Photosensitive resin composition and method for forming resist pattern

Abstract

The invention relates to a photosensitive resin composition and a method for forming a resist pattern. Provided is a photosensitive resin composition which exhibits excellent sensitivity, adhesion, line width reproducibility, and resolution when heated and then developed after exposure, and in particular, exhibits excellent adhesion even when the time from exposure to development is long. One embodiment of the present invention provides a photosensitive resin composition containing: (A) 10-90 mass% of an alkali-soluble polymer; (B) 5-70 mass% of a compound having an ethylenically unsaturated double bond; (C) 0.01% by mass to 20% by mass of a photopolymerization initiator; and (D) 1 ppm to 300 ppm of a phenolic polymerization inhibitor. The light transmittance of the photosensitive resin composition at at least one of 375 nm and 405 nm is 58% to 95%.

Description

[0001] This application is a divisional application of an application with an application date of August 7, 2019, an application number of 201980051908.6, and an invention title of "Photosensitive Resin Composition and Method for Forming Resist Pattern". Technical Field

[0002] The present invention relates to a photosensitive resin composition, a method for forming a resist pattern, and the like. Background Art

[0003] In electronic instruments such as personal computers and mobile phones, printed wiring boards and the like are used for mounting components, semiconductors, and the like. As a resist for manufacturing printed wiring boards and the like, a photosensitive resin laminate in which a photosensitive resin layer is laminated on a support film and, if necessary, a protective film is further laminated on the photosensitive resin layer, so-called dry film photoresist (hereinafter sometimes referred to as DF) has been conventionally used. As the photosensitive resin layer, an alkali-developable photosensitive resin layer using a weak alkali aqueous solution as a developer is generally used at present.

[0004] When manufacturing a printed wiring board or the like using DF, for example, the following process is performed. When DF has a protective film, first, the protective film is peeled off. Then, DF is laminated on a substrate for forming a permanent circuit such as a copper-clad laminate or a flexible substrate using a laminating device or the like, and exposed through a wiring pattern mask film or the like. Then, if necessary, the support film is peeled off, and the un-cured portion (for example, the un-exposed portion in the case of a negative type) of the photosensitive resin layer is dissolved or dispersed and removed using a developer, and a cured resist pattern (hereinafter sometimes simply referred to as a resist pattern) is formed on the substrate.

[0005] After forming the resist pattern, the process of forming a circuit is roughly divided into two methods. The first method is a method (etching method) in which the substrate surface not covered by the resist pattern (for example, the copper surface of a copper-clad laminate) is etched away and then the resist pattern portion is removed using an alkali aqueous solution stronger than the developer.

[0006] The second method is a method (plating method) in which after plating the above substrate surface with copper, solder, nickel, tin, or the like, the resist pattern portion is removed in the same manner as the first method, and then the exposed substrate surface (for example, the copper surface of a copper-clad laminate) is etched. Etching is performed using copper chloride, ferric chloride, a copper ammonia complex solution, or the like.

[0007] In recent years, with the miniaturization and light weight of electronic instruments, the miniaturization and high density of printed wiring boards have advanced. In the manufacturing processes as described above, there is a demand for providing high-performance DF with high resolution and high adhesion. As a technique for achieving such high resolution, a photosensitive resin composition having improved resolution by a specific thermoplastic resin, monomer, and photopolymerization initiator is described in Patent Document 1.

[0008] Prior art documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 2010-249884 Summary of the invention

[0011] Problems to be Solved by the Invention

[0012] After the exposure step, a heating step is sometimes performed on the photosensitive resin layer as needed, and then development is carried out. By carrying out such a heating step, the resolution and adhesion (i.e., the adhesion between the resist pattern and the substrate) can be further improved. However, there is the following problem: Even if a heating step is added after exposure, when using a conventional photosensitive resin composition, the adhesion and resolution are still insufficient, or good adhesion cannot be obtained if the time from exposure to development is prolonged.

[0013] The present invention has been made in view of such a conventional situation, and an object of one aspect of the present invention is to provide a photosensitive resin composition having good sensitivity, adhesion, line width reproducibility, and resolution when heated after exposure and then developed, and particularly achieving good adhesion even when the time from exposure to development is long.

[0014] Solutions for Solving the Problems

[0015] The present invention includes the following aspects.

[0016] [1] A photosensitive resin composition containing:

[0017] (A) An alkali-soluble polymer: 10% by mass to 90% by mass;

[0018] (B) A compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass;

[0019] (C) A photopolymerization initiator: 0.01% by mass to 20% by mass; and

[0020] (D) A phenolic inhibitor: 1 ppm to 300 ppm,

[0021] The photosensitive resin composition has a light transmittance of 58% to 95% at at least one of 375 nm and 405 nm.

[0022] [2] The photosensitive resin composition according to the above aspect 1, which contains methoxyphenol as the phenolic inhibitor (D).

[0023] [3] The photosensitive resin composition according to the above aspect 1 or 2, which contains dibutylhydroxytoluene as the phenolic inhibitor (D).

[0024] [4] The photosensitive resin composition according to the above-described Mode 3, wherein the content of the aforementioned dibutylhydroxytoluene is 1 to 200 ppm.

[0025] [5] The photosensitive resin composition according to the above-described Mode 3, wherein the content of the aforementioned dibutylhydroxytoluene is 10 to 150 ppm.

[0026] [6] The photosensitive resin composition according to any one of the above-described Modes 1 to 5, wherein the I / O value of the aforementioned (A) alkali-soluble polymer is 0.600 or less.

[0027] [7] The photosensitive resin composition according to any one of the above-described Modes 1 to 6, wherein the aforementioned (C) photopolymerization initiator contains one or more selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and their derivatives.

[0028] [8] The photosensitive resin composition according to the above-described Mode 7, wherein the aforementioned (C) photopolymerization initiator contains anthracene and / or anthracene derivatives.

[0029] [9] The photosensitive resin composition according to any one of the above-described Modes 1 to 8, wherein the structural unit of styrene and / or styrene derivative in the aforementioned (A) alkali-soluble polymer is 26% by mass or more.

[0030]

[10] The photosensitive resin composition according to any one of the above-described Modes 1 to 9, wherein the aforementioned (A) alkali-soluble polymer contains a structural unit of (meth)acrylic acid benzyl ester as a monomer component.

[0031]

[11] The photosensitive resin composition according to any one of the above-described Modes 1 to 10, wherein the glass transition temperature of the aforementioned (A) alkali-soluble polymer is 120°C or less.

[0032]

[12] The photosensitive resin composition according to any one of the above-described Modes 1 to 11, wherein the aforementioned (B) compound having an ethylenically unsaturated double bond contains a compound having 3 or more methacrylate groups in the molecule in an amount of 5% by mass or more based on the total solid content of the photosensitive resin composition.

[0033]

[13] The photosensitive resin composition according to any one of the above-described Modes 1 to 12, which is used to obtain an exposed resin cured product by using a first laser having a center wavelength of less than 390 nm and a second laser having a center wavelength of 390 nm or more.

[0034]

[14] The photosensitive resin composition according to the above-described method 13, wherein the central wavelength of the first laser is 350 nm or more and 380 nm or less, and the central wavelength of the second laser is 400 nm or more and 410 nm or less.

[0035]

[15] The photosensitive resin composition according to any one of the above-described methods 1 to 14 can form a pattern through the following steps:

[0036] An exposure step of exposing the photosensitive resin composition;

[0037] A heating step of heating the exposed photosensitive resin composition; and

[0038] A developing step of developing the heated photosensitive resin composition.

[0039]

[16] The photosensitive resin composition according to the above-described method 15, wherein the heating temperature in the heating step is in the range of 30°C to 150°C.

[0040]

[17] The photosensitive resin composition according to the above-described method 15 or 16, wherein the heating step is performed within 15 minutes after exposure.

[0041]

[18] A method for forming an anti-etching pattern, which includes the following steps:

[0042] An exposure step of exposing the photosensitive resin composition according to any one of the above-described methods 1 to 17;

[0043] A heating step of heating the exposed photosensitive resin composition; and

[0044] A developing step of developing the heated photosensitive resin composition.

[0045]

[19] The method for forming an anti-etching pattern according to the above-described method 18, wherein the heating temperature in the heating step is in the range of 30°C to 150°C.

[0046]

[20] The method for forming an anti-etching pattern according to the above-described method 18 or 19, wherein the heating step is performed within 15 minutes after exposure.

[0047]

[21] The method for forming an anti-etching pattern according to any one of the above-described methods 18 to 20, wherein the exposure step is performed by an exposure method of directly drawing a pattern or by an exposure method of projecting an image of a photomask through a lens.

[0048]

[22] The method for forming an anti-etching pattern according to the above-described method 21, wherein the exposure step is performed by an exposure method of directly drawing a pattern.

[0049]

[23] The method for forming a resist pattern according to the above-described method 22, wherein the exposure step is performed by a method of exposing using a first laser having a center wavelength of less than 390 nm and a second laser having a center wavelength of 390 nm or more.

[0050]

[24] The method for forming a resist pattern according to the above-described method 23, wherein the center wavelength of the first laser is 350 nm or more and 380 nm or less, and the center wavelength of the second laser is 400 nm or more and 410 nm or less.

[0051]

[25] A method for manufacturing a circuit board, which includes the following steps:

[0052] A resist pattern forming step of forming a resist pattern on a substrate by the method according to any one of the above-described methods 18 to 24; and

[0053] A circuit board forming step of forming a circuit board by performing etching or plating on the substrate having the resist pattern.

[0054] Effects of the Invention

[0055] According to the present invention, a photosensitive resin composition can be provided, which has good sensitivity, adhesion, line width reproducibility, and resolution when heated after exposure and then developed, and in particular, good adhesion can be achieved even when the time from exposure to development is long. Detailed Embodiments

[0056] Hereinafter, exemplary embodiments for implementing the present invention (hereinafter simply referred to as "embodiments") will be described in detail. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof. In addition, for various measured values in this specification, unless otherwise specified, they are measured according to the methods described in the [Examples] section of the present disclosure or methods understood by those skilled in the art to be equivalent thereto.

[0057] <Photosensitive Resin Composition>

[0058] In the present embodiment, the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a phenolic inhibitor. In addition, in the present embodiment, by applying the photosensitive resin composition to an arbitrary support, a photosensitive resin layer can be formed. The above composition of the photosensitive resin composition of the present embodiment is useful for obtaining a resin cured product by heating after exposure and then developing.

[0059] The photosensitive resin composition of this embodiment can be a photosensitive resin composition for obtaining a resin cured product by exposure to a first actinic light having a center wavelength of less than 390 nm and a second actinic light having a center wavelength of 390 nm or more. The actinic light is, for example, a laser. In this case, the photosensitive resin composition has photosensitivity to both the first actinic light having a center wavelength of less than 390 nm and the second actinic light having a center wavelength of 390 nm or more. The center wavelength of the first actinic light is preferably 350 to 380 nm, more preferably 355 to 375 nm, and particularly preferably 375 nm. The center wavelength of the second actinic light is preferably 400 to 410 nm, more preferably 402 to 408 nm, and particularly preferably 405 nm (h-ray).

[0060] The following describes each component contained in the photosensitive resin composition.

[0061] (A) Alkali-soluble polymer

[0062] (A) The alkali-soluble polymer is a polymer that can be dissolved in an alkali substance. From the viewpoint of alkali developability, (A) the alkali-soluble polymer preferably has a carboxyl group, and further preferably contains a copolymer containing a monomer having a carboxyl group as a copolymerization component. (A) The alkali-soluble polymer can be thermoplastic.

