Photosensitive resin composition and method for forming resist pattern

Abstract

Provided is a photosensitive resin composition having good sensitivity, adhesion, line width reproducibility and resolution when developing after heating after exposure, and in particular, good adhesion even when the time from exposure to development is long. One aspect of the present invention provides a photosensitive resin composition, which contains: (A) 10% to 90% by mass of an alkali-soluble polymer; (B) 5% to 70% by mass of a compound having an ethylenically unsaturated double bond; (C) 0.01% to 20% by mass of a photopolymerization initiator; and (D) 1 ppm to 300 ppm of a phenolic polymerization inhibitor, wherein the light transmittance of the photosensitive resin composition at at least one of 375 nm and 405 nm is 58% to 95%.

Description

Technical Field

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

[0002] Printed wiring boards are used in electronic devices such as personal computers and mobile phones to mount components and semiconductors. In the past, photosensitive resin laminates, which are formed by laminating a photosensitive resin layer on a supporting film and further laminating a protective film on the photosensitive resin layer as needed, were used as resists for manufacturing printed wiring boards. So-called dry film photoresists (hereinafter sometimes referred to as DF) are used. Currently, the photosensitive resin layer is generally an alkali-developable type photosensitive resin layer using a weak alkali aqueous solution as a developer.

[0003] When using DF to make a printed wiring board, for example, the following process is used. When DF has a protective film, the protective film is first peeled off. Then, DF is laminated on a substrate for permanent circuit production such as a copper-clad laminate or a flexible substrate using a laminating device, and exposed through a wiring pattern mask film. Then, the supporting film is peeled off as needed, and the photosensitive resin layer of the uncured portion (for example, the unexposed portion for a negative type) is dissolved or dispersed and removed using a developer to form a cured resist pattern (hereinafter sometimes simply referred to as a resist pattern) on the substrate.

[0004] After forming the resist pattern, the process of forming the circuit can be roughly divided into two methods. The first method is to remove the substrate surface not covered by the resist pattern (such as the copper surface of the copper-clad laminate) by etching, and then remove the resist pattern part using an alkaline aqueous solution stronger than the developer (etching method).

[0005] The second method is a method (plating method) in which the substrate surface is plated with copper, solder, nickel, tin, etc., and then the resist pattern is partially removed in the same manner as the first method, and the exposed substrate surface (e.g., the copper surface of a copper-clad laminate) is etched. Copper chloride, ferric chloride, a copper-ammine complex solution, etc. are used for etching.

[0006] In recent years, with the miniaturization and lightness of electronic devices, and the miniaturization and high density of printed wiring boards, a high-performance DF with high resolution and high adhesion is required in the above-mentioned manufacturing process. As a technology for achieving such high resolution, Patent Document 1 describes a photosensitive resin composition with improved resolution by using a specific thermoplastic resin, a monomer and a photopolymerization initiator.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2010-249884 Summary of the invention

[0010] Problem that the invention aims to solve

[0011] After the exposure process, the photosensitive resin layer is sometimes subjected to a heating process as needed, and then developed. By implementing such a heating process, 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 process is added after exposure, the adhesion and resolution are still insufficient when using the conventional photosensitive resin composition, or if the time from exposure to development is prolonged, good adhesion cannot be obtained.

[0012] The present invention is proposed in view of such actual situations in the past, and one aspect of the present invention aims to provide a photosensitive resin composition which has good sensitivity, adhesion, line width reproducibility and resolution when developing after heating after exposure, and in particular achieves good adhesion even when the time from exposure to development is long.

[0013] Solutions for solving problems

[0014] The present invention includes the following aspects.

[0015] [1] A photosensitive resin composition comprising:

[0016] (A) alkali-soluble polymer: 10% to 90% by mass;

[0017] (B) Compounds having an ethylenically unsaturated double bond: 5% to 70% by mass;

[0018] (C) photopolymerization initiator: 0.01% to 20% by mass; and

[0019] (D) Phenol-based polymerization inhibitor: 1 ppm to 300 ppm,

[0020] The photosensitive resin composition has a light transmittance of 58% to 95% at at least one of 375 nm and 405 nm.

[0021] [2] The photosensitive resin composition according to the above aspect 1, comprising p-hydroxyanisole as the (D) phenolic polymerization inhibitor.

[0022] [3] The photosensitive resin composition according to the above aspect 1 or 2, comprising dibutylhydroxytoluene as the (D) phenolic polymerization inhibitor.

[0023] [4] The photosensitive resin composition according to the above embodiment 3, wherein the content of the dibutylhydroxytoluene is 1 to 200 ppm.

[0024] [5] The photosensitive resin composition according to the above embodiment 3, wherein the content of the dibutylhydroxytoluene is 10 to 150 ppm.

[0025] [6] The photosensitive resin composition according to any one of aspects 1 to 5, wherein the I / O value of the alkali-soluble polymer (A) is 0.600 or less.

[0026] [7] The photosensitive resin composition according to any one of aspects 1 to 6, wherein the (C) photopolymerization initiator contains one or more selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof.

[0027] [8] The photosensitive resin composition according to the above aspect 7, wherein the (C) photopolymerization initiator contains anthracene and / or an anthracene derivative.

[0028] [9] The photosensitive resin composition according to any one of aspects 1 to 8, wherein the structural unit of styrene and / or a styrene derivative in the alkali-soluble polymer (A) is 26% by mass or more.

[0029]

[10] The photosensitive resin composition according to any one of aspects 1 to 9, wherein the alkali-soluble polymer (A) contains a structural unit of benzyl (meth)acrylate as a monomer component.

[0030]

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

[0031]

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

[0032]

[13] The photosensitive resin composition according to any one of aspects 1 to 12, which is used to obtain an exposed resin cured product using a first laser beam having a central wavelength of less than 390 nm and a second laser beam having a central wavelength of 390 nm or more.

[0033]

[14] The photosensitive resin composition according to any one of aspects 1 to 13, wherein the center wavelength of the first laser light is 350 nm to 380 nm, and the center wavelength of the second laser light is 400 nm to 410 nm.

[0034]

[15] The photosensitive resin composition according to any one of aspects 1 to 14 above, which can be patterned by the following steps:

[0035] an exposure step of exposing the photosensitive resin composition to light;

[0036] a heating step of heating the exposed photosensitive resin composition; and

[0037] A developing step of developing the heated photosensitive resin composition.

[0038]

[16] The photosensitive resin composition according to any one of aspects 1 to 15, wherein the heating temperature in the heating step is within a range of 30°C to 150°C.

[0039]

[17] The photosensitive resin composition according to any one of aspects 1 to 16, wherein the heating step is performed within 15 minutes after the exposure.

[0040]

[18] A method for forming a resist pattern, comprising the following steps:

[0041] an exposure step of exposing the photosensitive resin composition according to any one of the above aspects 1 to 17;

[0042] a heating step of heating the exposed photosensitive resin composition; and

[0043] A developing step of developing the heated photosensitive resin composition.

[0044]

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

[0045]

[20] A method for forming a resist pattern according to the above-mentioned embodiment 18 or 19, wherein the heating step is performed within 15 minutes after exposure.

[0046]

[21] A method for forming a resist pattern according to any one of the above-mentioned methods 18 to 20, wherein the above-mentioned exposure step is performed by an exposure method using direct drawing of a drawing pattern, or an exposure method using a lens to project an image of a photomask.

[0047]

[22] A method for forming a resist pattern according to the above-mentioned embodiment 21, wherein the exposure step is performed by an exposure method using direct drawing of a drawing pattern.

[0048]

[23] A method for forming an anti-etching pattern according to the above-mentioned method 22, wherein the above-mentioned exposure step is carried out by using a first laser with a central wavelength less than 390nm and a second laser with a central wavelength greater than 390nm for exposure.

[0049]

[24] A method for forming an anti-etching pattern according to the above-mentioned method 23, wherein the central wavelength of the aforementioned first laser is greater than 350nm and less than 380nm, and the central wavelength of the aforementioned second laser is greater than 400nm and less than 410nm.

[0050]

[25] A method for manufacturing a circuit substrate, comprising the following steps:

[0051] A resist pattern forming step of forming a resist pattern on a substrate by the method of any one of aspects 18 to 24 above; and

[0052] A circuit substrate forming step of forming a circuit substrate by etching or plating the substrate having the resist pattern.

[0053] Effects of the Invention

[0054] According to the present invention, there is provided a photosensitive resin composition which has excellent sensitivity, adhesion, line width reproducibility and resolution when developing after heating after exposure, and which achieves excellent adhesion even when the time from exposure to development is long. DETAILED DESCRIPTION

[0055] The following is a detailed description of the exemplary embodiments for implementing the present invention (hereinafter referred to as "embodiment"). It should be noted that the present invention is not limited to the following embodiments, and can be implemented in various ways within the scope of its purpose. In addition, for various measured values ​​in this specification, unless otherwise specified, they are measured according to the method described in the item of [Examples] of the present disclosure or understood by those skilled in the art as being equivalent to this method.

[0056] <Photosensitive resin composition>

[0057] 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 polymerization inhibitor. In addition, in the present embodiment, a photosensitive resin layer can be formed by applying the photosensitive resin composition to any support. The above composition of the photosensitive resin composition of the present embodiment is useful for obtaining a cured resin by heating after exposure and then developing.

