Q2) includes, for example, at least one selected from the group consisting of ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, and octanoic acid.

[0034] For example, the epoxy carboxylate (A) comprises an adduct (hereinafter also referred to as adduct (R)) of at least one of a polybasic acid and its anhydride to the reaction product (a1) of the epoxy resin (P) and the compound (Q). For example, the adduct (R) can be produced by reacting a hydroxy group in the reaction product (a1) with at least one of a polybasic acid and its anhydride. The adduct (R) formed by such a reaction can have a carboxy group. The carboxy group can further increase the solubility of a coating film prepared from the composition (X) in alkaline solutions, particularly aqueous solutions. This can further improve the developability of the light-irradiated portions of the coating film. Preferably, the adduct (R) comprises an adduct of a polybasic acid anhydride to the reaction product (a1).

[0035] In the reaction of the reaction product (a1) with at least one of a polybasic acid and its anhydride, the polybasic acid and its anhydride are preferably used in an amount such that the acid value of the epoxy carboxylate (A) is 30 mgKOH / g or more and 160 mgKOH / g or less. If the acid value is 30 mgKOH / g or more, the developability of the light-irradiated portion of the coating film can be further improved. If the acid value is 160 mgKOH / g or less, the developer resistance of the non-light-irradiated portion of the coating film is well maintained. The developer resistance refers to the resistance of the coating film to corrosion when contacted with a developer. The acid value is more preferably 40 mgKOH / g or more, and even more preferably 50 mgKOH / g or more. The acid value is more preferably 120 mgKOH / g or less, and even more preferably 90 mgKOH / g or less. The polybasic acid and anhydride thereof may include at least one selected from the group consisting of aliphatic carboxylic acids or anhydrides thereof, such as succinic acid, glutaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, and 1,2,3,4-butanetetracarboxylic acid; alicyclic carboxylic acids or anhydrides thereof, such as tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid; and aromatic carboxylic acids or anhydrides thereof, such as phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid. The polybasic acid and its anhydride preferably include at least one selected from the group consisting of tetrahydrophthalic anhydride and hexahydrophthalic anhydride, in which case the effects of the embodiment can be more effectively exhibited.

[0036] The weight-average molecular weight of the epoxy carboxylate (A) is preferably 1,000 or more and 15,000 or less. In this case, the resolution of the coating film is particularly improved, and the storage stability of the composition (X) is likely to be particularly good. The weight-average molecular weight is more preferably 1,500 or more, even more preferably 2,000 or more, and particularly preferably 3,000 or more. The weight-average molecular weight is more preferably 12,000 or less, even more preferably 10,000 or less, and particularly preferably 8,000 or less.

[0037] The weight-average molecular weight refers to the weight-average molecular weight measured using gel permeation chromatography (GPC) in terms of standard polystyrene, and can be measured under the following conditions.

[0038] GPC equipment: SHIMADZU SIL-20ACHT Column: SHODEX GPC KF-801 KF-803 KF-805 Mobile phase: THF Flow rate: 1ml / min Column temperature: 40℃ Detector: Differential refractive index detector (Novolac resin) The novolac resin (B) has one or more phenolic hydroxyl groups per molecule. In other words, the novolac resin (B) is alkali-soluble. The novolac resin (B) can be obtained by reacting a phenol with a condensing agent in the presence of an acid catalyst. It is preferable to react 1 mole of the phenol with 0.5 moles or more and 1.0 moles or less of the condensing agent.

[0039] Examples of phenols include cresols such as phenol, o-cresol, m-cresol, and p-cresol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; alkylphenols such as 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; 2,3, The compound contains at least one compound selected from the group consisting of trialkylphenols such as 5-trimethylphenol and 3,4,5-trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol and phloroglucinol; alkylpolyhydric phenols such as alkylresorcinol, alkylcatechol and alkylhydroquinone (all of the alkyl groups have 1 to 4 carbon atoms); naphthols such as α-naphthol and β-naphthol; biphenols such as 4,4'-biphenol; and bisphenols such as bisphenol A.

[0040] Among these, the phenols preferably contain at least one of m-cresol and p-cresol, and more preferably both. That is, the novolak resin (B) preferably has at least one of an m-cresol skeleton and a p-cresol skeleton, and more preferably both an m-cresol skeleton and a p-cresol skeleton. When the phenols contain both m-cresol and p-cresol, the mass ratio of m-cresol to p-cresol is preferably in the range of 3 / 7 to 8 / 2. When this mass ratio is 3 / 7 or more, the resolution of the coating film can be further improved. Furthermore, when this mass ratio is 8 / 2 or less, the enhanced heat resistance of the coating film can be maintained.

[0041] The condensing agent includes, for example, at least one aldehyde selected from the group consisting of formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, and the like.

[0042] The acidic catalyst may be a catalyst that can create an appropriate acidic condition, and includes at least one acid selected from the group consisting of inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and p-toluenesulfonic acid; and metal salts such as zinc acetate.

[0043] The softening point of the novolac resin (B) is preferably 140°C or higher. In this case, the heat resistance of the coating film produced from the composition (X) can be particularly enhanced. Specifically, when the softening point of the novolac resin (B) is 140°C or higher, the resist pattern is less likely to deform or the edges of the resist pattern become rounded when exposed to heat, making it easier to maintain the shape of the resist pattern. The softening point of the novolac resin (B) is more preferably 145°C or higher, and even more preferably 150°C or higher. The upper limit of the softening point of the novolac resin (B) is not particularly limited, but is, for example, 200°C or lower. The softening point of the novolac resin (B) can be adjusted by appropriately adjusting the components, composition ratios, and reaction conditions of the phenols, condensing agent, acid catalyst, and optional additives described above, and can be measured by the ring and ball method (JIS-K 7234).

[0044] The weight-average molecular weight of the novolac resin (B) is preferably 10,000 or more and 50,000 or less. In this case, the developability of the light-irradiated portion of the coating film is improved, and the resolution and heat resistance of the coating film can be further improved. This weight-average molecular weight is more preferably 11,000 or more, and even more preferably 12,000 or more. This weight-average molecular weight is more preferably 30,000 or less, and even more preferably 20,000 or less. The weight-average molecular weight of the novolac resin (B) can be measured under appropriate conditions using a GPC measurement device.

[0045] The proportion of the novolak resin (B) relative to the total solid content of the composition (X) is preferably 20% by mass or more and 80% by mass or less. In this case, the coating film prepared from the composition (X) can maintain higher heat resistance, and the developer resistance of the non-irradiated portions of the coating film can be further improved. This proportion is more preferably 28% by mass or more, and even more preferably 35% by mass or more. This proportion is more preferably 68% by mass or less, and even more preferably 55% by mass or less. The solid content here refers to the total amount of all components, excluding components such as organic solvents that volatilize during the process of preparing a coating film from the resist resin composition.