[0063] From the viewpoints of high resolution of the resist pattern and the shape of the curled edge (スソ shape), the photosensitive resin composition preferably contains a copolymer having an aromatic group as (A) the alkali-soluble polymer. The photosensitive resin composition particularly preferably contains a copolymer having an aromatic group in the side chain as (A) the alkali-soluble polymer. Examples of such an aromatic group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The ratio of the copolymer having an aromatic group in the component (A) is preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. The above ratio can be 100% by mass, but from the viewpoint of maintaining good alkali solubility, it is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass.

[0064] From the viewpoints of high resolution of the resist pattern and the shape of the curled edge, the copolymerization ratio of the copolymerization monomer having an aromatic group in (A) the alkali-soluble polymer is preferably 40% by mass or more, preferably 50% by mass or more, preferably 60% by mass or more, preferably 70% by mass or more, and preferably 80% by mass or more. There is no particular limitation on the upper limit of the copolymerization ratio, but from the viewpoint of maintaining good alkali solubility, it is preferably 95% by mass or less, more preferably 90% by mass or less.

[0065] Examples of the comonomer having an aromatic group described above include styrene, polymerizable styrene derivatives (e.g., methyl styrene, vinyl toluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.), monomers having an aralkyl group, etc. Among them, styrene and styrene derivatives are more preferred.

[0066] Regarding the ratio of the structural units of styrene and / or styrene derivatives in all of the (A) alkali-soluble polymers in total, from the viewpoint of being able to significantly improve the adhesion when heating is performed after exposure and then development is carried out, especially being able to obtain good adhesion even when the time from exposure to development is extended, it is preferably 15% by mass or more, more preferably 25% by mass or more, more preferably 26% by mass or more, more preferably 30% by mass or more, more preferably 35% by mass or more, more preferably 40% by mass or more. Since the styrene skeleton is hydrophobic, it can suppress the swelling property with respect to the developer and can exhibit good adhesion. However, when the content of the styrene skeleton is large, there is a tendency for the fluidity of the polymer to be low and the reactivity to decrease, and thus there is a tendency for the adhesion to decrease. In addition, when the time from exposure to development is extended, the free radicals in the system are inactivated, so the effect of improving adhesion achieved by heating after exposure is reduced. In the present invention, by performing heating after exposure and then development, even in a system with a large content of the styrene skeleton, the fluidity of the polymer can be improved by heating, and the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly balanced. As a result, it is considered that good adhesion can be achieved. It is also considered that good adhesion can be obtained even when the time from exposure to development is extended. Regarding the ratio of the structural units of styrene and / or styrene derivatives in all of the (A) alkali-soluble polymers in total, from the viewpoint of favorably obtaining the advantages achieved by the presence of other structural units, it is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.

[0067] Examples of the comonomer having an aralkyl group include monomers having a substituted or unsubstituted benzyl group, monomers having a substituted or unsubstituted phenylalkyl group (excluding benzyl), etc., but monomers having a substituted or unsubstituted benzyl group are preferred.

[0068] Examples of the comonomer having a benzyl group include (meth)acrylate esters having a benzyl group, such as benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, vinylbenzyl alcohol, etc.

[0069] (A) From the viewpoint of significantly improving the adhesion when heating and then developing after exposure, especially achieving good adhesion even when the time from exposure to development is extended, the alkali-soluble polymer preferably contains a structural unit of benzyl (meth)acrylate as a monomer component. The ratio of the structural unit of benzyl (meth)acrylate in the alkali-soluble polymer (A) is preferably 5 to 85% by mass, more preferably 10 to 80% by mass, still more preferably 15 to 60% by mass, still more preferably 20 to 40% by mass, and further preferably 20 to 30% by mass. Further, from the same viewpoint, the alkali-soluble polymer (A) preferably has both a structural unit of styrene and / or a styrene derivative and a structural unit of benzyl (meth)acrylate.

[0070] Examples of the copolymerizable monomer having a phenylalkyl (excluding benzyl) include phenethyl (meth)acrylate.

[0071] The copolymer having an aromatic group (preferably benzyl) in the side chain is preferably obtained by polymerizing at least one of (i) a monomer having an aromatic group and (ii) the first monomer described below and / or at least one of the second monomer described below.

[0072] The alkali-soluble polymer (A) other than the copolymer having an aromatic group in the side chain is preferably obtained by polymerizing at least one of the first monomers described below, and more preferably by copolymerizing at least one of the first monomers described below and at least one of the second monomers described below.

[0073] The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among them, (meth)acrylic acid is preferred.

[0074] It should be noted that in this specification, “(meth)acrylic acid” refers to acrylic acid or methacrylic acid, “(meth)acryloyl” refers to acryloyl or methacryloyl, and “(meth)acrylate” refers to “acrylate” or “methacrylate”.

[0075] Based on the total mass of all monomer components of the polymer obtained by polymerizing at least one of the first monomers, the copolymerization ratio of the first monomer is preferably 10 to 50% by mass. From the viewpoint of exhibiting good developability and from the viewpoints of controlling edge fuse properties, etc., the copolymerization ratio is preferably 10% by mass or more. From the viewpoints of high resolution of the resist pattern and the shape of the curled edge, and further from the viewpoint of the chemical resistance of the resist pattern, the copolymerization ratio is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, particularly preferably 22% by mass or less, and most preferably 20% by mass or less.

[0076] The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile, etc. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred.

[0077] (A) The alkali-soluble polymer can be produced by polymerizing one or more of the above-described monomers using a known polymerization method, preferably addition polymerization, more preferably radical polymerization.

[0078] From the viewpoints of chemical resistance, adhesion, high resolution, or curled edge shape of the resist pattern, it is preferred that the monomer contains a monomer having an aralkyl group and / or styrene. As the (A) alkali-soluble polymer, a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene, etc. are particularly preferred.

[0079] (A) The I / O value of the alkali-soluble polymer is preferably 0.600 or less. The I / O value represents the ratio of (inorganic value) / (organic value), which is a value for evaluating the polarity of various organic compounds based on the organic concept map and is one of the functional group contribution methods for setting parameters for each functional group in a compound. The I / O value is described in detail in non-patent literatures such as "Organic Concept Map" (Yoshio Kotoda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Items 1 to 16 (1954); Chemistry Field, Vol. 11, No. 10, Items 719 to 725 (1957); FRAGRANCE JOURNAL, No. 34, Items 97 to 111 (1979); FRAGRANCE JOURNAL, No. 50, Items 79 to 82 (1981)); etc. The concept of the I / O value is to classify the properties of a compound into an organic group representing covalent bond nature and an inorganic group representing ionic bond nature, and to represent all organic compounds as points on the coordinates of an orthogonal axis respectively named the organic axis and the inorganic axis. The closer the aforementioned I / O value is to 0, the more non-polar (i.e., hydrophobic or large in organic nature) the organic compound is, and the larger the value, the more polar (i.e., hydrophilic or large in inorganic nature) the organic compound is.

[0080] (A) In terms of the adhesion and resolution of the resist pattern when developing after heating after exposure, the I / O value of the alkali-soluble polymer is preferably 0.600 or less, more preferably 0.570 or less, still more preferably 0.520 or less, and particularly preferably 0.490 or less. In terms of the resolution and peelability when developing after heating after exposure, it is preferably 0.300 or more, more preferably 0.400 or more, and still more preferably 0.450 or more.

[0081] Regarding the glass transition temperature of the (A) alkali-soluble polymer, the value obtained by the Fox equation (when the (A) alkali-soluble polymer contains multiple polymers, for the glass transition temperature Tg of the entire mixture, that is, the weight average Tg of the glass transition temperature total ), in terms of the chemical resistance, adhesion, high resolution, or curled edge shape of the resist pattern, it is preferably 130 °C or less, more preferably 120 °C or less, 110 °C or less, 100 °C or less, 95 °C or less, 90 °C or less, or 80 °C or less. There is no limitation on the lower limit value of the glass transition temperature (Tg) of the (A) alkali-soluble polymer. In terms of controlling the edge fusion property, it is preferably 30 °C or more, more preferably 50 °C or more, and still more preferably 60 °C or more. It should be noted that as the glass transition temperature of the homopolymer containing monomers respectively identical to one or more monomers constituting the (A) alkali-soluble polymer, the values shown in the non-patent literature (Brandrup, J. Immergut, E. H. eds. "Polymer handbook, Third edition, John Wiley & sons, 1989, p. 209 Chapter VI ‘Glass transition temperatures of polymers’") are used.

[0082] (A) The acid equivalent of the alkali-soluble polymer (when the (A) component contains multiple copolymers, for the acid equivalent of the entire mixture) is preferably 100 or more in terms of the developability resistance of the photosensitive resin layer and the resolution and adhesion of the resist pattern, and preferably 600 or less in terms of the developability and peelability of the photosensitive resin layer. The acid equivalent of the (A) alkali-soluble polymer is more preferably 200 to 500, and still more preferably 250 to 450.

[0083] (A) The weight-average molecular weight of the alkali-soluble polymer (when the (A) component contains a plurality of copolymers, it is the weight-average molecular weight of the entire mixture) is preferably 5,000 to 500,000. From the viewpoints of maintaining the uniformity of the thickness of the dry film resist and obtaining resistance to the developer, the weight-average molecular weight of the (A) alkali-soluble polymer is preferably 5,000 or more. From the viewpoints of maintaining the developability of the dry film resist, the high resolution of the resist pattern and the shape of the curled edge, and further from the viewpoint of the chemical resistance of the resist pattern, it is preferably 500,000 or less. The weight-average molecular weight of the (A) alkali-soluble polymer is more preferably 10,000 to 200,000, further preferably 20,000 to 100,000, and particularly preferably 30,000 to 70,000. The dispersity of the molecular weight of the (A) alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 4.0, and still more preferably 1.0 to 3.0.

[0084] Based on the total solid content of the photosensitive resin composition (the same applies to each component contained hereinafter unless otherwise specified), the content of the (A) alkali-soluble polymer in the photosensitive resin composition is in the range of 10% by mass to 90% by mass, preferably in the range of 20% by mass to 80% by mass, and further preferably in the range of 40% by mass to 60% by mass. From the viewpoint of maintaining the alkali developability of the photosensitive resin layer, the content of the (A) alkali-soluble polymer is preferably 10% by mass or more. From the viewpoints of the resist pattern formed by exposure fully exhibiting the performance as a resist material, the high resolution of the resist pattern and the shape of the curled edge of the resist pattern, and further from the viewpoint of the chemical resistance of the resist pattern, it is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, and further preferably 60% by mass or less.

[0085] (B) Compound having an ethylenically unsaturated bond

[0086] (B) The compound having an ethylenically unsaturated bond is a compound having polymerizability by having an ethylenically unsaturated bond (i.e., a double bond) in its structure. The ethylenically unsaturated bond is more preferably derived from a methacryloyl group. From the viewpoints of adhesion and suppressing the foaming property of the developer, the compound (B) having an ethylenically unsaturated bond preferably has an oxyalkylene structure having 3 or more carbon atoms. The number of carbon atoms in the oxyalkylene structure is more preferably 3 to 6, and further preferably 3 to 4.

[0087] Examples of the (B) compound having one (meth)acryloyl group as an ethylenically unsaturated bond include a compound obtained by adding (meth)acrylic acid to one end of a polyoxyalkylene, or a compound obtained by adding (meth)acrylic acid to one end of a polyoxyalkylene and etherifying or allyl-etherifying the other end, a phthalic acid-based compound, etc., which are preferred from the viewpoints of peelability and flexibility of the cured film.

[0088] Examples of such compounds include, for example, phenoxy hexaethylene glycol mono(meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polyethylene glycol to phenyl; 4-n-nonylphenoxy heptaethylene glycol dipropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polypropylene glycol with an average addition of 2 moles of propylene oxide and polyethylene glycol with an average addition of 7 moles of ethylene oxide to nonylphenol; 4-n-nonylphenoxy heptaethylene glycol monopropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polypropylene glycol with an average addition of 1 mole of propylene oxide and polyethylene glycol with an average addition of 5 moles of ethylene oxide to nonylphenol; 4-n-nonylphenoxy octaethylene glycol (meth)acrylate, which is an acrylate of a compound obtained by adding polyethylene glycol with an average addition of 8 moles of ethylene oxide to nonylphenol (for example, manufactured by Toagosei Co., Ltd., M-114), etc.