[0058] The photosensitive resin composition of the present embodiment can be a photosensitive resin composition for obtaining a resin cured product by exposure to a first active light having a central wavelength of less than 390 nm and a second active light having a central wavelength of more than 390 nm. The active light is, for example, a laser. In this embodiment, the photosensitive resin composition has photosensitivity to both the first active light having a central wavelength of less than 390 nm and the second active light having a central wavelength of more than 390 nm. The central wavelength of the first active light is preferably 350 to 380 nm, more preferably 355 to 375 nm, and particularly preferably 375 nm. The central wavelength of the second active light is preferably 400 to 410 nm, more preferably 402 to 408 nm, and particularly preferably 405 nm (h-ray).

[0059] Hereinafter, each component contained in the photosensitive resin composition will be described.

[0060] (A) Alkali-soluble polymer

[0061] (A) The alkali-soluble polymer is a polymer that can be dissolved in an alkali substance. From the viewpoint of alkali developability, the alkali-soluble polymer (A) preferably has a carboxyl group, and more preferably is a copolymer containing a carboxyl group-containing monomer as a copolymer component. The alkali-soluble polymer (A) may be thermoplastic.

[0062] The photosensitive resin composition preferably contains a copolymer having an aromatic group as (A) an alkali-soluble polymer from the viewpoint of high resolution and curling shape (suso shape) of the resist pattern. The photosensitive resin composition particularly preferably contains a copolymer having an aromatic group in a side chain as (A) an alkali-soluble polymer. As such an aromatic group, for example, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group can be cited. 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.

[0063] From the viewpoint of high resolution and curling shape of the resist pattern, the copolymerization ratio of the comonomer having an aromatic group in the (A) 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 restriction 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, and more preferably 90% by mass or less.

[0064] Examples of the comonomer having an aromatic group include styrene, polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, 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.

[0065] For the total ratio of the structural units of styrene and / or styrene derivatives in all (A) alkali-soluble polymers, it is preferred that 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, and more preferably 40% by mass or more, from the viewpoint that the adhesion when heating after exposure and then developing can be significantly improved, especially even when the time from exposure to development is extended, good adhesion can be obtained. The styrene skeleton can suppress the swelling property to the developer and show good adhesion because it is hydrophobic. However, when the content of the styrene skeleton is high, there is a tendency that the fluidity of the polymer is low and the reactivity is reduced, and thus there is a tendency that the adhesion is reduced. In addition, if the time from exposure to development is extended, the free radicals in the system are deactivated, so the adhesion improvement effect achieved by heating after exposure is reduced. In the present invention, by heating after exposure and then developing, even if the system has a high content of styrene skeleton, the fluidity of the polymer will be improved by heating, and the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly taken into account, and it is believed that good adhesion can be achieved. It is also believed that good adhesion can be obtained even if the time from exposure to development is extended. For the total ratio of the structural units of styrene and / or styrene derivatives in all (A) alkali-soluble polymers, from the viewpoint of obtaining the advantages achieved by the presence of other structural units, preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less is appropriate.

[0066] Examples of the comonomer having an aralkyl group include a monomer having a substituted or unsubstituted benzyl group and a monomer having a substituted or unsubstituted phenylalkyl group (excluding a benzyl group). Among them, a monomer having a substituted or unsubstituted benzyl group is preferred.

[0067] Examples of the comonomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and benzyl (meth)acrylate chloride; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol.

[0068] The alkali-soluble polymer (A) preferably contains a structural unit of benzyl (meth)acrylate as a monomer component from the viewpoint that the adhesion when developing after heating after exposure can be significantly improved, especially that good adhesion can be achieved even when the time from exposure to development is extended. 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, more preferably 15 to 60% by mass, more preferably 20 to 40% by mass, and further preferably 20 to 30% by mass. In addition, from the same viewpoint, the alkali-soluble polymer (A) preferably has both structural units of styrene and / or styrene derivatives and structural units of benzyl (meth)acrylate.

[0069] Examples of the comonomer having a phenylalkyl group (excluding a benzyl group) include phenylethyl (meth)acrylate and the like.

[0070] The copolymer having an aromatic group (preferably a benzyl group) in a side chain is preferably obtained by polymerizing (i) a monomer having an aromatic group and (ii) at least one of the first monomers described below and / or at least one of the second monomers described below.

[0071] The (A) alkali-soluble polymer other than the copolymer having an aromatic group in a 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.

[0072] 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.

[0073] It should be noted that, in the present 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”.

[0074] The copolymerization ratio of the first monomer is preferably 10 to 50% by mass by taking the total mass of all monomer components of the polymer obtained by polymerizing at least one of the first monomers as a reference. The copolymerization ratio is preferably 10% to 50% by mass from the viewpoint of showing good developability and from the viewpoint of controlling edge fusion. The copolymerization ratio is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, particularly preferably 22% by mass or less, and most preferably 20% by mass or less from the viewpoint of high resolution and curling shape of the resist pattern and from the viewpoint of chemical resistance of the resist pattern.

[0075] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylate 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 and other (meth)acrylate esters; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and n-butyl (meth)acrylate are preferred.

[0076] (A) The alkali-soluble polymer can be produced by polymerizing one or more monomers described above by a known polymerization method, preferably addition polymerization, more preferably radical polymerization.

[0077] From the viewpoint of chemical resistance, adhesion, high resolution, or curling shape of the anti-etching pattern, it is preferred that the monomer contains a monomer having an aralkyl group and / or styrene. As (A) the 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.

[0078] (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), and 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 the compound. The I / O value is described in detail in, for example, non-patent literature (Organic Concept Map (written by Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Items 1 to 16 (1954); Field of Chemistry, 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)); and other literature. The concept of I / O value is to divide the properties of compounds into organic groups representing covalent bonds and inorganic groups representing ionic bonds, and to represent all organic compounds by positioning them as points on coordinates of orthogonal axes named organic axis and inorganic axis respectively. The closer the I / O value is to 0, the more non-polar (i.e., hydrophobic, or highly organic) organic compounds are, and the larger the I / O value is, the more polar (i.e., hydrophilic, or highly inorganic) organic compounds are.

[0079] The I / O value of the alkali-soluble polymer (A) is preferably 0.600 or less, more preferably 0.570 or less, further preferably 0.520 or less, and particularly preferably 0.490 or less, from the viewpoint of adhesion and resolution of the resist pattern when developing after heating after exposure, and is preferably 0.300 or more, more preferably 0.400 or more, and further preferably 0.450 or more, from the viewpoint of resolution and peelability when developing after heating after exposure.

[0080] The glass transition temperature of the (A) alkali-soluble polymer is a value obtained by the Fox equation (when the (A) alkali-soluble polymer contains a plurality of polymers, the glass transition temperature Tg of the entire mixture, i.e., the weight average value of the glass transition temperature Tg total ), from the viewpoint of chemical resistance, adhesion, high resolution, or curling shape of the resist pattern, 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 of the glass transition temperature (Tg) of the (A) alkali-soluble polymer, but from the viewpoint of controlling edge fusion, it is preferably 30°C or more, more preferably 50°C or more, and further preferably 60°C or more. It should be noted that as the glass transition temperature of a homopolymer containing the same monomers as one or more monomers constituting the (A) alkali-soluble polymer, the value shown in the non-patent literature (Brandrup, J. Immergut, EH, "Polymer handbook, Third edition, Johnwiley & sons, 1989, p. 209 Chapter VI 'Glass transition temperatures of polymers'") is used.

[0081] The acid equivalent of the alkali-soluble polymer (A) (the acid equivalent of the entire mixture when the component (A) contains a plurality of copolymers) is preferably 100 or more from the viewpoint of the development resistance of the photosensitive resin layer and the resolution and adhesion of the resist pattern, and is preferably 600 or less from the viewpoint of the developability and peelability of the photosensitive resin layer. The acid equivalent of the alkali-soluble polymer (A) is more preferably 200 to 500, and even more preferably 250 to 450.

[0082] The weight average molecular weight of the alkali-soluble polymer (A) (when the component (A) contains a plurality of copolymers, the weight average molecular weight of the entire mixture) is preferably 5,000 to 500,000. The weight average molecular weight of the alkali-soluble polymer (A) is preferably 5,000 or more from the viewpoint of maintaining a uniform thickness of the dry film resist and obtaining resistance to a developer, and is preferably 500,000 or less from the viewpoint of maintaining the developability of the dry film resist, from the viewpoint of high resolution and curling shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern. The weight average molecular weight of the alkali-soluble polymer (A) is more preferably 10,000 to 200,000, further preferably 20,000 to 100,000, and particularly preferably 30,000 to 70,000. The molecular weight dispersion of the alkali-soluble polymer (A) is preferably 1.0 to 6.0, more preferably 1.0 to 4.0, and more preferably 1.0 to 3.0.