[0046] The mass ratio of the epoxy carboxylate (A) to the novolac resin (B) is preferably 10 / 90 or more and 80 / 20 or less. In this case, the compatibility between the epoxy carboxylate (A) and the novolac resin (B) can be further improved. This mass ratio is more preferably 20 / 80 or more and 70 / 30 or less, and even more preferably 30 / 70 or more and 60 / 40 or less.

[0047] (Quinonediazide-containing compounds) Composition (X) contains a quinone diazide group-containing compound (C). For example, when composition (X) is irradiated with light, the quinone diazide group-containing compound (C) may undergo photolysis to produce an alkali-soluble compound. This may enhance the developability of the light-irradiated portion of the coating film. Furthermore, the azide group of the quinone diazide group-containing compound (C) may form a hydrogen bond with the phenolic hydroxyl group of the novolac resin (B), thereby eliminating the alkali-solubility of the novolac resin (B). As a result, the developer resistance of the non-irradiated portion of the coating film prepared from composition (X) may be enhanced.

[0048] The quinone diazide group-containing compound (C) may be, for example, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2 ,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2,3,3',4,4',5'-hexahydroxybenzophenone, and other polyhydroxybenzophenones; bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4 bis[(poly)hydroxyphenyl]alkanes such as 4,4'-{1-[4-[2-(4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol, 3,3'-dimethyl-{1-[4-[2-(3-methyl-4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol; tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenyl tris(hydroxyphenyl)methanes or methyl-substituted derivatives thereof, such as bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, and bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane;Bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes or their methyl-substituted derivatives, such as bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, and bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane; compounds having a hydroxyl group or an amino group, such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, and 4,4'-diaminobenzophenone;and at least one compound selected from the group consisting of a complete ester compound, a partial ester compound, an amidation product, or a partial amidation product of a novolak, a pyrogallol-acetone resin, a homopolymer of p-hydroxystyrene, or a copolymer of a monomer copolymerizable therewith, with a quinone diazide group-containing sulfonic acid such as naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, or orthoanthraquinone diazide sulfonic acid;

[0049] The quinone diazide group-containing sulfonic acid used as the quinone diazide group-containing compound (C) is not particularly limited, but preferred examples include naphthoquinone diazide sulfonic acids such as naphthoquinone-1,2-diazide-5-sulfonic acid and naphthoquinone-1,2-diazide-4-sulfonic acid. When these compounds are incorporated as the quinone diazide group-containing compound (C) into a positive-type photosensitive resin composition, the developability of the irradiated portions of the coating film can be further improved, and the developer resistance of the non-irradiated portions of the coating film can be further improved.

[0050] The content of the quinone diazide group-containing compound (C) relative to 100 parts by mass of the total of the epoxy carboxylate (A) and the novolac resin (B) is preferably 5 parts by mass or more and 40 parts by mass or less. In this case, the developability of the irradiated portions of the coating film can be further improved, and the developer resistance of the non-irradiated portions of the coating film can be further improved. This content is more preferably 6 parts by mass or more, and even more preferably 7 parts by mass or more. This content is more preferably 35 parts by mass or less, and even more preferably 30 parts by mass or less.

[0051] (Polyhydroxystyrene) The composition (X) preferably further contains polyhydroxystyrene (D), which can impart greater flexibility to the coating film.

[0052] The polyhydroxystyrene (D) can be obtained, for example, by polymerizing a monomer of hydroxystyrene or a hydroxystyrene derivative. Specifically, the polyhydroxystyrene (D) contains a polymer of at least one compound selected from the group consisting of 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, and a hydroxystyrene derivative. The polyhydroxystyrene (D) may contain, for example, a copolymer of hydroxystyrene and a hydroxystyrene derivative.

[0053] The hydroxystyrene derivative has a structure in which at least one hydrogen atom on the aromatic ring of hydroxystyrene is substituted with a substituent, and includes, for example, at least one compound selected from the group consisting of α-methyl-4-hydroxystyrene, α-methyl-3-hydroxystyrene, α-methyl-2-hydroxystyrene, α-ethyl-4-hydroxystyrene, α-ethyl-3-hydroxystyrene, and α-ethyl-2-hydroxystyrene.

[0054] The polyhydroxystyrene (D) more preferably contains at least one selected from the group consisting of hydroxystyrene homopolymers and 4-hydroxystyrene homopolymers, in which case the polyhydroxystyrene (D) can impart even greater flexibility to the coating film.

[0055] The weight-average molecular weight of the polyhydroxystyrene (D) is preferably 1,000 or more and 50,000 or less. In this case, the polyhydroxystyrene (D) can impart particularly high flexibility to the coating film. The weight-average molecular weight is more preferably 3,000 or more. The weight-average molecular weight is more preferably 35,000 or less.

[0056] The content of polyhydroxystyrene (D) is preferably 0.1 to 25 parts by mass per 100 parts by mass of the total of the epoxy carboxylate (A) and the novolac resin (B). In this case, the storage stability of the composition (X) is likely to be improved, and the flexibility and resolution of the coating film can be further enhanced. This content is more preferably 0.2 parts by mass or more, even more preferably 0.5 parts by mass or more, and particularly preferably 1 part by mass or more. This content is more preferably 20 parts by mass or less, even more preferably 18 parts by mass or less, and particularly preferably 16 parts by mass or less.

[0057] (organic solvent) The composition (X) may contain an organic solvent. The organic solvent is used for the purposes of liquefying or varnish-forming the composition (X), adjusting the viscosity, adjusting the coatability, adjusting the film-forming properties, etc.

[0058] The organic solvent may include at least one selected from the group consisting of linear, branched, secondary, or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol, and ethylene glycol; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; petroleum-based aromatic mixed solvents such as the Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.) and the Solvesso series (manufactured by Exxon Chemical Co., Ltd.); cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol; alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol ethyl methyl ether; alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate and propylene glycol methyl ether acetate; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, and carbitol acetate; and dialkyl glycol ethers. The organic solvents may be used alone or in any combination of two or more kinds in any proportion.

[0059] When composition (X) contains an organic solvent, the proportion of the organic solvent is preferably adjusted appropriately depending on the method for applying composition (X) to a substrate, etc. In particular, the proportion of the organic solvent is preferably an amount such that the solid content of composition (X) is 5 to 100 mass %, more preferably 15 to 70 mass %.

[0060] (additives) Composition (X) may contain a component (hereinafter, additive (E)) different from the components described above, as long as the effects of the present disclosure are not impaired.

[0061] The additive (E) may contain at least one component selected from the group consisting of a surfactant, an adhesion promoter, a rheology control agent, a colorant, a thixotropic agent, a polymerization inhibitor, an antihalation agent, a flame retardant, an antioxidant, and a polymer dispersant.

[0062] The surfactant can improve the coating properties, defoaming properties, leveling properties, etc. of the composition (X). As the surfactant, various surfactants such as acrylic, silicone, and fluorine-based surfactants can be used.

[0063] Examples of adhesion promoters include guanamine derivatives such as acetoguanamine (2,4-diamino-6-methyl-1,3,5-triazine) and benzoguanamine (2,4-diamino-6-phenyl-1,3,5-triazine); S-triazine derivatives such as 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct; silane coupling agents; and melamine derivatives.