[0089] In addition, if it contains γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl phthalate, it is also preferred not only from the above viewpoints but also from the viewpoints of sensitivity, resolution, and adhesion.

[0090] Examples of the compound having two (meth)acryloyl groups in the molecule include, for example, a compound having (meth)acryloyl groups at both ends of an alkylene oxide chain, or a compound having (meth)acryloyl groups at both ends of an alkylene oxide chain formed by randomly or block-bonding an ethylene oxide chain and a propylene oxide chain.

[0091] Examples of such compounds include polyalkylene glycol (meth)acrylates such as tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, and compounds having (meth)acryloyl groups at both ends of a 12-mole oxyethylene chain, and polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, etc. Examples of polyalkylene oxide di(meth)acrylate compounds containing oxyethylene and oxypropylene in the molecule include dimethacrylates of diols obtained by further adding an average of 3 moles of ethylene oxide to both ends of polypropylene glycol having an average of 12 moles of propylene oxide added, dimethacrylates of diols obtained by further adding an average of 15 moles of ethylene oxide to both ends of polypropylene glycol having an average of 18 moles of propylene oxide added, FA-023M, FA-024M, FA-027M (product names, manufactured by Hitachi Chemical Co., Ltd.), etc. They are preferred from the viewpoints of flexibility, resolution, adhesion, etc.

[0092] As other examples of the compound having two (meth)acryloyl groups in the molecule, compounds having (meth)acryloyl groups at both ends by modifying bisphenol A with an alkylene oxide are preferred from the viewpoints of resolution and adhesion.

[0093] Specifically, a compound represented by the following general formula (I) can be used.

[0094]

[0095] {In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group, A is C2H4, B is C3H6, n1 and n3 each independently are an integer of 0 to 39, and n1 + n3 is an integer of 0 to 40, n2 and n4 each independently are an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30. The arrangement of the repeating units of -(A-O)- and -(B-O)- can be random or block. Moreover, in the case of a block, either -(A-O)- or -(B-O)- can have a biphenyl side.}

[0096] For example, from the viewpoints of resolution and adhesion, polyalkylene glycol dimethacrylates obtained by adding an average of 5 moles of ethylene oxide to both ends of bisphenol A, polyalkylene glycol dimethacrylates obtained by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A, and polyalkylene glycol dimethacrylates obtained by adding an average of 1 mole of ethylene oxide to both ends of bisphenol A are preferred.

[0097] In addition, compounds in which the aromatic ring in the above general formula (I) has a heteroatom and / or a substituent can also be used.

[0098] Examples of the heteroatom include, for example, a halogen atom, etc. Further, examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, benzoylmethyl, an amino group, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a nitro group, a cyano group, a carbonyl group, a mercapto group, an alkylthio group having 1 to 10 carbon atoms, an aryl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group in which the alkyl has 1 to 10 carbon atoms, an acyl group in which the alkyl has 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms or a heterocyclic group-containing group, or an aryl group substituted with these substituents, etc. These substituents can form a condensed ring, or a hydrogen atom in these substituents is substituted with a heteroatom such as a halogen atom. When the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

[0099] As the compound (B) having an ethylenically unsaturated double bond, from the viewpoint of significantly improving the adhesion when heating is performed after exposure and then development is performed, particularly good adhesion can be obtained even when the time from exposure to development is extended, it is preferable to contain a (meth)acrylate compound having 3 or more ethylenically unsaturated double bonds (i.e., trifunctional or higher). From the same viewpoint, it is more preferable to contain a (meth)acrylate compound having 4 or more ethylenically unsaturated double bonds, further preferably contain a (meth)acrylate compound having 5 or more ethylenically unsaturated double bonds, and particularly preferably contain a (meth)acrylate compound having 6 or more ethylenically unsaturated double bonds. In addition, from the same viewpoint, it is preferable that they are methacrylate compounds. Compounds having 3 or more, 4 or more, 5 or more, 6 or more ethylenically unsaturated double bonds are considered to have the effect of increasing the crosslinking density when polymerized by exposure, but due to the steric hindrance caused by the large number of functional groups, the desired crosslinking density is mostly not obtained. In the present invention, it has been found that it is preferable to use a compound having 3 or more ethylenically unsaturated double bonds, more preferably a compound having 4 or more ethylenically unsaturated double bonds, further preferably a compound having 5 or more ethylenically unsaturated double bonds, and particularly preferably a compound having 6 or more ethylenically unsaturated double bonds. Even when heat treatment is performed after exposure, the fluidity in the system is improved, and thus, even if the number of functional groups is large, the influence of steric hindrance is reduced, and high adhesion can be obtained. As the content of the compound preferably having 3 or more ethylenically unsaturated double bonds, more preferably having 4 or more ethylenically unsaturated double bonds, further preferably having 5 or more ethylenically unsaturated double bonds, and particularly preferably having 6 or more ethylenically unsaturated double bonds, it is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, and particularly preferably 10% by mass or more based on the solid content of the photosensitive resin composition. In addition, as the upper limit value of the content, from the viewpoint of exhibiting the effect of heat treatment after exposure, it is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less.

[0100] Examples of the (meth)acrylate compound (b1) having 3 or more ethylenically unsaturated bonds include:

[0101] Tri(meth)acrylates such as ethoxylated glycerol tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate (for example, as preferred examples from the viewpoints of flexibility, adhesion, and exudation inhibition, tri(meth)acrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane and tri(meth)acrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane), etc.;

[0102] Tetra(meth)acrylates such as di(trimetylolpropane) tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.;

[0103] Penta(meth)acrylates such as dipentaerythritol penta(meth)acrylate, etc.;

[0104] Hexa(meth)acrylates such as dipentaerythritol hexa(meth)acrylate, etc.

[0105] Among them, tetra-, penta- or hexa-(meth)acrylate is preferred.

[0106] (b1) From the viewpoint of suppressing exudation, the (meth)acrylate compound having 3 or more ethylenically unsaturated bonds preferably has a weight average molecular weight of 500 or more, more preferably 700 or more, and still more preferably 900 or more.

[0107] As the tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate is preferred. As pentaerythritol tetra(meth)acrylate, tetra(meth)acrylate obtained by adding a total of 1 to 40 moles of alkylene oxide to the 4 terminals of pentaerythritol, etc. are preferred.

[0108] The tetra(meth)acrylate is more preferably a tetra(meth)acrylate compound represented by the following general formula (II):

[0109]

[0110] {In the formula, R3 to R6 each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, m1, m2, m3 and m4 are each independently an integer of 0 to 40, m1 + m2 + m3 + m4 is 1 to 40, and when m1 + m2 + m3 + m4 is 2 or more, a plurality of Xs may be the same or different from each other}.

[0111] Although not wishing to be bound by theory, it is considered that the tetramethacrylate compound represented by the general formula (II) can suppress the hydrolyzability in an alkaline solution by having the groups R3 to R6. From the viewpoint of significantly improving the adhesion when heating is performed after exposure and then development is performed, particularly achieving good adhesion even when the time from exposure to development is extended, it is preferred to use a photosensitive resin composition containing the tetramethacrylate compound represented by the general formula (II).

[0112] In the general formula (II), at least one of the groups R3 to R6 is preferably a methyl group, and more preferably all of the groups R3 to R6 are methyl groups.

[0113] From the viewpoints of obtaining desired resolution, curled edge shape, residual film ratio, etc. of the resist pattern, in the general formula (II), X is preferably -CH2-CH2-.

[0114] From the viewpoints of obtaining desired resolution, curled edge shape, residual film ratio, etc. of the resist pattern, in the general formula (II), m1, m2, m3 and m4 are each independently an integer of 1 to 20, more preferably an integer of 2 to 10. Further preferably, in the general formula (II), m1 + m2 + m3 + m4 is 1 to 36 or 4 to 36.

[0115] Examples of the compound represented by the general formula (II) include pentaerythritol (poly)alkoxy tetramethacrylate and the like. In addition, in the present disclosure, "pentaerythritol (poly)alkoxy tetramethacrylate" includes both "pentaerythritol alkoxy tetramethacrylate" in which m1 + m2 + m3 + m4 = 1 and "pentaerythritol polyalkoxy tetramethacrylate" in which m1 + m2 + m3 + m4 = 2 to 40 in the above general formula (II). Examples of the compound represented by the general formula (II) include the compounds listed in JP-A-2013-156369, such as pentaerythritol (poly)alkoxy tetramethacrylate and the like.

[0116] As the hexa(meth)acrylate compound, a hexa(meth)acrylate obtained by adding a total of 1 to 24 moles of ethylene oxide to 6 terminals of dipentaerythritol and a hexa(meth)acrylate obtained by adding a total of 1 to 10 moles of ε-caprolactone to 6 terminals of dipentaerythritol are preferred.

[0117] From the viewpoint of significantly improving the adhesion when heating is performed after exposure and then development is performed, especially achieving good adhesion even when the time from exposure to development is extended, in the photosensitive resin composition of the present embodiment, as the compound (B) having an ethylenically unsaturated bond, a (meth)acrylate compound having 4 or more ethylenically unsaturated bonds and having an alkylene oxide chain is particularly preferably contained. At this time, the ethylenically unsaturated bond is more preferably derived from a methacryloyl group, and the alkylene oxide chain is more preferably an ethylene oxide chain.

[0118] In the present embodiment, from the viewpoint of significantly improving the adhesion when heating is performed after exposure and then development is performed, particularly achieving good adhesion even when the time from exposure to development is extended, in the photosensitive resin composition, as the compound (B) having an ethylenically unsaturated bond, it is preferable to contain a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton. Examples of the alkylene oxide chain include an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, a pentylene oxide chain, a hexylene oxide chain, and the like. When the photosensitive resin composition contains a plurality of alkylene oxide chains, they may be the same as or different from each other. From the above viewpoint, as the alkylene oxide chain, an ethylene oxide chain, a propylene oxide chain, and a butylene oxide chain are more preferable, an ethylene oxide chain and a propylene oxide chain are further preferable, and an ethylene oxide chain is particularly preferable.

[0119] In the photosensitive resin composition, by using the combination of (A) an alkali-soluble polymer and a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, there is a tendency to maintain a balance among the chemical resistance, adhesion, and resolution of the resist pattern.

[0120] The (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton is an ester of a dipentaerythritol compound in which at least one of the plurality of hydroxyl groups is modified with an alkylene oxide and (meth)acrylic acid. Six hydroxyl groups of the dipentaerythritol skeleton may be modified with an alkylene oxide. The number of ester bonds in one molecule of the ester may be 1 to 6, preferably 6.

[0121] Examples of the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton include hexa(meth)acrylate obtained by adding an average of 4 to 30 moles, an average of 6 to 24 moles, or an average of 10 to 14 moles of an alkylene oxide to dipentaerythritol.

[0122] Specifically, as the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, from the viewpoint of significantly improving the adhesion when heating is performed after exposure and then development is performed, particularly achieving good adhesion even when the time from exposure to development is extended, the compound represented by the following general formula (III) is preferable:

[0123]

[0124] {In the formula, each R independently represents a hydrogen atom or a methyl group, and n is an integer of 0 to 30, and the total value of all n is 1 or more}. In the general formula (III), it is preferable that the average value of all n is 4 or more, or n is 1 or more respectively. As R, a methyl group is preferable.

[0125] From the same viewpoint, the content of the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton relative to the total solid content in the photosensitive resin composition is preferably in the range of 1% by mass to 50% by mass, more preferably in the range of 5% by mass to 40% by mass, and still more preferably in the range of 7% by mass to 30% by mass.