[0083] The content of the alkali-soluble polymer (A) in the photosensitive resin composition is in the range of 10% to 90% by mass, preferably in the range of 20% to 80% by mass, and more preferably in the range of 40% to 60% by mass, based on the total solid content of the photosensitive resin composition (hereinafter, the same for each component unless otherwise specified). The content of the alkali-soluble polymer (A) is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and is preferably 90% by mass or less, more preferably 80% by mass or less, more preferably 70% by mass or less, and more preferably 60% by mass or less from the viewpoint of the resist pattern formed by exposure fully exerting the performance as a resist material, from the viewpoint of the high resolution of the resist pattern and the curling shape of the resist pattern, and further from the viewpoint of the chemical resistance of the resist pattern.

[0084] (B) Compounds having an ethylenically unsaturated bond

[0085] (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 viewpoint of adhesion and from the viewpoint of suppressing the foaming property of the developer, the compound having an ethylenically unsaturated bond (B) preferably has an oxyalkylene structure having 3 or more carbon atoms. The carbon number of the oxyalkylene structure is more preferably 3 to 6, and further preferably 3 to 4.

[0086] Examples of the (B) compound having one (meth)acryloyl group as an ethylenically unsaturated bond include compounds obtained by adding (meth)acrylic acid to one terminal of a polyoxyalkylene group, compounds obtained by adding (meth)acrylic acid to one terminal of a polyoxyalkylene group and alkyl-etherifying or allyl-etherifying the other terminal, and phthalic acid-based compounds. These are preferred from the viewpoint of releasability and flexibility of the cured film.

[0087] Examples of such compounds include phenoxyhexaethylene glycol mono(meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polyethylene glycol to a phenyl group; 4-n-nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polypropylene glycol to which an average of 2 mol of propylene oxide is added and polyethylene glycol to which an average of 7 mol of ethylene oxide is added, and 2-nitro-4-nitro- ... 4-n-nonylphenoxy heptaethylene glycol monopropylene glycol (meth)acrylate which is a (meth)acrylate of a compound formed by adding a polypropylene glycol obtained by adding propylene oxide of 1 mol and a polyethylene glycol obtained by adding an average of 5 mol of ethylene oxide to nonylphenol; 4-n-nonylphenoxy octaethylene glycol (meth)acrylate which is an acrylate of a compound formed by adding a polyethylene glycol obtained by adding an average of 8 mol of ethylene oxide to nonylphenol (for example, M-114 manufactured by Toagosei Co., Ltd.); and the like.

[0088] Moreover, when γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-phthalate is contained, it is also preferable from the viewpoint of sensitivity, resolution, and adhesion in addition to the above viewpoints.

[0089] Examples of the compound having two (meth)acryloyl groups in the molecule include a compound having (meth)acryloyl groups at both ends of an oxyalkylene chain, and a compound having (meth)acryloyl groups at both ends of an oxyalkylene chain in which an oxyethylene chain and a oxypropylene chain are randomly or block-bonded.

[0090] Examples of such compounds include polyethylene 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 12 mols of ethylene oxide chains, as well as polypropylene glycol di(meth)acrylate and polybutylene glycol di(meth)acrylate. Examples of polyoxyalkylene di(meth)acrylate compounds containing oxyethylene groups and oxypropylene groups include dimethacrylates of diols obtained by further adding an average of 3 mols of ethylene oxide to both ends of polypropylene glycol to which an average of 12 mols of propylene oxide have been added, dimethacrylates of diols obtained by further adding an average of 15 mols of ethylene oxide to both ends of polypropylene glycol to which an average of 18 mols of propylene oxide have been added, FA-023M, FA-024M, FA-027M (product names, manufactured by Hitachi Chemical Industries, Ltd.), etc. These are preferred from the viewpoints of flexibility, resolution, adhesion, etc.

[0091] As another example of the compound having two (meth)acryloyl groups in the molecule, a compound having (meth)acryloyl groups at both terminals by modifying bisphenol A with an alkylene oxide is preferred from the viewpoint of resolution and adhesion.

[0092] Specifically, a compound represented by the following general formula (I) can be used.

[0093]

[0094] {In the formula, R 1 and R 2 Each independently represents a hydrogen atom or a methyl group, A is C 2 H 4 , B is C 3 H 6 , n 1 and n 3 are each independently an integer from 0 to 39, and n 1 +n 3 is an integer from 0 to 40, n 2 and n 4 are each independently an integer from 0 to 29, and n 2 +n 4 is an integer from 0 to 30, and the arrangement of the repeating units of -(AO)- and -(BO)- may be random or block. In the case of a block, any one of -(AO)- and -(BO)- may be a bisphenyl side.

[0095] For example, from the viewpoint of resolution and adhesion, preferred are polyethylene glycol dimethacrylates obtained by adding an average of 5 mol of ethylene oxide to both ends of bisphenol A, polyethylene glycol dimethacrylates obtained by adding an average of 2 mol of ethylene oxide to both ends of bisphenol A, and polyethylene glycol dimethacrylates obtained by adding an average of 1 mol of ethylene oxide to both ends of bisphenol A.

[0096] In addition, compounds in which the aromatic ring in the above general formula (I) has a heteroatom and / or a substituent may also be used.

[0097] Examples of the hetero atom include a halogen atom, and 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, a phenacyl group, 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 alkylmercapto 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 having 1 to 10 carbon atoms in an alkyl group, an acyl group having 1 to 10 carbon atoms in an alkyl group, 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, a heterocyclic ring-containing group, or an aryl group substituted with any of these substituents. These substituents may form a condensed ring, or hydrogen atoms in these substituents may be substituted with heteroatoms such as halogen atoms. When the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

[0098] As (B) a compound having an ethylenically unsaturated double bond, from the viewpoint that the adhesion when developing is performed after heating after exposure can be significantly improved, and in particular, good adhesion can be obtained even when the time from exposure to development is prolonged, it is preferred to contain a (meth)acrylate compound having more than 3 ethylenically unsaturated double bonds (i.e., trifunctional or more). From the same viewpoint, it is more preferred to contain a (meth)acrylate compound having more than 4 ethylenically unsaturated double bonds, further preferably a (meth)acrylate compound having more than 5 ethylenically unsaturated double bonds, and particularly preferably a (meth)acrylate compound having more than 6 ethylenically unsaturated double bonds. In addition, from the same viewpoint, they are preferably methacrylate compounds. Compounds having more than 3, more than 4, more than 5, or more than 6 ethylenically unsaturated double bonds are believed to have the effect of increasing the crosslinking density when polymerized by exposure, but due to the influence of steric hindrance caused by the large number of functional groups, the desired crosslinking density is mostly not obtained. In the present invention, it is found that it is preferred to use a compound having more than 3 ethylenically unsaturated double bonds, more preferably a compound having more than 4 ethylenically unsaturated double bonds, further preferably a compound having more than 5 ethylenically unsaturated double bonds, and particularly preferably a compound having more than 6 ethylenically unsaturated double bonds. Even if heat treatment is performed after exposure, the fluidity in the system is improved, so that 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 more than 3 ethylenically unsaturated double bonds, more preferably a compound having more than 4 ethylenically unsaturated double bonds, further preferably a compound having more than 5 ethylenically unsaturated double bonds, and particularly preferably a compound having more than 6 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 relative to the solid content of the aforementioned photosensitive resin composition. In addition, as the upper limit of the content, from the viewpoint of showing 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.

[0099] Examples of the (b1) (meth)acrylate compound having three or more ethylenically unsaturated bonds include:

[0100] 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 viewpoint of flexibility, adhesion, and suppression of bleed-out, tri(meth)acrylate obtained by adding 21 mol of ethylene oxide to trimethylolpropane on average, and tri(meth)acrylate obtained by adding 30 mol of ethylene oxide to trimethylolpropane on average);

[0101] Tetra(meth)acrylates, such as di(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.;

[0102] Penta(meth)acrylates, such as dipentaerythritol penta(meth)acrylate, etc.;

[0103] Hexa(meth)acrylate, for example, dipentaerythritol hexa(meth)acrylate, etc.

[0104] Among them, tetra-, penta- or hexa-(meth)acrylate is preferred.

[0105] The (meth)acrylate compound (b1) having three or more ethylenically unsaturated bonds preferably has a weight average molecular weight of 500 or more, more preferably 700 or more, and even more preferably 900 or more, from the viewpoint of suppressing bleed-out.

[0106] As the tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate is preferred. As the pentaerythritol tetra(meth)acrylate, a tetra(meth)acrylate obtained by adding 1 to 40 mol of alkylene oxide in total to four terminals of pentaerythritol is preferred.

[0107] The tetra(meth)acrylate is more preferably a tetra(meth)acrylate compound represented by the following general formula (II):

[0108]

[0109] {In the formula, R 3 ~R 6 Each independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, m 1 、m 2 、m 3 and m 4 are each independently an integer of 0 to 40, m 1 +m 2 +m 3 +m 4 is 1 to 40, and m 1 +m 2 +m 3 +m 4 When X is 2 or more, the plurality of Xs may be the same as or different from each other.

[0110] Although not intending to be bound by theory, it is believed that the tetramethacrylate compound represented by the general formula (II) has a group R 3 ~R 6 , with H 2Compared with tetramethacrylates having a C=CH-CO-O- portion, the hydrolysis in an alkaline solution can be suppressed. From the viewpoint of significantly improving the adhesion when developing after heating after exposure, and especially achieving good adhesion even when the time from exposure to development is prolonged, it is preferred to use a photosensitive resin composition containing a tetramethacrylate compound represented by general formula (II).