[0064] The rheology control agent can adjust the viscosity of composition (X). Examples of the rheology control agent include urea-modified medium-polarity polyamide (Big Chemie Japan Co., Ltd., product numbers BYK-430 and BYK-431), polyhydroxycarboxylic acid amide (Big Chemie Japan Co., Ltd., product number BYK-405), modified urea (Big Chemie Japan Co., Ltd., product numbers BYK-410, BYK-411, and BYK-420), polymeric urea derivative (Big Chemie Japan Co., Ltd., product number BYK-415), urea-modified urethane (Big Chemie Japan Co., Ltd., product number BYK-425), polyurethane (Big Chemie Japan Co., Ltd., product number BYK-428), castor oil wax, polyethylene wax, polyamide wax, bentonite, kaolin, and clay.

[0065] 2.2 Manufacturing method Composition (X) can be prepared by any suitable method. For example, composition (X) can be prepared by mixing and stirring the components (raw materials) that can be contained in composition (X) described above. Alternatively, dispersion can be performed using a dispersing device such as a dissolver or homogenizer. Composition (X) can also be prepared by kneading using an appropriate kneading method using a three-roll mill, ball mill, sand mill, or the like. When the raw materials contain liquid components, low-viscosity components, etc., composition (X) can be prepared by first kneading the raw materials excluding the liquid components, low-viscosity components, etc. to prepare a mixture, and then adding and mixing the liquid components, low-viscosity components, etc. to the resulting mixture. When composition (X) contains a solvent, some or all of the solvent can be first mixed among the raw materials, and then mixed with the remaining raw materials. Alternatively, composition (X) can be prepared by filtering the mixture of the above raw materials through a mesh, membrane filter, or the like.

[0066] 2.3 Form The composition (X) can take various forms. For example, a dry film containing the composition (X) can be prepared by applying the composition (X) to a support and drying it as necessary. The dry film can be used by peeling off the support and attaching it to an object. For example, when the object is a substrate used in a printed wiring board, the dry film can be used as a resist film.

[0067] 3.Application examples of resist resin compositions 3.1 Circuit formation substrate A coating film made from composition (X) can be used to prepare a circuit-forming substrate 100 for a printed wiring board.

[0068] For example, the resin layer 3 can be formed by applying the composition (X) onto the substrate 1 and then drying it. In this manner, a circuit-forming substrate 100 can be produced, which includes the substrate 1 and the resin layer 3 disposed on the substrate 1. Note that the resin layer 3 may also be formed by disposing a dry film containing the composition (X) on the substrate 1. Then, a resist film 30 made of the composition (X) can be produced on the substrate 1. In producing the resist film 30 from the resin layer 3, for example, the resin layer 3 can be partially exposed to light and then developed, thereby producing a patterned resist film 30 on the substrate 1. The thickness of the resist film 30 is not particularly limited, but can be, for example, 1 μm or more and 10 μm or less.

[0069] In this embodiment, the circuit-forming substrate 100 includes a core material 10 and a resin layer 3 disposed on the core material 10. The core material 10 includes a base material 1 and a conductor layer 2 disposed on the base material 1. The resin layer 3 is disposed on the base material 1 via the conductor layer 2 (see FIG. 1).

[0070] The substrate 1 may be a rigid substrate such as a glass epoxy substrate, a glass composite substrate, a Teflon (registered trademark) substrate, a silicon wafer, a metal substrate, or a ceramic substrate, or a flexible substrate such as a plastic substrate, a polyimide substrate, or a polyester substrate. The conductor layer 2 is made of a material having appropriate electrical conductivity. The conductor layer 2 is, for example, a metal foil. The metal foil includes, for example, a copper foil. The core material 10 may be a flexible substrate obtained by laminating the substrate 1 and the conductor layer 2 on the substrate 1, which is a polyimide substrate, by laminating, for example, a metal foil as the conductor layer 2.

[0071] The thickness of the resin layer 3 may be appropriately set depending on the circuit-forming substrate 100 and the intended use of the printed wiring board, but is preferably 1 μm or more and 30 μm or less, and more preferably 10 μm or less. Since the resin layer 3 contains the composition (X), it can have high heat resistance. Therefore, even if processing involving heating is performed during the manufacturing process of the printed wiring board, the resin layer 3 is less likely to change shape, and thus the conductor layer 2 of the circuit-forming substrate 100 can be adequately protected.

[0072] 3.2 Resist film manufacturing method Next, a method for producing the resist film 30 will be described with reference to Fig. 2 to Fig. 8. The method for producing the resist film 30 includes a step of applying a composition (X) to a substrate 1 to form a resin layer 3 (application step), a step of partially exposing the resin layer 3 to light (exposure step), and a step of removing the light-irradiated portion of the resin layer 3 (development step).

[0073] (preparation process) In the embodiment, the method may include a step (preparation step) of preparing a core material 10. In the preparation step, the core material 10 is prepared, which includes a substrate 1 and a conductor layer 2 disposed on the substrate 1. The substrate 1, the conductor layer 2, and the core material 10 may have the configurations already described.

[0074] (Placement process) Next, a resin layer 3 containing composition (X) is placed on the substrate 1. For example, the resin layer 3 can be formed by applying composition (X) to the substrate 1 and drying it. In this embodiment, a core material 10 is used that includes a substrate 1 and a conductor layer 2 on the substrate 1. Therefore, composition (X) is applied to the conductor layer 2 and then dried appropriately to form the resin layer 3 on the substrate 1 via the conductor layer 2. The method for applying composition (X) may be any appropriate method, such as dipping, spraying, spin coating, roll coating, curtain coating, or screen printing. The drying conditions for composition (X) can be adjusted appropriately depending on the composition of composition (X), the type and amount of organic solvent, if any, used, and the like. For example, the heating temperature is preferably 80°C or higher and 150°C or lower. In this case, the heating time is preferably 180 seconds or higher and 1800 seconds or lower, and more preferably 240 seconds or higher and 600 seconds or lower.

[0075] By undergoing the arrangement process and the like in this manner, a circuit-forming substrate 100 can be produced that includes a base material 1 and a resin layer 3 disposed on the base material 1 (see FIG. 1). When the circuit-forming substrate 100 includes a core material 10 that is a flexible base material such as a polyimide substrate, as in the embodiment, the resin layer 3 disposed on the core material 10 has high flexibility, so that even when the circuit-forming substrate 100 is processed into a roll, cracks are unlikely to occur in the resin layer 3, and chips are also unlikely to occur in the resin layer 3. In other words, the circuit-forming substrate 100 according to the embodiment has the advantage that it can be stored in a roll.