[0126] Relative to the total solid content of the photosensitive resin composition, the content of the (b1) (meth)acrylate compound having 3 or more ethylenically unsaturated bonds (i.e., a compound having 3 or more (meth)acrylate groups) is preferably more than 0% by mass and 50% by mass or less. If the content exceeds 0% by mass, it is more advantageous from the viewpoint of significantly improving the adhesion when heating is performed after exposure and then development, and particularly from the viewpoint of achieving good adhesion even when the time from exposure to development is extended. If it is 50% by mass or less, there is a tendency to improve the flexibility of the cured resist and shorten the peeling time. The content is more preferably 2% by mass or more and 40% by mass or less, and still more preferably 4% by mass or more and 35% by mass or less. In a more preferred embodiment, the (B) compound having an ethylenically unsaturated double bond is contained in an amount of preferably 5% by mass or more, more preferably 9% by mass or more, still more preferably 13% by mass or more, particularly preferably 20% by mass or more, and additionally preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, relative to the total solid content of all the photosensitive resin compositions, of a compound having 3 or more methacrylate groups in the molecule.

[0127] From the viewpoint of adhesion and from the viewpoint of suppressing the foaming property of the developer, in the photosensitive resin composition, as the (B) compound having an ethylenically unsaturated double bond, it is preferable to contain the (b2) compound having an oxytetramethylene chain or an oxypropylene chain and 1 or 2 (meth)acryloyl groups.

[0128] (b2) The compound having an oxytetramethylene chain or an oxypropylene chain and 1 or 2 (meth)acryloyl groups preferably has a molecular weight of 500 or more, more preferably 700 or more, and still more preferably 1000 or more, from the viewpoint of suppressing bleeding.

[0129] Examples of the (b2) compound having an oxytetramethylene chain or an oxypropylene chain and 1 or 2 (meth)acryloyl groups include polypropylene glycol (meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol (meth)acrylate, polytetramethylene glycol di(meth)acrylate, etc. The (b2) compound having an oxytetramethylene chain or an oxypropylene chain and 1 or 2 (meth)acryloyl groups may contain an oxyethylene chain in addition to the oxytetramethylene chain or the oxypropylene chain.

[0130] Specifically, the compound (b2) having an oxybutylene chain or an oxypropylene chain and one or two (meth)acryloyl groups is preferably a (meth)acrylate or di(meth)acrylate of C4H8O or C3H6O having 1 to 20, more preferably 4 to 15, and further preferably 6 to 12 units.

[0131] With respect to the total amount of the solid components of the photosensitive resin composition, the content of the compound (b2) having an oxybutylene chain or an oxypropylene chain and one or two (meth)acryloyl groups is preferably more than 0% by mass and 20% by mass or less.

[0132] In the present embodiment, in order to suppress the bleeding of the components constituting the dry film resist and improve the storage stability, based on the total amount of the solid components of the compound (B) having an ethylenically unsaturated bond, it is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass of a compound having a weight average molecular weight of 500 or more. From the viewpoints of suppressing bleeding and the chemical resistance of the resist pattern, the weight average molecular weight of the compound (B) having an ethylenically unsaturated bond is preferably 760 or more, more preferably 800 or more, further preferably 830 or more, and particularly preferably 900 or more. The weight average molecular weight of the compound (B) having an ethylenically unsaturated bond can be determined as the molecular weight calculated from the molecular structure of the compound (B) having an ethylenically unsaturated bond. When there are multiple compounds (B) having an ethylenically unsaturated bond, it can be determined by weighted averaging the molecular weights of the respective compounds according to their contents.

[0133] From the viewpoints of the chemical resistance, adhesion, high resolution, and curl shape of the resist pattern, the concentration of methacryloyl groups in the compound (B) having an ethylenically unsaturated bond is preferably 0.20 mol / 100 g or more, more preferably 0.30 mol / 100 g or more, and further preferably 0.35 mol / 100 g or more. The upper limit value of the concentration of methacryloyl groups is not limited as long as the polymerizability and alkali developability are ensured, and can be, for example, 0.90 mol / 100 g or less or 0.80 mol / 100 g or less.

[0134] From the same viewpoints, the value of the concentration of methacryloyl groups in the compound (B) having an ethylenically unsaturated bond / (the concentration of methacryloyl groups + the concentration of acryloyl groups) is preferably 0.50 or more, more preferably 0.60 or more, further preferably 0.80 or more, particularly preferably 0.90 or more, and most preferably 0.95 or more.

[0135] The above-described (meth)acrylate compounds can be used independently or in combination. The photosensitive resin composition may further contain other compounds as (B) compounds having an ethylenically unsaturated bond. Examples of other compounds include (meth)acrylates having a urethane bond, compounds obtained by reacting a polyol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a compound containing a glycidyl group with an α,β-unsaturated carboxylic acid, 1,6-hexanediol di(meth)acrylate, and the like.

[0136] The ratio of (B) the compound having an ethylenically unsaturated double bond to the total solid content mass of the photosensitive resin composition is preferably 5% by mass to 70% by mass. A ratio of 5% by mass or more is preferable from the viewpoints of sensitivity, resolution, and adhesion. The ratio is more preferably 10% by mass or more, still more preferably 20% by mass or more, and further preferably 30% by mass or more. On the other hand, from the viewpoints of suppressing edge fusion and delaying peeling of the cured resist, it is preferable that the ratio is 70% by mass or less. More preferably, the ratio is 50% by mass or less.

[0137] (C) Photoinitiator

[0138] (C) The photoinitiator is a compound that polymerizes monomers by light. From the viewpoint of significantly improving the adhesion during heating and development after exposure, particularly good adhesion can be obtained even when the time from exposure to development is extended. (C) The photoinitiator preferably contains one or more selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and their derivatives. More preferably, it contains anthracene and / or anthracene derivatives, and further preferably contains anthracene derivatives. In addition, anthracene, pyrazoline, triphenylamine, coumarin, and their derivatives, particularly anthracene and / or anthracene derivatives, absorb the first active light with a center wavelength of less than 390 nm and the second active light with a center wavelength of 390 nm or more and function well as polymerization initiators. Therefore, in one aspect, the photosensitive resin composition can have photosensitivity to the first active light and the second active light and can also be used for two-wavelength exposure. (C) The photoinitiator can also be selected so as to have multiple absorption maxima in the wavelength ranges of the first active light and the second active light.

[0139] The total content of (C) the photoinitiator in the photosensitive resin composition is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.05% by mass to 10% by mass, further preferably in the range of 0.1% by mass to 7% by mass, and particularly preferably in the range of 0.1% by mass to 6% by mass. The total content of (C) the photoinitiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and preferably 20% by mass or less from the viewpoint of sufficiently transmitting light to the bottom surface of the resist and obtaining good high resolution.

[0140] Anthracene and anthracene derivatives are advantageous from the viewpoint of significantly improving the adhesion during heating after exposure and then development, particularly achieving good adhesion even when the time from exposure to development is extended. From the same viewpoint, anthracene derivatives preferably have an alkoxy group having 1 to 40 carbon atoms which may optionally have a substituent and / or an aryl group having 6 to 40 carbon atoms which may optionally have a substituent at the 9-position and / or 10-position, more preferably at the 9,10-positions.

[0141] In one aspect, from the viewpoint of significantly improving the adhesion during heating after exposure and then development, particularly achieving good adhesion even when the time from exposure to development is extended, anthracene derivatives preferably have an alkoxy group having 1 to 40 carbon atoms which may optionally have a substituent at at least one of the 9-position or 10-position, more preferably an alkoxy group having 1 to 30 carbon atoms which may optionally have a substituent at at least one of the 9-position or 10-position. From the viewpoint of obtaining good adhesion and resolution, it is preferred to have an alkoxy group having 1 to 40 carbon atoms which may optionally have a substituent at the 9,10-positions, more preferably an alkoxy group having 1 to 30 carbon atoms which may optionally have a substituent at the 9,10-positions. The carbon numbers of the groups at the 9-position and 10-position may be the same or different.

[0142] Examples of the alkoxy group which may optionally have a substituent include:

[0143] Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, 2-methylpropoxy, 1-methylpropoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, eicosyloxy, cyclohexyloxy, norbornyloxy, tricyclodecyloxy, tetracyclododecyloxy, adamantyloxy, methyladamantyloxy, ethyladamantyloxy and butyladamantyloxy;

[0144] An alkoxy group modified with a halogen, such as chlorobutoxy, chloropropoxy;

[0145] An alkoxy group formed by adding a hydroxyl group, such as hydroxybutoxy;

[0146] An alkoxy group formed by adding a cyano group, such as cyanobutoxy;

[0147] An alkoxy group formed by adding an alkylene oxide, such as methoxybutoxy;

[0148] An alkoxy group formed by adding an aryl group, such as phenoxybutoxy, etc. Among them, n-butoxy is more preferred.

[0149] In one embodiment, considering the viewpoint that the anthracene derivative can significantly improve the adhesion during heating after exposure and then development, especially achieving good adhesion even when the time from exposure to development is extended, it is preferably to have an aryl group with 6 to 40 carbon atoms which may optionally have substituents at at least one of the 9-position or 10-position, and more preferably to have an aryl group with 6 to 30 carbon atoms which may optionally have substituents at at least one of the 9-position or 10-position.

[0150] Considering the viewpoint that the anthracene derivative can significantly improve the adhesion during heating after exposure and then development, especially achieving good adhesion even when the time from exposure to development is extended, it is preferably to have an aryl group with 6 to 40 carbon atoms which may optionally have substituents at the 9- and 10-positions, and more preferably to have an aryl group with 6 to 30 carbon atoms which may optionally have substituents at the 9- and 10-positions. The carbon numbers of the groups at the 9-position and 10-position may be the same or different. In addition, the groups at the 9-position and 10-position may be the same group or different groups. For example, the group at the 9-position may be an alkoxy group with 1 to 40 carbon atoms which may optionally have substituents, and the group at the 10-position may be an aryl group with 6 to 40 carbon atoms which may optionally have substituents.

[0151] Examples of the aryl group with 6 to 40 carbon atoms which may optionally have substituents include phenyl, biphenyl, naphthyl, anthryl; aryl groups formed by adding an alkoxy group, such as methoxyphenyl, ethoxyphenyl; aryl groups formed by adding an alkyl group, such as tolyl, xylyl, 2,4,6-trimethylphenyl, nonylphenyl; aryl groups formed by adding a halogen, such as chlorophenyl; aryl groups formed by adding a hydroxyl group, such as hydroxyphenyl, etc. Among them, phenyl is more preferred.

[0152] The anthracene derivative is preferably represented by the following general formula (IV).

[0153]

[0154] R 1 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group with 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group with 3 to 20 carbon atoms, an alkenyl group with 2 to 4 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group or an N(R’)2 group, and two or more R 1 may bond to each other to form a cyclic structure, and the cyclic structure may contain a heteroatom.

[0155] X independently represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, a -N(R’)- group, a -CO-O- group, a -CO-S- group, a -SO2-O- group, a -SO2-S- group, a -SO2-N(R’)- group, an -O-CO- group, a -S-CO- group, an -O-SO2- group or an S-SO2- group. However, the combination where X is a single bond and R 1 is a hydrogen atom (i.e., unsubstituted anthracene) is excluded.

[0156] In the above, R'represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group. R'may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a heteroatom.

[0157] p is an integer from 1 to 10, preferably 2 to 4.

[0158] As the above R 1 Examples of the substituted or unsubstituted alkyl group having 1 to 40 carbon atoms in R and R' specifically include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-icosyl, isopropyl, isobutyl, sec-butyl, and tert-butyl.

[0159] As the above R 1 Specific examples of the substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms in R and R' include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and bridged alicyclic hydrocarbon groups having 6 to 20 carbon atoms (such as norbornyl, tricyclodecyl, tetracyclododecyl, adamantyl, methyladamantyl, ethyladamantyl, and butyladamantyl, etc.).