[0111] In the general formula (II), the group R 3 ~R 6 At least one of them is preferably a methyl group, and more preferably a group R 3 ~R 6 All are methyl.

[0112] From the viewpoint of obtaining the desired resolution, curling shape, and residual film rate for the resist pattern, it is preferred that in the general formula (II), X is -CH 2 -CH 2 -.

[0113] From the viewpoint of obtaining the desired resolution, curling shape, and residual film rate for the resist pattern, it is preferred that in the general formula (II), m 1 、m 2 、m 3 and m 4 Each independently represents an integer of 1 to 20, more preferably an integer of 2 to 10. In the general formula (II), m 1 +m 2 +m 3 +m 4 1~36 or 4~36.

[0114] Examples of the compound represented by the general formula (II) include pentaerythritol (poly) alkoxytetramethacrylate and the like. In the present disclosure, the term "pentaerythritol (poly) alkoxytetramethacrylate" includes compounds represented by the general formula (II) above, wherein m 1 +m 2 +m 3 +m 4 =1 "pentaerythritol alkoxytetramethacrylate" and m 1 +m 2 +m 3 +m 4 =2 to 40. Examples of the compound represented by the general formula (II) include compounds listed in JP-A-2013-156369, for example, pentaerythritol (poly) alkoxytetramethacrylate.

[0115] The hexa(meth)acrylate compound is preferably a hexa(meth)acrylate obtained by adding 1 to 24 mol of ethylene oxide in total to the six terminals of dipentaerythritol, or a hexa(meth)acrylate obtained by adding 1 to 10 mol of ε-caprolactone in total to the six terminals of dipentaerythritol.

[0116] In the photosensitive resin composition of the present embodiment, the compound (B) having an ethylenically unsaturated bond preferably contains a (meth)acrylate compound having 4 or more ethylenically unsaturated bonds and an oxyalkylene chain, from the viewpoint that the adhesion when developing after heating after exposure can be significantly improved, and in particular, good adhesion can be achieved even when the time from exposure to development is prolonged. In this case, the ethylenically unsaturated bond is more preferably derived from a methacryloyl group, and the oxyalkylene chain is more preferably an oxyethylene chain.

[0117] In the present embodiment, from the viewpoint that the adhesion when developing after heating after exposure can be significantly improved, especially the good adhesion can be achieved even when the time from exposure to development is extended, in the photosensitive resin composition, as (B) a compound having an ethylenically unsaturated bond, it is preferred to contain a (methyl) acrylate compound having an oxidized alkylene chain and a dipentaerythritol skeleton. As an oxidized alkylene chain, for example, an oxidized ethylene chain, an oxidized propylene chain, an oxidized butylene chain, an oxidized pentylene chain, an oxidized hexylene chain, etc. can be listed. In the case where the photosensitive resin composition contains a plurality of oxidized alkylene chains, they may be the same or different from each other. From the above viewpoint, as an oxidized alkylene chain, an oxidized ethylene chain, an oxidized propylene chain and an oxidized butylene chain are more preferably used, an oxidized ethylene chain and an oxidized propylene chain are further preferred, and an oxidized ethylene chain is particularly preferred.

[0118] In the photosensitive resin composition, by using the (A) alkali-soluble polymer and the (meth)acrylate compound having an oxyalkylene chain and a dipentaerythritol skeleton in combination, the chemical resistance, adhesion, and resolution of the resist pattern tend to be well balanced.

[0119] The (meth)acrylate compound having an oxyalkylene chain and a dipentaerythritol skeleton is an ester of a dipentaerythritol compound and (meth)acrylic acid in which at least one of the multiple hydroxyl groups is modified with an oxyalkylene group. The six hydroxyl groups of the dipentaerythritol skeleton may be modified with an oxyalkylene group. The number of ester bonds in one ester molecule may be 1 to 6, preferably 6.

[0120] Examples of the (meth)acrylate compound having an oxyalkylene chain and a dipentaerythritol skeleton include hexa(meth)acrylates obtained by adding 4 to 30 mol, 6 to 24 mol, or 10 to 14 mol of alkylene oxide to dipentaerythritol.

[0121] Specifically, as the (meth)acrylate compound having an oxyalkylene chain and a dipentaerythritol skeleton, the compound represented by the following general formula (III) is preferred from the viewpoint that the adhesion when developing is performed after heating after exposure can be significantly improved, and in particular, good adhesion can be achieved even when the time from exposure to development is prolonged:

[0122]

[0123] {wherein, R each 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 preferred that the average value of all n is 4 or more, or that each n is 1 or more. R is preferably a methyl group.

[0124] From the same viewpoint, the content of the (meth)acrylate compound having an oxyalkylene chain and a dipentaerythritol skeleton 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 further preferably in the range of 7% by mass to 30% by mass, relative to the total solid content.

[0125] The content of (b1) a (meth)acrylate compound having three or more ethylenically unsaturated bonds (i.e., a compound having three or more (meth)acrylate groups) is preferably greater than 0% by mass and less than 50% by mass relative to the total solid content of the photosensitive resin composition. If the content exceeds 0% by mass, it is more advantageous from the viewpoint of significantly improving adhesion when heating after exposure and then developing, especially from the viewpoint of achieving good adhesion even when the time from exposure to development is extended. If it is less than 50% by mass, there is a tendency to improve the flexibility of the cured resist and shorten the stripping time. The content is more preferably greater than 2% by mass and less than 40% by mass, and further preferably greater than 4% by mass and less than 35% by mass. In a more preferred embodiment, the compound (B) having an ethylenically unsaturated double bond contains a compound having three or more methacrylate groups in the molecule in an amount of preferably 5% by mass or more, more preferably 9% by mass or more, further preferably 13% by mass or more, particularly preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, relative to the solid content of the entire photosensitive resin composition.

[0126] From the viewpoint of adhesion and from the viewpoint of suppressing the foaming of the developer, the photosensitive resin composition preferably contains (b2) a compound having an oxybutylene chain or an oxypropylene chain and 1 or 2 (meth)acryloyl groups as the compound having an ethylenically unsaturated bond (B).

[0127] The (b2) compound having an oxybutylene chain or an oxypropylene chain and one or two (meth)acryloyl groups preferably has a molecular weight of 500 or more, more preferably 700 or more, and even more preferably 1000 or more, from the viewpoint of suppressing bleed-out.

[0128] Examples of the compound (b2) having an oxidized butylene chain or an oxidized propylene chain and one or two (meth)acryloyl groups include polypropylene glycol (meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol (meth)acrylate, polytetramethylene glycol di(meth)acrylate, etc. The compound (b2) having an oxidized butylene chain or an oxidized propylene chain and one or two (meth)acryloyl groups may further contain an oxidized ethylene chain in addition to the oxidized butylene chain or the oxidized propylene chain.

[0129] Specifically, the compound (b2) having an oxybutylene chain or an oxypropylene chain and one or two (meth)acryloyl groups preferably has 1 to 20, more preferably 4 to 15, and even more preferably 6 to 12 C 4 H 8 O or C 3 H 6 O (meth)acrylate or di(meth)acrylate.

[0130] 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 not more than 20% by mass based on the total solid content of the photosensitive resin composition.

[0131] In the present embodiment, in order to suppress the oozing out of the constituent components of the dry film resist and improve the storage stability, the total solid content of the compound (B) having an ethylenically unsaturated bond is used as a reference, 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 is a compound having a weight average molecular weight of 500 or more. From the viewpoint of suppressing oozing out 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 obtained as a molecular weight calculated from the molecular structure of the compound (B) having an ethylenically unsaturated bond. In the case where there are multiple (B) compounds having an ethylenically unsaturated bond, the molecular weight of each compound can be obtained by weighted averaging the molecular weight according to the content.

[0132] From the viewpoint of chemical resistance, adhesion, high resolution and curling shape of the resist pattern, the concentration of the methacryloyl group 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 of the concentration of the methacryloyl group is not limited as long as polymerizability and alkali developability are ensured, and may be, for example, 0.90 mol / 100 g or less or 0.80 mol / 100 g or less.

[0133] From the same viewpoint, the value of the concentration of methacryloyl groups in the compound (B) having an ethylenically unsaturated bond / (concentration of methacryloyl groups + 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.

[0134] The (meth)acrylate compounds described above can be used independently or in combination. The photosensitive resin composition may further contain other compounds as (B) compounds having ethylenically unsaturated bonds. Other compounds include (meth)acrylates having urethane bonds, compounds obtained by reacting polyols with α,β-unsaturated carboxylic acids, compounds obtained by reacting glycidyl-containing compounds with α,β-unsaturated carboxylic acids, 1,6-hexanediol di(meth)acrylate, and the like.

[0135] (B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid content mass of the photosensitive resin composition is preferably 5% to 70% by mass. The ratio of 5% by mass or more is preferred from the viewpoints of sensitivity, resolution and adhesion. The ratio is more preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. On the other hand, from the viewpoint of suppressing edge fusion and delayed peeling of the cured resist, the ratio is preferably 70% by mass or less. More preferably, the ratio is 50% by mass or less.