[0076] (Exposure process) Next, the resin layer 3 is exposed to light. More specifically, a mask M having a predetermined circuit pattern is placed on the resin layer 3 side of the circuit-forming substrate 100, and light is irradiated through the mask M (see FIG. 2). The mask M is a phototool such as a mask film or a dry plate. The mask M has a light-transmitting portion Ma that transmits light and a light-shielding portion Mb that shields light. Therefore, the resin layer 3 is selectively irradiated with light. The composition (X) is a positive type. Therefore, the mask M is a positive type mask. When the coating film is irradiated with light through the mask M, the positions corresponding to the light-transmitting portions Ma of the mask M become exposed portions 31 of the resin layer 3, and the positions corresponding to the light-shielding portions Mb of the mask M become unexposed portions 32 of the resin layer 3 (see FIGS. 2 and 3). In this way, by interposing the mask M, the resin layer 3 can be selectively exposed to light to form light-irradiated portions (exposed portions 31) and unirradiated portions (unexposed portions 32).

[0077] The light irradiated onto the resin layer 3 may be light emitted from an appropriate light source. Examples of the light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a YAG laser, and an LED, which emit light with wavelengths of approximately 365 nm (i-line), 405 nm (h-line), and 435 nm (g-line). Alternatively, the light source may be an ArF excimer laser, a KrF excimer laser, an F2 excimer laser, an extreme ultraviolet (EUV), a vacuum ultraviolet (VUV), an electron beam (EB), an X-ray, or a soft X-ray. To prevent light of a specific wavelength from being irradiated onto the exposed portion 31 of the resin layer 3, a wavelength cut filter may be disposed between the mask M and the resin layer 3 or on the side of the mask M opposite the resin layer 3. The exposure method may be a method other than irradiating light through the mask M. For example, the resin layer 3 may be exposed by a so-called direct writing method, in which light emitted from a light source is irradiated only onto the portion of the resin layer 3 to be irradiated. The light source used in the direct writing method is selected from the group consisting of, for example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a YAG laser, an LED, g-line, h-line, i-line, and a combination of two or more of g-line, h-line, and i-line. In addition, when exposing the resin layer 3, an appropriate covering layer (not shown) may be provided on the resin layer 3.

[0078] (Development process) Next, the irradiated portions of the resin layer 3 are removed. More specifically, a resist film 30 can be produced from the resin layer 3 by subjecting the exposed resin layer 3 to a development process. The development process removes the exposed portions 31 of the resin layer 3. The unexposed portions 32 of the resin layer 3 remain, and the unexposed portions 32 become a patterned resist film 30 (see FIG. 4). In this way, a patterned resist film 30 is produced from the composition (X).

[0079] In the development process, an appropriate developer can be used depending on the composition of composition (X). The developer is, for example, a solution containing at least one selected from the group consisting of inorganic bases and organic bases. This solution contains at least one selected from the group consisting of water and lower alcohols. The inorganic base includes, for example, at least one selected from the group consisting of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and lithium hydroxide. The organic base includes, for example, at least one selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and tetramethylammonium hydroxide. The developer is preferably an alkaline aqueous solution containing an inorganic base, and particularly preferably an aqueous sodium hydroxide solution. In this case, an improvement in the working environment and a reduction in the burden of waste disposal can be achieved. The development process is not particularly limited, but for example, when a 1% by mass aqueous solution of sodium hydroxide is used, the circuit-forming substrate 100 having the core material 10 and the resin layer 3 is immersed and shaken in a liquid bath at a liquid temperature of 20°C or higher and 30°C or lower, and then removed and washed (rinsed) with water or the like.

[0080] Furthermore, a post-baking process may be performed after the development process. By performing the post-baking process, the etching resistance of the resist film 30 can be improved. The post-baking conditions can be adjusted as appropriate. The heating temperature at this time is preferably 100°C or higher and 180°C or lower. The resist film 30 is made of the composition (X). Therefore, the resist film 30 can have high heat resistance, and the shape of the resist film 30 is less likely to change due to heating during post-baking. This can prevent the line width formed by the resist film 30 from becoming thicker.

[0081] By following the above-described procedure, it is possible to manufacture the resist film 30. More specifically, it is possible to manufacture a circuit-forming substrate 101 from the circuit-forming substrate 100, which includes a patterned resist film 30 that partially covers the conductor layer 2 of the core material 10 (see FIG. 4).

[0082] 3.3 Etching In this embodiment, after the development step, unnecessary portions of the conductor layer 2 of the circuit-forming substrate 101 are removed (etched). In the etching, the circuit-forming substrate 101, on which the resist film 30 is partially formed on the conductor layer 2, is immersed in a liquid bath containing an etching solution. Then, the portions of the conductor layer 2 that are not covered with the resist film 30 are removed. In this way, conductor wiring 20 is produced from the conductor layer 2 (see FIG. 5).

[0083] The etching solution may be any etching solution having an appropriate composition, such as an aqueous solution of ferric chloride. After the circuit-forming substrate 101 is immersed in the liquid bath for a while, it is removed from the liquid bath, and any remaining etching solution is removed by washing with water, if necessary. The etching method described above is a wet etching method using a liquid phase, but is not limited to this, and dry etching using a gas phase may also be used.

[0084] By performing etching according to the above method, a circuit-forming substrate 102 can be produced, which includes a substrate 1, conductor wiring 20 disposed on the substrate 1, and a resist film 30 disposed on the conductor wiring 20 (see FIG. 5). The resist film 30 made of composition (X) is resistant to film loss (thinning of the coating film) and chipping. Therefore, the conductor wiring 20 can be adequately protected by the resist film 30.

[0085] 3.4 Stripping of resist film The resist film 30 on the circuit-forming substrate 102 fabricated by the above steps is stripped off with an appropriate stripping solution, thereby completing the production of a printed wiring board.

[0086] The stripping treatment is not particularly limited, but for example, when a 3% by mass aqueous solution of sodium hydroxide is used, the circuit-forming substrate 102 is immersed in a liquid bath at a liquid temperature of 30°C to 60°C, shaken, removed, and then washed (rinsed) with water or the like. The composition (X) contains an epoxy carboxylate (A). This appropriately enhances the solubility of the coating film made of the composition (X), i.e., the resist film 30, in alkaline solutions. As a result, the resist film 30 can be easily removed by treating the circuit-forming substrate 102 with the stripping solution.

[0087] 3.5 Other examples of circuit boards The substrate 1 included in the circuit-forming substrate 100 does not need to be flat. For example, a coating film made from the composition (X) can be used to produce a circuit-forming substrate 103 including a substrate 1 having an opening 12 (see FIG. 6). Electronic components and the like can be incorporated into the opening 12 of the substrate 1. In describing the circuit-forming substrate 103, explanations of the same configuration as the circuit-forming substrates 100, 101, and 102 will be omitted.

[0088] In the circuit-forming board 103, a core material 10 is prepared in the same manner as in the circuit-forming board 100. However, in the circuit-forming board 103, the core material 10 is produced by drilling a plurality of holes in a base material 1 to form openings 12, and then attaching a conductor layer 2 such as copper foil so as to cover the base material 1 and the plurality of openings 12. That is, in this modified example, the core material 10 includes a base material 1 having openings 12 and a conductor layer 2 on the base material 1.