[0160] As the above R 1 Specific examples of the alkenyl group having 2 to 4 carbon atoms in R and R' include vinyl and propenyl.

[0161] As the above R 1 Specific examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms in R and R' include phenyl, biphenyl, naphthyl, anthryl, methoxyphenyl, ethoxyphenyl, tolyl, xylyl, 2,4,6-trimethylphenyl, nonylphenyl, chlorophenyl, and hydroxyphenyl.

[0162] As the above R 1 Examples of the substituted or unsubstituted heteroaryl group in R and R' include groups containing one or more heteroatoms such as sulfur, oxygen, and nitrogen atoms in the substituted or unsubstituted aryl group, such as pyridyl, imidazolyl, morpholinyl, piperidinyl, and pyrrolidinyl.

[0163] In addition, the above R 1Each of the hydrocarbon groups of R and R' may be substituted with a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a hydroxyalkyl group having 1 to 4 carbon atoms (such as hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.), an alkoxy group having 1 to 4 carbon atoms (such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, tert-butoxy, etc.), a cyano group, a cyanoalkyl group having 2 to 5 carbon atoms (such as cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, etc.), an alkoxycarbonyl group (such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, etc.), an alkoxycarbonylalkoxy group (such as methoxycarbonylmethoxy, ethoxycarbonylmethoxy, tert-butoxycarbonylmethoxy, etc.), a halogen atom (such as fluorine, chlorine, etc.), and a fluoroalkyl group (such as fluoromethyl, trifluoromethyl, pentafluoroethyl, etc.). The above R 1 Each of the hydrocarbon groups of R and R' is preferably substituted with a halogen atom. In particular, the anthracene derivative preferably has an alkoxy group substituted with a halogen atom at the 9-position and / or 10-position.

[0164] As the above R 1 Preferred specific examples of R and R' include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a cyclopentyl group, a cyclohexyl group, a camphoroyl group, a norbornyl group, a p-toluoyl group, a benzyl group, a methylbenzyl group, a phenyl group, and a 1-naphthyl group.

[0165] Preferred specific examples of the above X include a single bond, an oxygen atom, a sulfur atom, a -N(R')- group, a -O-CO- group, and an O-SO2- group. Here, when the above X is a -N(R')- group, the above R' is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a cyclopentyl group, a cyclohexyl group, a camphoroyl group, a norbornyl group, or a benzyl group.

[0166] Examples of the compound represented by the above general formula (IV) include, for example, 1-methylanthracene, 2-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 9-methylanthracene, 9,10-dimethylanthracene, 9-vinylanthracene, 9-phenylanthracene, 9,10-diphenylanthracene, 2-bromo-9,10-diphenylanthracene, 9-(4-bromophenyl)-10-phenylanthracene, 9-(1-naphthyl)anthracene, 9-(2-naphthyl)anthracene, 2-bromo-9,10-bis(2-naphthyl)anthracene, 2,6-dibromo-9,10-bis(2-naphthyl)anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-bis(2-ethylhexoxy)anthracene, 1,2-benzanthracene, anthranol, 1,4,9,10-tetrahydroxyanthracene, 9-anthracenemethanol, 1-aminoanthracene, 2-aminoanthracene, 9-(methylaminomethyl)anthracene, 9-acetylanthracene, 9-anthracenecarbaldehyde, 10-methyl-9-anthracenecarbaldehyde, 1,8,9-triacetoxyanthracene, etc. Among them, 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-bis(2-ethylhexoxy)anthracene, 9,10-bis-(3-chloropropoxy)anthracene are preferred. Particularly, from the viewpoint of significantly improving the adhesion when heating is carried out after exposure and then development, especially achieving good adhesion even when the time from exposure to development is extended, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-bis-(3-chloropropoxy)anthracene are more preferred. 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-bis-(3-chloropropoxy)anthracene are particularly preferred. The compound represented by the above general formula (IV) can be used alone or in combination of two or more.

[0167] From the viewpoint of significantly improving the adhesion when heating is carried out after exposure and then development, especially obtaining good adhesion even when the time from exposure to development is extended, the (C) photopolymerization initiator preferably (1) contains 9,10-diphenylanthracene; (2) contains 9,10-dialkoxyanthracene; (3) contains an anthracene derivative having a halogen atom; (4) contains a halogen-substituted product of 9,10-dialkoxyanthracene; (5) contains a compound in which the alkoxy group at the 9-position and / or 10-position of 9,10-dialkoxyanthracene is modified by one or more halogen atoms; and / or (6) contains a compound having a halogen atom directly bonded to the anthracene skeleton.

[0168] The compound represented by the above general formula (IV) is advantageous in view of significantly improving the adhesion when heating is performed after exposure and then development, particularly in that good adhesion can be obtained even when the time from exposure to development is extended. Further, it is also advantageous from the viewpoint of providing a photosensitive resin composition that can be used for two-wavelength exposure using a first actinic light having a center wavelength of less than 390 nm and a second actinic light having a wavelength of 390 nm or more, and that exhibits excellent sensitivity, adhesion, and resolution.

[0169] In one aspect, the (C) photoinitiator preferably contains an anthracene derivative having a halogen atom. Preferred examples of the anthracene derivative having a halogen atom are halogen substituents of 9,10-dialkoxyanthracene. Preferred examples of the halogen substituent are compounds in which the alkoxy groups at the 9-position and / or 10-position of 9,10-dialkoxyanthracene are modified with one or more halogen atoms. As the preferred alkoxy group, the alkoxy groups exemplified above having 1 to 40 carbon atoms can be mentioned.

[0170] In one aspect, as the anthracene derivative, a compound having a halogen atom directly bonded to the anthracene skeleton is also preferred. Examples of such anthracene compounds include 9-bromo-10-phenylanthracene, 9-chloro-10-phenylanthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl)anthracene, 9-(2-biphenyl)-10-bromoanthracene, 9-(4-biphenyl)-10-bromoanthracene, 9-bromo-10-(9-phenanthryl)anthracene, 2-bromoanthracene, 9-bromoanthracene, 2-chloroanthracene, 9,10-dibromoanthracene.

[0171] The total amount of anthracene and anthracene derivatives, or the amount of the compound represented by the above general formula (IV) in a preferred embodiment, is preferably in the range of 0.05 to 5% by mass, more preferably in the range of 0.1 to 3% by mass, and particularly preferably in the range of 0.1 to 1.0% by mass with respect to the total solid content of the photosensitive resin composition.

[0172] Pyrazoline and pyrazoline derivatives are preferred from the viewpoints of the peeling characteristics, sensitivity, resolution, and adhesion of the photosensitive resin layer.

[0173] As pyrazoline derivatives, for example, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzoxazol-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, etc. are preferred from the above viewpoints, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferred.

[0174] As coumarin derivatives, 7-diethylamino-4-methylcoumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, etc. can be exemplified. Among them, 7-diethylamino-4-methylcoumarin is preferred from the viewpoints of sensitivity, resolution, and adhesion.

[0175] As further examples of the (C) photoinitiator, quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoates, oxime esters, acridines (for example, 9-phenylacridine, bisacridylheptane, 9-(p-methylphenyl)acridine, 9-(m-methylphenyl)acridine are preferred from the viewpoints of sensitivity, resolution, and adhesion), hexaarylbiimidazole, N-aryl amino acids or their ester compounds (for example, N-phenylglycine is preferred from the viewpoints of sensitivity, resolution, and adhesion), and halogen compounds (for example, tribromomethylphenyl sulfone) etc. can be mentioned. They may be used alone or in combination of two or more. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-oxide-phosphine, triphenylphosphine oxide etc. can also be used.

[0176] As the aromatic ketones, for example, benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone can be mentioned. They may be used alone or in combination of two or more. Among them, 4,4'-bis(diethylamino)benzophenone is preferred from the viewpoint of adhesion. Further, from the viewpoint of transmittance, the content of the aromatic ketones in the photosensitive resin composition is preferably in the range of 0.01 mass% to 0.5 mass%, more preferably in the range of 0.02 mass% to 0.3 mass%.

[0177] Examples of the hexaarylbiimidazole include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, etc. They can be used alone or in combination of two or more. From the viewpoints of sensitivity, resolution, and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

[0178] From the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin layer, the content of the hexaarylbiimidazole in the photosensitive resin composition is preferably in the range of 0.05% by mass to 8% by mass, more preferably in the range of 0.1% by mass to 7% by mass, and further preferably in the range of 1% by mass to 6% by mass.

[0179] (D) Phenolic polymerization inhibitor

[0180] In the photosensitive resin composition, in order to improve the thermal stability and storage stability, a phenolic inhibitor (D) is contained. In the present disclosure, the phenolic inhibitor (D) is a compound having one or more phenolic hydroxyl groups. The phenolic inhibitor has the property of hindering the polymerization reaction caused by heat or the like and improving the storage stability. The phenolic inhibitor may have one or more substituents selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. In a preferred embodiment, the phenolic inhibitor (D) is a monovalent phenol (i.e., a compound having one phenolic hydroxyl group in the molecule). More specific preferred examples of the phenolic inhibitor (D) include p-methoxyphenol, dibutylhydroxytoluene, hydroquinone, pentaerythritol tetra(3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl)propionate), 2,2’-thiobis(ethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)), stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N’-hexamethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide), octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 2,4,6-tris(3’,5’-di-tert-butyl-4’-hydroxybenzyl)mesitylene, 2,4-bis(dodecylthiomethyl)-6-methylphenol, 2,4-bis(octylthiomethyl)-6-methylphenol, bis(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid)(ethylenebis(oxyethylene))ester, 1,6-hexanediol bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 1,3,5-tris((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol, etc. From the viewpoint of being less likely to cause a difference in the shortest development time between heating and non-heating after exposure, p-methoxyphenol and dibutylhydroxytoluene are particularly preferred.

[0181] Regarding the amount of the phenolic polymerization inhibitor (D) based on the mass basis when the total solid content mass of the photosensitive resin composition is 100% by mass, it is 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, further preferably 15 ppm or more, particularly preferably 20 ppm or more from the viewpoint of obtaining the desired polymerization inhibition effect for the photosensitive resin composition. From the viewpoint of achieving good adhesion when heating is performed after exposure and then development, particularly when the time from exposure to development is extended, it is 300 ppm or less, preferably 200 ppm or less, more preferably 150 ppm or less, further preferably 100 ppm or less, further preferably 75 ppm or less, further preferably 50 ppm, particularly preferably 40 ppm or less. Although the photosensitive resin composition contains the phenolic polymerization inhibitor (D), the amount thereof is small, which is advantageous from the viewpoint of enabling the polymerization reaction during exposure in the photosensitive resin composition to proceed well and promoting the reaction of the polymer (thus improving adhesion) with good fluidity improvement effect achieved by heating the polymer when heating is performed after exposure and then development. For example, for a system in which the polymer has a bulky molecular structure (for example, a relatively large amount of styrene skeleton), when post-exposure heating intended to improve adhesion is performed, the fluidity improvement effect achieved by heating the polymer may be low (thus the adhesion improvement effect may be low). However, according to the photosensitive resin composition of the present embodiment, by the amount of the phenolic polymerization inhibitor (D) being within the above range, even in the presence of such a bulky polymer, the adhesion improvement effect achieved by post-exposure heating is obtained well.

[0182] In a particularly preferred embodiment, the content of dibutylhydroxytoluene in the photosensitive resin composition is 1 to 200 ppm, or 10 to 150 ppm.

[0183] [Optional Component]

[0184] The photosensitive resin composition may further contain optional components as needed in addition to the above components (A) to (D). Examples of the optional components include (d) additional polymerization inhibitors other than the phenolic polymerization inhibitor (D), dyes, coloring substances, plasticizers, antioxidants, stabilizers, etc. For example, the additives listed in Japanese Patent Application Laid-Open No. 2013-156369 can be used.