[0136] (C) Photopolymerization initiator

[0137] (C) Photopolymerization initiator is a compound that polymerizes monomers by light. From the viewpoint that the adhesion when developing after heating after exposure can be significantly improved, especially when the time from exposure to development can be extended, good adhesion can be obtained, (C) photopolymerization initiator preferably contains one or more selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and their derivatives, more preferably anthracene and / or anthracene derivatives, and further preferably anthracene derivatives. In addition, anthracene, pyrazoline, triphenylamine, coumarin, and their derivatives, especially anthracene and / or anthracene derivatives absorb the first active light with a central wavelength of less than 390nm and the second active light with a central wavelength of more than 390nm and function well as a polymerization initiator. Therefore, in one embodiment, the photosensitive resin composition can have photosensitivity to the first active light and the second active light, and can also be used for 2-wavelength exposure. (C) Photopolymerization initiator can also be selected in a manner having multiple absorption maxima within the wavelength range of the first active light and the second active light.

[0138] The total content of the photopolymerization initiator (C) 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 to 10% by mass, further preferably in the range of 0.1 to 7% by mass, and particularly preferably in the range of 0.1 to 6% by mass. The total content of the photopolymerization initiator (C) is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and is 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.

[0139] Anthracene and anthracene derivatives are advantageous from the viewpoint of significantly improving the adhesion when developing after heating after exposure, and especially achieving good adhesion even when the time from exposure to development is prolonged. From the same viewpoint, anthracene derivatives preferably have an alkoxy group having 1 to 40 carbon atoms and / or an aryl group having 6 to 40 carbon atoms which may have a substituent at the 9- and / or 10-positions, more preferably at the 9- and 10-positions.

[0140] In one embodiment, the anthracene derivative preferably has an alkoxy group having 1 to 40 carbon atoms which may be substituted at at least one of the 9-position or the 10-position, and more preferably has an alkoxy group having 1 to 30 carbon atoms which may be substituted at at least one of the 9-position or the 10-position, from the viewpoint of significantly improving the adhesion when developing after heating after exposure, and especially achieving good adhesion even when the time from exposure to development is prolonged. From the viewpoint of obtaining good adhesion and resolution, it is preferred that an alkoxy group having 1 to 40 carbon atoms which may be substituted at the 9- and 10-positions, and more preferably has an alkoxy group having 1 to 30 carbon atoms which may be substituted at the 9- and 10-positions. The carbon numbers of the groups at the 9- and 10-positions may be the same or different.

[0141] Examples of the alkoxy group which may have a substituent include:

[0142] 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;

[0143] Alkoxy groups modified with halogen, such as chlorobutoxy and chloropropoxy;

[0144] Alkoxy groups to which hydroxy groups are added, such as hydroxybutoxy;

[0145] Alkoxy groups to which cyano groups are added, such as cyanobutyloxy;

[0146] Alkoxy groups to which oxyalkylene groups are added, such as methoxybutoxy;

[0147] Alkoxy groups to which an aryl group is added include, for example, phenoxybutoxy groups, etc. Among them, n-butoxy groups are more preferred.

[0148] In one embodiment, the anthracene derivative preferably has an aromatic group having 6 to 40 carbon atoms which may have a substituent at at least one of the 9-position or the 10-position, and more preferably has an aromatic group having 6 to 30 carbon atoms which may have a substituent at at least one of the 9-position or the 10-position, from the viewpoint that the adhesion when the development is performed after heating after exposure can be significantly improved, and in particular, good adhesion can be achieved even when the time from exposure to development is prolonged.

[0149] From the viewpoint of significantly improving the adhesion when developing after heating after exposure, and especially achieving good adhesion even when the time from exposure to development is prolonged, it is preferred to have an aryl group with 6 to 40 carbon atoms which may have a substituent at the 9th and 10th positions, and more preferably an aryl group with 6 to 30 carbon atoms which may have a substituent at the 9th and 10th positions. The carbon numbers of the groups at the 9th and 10th positions may be the same or different. In addition, the groups at the 9th and 10th positions may be the same group or different groups. For example, the group at the 9th position may be an alkoxy group with 1 to 40 carbon atoms which may have a substituent, and the group at the 10th position may be an aryl group with 6 to 40 carbon atoms which may have a substituent.

[0150] Examples of the aryl group having 6 to 40 carbon atoms and optionally having a substituent include phenyl, biphenyl, naphthyl, anthracenyl, aryl groups to which an alkoxy group is added, such as methoxyphenyl and ethoxyphenyl, aryl groups to which an alkyl group is added, such as tolyl, xylyl, mesityl, and nonylphenyl, aryl groups to which a halogen is added, such as chlorophenyl, and aryl groups to which a hydroxyl group is added, such as hydroxyphenyl, etc. Among these, phenyl groups are more preferred.

[0151] The anthracene derivative is preferably represented by the following general formula (IV).

[0152]

[0153] R 1 independently represent 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, a substituted or unsubstituted heteroaryl group, or N(R') 2 Base, 2 or more R 1 They may be bonded to each other to form a ring structure, and the ring structure may contain a heteroatom.

[0154] 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 -SO 2 -O-base, -SO 2 -S-base, -SO 2 -N(R')-based, -O-CO-based, -S-CO-based, -O-SO 2 -base or S-SO 2 - group. However, X is a single bond, and R 1 The exception is the combination of hydrogen atoms (ie, unsubstituted anthracene).

[0155] 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 or a substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms, and R' groups may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a heteroatom.

[0156] p is an integer of 1-10, preferably 2-4.

[0157] As the above R 1 and R', and the substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, specifically, 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-eicosyl, isopropyl, isobutyl, sec-butyl and tert-butyl.

[0158] As the above R 1 Specific examples of the substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms in R' include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and bridged alicyclic hydrocarbon groups having 6 to 20 carbon atoms (e.g., norbornyl, tricyclodecanyl, tetracyclododecyl, adamantyl, methyladamantyl, ethyladamantyl and butyladamantyl).

[0159] As the above R 1 Specific examples of the alkenyl group having 2 to 4 carbon atoms in R' include vinyl group and propenyl group.

[0160] As the above R 1 Specific examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms in R′ include phenyl, biphenyl, naphthyl, anthracenyl, methoxyphenyl, ethoxyphenyl, tolyl, xylyl, mesityl, nonylphenyl, chlorophenyl, and hydroxyphenyl.

[0161] As the above R 1 Examples of the substituted or unsubstituted heteroaryl group in R' include groups containing one or more heteroatoms such as sulfur atoms, oxygen atoms, and nitrogen atoms in substituted or unsubstituted aryl groups, such as pyridyl, imidazolyl, morpholinyl, piperidinyl, and pyrrolidinyl.

[0162] In addition, the above R 1 Each of the hydrocarbon groups of R and R' may be substituted with a substituent. Examples of such substituents include hydroxyl, carboxyl, hydroxyalkyl having 1 to 4 carbon atoms (e.g., hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.), alkoxy having 1 to 4 carbon atoms (e.g., methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, tert-butoxy, etc.), cyano, cyanoalkyl having 2 to 5 carbon atoms (e.g., cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, etc.), alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, etc.), alkoxycarbonylalkoxy (e.g., methoxycarbonylmethoxy, ethoxycarbonylmethoxy, tert-butoxycarbonylmethoxy, etc.), halogen atoms (e.g., fluorine, chlorine, etc.), and fluoroalkyl (e.g., fluoromethyl, trifluoromethyl, pentafluoroethyl, etc.). The above R 1 Each hydrocarbon group 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 the 10-position.

[0163] As the above R 1Preferred specific examples of R' include a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopentyl, cyclohexyl, camphoryl, norbornyl, p-toluoyl, benzyl, methylbenzyl, phenyl and 1-naphthyl.

[0164] Preferred specific examples of X include a single bond, an oxygen atom, a sulfur atom, an -N(R')- group, an -O-CO- group, and an O-SO 2 Here, when X is a -N(R')- group, 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 camphoryl group, a norbornyl group or a benzyl group.

[0165] Examples of the compound represented by the general formula (IV) include 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-di(2-ethylhexyloxy)anthracene, 1,2-benzanthracene, anthracenol, 1,4,9,10-tetrahydroxyanthracene, 9-anthracenemethanol, 1-aminoanthracene, 2-aminoanthracene, 9-(methylaminomethyl)anthracene, 9-acetylanthracene, 9-anthracenecarboxaldehyde, 10-methyl-9-anthracenecarboxaldehyde, 1,8,9-triacetoxyanthracene, etc. Among them, 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di(2-ethylhexyloxy)anthracene, and 9,10-bis-(3-chloropropoxy)anthracene are preferred. In particular, from the viewpoint that the adhesion when developing after heating after exposure can be significantly improved, and good adhesion can be achieved even when the time from exposure to development is prolonged, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-bis-(3-chloropropoxy)anthracene are more preferred, and 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.

[0166] From the viewpoint of significantly improving the adhesion when developing after heating after exposure, and in particular obtaining good adhesion even when the time from exposure to development is prolonged, 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 form 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 with one or more halogen atoms; and / or (6) contains a compound having a halogen atom directly bonded to the anthracene skeleton.