[0089] The circuit-forming substrate 103 is also etched in the same manner as the circuit-forming substrate 101. However, the circuit-forming substrate 103 has an opening 12 formed in the base material 1. Therefore, before etching the circuit-forming substrate 103, a protective film 50 is formed on the side of the base material 1 opposite the resist film 30 (see FIG. 7). The protective film 50 prevents corrosion of the conductor layer 2, which is intended to remain, by the etching solution, thereby preventing defects from occurring in the desired circuit pattern. After the development process, a backing agent is applied to the surface of the core material 10 opposite the side on which the resist film 30 is formed, so as to cover the base material 1, the opening 12 of the base material 1, and the conductor layer 2. The backing agent is then heated to form the protective film 50 on the core material 10. If the resist film 30 has low heat resistance when the backing agent is heated, the resist film 30 may be damaged, which may result in defects in the conductor wiring 20 formed on the circuit-forming substrate 103. However, since the resist film 30 is made of the composition (X), it can have high heat resistance. Therefore, even if the circuit-forming substrate 103 is heated when the protective film 50 is formed, the resist film 30 is unlikely to be damaged.

[0090] Next, while the resist film 30 remains partially covering the surface of the core material 10 on which the conductor layer 2 is provided, the portion of the conductor layer 2 that is not covered by the resist film 30 is removed, thereby forming the conductor wiring 20 from the conductor layer 2. This allows the production of a circuit-forming substrate 103 that includes the base material 1, the conductor wiring 20 disposed on the base material 1, and the resist film 30 disposed on the conductor wiring 20 (see FIG. 8).

[0091] Then, the resist film 30 and the protective film 50 on the circuit-forming substrate 103 (see FIG. 8) produced by the above steps are stripped with an appropriate stripping solution, thereby producing a printed wiring board. The stripping treatment can be performed using the same method as that used to treat the circuit-forming substrate 102, but when using a 3 mass % aqueous sodium hydroxide solution, for example, the circuit-forming substrate 103 is immersed and shaken in a liquid bath at a liquid temperature of 30° C. to 60° C., and then removed and washed (rinsed) with water or the like.

[0092] The method for manufacturing the resist film 30 has been described. In the above explanation, the circuit-forming substrate 100 has been described as an example in which the resin layer 3 is disposed on the conductor layer 2 of the core material 10, but the present invention can also be applied to a case in which the resin layer 3 is disposed directly on the base material 1, that is, a case in which the conductor layer 2 is not disposed on the base material 1.

[0093] 3.6 Summary Although application examples of the coating film prepared from composition (X) have been described, the coating film can be used for various purposes other than preparing a circuit-forming substrate.

[0094] 4. Aspects As is clear from the above-described embodiment and modifications, the present invention includes the following aspects. In the following, reference numerals are given in parentheses only to clarify the correspondence with the embodiment.

[0095] The resist resin composition according to the first aspect of the present disclosure contains an epoxy carboxylate (A), a novolac resin (B), and a quinone diazide group-containing compound (C). The epoxy carboxylate (A) is a reaction product of an epoxy resin (P) and a compound (Q) having a carboxy group.

[0096] According to this embodiment, the resist resin composition has good storage stability, and the coating film can have improved resolution, heat resistance, and flexibility.

[0097] In the resist resin composition according to the second aspect of the present disclosure, the epoxy resin (P) comprises a copolymer of a monomer (M1) having an epoxy group and an ethylenically unsaturated group and a monomer (M2) having an ethylenically unsaturated group different from the monomer (M1).

[0098] In the resist resin composition according to the third aspect of the present disclosure, in the first or second aspect, the epoxy carboxylate (A) comprises an adduct of at least one of a polybasic acid and an anhydride thereof to a reaction product of an epoxy resin (P) and a compound (Q).

[0099] In the resist resin composition according to the fourth aspect of the present disclosure, in the second or third aspect, the monomer (M1) includes glycidyl (meth)acrylate.

[0100] In the resist resin composition according to the fifth aspect of the present disclosure, in any one of the first to fourth aspects, the compound (Q) includes a compound (Q1) having an ethylenically unsaturated group.

[0101] A sixth aspect of the present disclosure relates to a resist resin composition according to the fifth aspect, wherein the compound (Q1) includes (meth)acrylic acid.

[0102] A seventh aspect of the present disclosure relates to a resist resin composition in any one of the first to sixth aspects, wherein the mass ratio of the epoxy carboxylate (A) to the novolac resin (B) is 10 / 90 or more and 80 / 20 or less.

[0103] The resist resin composition according to an eighth aspect of the present disclosure is any one of the first to seventh aspects, wherein the weight average molecular weight of the epoxy carboxylate (A) is 1,000 or more and 15,000 or less.

[0104] A resist resin composition according to a ninth aspect of the present disclosure is any one of the first to eighth aspects, wherein the weight average molecular weight of the novolac resin (B) is 10,000 or more and 50,000 or less.

[0105] A resist resin composition according to a tenth aspect of the present disclosure is any one of the first to ninth aspects, further comprising polyhydroxystyrene (D).

[0106] A resist resin composition according to an eleventh aspect of the present disclosure is the tenth aspect, wherein the weight average molecular weight of the polyhydroxystyrene (D) is 1,000 or more and 50,000 or less.

[0107] A resist resin composition according to a twelfth aspect of the present disclosure is the tenth or eleventh aspect, wherein the polyhydroxystyrene (D) is 0.1 parts by mass or more and 25 parts by mass or less per 100 parts by mass of the total of the epoxy carboxylate (A) and the novolac resin (B).

[0108] A method for producing a resist film according to a thirteenth aspect of the present disclosure includes a placement step of placing a resin layer (3) containing a resist resin composition according to any one of the first to twelfth aspects on a substrate (1), an exposure step of partially exposing the resin layer (3), and a development step of removing the light-irradiated portion of the resin layer (3).

[0109] A resist film according to a fourteenth aspect of the present disclosure is made from a resist resin composition according to any one of the first to twelfth aspects.

[0110] The resist film of the fifteenth embodiment of the present disclosure is patterned in the fourteenth embodiment.

[0111] A dry film according to a sixteenth aspect of the present disclosure contains the resist resin composition according to any one of the first to twelfth aspects. [Example]

[0112] Specific examples of the embodiment will be presented below, but the embodiment is not limited to the following examples.

[0113] 1. Ingredients The components contained in the resist resin composition are described below.