[0185] ((d) Additional Polymerization Inhibitor)

[0186] Examples of the additional polymerization inhibitor include radical polymerization inhibitors other than the above phenolic polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles.

[0187] Examples of the radical polymerization inhibitor include, for example, naphthylamine, cuprous chloride, aluminum salt of nitrosophenylhydroxylamine, diphenylnitrosamine, etc. Aluminum salt of nitrosophenylhydroxylamine is preferred in order not to impair the sensitivity of the photosensitive resin composition.

[0188] Examples of the benzotriazoles include, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylidene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylidene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylidene-1,2,3-benzotriazole, etc.

[0189] Examples of the carboxybenzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylidene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylidene carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylidene carboxybenzotriazole, etc.

[0190] In one mode, when the total mass of the solid components of the photosensitive resin composition is set to 100% by mass, the total amount of the additional polymerization inhibitor is preferably 0.001 to 3% by mass, more preferably 0.01% to 1% by mass. It is preferable that the total amount is 0.001% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, it is preferable that the total amount is 3% by mass or less from the viewpoints of maintaining sensitivity and suppressing dye decoloration.

[0191] (Dyes and coloring substances)

[0192] In the present embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of dyes (such as leuco dyes, fluorane dyes, etc.) and coloring substances, as needed.

[0193] Examples of the coloring substance include magenta, phthalocyanine green, basic flavine, para magenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (e.g., AIZEN (registered trademark) MALACHITE GREEN manufactured by HODOGAYA CHEMICAL CO., LTD.), basic blue 20, diamond green (e.g., AIZEN (registered trademark) DIAMOND GREEN GH manufactured by HODOGAYA CHEMICAL CO., LTD.). When the total solid content mass of the photosensitive resin composition is set to 100% by mass, the content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass. It is preferable that the content is 0.001% by mass or more from the viewpoint of improving the processability of the photosensitive resin composition and the like. On the other hand, from the viewpoint of maintaining the storage stability of the photosensitive resin composition and the like, it is preferable that the content is 1% by mass or less.

[0194] Since the photosensitive resin composition develops color in the exposed portion by containing a dye, it is preferable from the viewpoint of visibility. In addition, when a registration marker for exposure is read by an inspection machine or the like, it is easy to identify and advantageous when the contrast between the exposed portion and the unexposed portion is large. Examples of the dye preferably used from this viewpoint include leuco dyes and fluorane dyes.

[0195] Examples of the leuco dye include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leuco malachite green], and the like. In particular, from the viewpoint of good contrast, leuco crystal violet is preferably used as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass relative to the total solid content mass of the photosensitive resin composition. From the viewpoint of making the contrast between the exposed portion and the unexposed portion good, it is preferable that the content is 0.1% by mass or more. The content is more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more. On the other hand, from the viewpoint of maintaining storage stability, it is preferable that the content is 10% by mass or less. The content is more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

[0196] In addition, in the photosensitive resin composition, from the viewpoint of optimizing the adhesion and contrast, it is preferable to use a leuco dye and the halogen compound described above in the (C) photopolymerization initiator in combination. When the leuco dye and the halogen compound are used in combination, from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer, the content of the halogen compound in the photosensitive resin composition is preferably 0.01% by mass to 3% by mass when the total solid content mass of the photosensitive resin composition is set to 100% by mass.

[0197] In the present embodiment, the photosensitive resin composition may further contain an epoxy compound of bisphenol A. Examples of the epoxy compound of bisphenol A include a compound obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminal ends, etc.

[0198] In the present embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalic acid esters (e.g., diethyl phthalate, etc.), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyltriethyl citrate, acetyltri-n-propyl citrate, acetyltri-n-butyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, etc. In addition, compounds having a bisphenol skeleton such as Adekanol SDX-1569, Adekanol SDX-1570, Adekanol SDX-1571, Adekanol SDX-479 (manufactured by Asahi Denka Co., Ltd.), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, Newpol BPE-20T, Newpol BPE-60, Newpol BPE-100, Newpol BPE-180 (manufactured by Sanyo Chemical Industries, Ltd.), UNIOL DB-400, UNIOL DAB-800, UNIOL DA-350F, UNIOL DA-400, UNIOL DA-700 (manufactured by NOF Corporation), BA-P4UGlycol, BA-P8Glycol (manufactured by Nippon Emulsion Co., Ltd.) are also exemplified.

[0199] The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, relative to the total solid content mass of the photosensitive resin composition. From the viewpoints of suppressing the delay of the development time and imparting flexibility to the cured film, it is preferable that the content is 1% by mass or more. On the other hand, from the viewpoints of suppressing insufficient curing and cold flow, it is preferable that the content is 50% by mass or less.

[0200] If the amount of moisture in the photosensitive resin composition is large, local plasticization of the photosensitive resin composition is rapidly promoted, resulting in edge fusion. From the viewpoint of suppressing edge fusion, based on the photosensitive resin composition preparation liquid coated on the support film and the dried photosensitive resin composition, in terms of mass basis, the amount of moisture in the photosensitive resin composition is preferably 0.7% or less. The amount of moisture in the photosensitive resin composition is preferably 0.65% or less, preferably 0.6% or less, preferably 0.55% or less, preferably 0.5% or less, preferably 0.45% or less, preferably 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, preferably 0.25% or less, preferably 0.2% or less.

[0201] [Solvent]

[0202] The photosensitive resin composition can be dissolved in a solvent and used in the form of a photosensitive resin composition preparation liquid for the manufacture of a photosensitive resin laminate. Examples of the solvent include ketones, alcohols, etc. The aforementioned ketones are represented by methyl ethyl ketone (MEK) and acetone. The aforementioned alcohols are represented by methanol, ethanol, and isopropyl alcohol. The solvent is preferably added to the photosensitive resin composition in an amount such that the viscosity of the photosensitive resin composition preparation liquid coated on the support film at 25 °C is 500 mPa·s to 4000 mPa·s when manufacturing the photosensitive resin laminate.

[0203] [Light transmittance of the photosensitive resin composition]

[0204] Regarding the light transmittance of the photosensitive resin composition of the present embodiment at at least one of 375 nm and 405 nm, from the viewpoint of providing a photosensitive resin composition with good sensitivity, adhesion, line width reproducibility, and resolution when heated after exposure and then developed, especially achieving good adhesion even when the time from exposure to development is long, it is 58% to 95%. 375 nm and 405 nm correspond to the typical exposure wavelengths in the photosensitive resin composition of the present embodiment. This light transmittance is 58% or more, preferably 60% or more, more preferably 62% or more, more preferably 64% or more, further preferably 65% or more from the viewpoint of obtaining good sensitivity, adhesion, line width reproducibility, and resolution by allowing the exposure light to reach a deeper region of the photosensitive resin composition during exposure, and is 95% or less, preferably 85% or less, more preferably 80% or less, more preferably 75% or less, further preferably 70% or less from the viewpoint of obtaining a good curled edge shape by suppressing the diffuse reflected light from the substrate surface.

[0205] As a means of controlling the light transmittance at at least one of 375 nm and 405 nm within the above range, without being limited to them, examples include controlling the addition amount of a photoinitiator, a dye, or a coloring substance.

[0206] [Photosensitive resin laminate]

[0207] This embodiment also provides a photosensitive resin laminate having a photosensitive resin layer formed from the aforementioned photosensitive resin composition and a support film. As the support film, a transparent support film that transmits light emitted from an exposure light source is preferred. Examples of such support films include polyethylene terephthalate films, polyvinyl alcohol films, polyvinyl chloride films, vinyl chloride copolymer films, polyvinylidene chloride films, vinylidene chloride copolymer films, polymethyl methacrylate copolymer films, polystyrene films, polyacrylonitrile films, styrene copolymer films, polyamide films, cellulose derivative films, etc. As these films, stretched films can also be used as needed.

[0208] Regarding the haze of the support film, from the viewpoint of suppressing light scattering during exposure, it is preferably 5% or less, more preferably 2% or less, further preferably 1.5% or less, and particularly preferably 1.0% or less. From the same viewpoint, the surface roughness Ra of the surface in contact with the photosensitive layer is preferably 30 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less. The thinner the thickness of the film, the more improved the image formability and economy, which is therefore advantageous. However, in order to maintain the strength of the photosensitive resin laminate, a film with a thickness of 10 μm to 30 μm is preferably used. The size of fine particles such as lubricants contained in the support film is preferably less than 5 μm.

[0209] The support film can have a single-layer structure or a multilayer structure formed by laminating multiple resin layers with different compositions. In the case of a multilayer structure, an antistatic layer may also be present. In the case of a multilayer structure such as a two-layer structure or a three-layer structure, for example, a resin layer containing fine particles can be formed on one surface A, and on the other surface B, (1) it contains fine particles in the same manner as surface A, (2) it contains a smaller amount of fine particles than surface A, (3) it contains finer fine particles than surface A, (4) it does not contain fine particles, etc. In the case of the structures (2), (3), and (4), it is preferred to form the photosensitive resin layer on the surface B side. At this time, if a resin layer containing fine particles exists on the surface A side, it is preferred from the viewpoints of the smoothness of the film, etc. The size of the fine particles at this time is preferably less than 1.5 μm. It should be noted that the size of the above-mentioned fine particles is a value obtained by measurement using a scanning electron microscope calibrated with a standard specimen.

[0210] An important characteristic of the protective layer used in the photosensitive resin laminate is that its adhesion to the photosensitive resin layer is sufficiently smaller than that of the support film, and it can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. In addition, a film with excellent peelability shown in Japanese Patent Laid-Open No. 59-202457 can also be used. The film thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

[0211] Gels called fish eyes may exist on the surface of the polyethylene film. When using a polyethylene film with fish eyes as the protective layer, the fish eyes may be transferred to the photosensitive resin layer. If the fish eyes are transferred to the photosensitive resin layer, air may be entrapped during lamination to form voids, resulting in defects in the resist pattern. From the viewpoint of preventing fish eyes, as the material of the protective layer, stretched polypropylene is preferred. As a specific example, ALPHAN E-200A manufactured by Oji Paper Co., Ltd. can be cited.

[0212] The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the use, and is preferably 1 μm to 300 μm, more preferably 3 μm to 100 μm, particularly preferably 5 μm to 60 μm, and most preferably 10 μm to 30 μm. The thinner the thickness of the photosensitive resin layer, the better the resolution, and the thicker the thickness, the better the film strength.

[0213] The light transmittance at a wavelength of 630 nm of the laminate of the support film and the photosensitive resin layer is an index for the decolorization of the dye. A high light transmittance at a wavelength of 630 nm indicates that the dye is decolorized. The light transmittance of the laminate of the support film and the photosensitive resin layer at a wavelength of 630 nm is preferably 80% or less, preferably 78% or less, preferably 75% or less, preferably 72% or less, preferably 70% or less, preferably 68% or less, preferably 65% or less, preferably 62% or less, preferably 60% or less, preferably 58% or less, preferably 55% or less, preferably 52% or less, preferably 50% or less. This light transmittance is the value of the laminate of the support film and the photosensitive resin layer (i.e., not including the protective layer).

[0214] Next, a method for manufacturing the photosensitive resin laminate will be described.

[0215] As a method for sequentially laminating the support film, the photosensitive resin layer, and, if necessary, the protective layer to produce the photosensitive resin laminate, a known method can be employed. For example, the photosensitive resin composition used in the photosensitive resin layer is mixed with a solvent for dissolving it to form a uniform solution, which is first coated on the support film using a bar coater or a roll coater, and then dried to remove the aforementioned solvent, whereby a photosensitive resin layer formed from the photosensitive resin composition can be laminated on the support film. Next, if necessary, a protective layer is laminated on the photosensitive resin layer, whereby a photosensitive resin laminate can be produced.