[0167] The compound represented by the general formula (IV) is advantageous from the viewpoint of significantly improving the adhesion when developing after heating after exposure, and in particular, obtaining good adhesion even when the time from exposure to development is prolonged. It is also advantageous from the viewpoint of being able to provide a photosensitive resin composition that can be used for two-wavelength exposure using a first active light having a central wavelength of less than 390 nm and a second active light having a central wavelength of more than 390 nm, and exhibits excellent sensitivity, adhesion and resolution.

[0168] In one embodiment, the photopolymerization initiator (C) preferably contains an anthracene derivative having a halogen atom. A preferred example of the anthracene derivative having a halogen atom is a halogen-substituted form of 9,10-dialkoxyanthracene. A preferred example of the halogen-substituted form is a compound in which the alkoxy group at the 9-position and / or 10-position of 9,10-dialkoxyanthracene is modified with one or more halogens. Preferred alkoxy groups include the alkoxy groups exemplified above as alkoxy groups having 1 to 40 carbon atoms.

[0169] In one embodiment, as an 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-phenanthracene), 2-bromoanthracene, 9-bromoanthracene, 2-chloroanthracene, and 9,10-dibromoanthracene.

[0170] The total amount of anthracene and anthracene derivatives, or in a preferred embodiment, the amount of the compound represented by the general formula (IV) 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, relative to the total solid content of the photosensitive resin composition.

[0171] Pyrazoline and pyrazoline derivatives are preferred from the viewpoint of the peeling property, sensitivity, resolution, and adhesion of the photosensitive resin layer.

[0172] Examples of the pyrazoline derivatives include 1-phenyl-3-(4-tert-butyl-phenyl-vinyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzoxazol-2-yl)phenyl)-3-(4-tert-butyl-phenyl-vinyl)-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-isopropylphenyl-vinyl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3-(4-methoxyphenyl-vinyl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxyphenyl-vinyl)-5-(3,5- From the above viewpoint, 1-phenyl-3-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxyphenyl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxyphenyl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxyphenyl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxyphenyl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxyphenyl)-5-(2,4-dimethoxyphenyl)-pyrazoline and the like are preferred, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferred.

[0173] Examples of the coumarin derivative include 7-diethylamino-4-methylcoumarin, 3,3′-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, etc. Among them, 7-diethylamino-4-methylcoumarin is preferred from the viewpoints of sensitivity, resolution, and adhesion.

[0174] Further examples of the (C) photopolymerization initiator include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, 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), hexaarylbiimidazoles, N-aryl amino acids or ester compounds thereof (for example, N-phenylglycine is preferred from the viewpoints of sensitivity, resolution and adhesion), and halogen compounds (for example, tribromomethylphenylsulfone). These 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-morpholinopropane-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, triphenylphosphine oxide, and the like can also be used.

[0175] As aromatic ketones, for example, benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone can be listed. One of them can be used alone or two or more can be used in combination. Among them, 4,4'-bis(diethylamino)benzophenone is preferred from the viewpoint of adhesion. Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably in the range of 0.01% to 0.5% by mass, and more preferably in the range of 0.02% to 0.3% by mass.

[0176] 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'-tetra- (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., which can be used alone or in combination of two or more. From the viewpoint of sensitivity, resolution and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

[0177] 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, from the viewpoint of improving the release characteristics and / or sensitivity of the photosensitive resin layer.

[0178] (D) Phenol-based inhibitors

[0179] The photosensitive resin composition contains (D) a phenolic polymerization inhibitor in order to improve thermal stability and storage stability. In the present disclosure, the (D) phenolic polymerization inhibitor is a compound having one or more phenolic hydroxyl groups. The phenolic polymerization inhibitor has the property of inhibiting polymerization reactions caused by heat or the like and improving storage stability. The phenolic polymerization 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 (D) phenolic polymerization inhibitor is a monovalent phenol (i.e., a compound having one phenolic hydroxyl group in the molecule). (D) More specific preferred examples of the phenolic polymerization inhibitor include p-hydroxyanisole, dibutylhydroxytoluene, hydroquinone, pentaerythritol tetrakis(3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate), 2,2'-thiodiethylbis(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)propaneamide), octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid, 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)propionate)(ethylenebis(oxyethylene)), 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, and the like are particularly preferred, and p-hydroxyanisole and dibutylhydroxytoluene are particularly preferred from the viewpoint of less likely to cause a difference in the shortest development time between heating and not heating after exposure.

[0180] The amount of the phenolic polymerization inhibitor (D) based on the mass of the total solid content of the photosensitive resin composition as 100 mass % is 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, further preferably 15 ppm or more, and particularly preferably 20 ppm or more from the viewpoint of obtaining the desired polymerization inhibition effect on the photosensitive resin composition, and 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 or less, and particularly preferably 40 ppm or less from the viewpoint of achieving good adhesion when developing after exposure and heating, especially when the time from exposure to development is extended. Although the photosensitive resin composition contains the phenolic polymerization inhibitor (D), the amount is small, which is advantageous from the viewpoint that the polymerization reaction in the photosensitive resin composition during exposure can be well performed when developing after exposure and heating, and the reaction of the polymer can be promoted (therefore, the adhesion is improved) by the good fluidity improvement effect of the polymer due to heating. For example, in a system where the polymer has a bulky molecular structure (for example, a relatively large amount of styrene skeleton), when post-exposure heating is performed with the intention of improving adhesion, the fluidity improvement effect achieved by heating the polymer may be low (and therefore the adhesion improvement effect may be low). However, according to the photosensitive resin composition of this embodiment, the amount of (D) phenolic inhibitor is within the above-mentioned range, so that even in the presence of such a bulky polymer, the adhesion improvement effect achieved by post-exposure heating can be well obtained.

[0181] In a particularly preferred embodiment, the content of dibutylhydroxytoluene in the photosensitive resin composition is 1 to 200 ppm, or 10 to 150 ppm.

[0182] [Optional Ingredients]

[0183] The photosensitive resin composition may contain any component as needed in addition to the components (A) to (D) above. As the optional component, additional polymerization inhibitors, dyes, coloring substances, plasticizers, antioxidants, stabilizers, etc. other than (d) (D) phenolic polymerization inhibitors may be listed. For example, additives listed in Japanese Patent Publication No. 2013-156369 may be used.

[0184] ((d) Additional inhibitor)

[0185] Examples of the additional polymerization inhibitor include radical polymerization inhibitors other than the above-mentioned phenolic polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles.

[0186] Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, diphenylnitrosoamine, etc. Nitrosophenylhydroxylamine aluminum salt is preferred in order not to impair the sensitivity of the photosensitive resin composition.

[0187] Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0188] Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole.

[0189] In one embodiment, the total amount of the additional polymerization inhibitor when the total solid content mass of the photosensitive resin composition is 100 mass % is preferably 0.001 to 3 mass %, more preferably 0.01 to 1 mass %. It is preferred to set the total amount to 0.001 mass % or more from the viewpoint of providing storage stability to the photosensitive resin composition. On the other hand, it is preferred to set the total amount to 3 mass % or less from the viewpoint of maintaining sensitivity and inhibiting dye fading.

[0190] (Dyes and coloring matter)

[0191] In the present embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of dyes (eg, leuco dyes, fluoran dyes, etc.) and coloring substances, as necessary.

[0192] As coloring materials, for example, magenta, phthalocyanine green, basic yellow, para magenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (for example, AIZEN (registered trademark) MALACHITE GREEN manufactured by HODOGAYA CHEMICAL CO., LTD.), basic blue 20, diamond green (for example, AIZEN (registered trademark) DIAMOND GREEN GH manufactured by HODOGAYA CHEMICAL CO., LTD.) can be cited. The content of the coloring material in the photosensitive resin composition is preferably 0.001% to 1% by mass when the total solid content mass of the photosensitive resin composition is 100% by mass. It is preferred to make the content 0.001% by mass or more from the viewpoint of improving the handling property of the photosensitive resin composition. On the other hand, from the viewpoint of maintaining the storage stability of the photosensitive resin composition, it is preferred to make the content 1% by mass or less.

[0193] The photosensitive resin composition contains a dye, so that the exposed part develops color, which is preferred from the viewpoint of visibility. In addition, when the alignment mark used for exposure is read by an inspection machine, it is advantageous to easily identify the exposed part when the contrast between the exposed part and the unexposed part is large. Preferred dyes from this viewpoint include leuco dyes and fluorane dyes.

[0194] As leuco dyes, tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenyl methane [leuco malachite green], etc. can be cited. In particular, from the viewpoint of good contrast, leuco crystal violet is preferably used as a 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 part and the unexposed part good, it is preferred 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 preferred 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.

[0195] In addition, in the photosensitive resin composition, from the viewpoint of optimizing adhesion and contrast, it is preferred to use a leuco dye in combination with the halogen compound described above in the (C) photopolymerization initiator. When a leuco dye is used in combination with the halogen compound, from the viewpoint of maintaining the storage stability of the color tone 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 100% by mass.

[0196] In this embodiment, the photosensitive resin composition may further contain epoxy compounds of bisphenol A. Examples of epoxy compounds of bisphenol A include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminal thereof.