[0114] (Epoxycarboxylate (A)) Synthesis of epoxy carboxylate solution A1 A four-neck flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate, 10 parts by mass of a polymerization initiator (2,2'-azobisisobutyronitrile), 60 parts by mass of glycidyl methacrylate, 10 parts by mass of methyl methacrylate, 5 parts by mass of t-butyl acrylate, 5 parts by mass of tert-butyl methacrylate, 10 parts by mass of benzyl methacrylate, and 10 parts by mass of N-phenylmaleimide. Polymerization was carried out for 9 hours at 95°C in a nitrogen atmosphere. Subsequently, 0.1 parts by mass of 4-methoxyphenol, 30.24 parts by mass of acrylic acid, 1 part by mass of triphenylphosphine, and 95.36 parts by mass of propylene glycol monomethyl ether acetate were added, and an addition reaction was carried out at 110°C for 24 hours while stirring with air bubbling, to obtain an epoxy carboxylate solution A1 having a polystyrene-equivalent weight average molecular weight of 6,200 and a solids concentration of 40% by weight.

[0115] Synthesis of epoxy carboxylate solution A2 A four-neck flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate, 10 parts by mass of a polymerization initiator (2,2'-azobisisobutyronitrile), 60 parts by mass of glycidyl methacrylate, 10 parts by mass of methyl methacrylate, 5 parts by mass of t-butyl acrylate, 5 parts by mass of tert-butyl methacrylate, 10 parts by mass of benzyl methacrylate, and 10 parts by mass of N-phenylmaleimide. Polymerization was carried out for 9 hours at 95°C in a nitrogen atmosphere. Next, 0.1 parts by mass of 4-methoxyphenol, 30.24 parts by mass of acrylic acid, 1 part by mass of triphenylphosphine, and 95.36 parts by mass of propylene glycol monomethyl ether acetate were added, and an addition reaction was carried out at 110°C for 24 hours while stirring and air bubbling. Subsequently, 31.92 parts by mass of tetrahydrophthalic anhydride and 48 parts by mass of propylene glycol monomethyl ether acetate were added, and a reaction was carried out at 80°C for 3 hours while stirring and air bubbling, thereby obtaining an epoxy carboxylate solution A2 having a polystyrene-equivalent weight average molecular weight of 7,000, an acid value of 73 mgKOH / g, and a solids concentration of 40% by mass.

[0116] Synthesis of epoxy carboxylate solution A3 Into a four-neck flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate, 8 parts by mass of a polymerization initiator (2,2'-azobisisobutyronitrile), 70 parts by mass of glycidyl methacrylate, and 30 parts by mass of styrene were added. Polymerization was carried out in a nitrogen atmosphere at 95°C for 9 hours. Next, 0.1 parts by mass of 4-methoxyphenol, 35.28 parts by mass of acrylic acid, 1 part by mass of triphenylphosphine, and 102.92 parts by mass of propylene glycol monomethyl ether acetate were added, and an addition reaction was carried out at 110°C for 24 hours while stirring and air bubbling. Subsequently, 37.73 parts by mass of hexahydrophthalic anhydride and 56.6 parts by mass of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 80°C for 3 hours while stirring and air bubbling, yielding an epoxy carboxylate solution A3 having a polystyrene-equivalent weight average molecular weight of 9,800, an acid value of 80 mgKOH / g, and a solids concentration of 40% by mass.

[0117] Synthesis of epoxy carboxylate solution A4 A four-neck flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate, 12 parts by mass of a polymerization initiator (2,2'-azobisisobutyronitrile), 60 parts by mass of glycidyl methacrylate, 15 parts by mass of methyl methacrylate, 10 parts by mass of t-butyl acrylate, and 15 parts by mass of tert-butyl methacrylate. Polymerization was carried out for 9 hours at 95°C in a nitrogen atmosphere. Next, 0.1 parts by mass of 4-methoxyphenol, 30.24 parts by mass of acrylic acid, 1 part by mass of triphenylphosphine, and 95.36 parts by mass of propylene glycol monomethyl ether acetate were added, and an addition reaction was carried out at 110°C for 24 hours while stirring and air bubbling. Subsequently, 25.54 parts by mass of tetrahydrophthalic anhydride and 38.3 parts by mass of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 80°C for 3 hours while stirring and air bubbling, yielding an epoxy carboxylate solution A4 having a polystyrene-equivalent weight average molecular weight of 6,200, an acid value of 61 mgKOH / g, and a solids concentration of 40% by mass.

[0118] Synthesis of epoxy carboxylate solution A5 A four-neck flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate, 6 parts by mass of a polymerization initiator (2,2'-azobisisobutyronitrile), 60 parts by mass of glycidyl methacrylate, 15 parts by mass of methyl methacrylate, 10 parts by mass of t-butyl acrylate, and 15 parts by mass of tert-butyl methacrylate. Polymerization was carried out for 9 hours at 95°C in a nitrogen atmosphere. Next, 0.1 parts by mass of 4-methoxyphenol, 30.24 parts by mass of acrylic acid, 1 part by mass of triphenylphosphine, and 95.36 parts by mass of propylene glycol monomethyl ether acetate were added, and an addition reaction was carried out at 110°C for 24 hours while stirring and air bubbling. Subsequently, 25.54 parts by mass of tetrahydrophthalic anhydride and 38.3 parts by mass of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 80°C for 3 hours while stirring and air bubbling, yielding an epoxy carboxylate solution A5 having a polystyrene-equivalent weight average molecular weight of 10,500, an acid value of 61 mgKOH / g, and a solids concentration of 40% by mass.

[0119] Synthesis of epoxy carboxylate solution A6 A four-neck flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate, 4 parts by mass of a polymerization initiator (2,2'-azobisisobutyronitrile), 60 parts by mass of glycidyl methacrylate, 15 parts by mass of methyl methacrylate, 10 parts by mass of t-butyl acrylate, and 15 parts by mass of tert-butyl methacrylate. Polymerization was carried out for 9 hours at 95°C in a nitrogen atmosphere. Next, 0.1 parts by mass of 4-methoxyphenol, 30.24 parts by mass of acrylic acid, 1 part by mass of triphenylphosphine, and 95.36 parts by mass of propylene glycol monomethyl ether acetate were added, and an addition reaction was carried out at 110°C for 24 hours while stirring and air bubbling. Subsequently, 25.54 parts by mass of tetrahydrophthalic anhydride and 38.3 parts by mass of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 80°C for 3 hours while stirring and air bubbling, yielding an epoxy carboxylate solution A6 having a polystyrene-equivalent weight average molecular weight of 13,200, an acid value of 61 mgKOH / g, and a solids concentration of 40% by mass.

[0120] Synthesis of epoxy carboxylate solution A7 A four-neck flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer was charged with 283 parts by mass of propylene glycol monomethyl ether acetate, 211 parts by mass of cresol novolac epoxy resin (DIC Corporation, product number EPICLON N-680, epoxy equivalent 211 g / eq.), 0.2 parts by mass of 4-methoxyphenol, 72 parts by mass of acrylic acid, and 2 parts by mass of triphenylphosphine. The mixture was subjected to an addition reaction at 110°C for 24 hours with stirring and air bubbling. Subsequently, 60.8 parts by mass of tetrahydrophthalic anhydride and 232.7 parts by mass of propylene glycol monomethyl ether acetate were added, and the mixture was subjected to a reaction at 80°C for 3 hours with stirring and air bubbling. This produced an epoxy carboxylate solution A7 having a polystyrene-equivalent weight average molecular weight of 8,300, an acid value of 66 mgKOH / g, and a solids concentration of 40% by mass.