[0216] <Method for Forming Resist Pattern>

[0217] Next, an example of a method for manufacturing a resist pattern using the photosensitive resin laminate of the present embodiment will be described. This method may include an exposure step of exposing the photosensitive resin composition, a heating step of heating the exposed photosensitive resin composition, and a developing step of developing the photosensitive resin composition.

[0218] Examples of the resist pattern include patterns such as printed wiring boards, semiconductor elements, printing plates, liquid crystal display panels, touch panels, flexible substrates, lead frame substrates, substrates for COF (chip on film), substrates for semiconductor packages, transparent electrodes for liquid crystals, wirings for TFTs for liquid crystals, and electrodes for PDP (plasma display panels). As an example, the manufacturing method of a printed wiring board will be described below.

[0219] The printed wiring board is manufactured through the following respective processes.

[0220] (1) Lamination process

[0221] First, in the lamination process, a photosensitive resin layer is formed on the substrate using a lamination device. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed onto the substrate surface using the lamination device for lamination. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), etc.

[0222] In this embodiment, the photosensitive resin layer can be laminated only on one side of the substrate surface or on both sides as needed. The heating temperature during lamination is usually 40°C to 160°C. In addition, by performing heat-pressing during lamination two or more times, the adhesion of the obtained resist pattern to the substrate can be improved. During heat-pressing, a two-stage lamination device equipped with double rollers can be used, or the laminate of the substrate and the photosensitive resin layer can be passed through the rollers several times for pressing.

[0223] (2) Exposure process

[0224] In this process, the photosensitive resin layer is exposed by the following methods: an exposure method in which a mask film having a desired wiring pattern is adhered to a support film and an active light source is used; an exposure method by direct drawing of a drawing pattern as the desired wiring pattern; or an exposure method using projection of an image of a photomask through a lens.

[0225] The exposure process is preferably performed by the following methods: an exposure method by direct drawing of a drawing pattern; or an exposure method by projection of an image of a photomask through a lens, and more preferably by an exposure method by direct drawing of a drawing pattern. The advantage of the photosensitive resin composition of this embodiment is more significant in the exposure method by direct drawing of a drawing pattern or the exposure method by projection of an image of a photomask through a lens, and particularly significant in the exposure method by direct drawing of a drawing pattern.

[0226] When the exposure process uses a direct drawing exposure method, it is preferable to use a laser with a center wavelength of less than 390 nm or a laser with a center wavelength of 390 nm or more. More preferably, a laser with a center wavelength of 350 nm or more and 380 nm or less, or a laser with a center wavelength of 400 nm or more and 410 nm or less. Further preferably, the exposure is performed by a method using a first laser with a center wavelength of less than 390 nm and a second laser with a center wavelength of 390 nm or more. Additionally, it is more preferable that the center wavelength of the first laser is 350 nm or more and 380 nm or less, and the center wavelength of the second laser is 400 nm or more and 410 nm or less.

[0227] (3) Heating process

[0228] In this process, it is preferable to perform a heating process on the exposed photosensitive resin composition at about 30°C to about 200°C, more preferably in the range of 30°C to 150°C, and further preferably in the range of 60°C to 120°C. By performing this heating process, the resolution and adhesion can be improved. Heating can be carried out using a heating furnace, constant temperature bath, hot plate, hot air dryer, infrared dryer, hot roll, etc. in the form of hot air, infrared rays, or far-infrared rays. If the heating method is a hot roll, it is preferable from the viewpoint of being able to perform processing in a short time, and the hot roll is more preferably double or more.

[0229] Especially in the present invention, by using a (D) phenolic polymerization inhibitor in a small amount and controlling the light transmittance of the resin composition at a specific wavelength within a specific range, the fluidity of the polymer is improved according to heating during development after exposure. For example, even in the case of a system with a relatively high content of styrene backbone, the hydrophobicity of the styrene backbone and the reactivity of the carbon-carbon double bond can be highly balanced. As a result, the sensitivity, adhesion, line width reproducibility, and resolution can be significantly improved. Moreover, due to the significant improvement in adhesion, good adhesion can be obtained even when the time from exposure to development is long. Additionally, from the viewpoint of the effects of the present invention, it is preferable that the aforementioned heating process is performed within 15 minutes after exposure, and more preferably within 10 minutes.

[0230] (4) Development process

[0231] In this process, after exposure, the support film on the photosensitive resin layer is peeled off, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution, thereby forming a resist pattern on the substrate.

[0232] As the alkaline aqueous solution, an aqueous solution of Na2CO3 or K2CO3 is used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but a concentration of about 0.2 mass% to about 2 mass% and an aqueous solution of Na2CO3 at about 20°C to about 40°C are preferred.

[0233] In an exemplary manner, the time from exposure to development (i.e., the time from the end of exposure to the start of development) can be 5 minutes or more, or 60 minutes or more, or 180 minutes or more, and can also be 1440 minutes or less, or 720 minutes or less, or 300 minutes or less.

[0234] The resist pattern can be obtained through the above-mentioned steps (1) to (4).

[0235] In the method for manufacturing a circuit board of the present invention, a circuit board is formed by performing etching or plating on a substrate having a resist pattern manufactured by the above method.

[0236] (5) Etching step or plating step

[0237] Etching or plating is performed on the substrate surface (e.g., the copper surface of a copper-clad laminate) exposed by development to manufacture a conductor pattern.

[0238] (6) Stripping step

[0239] Then, if necessary, the resist pattern is peeled off from the substrate using an appropriate stripping solution. As the stripping solution, for example, an alkaline aqueous solution, an amine-based stripping solution, etc. can be cited. However, the resist pattern formed by heating after exposure of the photosensitive resin composition of the present invention has the following advantages: while showing good stripping properties with respect to the amine-based stripping solution, the stripping film is not overly refined. Therefore, if an amine-based stripping solution is used as the stripping solution, the advantageous effects of the present invention are further exerted and it is preferred.

[0240] The amine contained in the amine-based stripping solution can be an inorganic amine or an organic amine.

[0241] As the inorganic amine, for example, ammonia, hydroxylamine, hydrazine, etc. can be cited.

[0242] As the organic amine, for example, ethanolamine, propanolamine, alkylamine, cyclic amine, quaternary ammonium salt, etc. can be cited. As specific examples thereof,

[0243] As ethanolamine, for example, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, aminoethoxyethanol, etc.;

[0244] As propanolamine, for example, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, etc.;

[0245] As alkylamine, for example, monomethylamine, dimethylamine, trimethylamine, ethylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, tetraethylenepentamine, etc.;

[0246] As cyclic amines, such as choline, morpholine, etc.;

[0247] As quaternary ammonium salts, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, N,N,N-triethyl-N-(2-hydroxyethyl)ammonium hydroxide, N,N-diethyl-N,N-bis(2-hydroxyethyl)ammonium hydroxide, etc.

[0248] The amine-based stripping solution can be an aqueous solution containing one or more of the above-exemplified amines. The concentration of the amine in the aqueous solution can be appropriately set according to the purpose, the composition of the photosensitive resin layer, the developing conditions, etc.

[0249] The amine-based stripping solution can also contain additives commonly used in stripping agents, such as surfactants, defoamers, pH adjusters, preservatives, anti-redeposition agents, etc.

[0250] The stripping process is carried out, for example, at a temperature of 0°C or higher and 100°C or lower, preferably at a temperature of room temperature (23°C) or higher and 50°C or lower, for a time of 1 second or longer and 1 hour or shorter, preferably 10 seconds or longer and 10 minutes or shorter.

[0251] After the stripping process, if necessary, the substrate after removing the resist pattern can be washed with, for example, pure water.

[0252] The photosensitive resin laminate of the present embodiment is a photosensitive resin laminate suitable for manufacturing conductor patterns for printed wiring boards, flexible substrates, lead frame substrates, touch panel substrates, substrates for COF, substrates for semiconductor packages, transparent electrodes for liquid crystals, wirings for TFTs for liquid crystals, electrodes for PDPs, etc.

[0253] It should be noted that for the above various parameters, unless otherwise specified, they are measured according to the measurement methods in the following examples or methods understood by those skilled in the art to be equivalent thereto.

[0254] Examples

[0255] Next, examples and comparative examples are listed to more specifically illustrate the present embodiment. However, the present embodiment is not limited by the following examples as long as it does not deviate from its gist. The physical properties in the examples are measured by the following methods.

[0256] The measurement of the physical property values of the polymer and the method for producing the evaluation samples in the examples and comparative examples are described. In addition, the evaluation method for the obtained samples and the evaluation results are shown.

[0257] (1) Measurement and calculation of physical property values

[0258] <Measurement of the weight average molecular weight or number average molecular weight of the polymer>

[0259] The weight-average molecular weight or number-average molecular weight of the polymer is determined in terms of polystyrene conversion by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, model PU-1580, chromatographic columns: four Shodex (registered trademark) columns (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko K.K. connected in series, mobile phase solvent: tetrahydrofuran, using a standard curve obtained with a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.)).

[0260] Furthermore, the dispersity of the polymer is calculated as the ratio of the weight-average molecular weight to the number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0261] <Acid equivalent>

[0262] In the present disclosure, the acid equivalent refers to the mass (grams) of a polymer having 1 equivalent of carboxyl groups in the molecule. The acid equivalent is measured by potentiometric titration using a Hiranuma Automatic Titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. and a 0.1 mol / L aqueous sodium hydroxide solution.

[0263] <I / O value>

[0264] The I / O value of the alkali-soluble polymer is derived by the following method. First, the I value and O value of each comonomer constituting the polymer are calculated by the methods described in non-patent documents (Organic Conceptual Diagram (written by Yoshio Koda, Sankyo Publishing Co., Ltd. (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Items 1 to 16 (1954); Chemical Field, Vol. 11, No. 10, Items 719 to 725 (1957); FRAGRANCE JOURNAL, No. 34, Items 97 to 111 (1979); FRAGRANCE JOURNAL, No. 50, Items 79 to 82 (1981)). Then, the aforementioned I value and O value are averaged using the molar ratio of the comonomers, thereby obtaining the I average value and O average value. Then, the obtained I average value is divided by the O average value, thereby deriving the I / O value.

[0265] <Glass transition temperature Tg>

[0266] The glass transition temperature Tg of the alkali-soluble polymer is determined by the Fox equation. When determining the glass transition temperature Tg, the glass transition temperature of the homopolymer containing the comonomer corresponding to the formation of the alkali-soluble polymer is used, and the values shown in the non-patent literature (Brandrup, J. Immergut, E. H. eds., "Polymer handbook, Third edition, John wiley&sons, 1989, p. 209, Chapter VI 'Glass transition temperatures of polymers'") are used. It should be noted that in the examples, the glass transition temperatures of the homopolymers containing each comonomer used in the calculation are shown in Table 1. When the alkali-soluble polymer is composed of two or more polymers, the value obtained by the following formula is the glass transition temperature of the alkali-soluble polymer.

[0267]

[0268] {In the formula, W i is the solid weight of each alkali-soluble polymer, Tg i is the glass transition temperature of each alkali-soluble polymer determined by the Fox equation, W total is the total solid weight of each alkali-soluble polymer, and n is the number of types of alkali-soluble polymers contained in the photosensitive resin composition}

[0269] (2) Method for producing the evaluation sample

[0270] The evaluation sample is produced as follows.

[0271] <Production of the photosensitive resin laminate>

[0272] The components shown in Tables 1 to 3 below (where the numbers of the respective components represent the compounding amounts (parts by mass) as solid components) and a solvent are sufficiently stirred and mixed to obtain a photosensitive resin composition preparation liquid. The details of the components shown in Tables 1 and 2 are shown in Table 3. As the support film, a 16-μm-thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., FB-40) is used, and the preparation liquid is uniformly coated on its surface using a bar coater and dried in a dryer at 95°C for 3 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer is 30 μm.