[0197] In the present embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalates (e.g., diethyl phthalate, etc.), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, acetyl tri-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 (all manufactured by Asahi Denka Corporation), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, Newpol BPE-20T, Newpol BPE-60, Newpol BPE-100, Newpol BPE-180 (all manufactured by Sanyo Chemical Co., Ltd.), UNIOL DB-400, UNIOL DAB-800, UNIOL DA-350F, UNIOL DA-400, UNIOL DA-700 (all manufactured by NOF Corporation), BA-P4U Glycol, BA-P8 Glycol (all manufactured by Nippon Emulsifier Co., Ltd.) can also be mentioned.

[0198] The content of the plasticizer in the photosensitive resin composition is preferably 1% to 50% by mass, more preferably 1% to 30% by mass, relative to the total solid content of the photosensitive resin composition. From the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film, it is preferred that the content be 1% by mass or more. On the other hand, from the viewpoint of suppressing insufficient curing and cold flow, it is preferred that the content be 50% by mass or less.

[0199] If the amount of water in the photosensitive resin composition is high, local plasticization of the photosensitive resin composition is rapidly promoted, resulting in edge fusion. From the viewpoint of suppressing edge fusion, the amount of water in the photosensitive resin composition is preferably 0.7% or less on a mass basis, taking the photosensitive resin composition after the prepared liquid of the photosensitive resin composition is applied to the support film and dried as a reference. The amount of water 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.

[0200] [Solvent]

[0201] The photosensitive resin composition can be dissolved in a solvent and used in the form of a photosensitive resin composition prepared liquid for the manufacture of a photosensitive resin laminate. Examples of the solvent include ketones, alcohols, and the like. The aforementioned ketones are represented by methyl ethyl ketone (MEK) and acetone. The aforementioned alcohols are represented by methanol, ethanol, and isopropanol. The solvent is preferably added to the photosensitive resin composition in an amount such that the viscosity of the photosensitive resin composition prepared liquid applied to the supporting film at 25° C. is 500 mPa·s to 4000 mPa·s when manufacturing the photosensitive resin laminate.

[0202] [Light Transmittance of Photosensitive Resin Composition]

[0203] The transmittance of the photosensitive resin composition of the present embodiment at at least one of 375 nm and 405 nm is 58% to 95% from the viewpoint of providing a photosensitive resin composition having good sensitivity, adhesion, line width reproducibility and resolution when developing after heating after exposure, and especially achieving good adhesion even when the time from exposure to development is long. 375 nm and 405 nm correspond to typical exposure wavelengths in the photosensitive resin composition of the present embodiment. The transmittance is 58% or more, preferably 60% or more, more preferably 62% or more, more preferably 64% or more, and 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, and further preferably 70% or less from the viewpoint of obtaining a good curling shape by suppressing diffusely reflected light from the substrate surface.

[0204] The means for controlling the light transmittance at at least one of 375 nm and 405 nm to be within the above range is not limited thereto, and examples thereof include controlling the amount of a photopolymerization initiator, a dye, or a coloring substance added.

[0205] [Photosensitive resin laminate]

[0206] The present embodiment also provides a photosensitive resin laminate having a photosensitive resin layer formed by the above-mentioned photosensitive resin composition and a supporting film. As the supporting film, a transparent supporting film that transmits light radiated from an exposure light source is preferred. As such a supporting film, for example, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. can be cited. As these films, stretched films can also be used as needed.

[0207] From the viewpoint of suppressing light scattering during exposure, the haze of the supporting film 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 30nm or less, more preferably 20nm or less, and particularly preferably 10nm or less. The thinner the film, the better the image forming properties and economic efficiency, so it is advantageous, but in order to maintain the strength of the photosensitive resin laminate, it is preferred to use a film of 10μm to 30μm. The size of fine particles such as lubricants contained in the supporting film is preferably less than 5μm.

[0208] The supporting film may be a single-layer structure or a multilayer structure in which multiple resin layers with different compositions are stacked. 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 may be formed on one side A, and the other side B may (1) contain fine particles in the same manner as side A, (2) contain a smaller amount of fine particles than side A, (3) contain fine particles finer than side A, or (4) contain no fine particles. In the case of structures (2), (3), and (4), it is preferred to form a photosensitive resin layer on the side of side B. At this time, if a resin layer containing fine particles is present on the side of side A, it is preferred from the viewpoint of the smoothness of the film. At this time, the size of the fine particles is preferably less than 1.5 μm. It should be noted that the size of the fine particles is a value obtained by measuring using a scanning electron microscope calibrated with a standard sample.

[0209] The important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesion with the photosensitive resin layer is sufficiently smaller than that of the supporting 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 Publication 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.

[0210] There may be gel called fish eyes on the surface of the polyethylene film. When a polyethylene film with fish eyes is used as a 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 drawn in during lamination to form gaps, resulting in defects in the resist pattern. From the viewpoint of preventing fish eyes, stretched polypropylene is preferably used as the material of the protective layer. As a specific example, ALPHAN E-200A manufactured by Oji Paper Co., Ltd. can be cited.

[0211] The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, but 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 photosensitive resin layer, the better the resolution, and the thicker the photosensitive resin layer, the better the film strength.

[0212] The transmittance at a wavelength of 630 nm of the laminate of the supporting film and the photosensitive resin layer is an indicator of the decolorization of the dye, and a high transmittance at a wavelength of 630 nm indicates that the dye is decolorized. The transmittance at a wavelength of 630 nm of the laminate of the supporting film and the photosensitive resin layer 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. The transmittance is a value of the laminate of the supporting film and the photosensitive resin layer (i.e., excluding the protective layer).

[0213] Next, a method for producing a photosensitive resin laminate will be described.

[0214] As a method for producing a photosensitive resin laminate by laminating a supporting film and a photosensitive resin layer, and a protective layer as required, a known method can be adopted. For example, a photosensitive resin composition used in a photosensitive resin layer is mixed with a solvent that dissolves the photosensitive resin composition to form a uniform solution, which is first applied to a supporting film using a rod coater or a roller coater, and then dried to remove the solvent, thereby laminating a photosensitive resin layer formed of the photosensitive resin composition on the supporting film. Then, a protective layer is laminated on the photosensitive resin layer as required, thereby producing a photosensitive resin laminate.

[0215] <Method for forming resist pattern>

[0216] Next, an example of a method for producing a resist pattern using the photosensitive resin laminate of this embodiment is described. This method may include an exposure step of exposing a photosensitive resin composition, a heating step of heating the exposed photosensitive resin composition, and a developing step of developing the photosensitive resin composition.

[0217] As the anti-etching pattern, for example, patterns of printed wiring boards, semiconductor elements, printed plates, liquid crystal display panels, touch panels, flexible substrates, lead frame substrates, COF (chip on film) substrates, semiconductor packaging substrates, transparent electrodes for liquid crystals, wiring for liquid crystal TFTs, PDP (plasma display panel) electrodes, etc. can be listed. As an example, the method for manufacturing a printed wiring board is described as follows.

[0218] A printed wiring board is manufactured through the following steps.

[0219] (1) Lamination process

[0220] First, in the lamination process, a photosensitive resin layer is formed on a substrate using a laminating device. Specifically, if the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heated and pressed onto the substrate surface using a laminating device for lamination. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like.

[0221] In this embodiment, the photosensitive resin layer can be laminated only on one side of the substrate surface, or laminated 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 more than 2 times, the adhesion of the obtained anti-etching pattern to the substrate can be improved. During heat pressing, a two-stage laminating device with a double roller can be used, or the laminate of the substrate and the photosensitive resin layer can be pressed by repeatedly passing the roller several times.

[0222] (2) Exposure process

[0223] 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 closely attached to a supporting film and an active light source is used for exposure; an exposure method by directly drawing a drawing pattern that is the desired wiring pattern; or an exposure method by projecting an image of a photomask through a lens.

[0224] The exposure step is preferably performed by an exposure method by direct drawing of a drawing pattern or an exposure method by projecting 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 projecting an image of a photomask through a lens, and is particularly significant in the exposure method by direct drawing of a drawing pattern.

[0225] In the case where the exposure process is an exposure method using direct drawing, a laser having a central wavelength of less than 390nm or a laser having a central wavelength of more than 390nm is preferred. A laser having a central wavelength of more than 350nm and less than 380nm or a laser having a central wavelength of more than 400nm and less than 410nm is more preferred. It is further preferred that the exposure is performed by a method using a first laser having a central wavelength of less than 390nm and a second laser having a central wavelength of more than 390nm. In addition, it is more preferred that the central wavelength of the first laser be more than 350nm and less than 380nm, and the central wavelength of the second laser be more than 400nm and less than 410nm.

[0226] (3) Heating process

[0227] In this process, it is preferred to heat 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 implementing this heating process, the resolution and adhesion can be improved. Heating can be performed using a heating furnace, a thermostatic bath, a heating plate, a hot air dryer, an infrared dryer, a hot roller, etc. using hot air, infrared rays, or far infrared rays. If the heating method is a hot roller, it is preferred from the viewpoint of being able to process in a short time, and a double hot roller is more preferred.

[0228] In particular, in the present invention, by using (D) a phenolic polymerization inhibitor and making its amount a small amount and controlling the transmittance of the resin composition at a specific wavelength within a specific range, the fluidity of the polymer is improved by heating when heating and then developing after exposure. For example, even in the case of a system with a relatively high content of styrene skeleton, the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly taken into account. As a result, sensitivity, adhesion, line width reproducibility and resolution can be significantly improved. Moreover, by significantly improving adhesion, good adhesion can be obtained even in the case of a long time from exposure to development. In addition, from the viewpoint of the effect of the present invention, it is preferred that the aforementioned heating process is carried out within 15 minutes after exposure, and more preferably within 10 minutes.