[0121] (Acrylic resin (A')) Synthesis of acrylic resin solution A'1 A four-neck flask equipped with a reflux condenser, thermometer, nitrogen inlet, and stirrer was charged with 125 parts by weight of propylene glycol monomethyl ether acetate, 0.3 parts by weight of α-methylstyrene dimer, 5 parts by weight of a polymerization initiator (2,2'-azobisisobutyronitrile), 25 parts by weight of methacrylic acid, 40 parts by weight of methyl methacrylate, and 35 parts by weight of octadecyl methacrylate. Polymerization was carried out in a nitrogen atmosphere at 80°C for 6 hours to obtain acrylic resin solution A'1 with a polystyrene-equivalent weight-average molecular weight of 21,000, an acid value of 162 mgKOH / g, and a solids concentration of 40% by weight.

[0122] Synthesis of acrylic resin solution A'2 A four-neck flask equipped with a reflux condenser, thermometer, nitrogen inlet, and stirrer was charged with 125 parts by weight of propylene glycol monomethyl ether acetate, 0.3 parts by weight of α-methylstyrene dimer, 5 parts by weight of a polymerization initiator (2,2'-azobisisobutyronitrile), 25 parts by weight of methacrylic acid, 40 parts by weight of methyl methacrylate, and 35 parts by weight of styrene. Polymerization was carried out in a nitrogen atmosphere at 80°C for 6 hours, yielding acrylic resin solution A'2 with a polystyrene-equivalent weight-average molecular weight of 18,000, an acid value of 162 mgKOH / g, and a solids concentration of 40% by weight.

[0123] Synthesis of acrylic resin solution A'3 A four-neck flask equipped with a reflux condenser, thermometer, nitrogen inlet, and stirrer was charged with 125 parts by weight of propylene glycol monomethyl ether acetate, 0.3 parts by weight of α-methylstyrene dimer, 10 parts by weight of a polymerization initiator (2,2'-azobisisobutyronitrile), 11 parts by weight of methacrylic acid, 54 parts by weight of methyl methacrylate, and 35 parts by weight of styrene. Polymerization was carried out in a nitrogen atmosphere at 80°C for 6 hours, yielding acrylic resin solution A'3 with a polystyrene-equivalent weight-average molecular weight of 9,500, an acid value of 72 mgKOH / g, and a solids concentration of 40% by weight.

[0124] (Novolac resin (B)) Novolac resin solution B1: Weight average molecular weight 30,000, softening point 165°C, solids concentration 40% by mass (solvent: propylene glycol monomethyl ether acetate), contains m-cresol:p-cresol as skeleton in a ratio of 6:4.

[0125] Novolac resin solution B2: Weight average molecular weight 15,000, softening point 160°C, solids concentration 40% by mass (solvent: propylene glycol monomethyl ether acetate), skeleton contains m-cresol: p-cresol in a 5:5 ratio.

[0126] Novolac resin solution B3: Weight average molecular weight 1,500, softening point 73°C, solids concentration 40% by mass (solvent: propylene glycol monomethyl ether acetate), contains a biphenylene skeleton.

[0127] (Quinonediazide-containing compound (C)) Quinone diazide group-containing compound C1: Toyo Gosei Co., Ltd., trade name TPPA-300A (a compound in which some or all of the hydrogen atoms of all phenolic hydroxyl groups of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol have been substituted with 1,2-naphthoquinone diazide sulfonyl groups).

[0128] (Polyhydroxystyrene (D)) Polyhydroxystyrene solution D1: Maruzen Petrochemical Co., Ltd., trade name: Marukalinker (registered trademark) M2VPM. Weight average molecular weight: 5,000. Solid content: 30% by mass (solvent: propylene glycol monomethyl ether acetate 70% by mass).

[0129] Polyhydroxystyrene solution D2: MARUKA LINCAR (registered trademark) HPS-H10K manufactured by Maruzen Petrochemical Co., Ltd. Weight average molecular weight: 10,000 Solids concentration: 30% by mass (solvent: propylene glycol monomethyl ether acetate 70% by mass).

[0130] Polyhydroxystyrene solution D3: MARUKA LINCAR (registered trademark) HPS-10K manufactured by Maruzen Petrochemical Co., Ltd. Weight average molecular weight: 30,000 Solids concentration: 30% by mass (solvent: propylene glycol monomethyl ether acetate 70% by mass).

[0131] (Additive (E)) Additive E1: Surface conditioner. BYK-307 manufactured by BYK Japan Co., Ltd. Polyether-modified polydimethylsiloxane.

[0132] 2. Preparation of Resist Resin Composition The components shown in the table were mixed at room temperature in the parts by mass shown in the table to obtain a resist resin composition for producing a coating film. The values ​​in parentheses in the table indicate the solid content excluding the solvent.

[0133] 3. Preparation of test pieces First, a 10 cm x 10 cm polyimide substrate with copper foil attached was prepared, and each of the resist resin compositions of the Examples and Comparative Examples was coated onto the substrate. The coated film was placed in a box oven and dried at 110°C for 420 seconds to obtain a resin layer with a coating thickness of 5 μm.

[0134] Next, the prepared resin layer was exposed to 240 mJ / cm through a mask with a predetermined light-blocking pattern drawn on it, and a wavelength cut filter was used to allow only light of 340-440 nm to pass through. 2 The specimen was irradiated with light under the conditions of a high-pressure mercury lamp.

[0135] Next, the exposed resin layer was immersed in a 1% aqueous sodium hydroxide solution at 30°C as a developer for 60 seconds, shaken, and then rinsed with water for 20 seconds, thereby producing a patterned resist film from the resin layer and obtaining a test piece.

[0136] 4.Evaluation Test 4.1 Developability Test pieces prepared according to the method described in "3. Preparation of Test Pieces" were visually observed and the developability was evaluated according to the following criteria. A: After exposure and development, no development residue was observed on the substrate in the light-irradiated areas of the resin layer. B: After exposure and development, no development residue was observed in the irradiated portions of the resin layer on the substrate, but slight discoloration was observed in the non-irradiated portions. C: After exposure and development, slight development residue was observed on the substrate in the irradiated area of ​​the resin layer. D: After exposure and development, development residues were observed on the substrate in the irradiated areas of the resin layer.

[0137] For Comparative Example 2, since development residues were observed all over the substrate, evaluations of "4.3 Resolution," "4.4 Heat resistance (shape retention)," and "4.7 Developability after storage at 40°C for 3 weeks (stability)" were not performed.