[0273] Next, a 19-μm-thick polyethylene film (manufactured by TAMAPOLY CO., LTD., GF-18) as a protective layer is laminated on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film is not laminated, to obtain a photosensitive resin laminate.

[0274] It should be noted that the amounts of methoxyphenol and butylated hydroxytoluene in Tables 1 and 2 refer to the concentrations of the respective components based on the total amount of the solid components in the photosensitive resin composition.

[0275] <Entire substrate surface>

[0276] As an image evaluation substrate, for a 0.4 mm thick copper-clad laminate with a 35 μm rolled copper foil laminated, using an abrasive (manufactured by Uji Electrochemical Industry Co., Ltd., #400) at a jet pressure of 0.2 MPa, after jet flushing, the substrate surface was washed with a 10 mass% H2SO4 aqueous solution.

[0277] <Lamination>

[0278] While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, on the copper-clad laminate preheated to 50 °C, the photosensitive resin laminate was laminated through a hot roll laminating device (manufactured by Asahi Kasei Corporation, AL-700) at a roll temperature of 105 °C. The air pressure was set to 0.35 MPa and the lamination speed was set to 1.5 m / minute.

[0279] <Exposure>

[0280] For the evaluation substrate after 2 hours of lamination, through a direct drawing exposure machine (manufactured by Orbotech Ltd., Nuvogo Fine 10, light source: 375 nm (30%) + 405 nm (70%)), exposure was performed using a Stauffer 41-step exposure meter. Exposure was performed at an exposure amount such that the highest remaining film step number during exposure and development using the aforementioned Stauffer 41-step exposure meter as a mask was 14 steps.

[0281] <Heating>

[0282] For the evaluation substrate after 7 minutes of exposure, heating was performed through a hot roll laminating device (manufactured by Asahi Kasei Corporation, AL-700). The roll temperature was set to 105 °C, the air pressure was set to 0.30 MPa, and the lamination speed was set to 1 m / minute. It should be noted that if the time from exposure to development is extended, the heating effect is lost, so usually heating is performed for about 1 minute after exposure. Therefore, the heating 7 minutes after exposure in this example is a very strict condition.

[0283] <Development>

[0284] After peeling off the polyethylene terephthalate film (support film), a soda developer (manufactured by FUJI KIKOU CO., LTD., a developer for dry film) is used to spray a 1% by mass aqueous Na2CO3 solution at 30°C for a specified time for development. The development spraying time is set to twice the shortest development time, and the post-development water washing spraying time is set to three times the shortest development time. At this time, the shortest time required for the complete dissolution of the unexposed part of the photosensitive resin layer is taken as the shortest development time.

[0285] (3) Evaluation method of samples

[0286] <Amount of p-methoxyphenol>

[0287] The amount of p-methoxyphenol in the photosensitive resin composition is determined by the internal standard method using a gas chromatograph (hereinafter simply referred to as GC) manufactured by Shimadzu Corporation. The detector is a flame ionization detector (hereinafter simply referred to as FID), and n-docosane is used as the internal standard.

[0288] <Amount of dibutylhydroxytoluene>

[0289] The amount of dibutylhydroxytoluene in the photosensitive resin composition is determined by GC in the same manner as the amount of p-methoxyphenol. n-Octadecane is used as the internal standard.

[0290] <Transmittance>

[0291] The transmittance of each resin composition at 375 nm and 405 nm is measured by the following method.

[0292] For the transmittance of each wavelength of the photosensitive resin laminate from which the polyethylene film (protective layer) has been peeled off, a spectrophotometer (Hitachi High-Tech Corporation., U-3010) is used for measurement. At this time, the measurement is carried out by setting it so that the transmitted light passes through in the film thickness direction of the photosensitive resin laminate.

[0293] <Sensitivity evaluation>

[0294] In the above exposure process, after exposure through a mask of a Stauffer 41-step stepwise exposure table, development is carried out, and the exposure amount (mJ / cm 2 ) at which the highest residual film level is 14 is determined as the sensitivity value.

[0295] <Line width reproducibility>

[0296] In the above exposure process, exposure is carried out using drawing data of a line pattern having a ratio of the width of the exposed part to the unexposed part of 20 μm:20 μm. Development is carried out according to the above development conditions to form a cured resist line.

[0297] The line width of the cured resist line is determined as the value of line width reproducibility.

[0298] <Resolution>

[0299] In the above exposure process, exposure is performed using the drawing data of a line pattern having a ratio of the width of the exposed portion to the unexposed portion of 1:1. Development is carried out according to the above development conditions to form a cured resist line.

[0300] The minimum line width at which the cured resist line is normally formed is determined as the value of resolution.

[0301] <Adhesion>

[0302] In the above exposure process, exposure is performed using the drawing data of a line pattern having a ratio of the width of the exposed portion to the unexposed portion of x μm:200 μm. Development is carried out according to the above development conditions, and the minimum line width at which the cured resist line is normally formed is measured by an optical microscope. This measurement is performed for 4 lines, and the average value of these 4 line widths is determined as the value of adhesion.

[0303] For the evaluation of adhesion only, evaluation is performed in two cases: when heating is performed 1 minute after exposure and when heating is performed 7 minutes after exposure.

[0304] <Delay of the shortest development time>

[0305] In the above development process, for the case where development is performed without heating after exposure and the case where development is performed after heating 7 minutes after exposure, the shortest time required for the photosensitive resin layer of the unexposed portion to be completely dissolved, that is, the shortest development time, is measured and classified according to the following criteria.

[0306] Good: There is no difference in the shortest development time between when heating is performed after exposure and when heating is not performed after exposure.

[0307] Pass: The shortest development time when heating is performed after exposure is delayed by 1 second or less compared to when heating is not performed after exposure.

[0308] Fail: The shortest development time when heating is performed after exposure is delayed by more than 1 second compared to when heating is not performed after exposure.

[0309] The results are shown in Tables 1 and 2.

[0310] Since the post-exposure heating conditions in this embodiment are for heating 7 minutes after exposure, they are very strict conditions. For example, for the compositions of Example 3 and Comparative Example 2, the adhesion when developing without heating after exposure is 13.8 μm in both cases. That is, in the composition of Comparative Example 1, no effect was found when heating 7 minutes after exposure, but in Example 3, even under very strict conditions, the adhesion can be improved. In addition, under the condition of heating 1 minute after exposure, the adhesion of 10.8 μm was obtained in both the compositions of Example 7 and Comparative Example 1. From the above results, it can be seen that even when the adhesion is good under normal post-exposure heating conditions, the adhesion does not become good under the strict condition of heating 7 minutes after exposure. However, by the present invention, initially even under such strict post-exposure heating conditions, the adhesion can be made good. Thus, when manufacturing a circuit board, good adhesion can be obtained even if the time from exposure to development is extended, and therefore a highly fine circuit pattern can be stably formed.

[0311] [Table 1]

[0312]

[0313] [Table 2]

[0314]

[0315] [Table 3]

[0316]

[0317] Industrial Applicability

[0318] The photosensitive resin composition provided by the present invention has good sensitivity, adhesion, line width reproducibility and resolution when heating after exposure and then developing. Especially, good adhesion can be achieved even when the time from exposure to development is long. Therefore, it can be widely used as a photosensitive resin composition.

Claims

1. A photosensitive resin composition, comprising: (A) An alkali-soluble polymer: 10% by mass to 90% by mass; (B) A compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; (C) A photopolymerization initiator: 0.01% by mass to 20% by mass; and (D) A phenolic inhibitor: 40 ppm to 300 ppm, wherein the phenolic inhibitor contains p-methoxyphenol and / or dibutylhydroxytoluene, and the photosensitive resin composition has a light transmittance of 58% to 95% at at least one of 375 nm and 405 nm.

2. The photosensitive resin composition according to claim 1, which contains p-methoxyphenol as the (D) phenolic inhibitor.

3. The photosensitive resin composition according to claim 1 or 2, which contains dibutylhydroxytoluene as the (D) phenolic inhibitor.

4. The photosensitive resin composition according to claim 3, wherein, The content of the dibutylhydroxytoluene is 1 to 200 ppm.

5. The photosensitive resin composition according to claim 3, wherein, The content of the dibutylhydroxytoluene is 10 to 150 ppm.

6. The photosensitive resin composition according to claim 1 or 2, wherein The I / O value of the (A) alkali-soluble polymer is 0.600 or less.

7. The photosensitive resin composition according to claim 1 or 2, wherein The (C) photopolymerization initiator contains one or more selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and their derivatives.

8. The photosensitive resin composition according to claim 7, wherein, The (C) photopolymerization initiator contains anthracene and / or an anthracene derivative.

9. The photosensitive resin composition according to claim 1 or 2, wherein The structural unit of styrene and / or a styrene derivative in the (A) alkali-soluble polymer is 26% by mass or more.

10. The photosensitive resin composition according to claim 1 or 2, wherein, The (A) alkali-soluble polymer contains a structural unit of benzyl (meth)acrylate as a monomer component.

11. The photosensitive resin composition according to claim 1 or 2, wherein The glass transition temperature of the (A) alkali-soluble polymer is 120°C or less.

12. The photosensitive resin composition according to claim 1 or 2, wherein The (B) compound having an ethylenically unsaturated double bond contains a compound having three or more methacrylate groups in the molecule in an amount of 5% by mass or more based on the total solid content of the photosensitive resin composition.

13. The photosensitive resin composition according to claim 1 or 2, which is used to obtain an exposed resin cured product by using a first laser having a center wavelength of less than 390 nm and a second laser having a center wavelength of 390 nm or more.

14. The photosensitive resin composition according to claim 13, wherein, The center wavelength of the first laser is 350 nm or more and 380 nm or less, and the center wavelength of the second laser is 400 nm or more and 410 nm or less.

15. The photosensitive resin composition according to claim 1 or 2, which can form a pattern through the following steps: An exposure step of exposing the photosensitive resin composition; A heating step of heating the exposed photosensitive resin composition; and A developing step of developing the heated photosensitive resin composition.

16. The photosensitive resin composition according to claim 15, wherein, The heating temperature in the heating step is in the range of 30°C to 150°C.

17. The photosensitive resin composition according to claim 15, wherein, The heating step is performed within 15 minutes after exposure.

18. A method for forming an etching pattern, comprising the following steps: An exposure step of exposing the photosensitive resin composition according to any one of claims 1 to 17; A heating step of heating the exposed photosensitive resin composition; and A developing step of developing the heated photosensitive resin composition.

19. The method for forming a resist pattern according to claim 18, wherein, The heating temperature in the heating step is in the range of 30°C to 150°C.

20. The method for forming a resist pattern according to claim 18 or 19, wherein, The heating process is carried out within 15 minutes after exposure.

21. The method for forming a resist pattern according to claim 18 or 19, wherein, The exposure process is carried out by an exposure method of directly drawing a pattern to be drawn or by an exposure method of projecting an image of a photomask through a lens.

22. The method for forming a resist pattern according to claim 21, wherein, The exposure process is carried out by an exposure method of directly drawing a pattern to be drawn.

23. The method for forming a resist pattern according to claim 22, wherein, The exposure process is carried out by a method of performing exposure using a first laser having a center wavelength of less than 390 nm and a second laser having a center wavelength of 390 nm or more.

24. The method for forming a resist pattern according to claim 23, wherein, The center wavelength of the first laser is 350 nm or more and 380 nm or less, and the center wavelength of the second laser is 400 nm or more and 410 nm or less.

25. A method for manufacturing a circuit board, comprising the following processes: An anti-resist pattern forming process of forming an anti-resist pattern on a substrate by the method according to any one of claims 18 to 24; and A circuit board forming process of forming a circuit board by performing etching or plating on the substrate having the anti-resist pattern.

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