[0138] 4.2 Developer resistance (film loss) The thickness of the resist film on the test piece prepared according to the method described in "3. Preparation of test piece" was measured, the ratio of the resin layer thickness (5 μm) to the resist film thickness was calculated, and the ratio was multiplied by 100 to obtain the "unexposed area remaining film ratio (%)." The developer resistance was then evaluated according to the following criteria. A: The remaining film rate in the unexposed area was 95% or more, and no roughness was observed on the surface of the resist film (the part of the resin layer that was not irradiated with light). B: The remaining film rate in the unexposed area was 95% or more, but roughness was observed in some parts of the surface of the resist film (the part of the resin layer that was not irradiated with light). C: The remaining film rate in the unexposed area was 90% or more and less than 95%, and roughness and irregularities were observed in some parts of the surface of the resist film (the part of the resin layer that was not irradiated with light). D: The remaining film rate in the unexposed area was less than 90%, and roughness or irregularities were observed on the surface of the resist film (the portion of the resin layer that was not irradiated with light), or exposure was observed on part of the surface of the substrate.

[0139] 4.3 Resolution A 10 μm wide space line on a test piece prepared according to the method described in "3. Preparation of test piece" was observed under a microscope, and the resolution was evaluated according to the following criteria. A: No wobbling of the line was observed. B: There was a slight wobble in the line. C: Overall line irregularities were observed, but no chipping of the resist film was observed. D: Overall line irregularities are observed and there are some areas where the resist film is missing.

[0140] 4.4 Heat resistance (shape retention) The test pieces prepared according to the method described in "3. Preparation of Test Pieces" were then placed in an IR drying oven set at 130°C and post-baked for 10 minutes. The shape of the 10 μm-wide resist lines, which had changed in size in the thickening direction, was observed using a scanning electron microscope (SEM) before and after post-baking. The results obtained by the observation were evaluated according to the following criteria. A: The dimensional change in the line width of the 10 μm-wide resist film was 2 μm or less. B: The dimensional change in the line width of the 10 μm-wide resist film was more than 2 μm and 4 μm or less. C: The dimensional change in the line width of the 10 μm-wide resist film was more than 4 μm and 6 μm or less. D: The dimensional change in the line width of the 10 μm-wide resist film exceeded 6 μm.

[0141] 4.5 Flexibility The test pieces prepared according to the method described in "3. Preparation of test pieces" were further placed in an IR drying oven set at a temperature of 130°C and post-baked for 10 minutes, after which a bending test was carried out for 1 minute using a bending tester (manufactured by Toyo Seiki Co., Ltd.) in accordance with JIS-K 5600. The condition of the test pieces after 1 minute was checked and evaluated according to the following criteria. A: Even when a bending test was performed using a cylindrical mandrel with an outer diameter of 6 mm, no cracks or breaks occurred in the resist film. B: When a bending test was performed using a cylindrical mandrel with an outer diameter of φ6 mm, cracks and breaks occurred in the resist film, but when a bending test was performed using a cylindrical mandrel with an outer diameter of φ8 mm, no cracks or breaks occurred in the resist film. C: When a bending test was performed using a cylindrical mandrel with an outer diameter of φ8 mm, cracks and breaks occurred in the resist film, but when a bending test was performed using a cylindrical mandrel with an outer diameter of φ10 mm, no cracks or breaks occurred in the resist film. D: When a bending test was performed using a cylindrical mandrel with an outer diameter of φ10 mm, cracks and fractures occurred in the resist film.

[0142] 4.6 Alkali strippability The test pieces prepared according to the method described in "3. Preparation of test pieces" were further placed in an IR drying oven set at a temperature of 130°C and post-baked for 10 minutes. After that, the test pieces were treated by contacting them with a 3% by mass aqueous solution of sodium hydroxide at 40°C for 120 seconds, and then the test pieces were observed and evaluated according to the following criteria. A: No remaining resist film was observed on the test piece. B: No remaining resist film was observed on the test piece, but discoloration of the copper foil was observed. C: A small amount of resist film was found remaining on the test piece. D: The resist film was not removed and remained on the test piece.

[0143] 4.7 Development (stability) after storage at 40°C for 3 weeks The resist resin composition was stored at 40° C. for 3 weeks, and then evaluated in the same manner as in “4.1 Developability” and rated according to the following criteria. A: No development residues were observed on the substrate after exposure and development from the exposed areas of the coating film. B: After exposure and development, no development residue was observed in the exposed areas of the coating film on the substrate, but slight discoloration was observed in the unexposed areas. C: After exposure and development, slight development residues of the exposed areas of the coating film were observed on the substrate. D: After exposure and development, development residues of the exposed areas of the coating film were observed on the substrate.

[0144] [Table 1]

[0145] [Table 2]

[0146] [Table 3] [Explanation of symbols]

[0147] 1 Base material 3 Resin layer 30 Resist film

Claims

1. The composition contains an epoxy carboxylate (A), a novolak resin (B), and a quinone diazide group-containing compound (C), The epoxy carboxylate (A) is a reaction product of an epoxy resin (P) and a compound (Q) having a carboxy group. A resist resin composition.

2. The epoxy resin (P) comprises a copolymer of a monomer (M1) having an epoxy group and an ethylenically unsaturated group and a monomer (M2) having an ethylenically unsaturated group different from the monomer (M1). The resist resin composition according to claim 1 .

3. The epoxy carboxylate (A) comprises an adduct of at least one of a polybasic acid and an anhydride thereof to the reaction product of the epoxy resin (P) and the compound (Q). The resist resin composition according to claim 1 .

4. The monomer (M1) includes glycidyl (meth)acrylate. The resist resin composition according to claim 2 .

5. The compound (Q) includes a compound (Q1) having an ethylenically unsaturated group. The resist resin composition according to claim 1 .

6. The compound (Q1) contains (meth)acrylic acid. The resist resin composition according to claim 5 .

7. a mass ratio of the epoxy carboxylate (A) to the novolac resin (B) is 10 / 90 or more and 80 / 20 or less; The resist resin composition according to claim 1 .

8. The weight average molecular weight of the epoxy carboxylate (A) is 1,000 or more and 15,000 or less. The resist resin composition according to claim 1 .

9. The weight average molecular weight of the novolac resin (B) is 10,000 or more and 50,000 or less. The resist resin composition according to claim 1 .

10. Further containing polyhydroxystyrene (D), The resist resin composition according to claim 1 .

11. The weight average molecular weight of the polyhydroxystyrene (D) is 1,000 or more and 50,000 or less. The resist resin composition according to claim 10.

12. the polyhydroxystyrene (D) is 0.1 parts by mass or more and 25 parts by mass or less relative to 100 parts by mass of the total amount of the epoxy carboxylate (A) and the novolac resin (B); The resist resin composition according to claim 10.

13. a disposing step of disposing a resin layer containing the resist resin composition according to any one of claims 1 to 12 on a substrate; an exposure step of partially exposing the resin layer; a development step of removing the light-irradiated portion of the resin layer, A method for manufacturing a resist film.

14. A resist resin composition comprising the resist resin composition according to any one of claims 1 to 12. Resist film.

15. It is patterned, The resist film according to claim 14.

16. A resist resin composition comprising the resist resin composition according to any one of claims 1 to 12. Dry film.

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