[0229] (4) Development process

[0230] In this step, 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.

[0231] As the aqueous alkali solution, Na 2 CO 3 or K 2 CO 3The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but preferably has a concentration of about 0.2% to about 2% by mass and a Na 2 CO 3 Aqueous solution.

[0232] In the exemplary embodiment, the time from exposure to development (i.e., the time from the end of exposure to the start of development) can be more than 5 minutes, or more than 60 minutes, or more than 180 minutes, or less than 1440 minutes, or less than 720 minutes, or less than 300 minutes.

[0233] The resist pattern can be obtained through the above-mentioned steps (1) to (4).

[0234] In the method for producing a circuit board of the present invention, the circuit board is formed by etching or plating the substrate having the resist pattern produced by the above method.

[0235] (5) Etching process or plating process

[0236] The substrate surface (for example, the copper surface of a copper-clad laminate) exposed by development is etched or plated to produce a conductor pattern.

[0237] (6) Peeling process

[0238] Then, the resist pattern is peeled off from the substrate using an appropriate stripping solution as required. Examples of the stripping solution include alkaline aqueous solutions and amine stripping solutions. However, the resist pattern formed by the photosensitive resin composition of the present invention after exposure and heating has the following advantages: while exhibiting good stripping properties to the amine stripping solution, the stripping sheet will not be excessively miniaturized. Therefore, if an amine stripping solution is used as the stripping solution, the advantageous effects of the present invention are further exerted and it is preferred.

[0239] The amine contained in the amine-based stripping liquid may be an inorganic amine or an organic amine.

[0240] Examples of the inorganic amine include ammonia, hydroxylamine, and hydrazine.

[0241] Examples of organic amines include ethanolamine, propanolamine, alkylamine, cyclic amine, and quaternary ammonium salts. Specific examples thereof include

[0242] As the ethanolamine, for example, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, aminoethoxyethanol, etc.;

[0243] Examples of the propanolamine include 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, and 2-amino-2-methyl-1,3-propanediol.

[0244] Examples of the alkylamine include monomethylamine, dimethylamine, trimethylamine, ethyleneamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, and tetraethylenepentamine;

[0245] as cyclic amines, such as choline, morpholine, etc.;

[0246] Examples of the quaternary ammonium salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, N,N,N-triethyl-N-(2-hydroxyethyl)ammonium hydroxide, and N,N-diethyl-N,N-di(2-hydroxyethyl)ammonium hydroxide.

[0247] The amine stripping solution may be an aqueous solution containing one or more of the amines exemplified above. The concentration of the amine in the aqueous solution may be appropriately set depending on the purpose, the composition of the photosensitive resin layer, the development conditions, and the like.

[0248] The amine-based stripping liquid may further contain additives generally used in stripping agents, such as a surfactant, a defoaming agent, a pH adjuster, an antiseptic, and an anti-reattachment agent.

[0249] The peeling step is performed at a temperature of, for example, 0°C to 100°C, preferably room temperature (23°C) to 50°C, for, for example, 1 second to 1 hour, preferably 10 seconds to 10 minutes.

[0250] After the stripping step, the substrate from which the resist pattern has been removed may be washed with, for example, pure water, as necessary.

[0251] The photosensitive resin laminate of this embodiment is a photosensitive resin laminate suitable for manufacturing conductor patterns such as printed wiring boards, flexible substrates, lead frame substrates, touch panel substrates, COF substrates, semiconductor package substrates, transparent electrodes for liquid crystals, wiring for liquid crystal TFTs, and electrodes for PDPs.

[0252] It should be noted that the above-mentioned various parameters are measured according to the measurement methods in the examples described below or methods understood by those skilled in the art to be equivalent thereto unless otherwise specified.

[0253] Example

[0254] Next, the present embodiment will be described in more detail with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it deviates from the gist of the present embodiment. The physical properties in the examples were measured by the following methods.

[0255] The following describes the measurement of the physical property values ​​of polymers and the method for preparing samples for evaluation of Examples and Comparative Examples. In addition, the evaluation method for the obtained samples and the evaluation results thereof are shown.

[0256] (1) Determination and calculation of physical property values

[0257] <Measurement of weight average molecular weight or number average molecular weight of polymer>

[0258] The weight average molecular weight or number average molecular weight of the polymer is determined in terms of polystyrene by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 model, chromatographic columns: four Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko K.K. connected in series, mobile layer solvent: tetrahydrofuran, using a calibration curve obtained using a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.)).

[0259] Furthermore, the polymer dispersion degree 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).

[0260] <Acid equivalent>

[0261] In the present disclosure, acid equivalent refers to the mass (g) of a polymer having 1 equivalent of a carboxyl group in a molecule. The acid equivalent was measured by potentiometric titration using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. using a 0.1 mol / L sodium hydroxide aqueous solution.

[0262] <I / O value>

[0263] The I / O value of the alkali-soluble polymer is derived by the following method. First, the I value and O value of each of the constituent comonomers are calculated by the method described in the non-patent literature (Organic Concept Diagram (written by Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Items 1 to 16 (1954); Field of Chemistry, 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)), and then the aforementioned IO value and O value are averaged by the molar ratio of the comonomers, thereby obtaining I / O value. average Value and O average Then, the obtained I average Divide the value by O averagevalue, thereby deriving the I / O value.

[0264] <Glass transition temperature Tg>

[0265] The glass transition temperature Tg of the alkali-soluble polymer is obtained by the Fox formula. When the glass transition temperature Tg is obtained, the value shown in the non-patent literature (Brandrup, J. Immergut, EH, "Polymer handbook, Third edition, John wiley & sons, 1989, p. 209 Chapter VI 'Glass transition temperatures of polymers'") is used as the glass transition temperature of the homopolymer containing the comonomer forming the corresponding alkali-soluble polymer. It should be noted that in the examples, the glass transition temperatures of the homopolymer 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 using the following formula is the glass transition temperature of the alkali-soluble polymer.

[0266]

[0267] {W i is the solid weight of each alkali-soluble polymer, Tg i is the glass transition temperature of each alkali-soluble polymer obtained 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}

[0268] (2) Method for preparing samples for evaluation

[0269] Evaluation samples were prepared as follows.

[0270] <Production of photosensitive resin laminate>

[0271] The components shown in Tables 1 to 3 described later (wherein the numbers of each component represent the amount of solid components (parts by mass)) and the solvent are fully stirred and mixed to obtain a photosensitive resin composition prepared liquid. The details of the components shown in Tables 1 and 2 are shown in Table 3. As a supporting film, a 16 μm thick polyethylene terephthalate film (Toray Industries, Inc., FB-40) was used, and the prepared liquid was evenly applied on its surface using a rod 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.

[0272] Next, a 19 μm thick polyethylene film (GF-18 manufactured by TAMAPOLY CO., LTD.) was bonded as a protective layer to the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film was not laminated, thereby obtaining a photosensitive resin laminate.

[0273] In addition, the amount of p-hydroxyanisole and the amount of butylated hydroxytoluene in Tables 1 and 2 refer to the concentration of each component based on the total solid content in the photosensitive resin composition.

[0274] <Entire substrate>

[0275] As a substrate for evaluating image properties, a 0.4 mm thick copper-clad laminate laminated with a 35 μm rolled copper foil was sprayed with a grinding agent (manufactured by Uji Denka Kogyo Co., Ltd., #400) at a spray pressure of 0.2 MPa, and then spray-rinsed with 10 mass % H 2 SO 4 The aqueous solution washes the substrate surface.

[0276] <Lamination>

[0277] While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate was laminated on a copper-clad laminate preheated to 50° C. using a hot roll laminator (AL-700 manufactured by Asahi Kasei Corporation) at a roll temperature of 105° C. The air pressure was 0.35 MPa and the lamination speed was 1.5 m / min.

[0278] <Exposure>

[0279] The evaluation substrate was exposed 2 hours after lamination by a direct drawing exposure machine (Nuvogo Fine 10 manufactured by Orbotech Ltd., light source: 375 nm (30%) + 405 nm (70%)) using a Stauffer 41-step step exposure meter. The exposure was performed with an exposure amount such that the maximum residual film level during development was 14 levels using the Stauffer 41-step step exposure meter as a mask.

[0280] <Heating>

[0281] The evaluation substrate was heated by a hot roller laminating device (AL-700 manufactured by Asahi Kasei Corporation) 7 minutes after exposure. The roller temperature was set to 105°C, the air pressure was set to 0.30 MPa, and the laminating speed was set to 1 m / min. It should be noted that if the time from exposure to development is extended, the heating effect is lost, so it is usually heated for about 1 minute after exposure. Therefore, the heating after 7 minutes of exposure in this example is a very strict condition.

[0282] <Development>

[0283] After the polyethylene terephthalate film (support film) was peeled off, an alkali developer (manufactured by FUJI KIKOU CO., LTD., developer for dry films) was used to spray 1 mass % NaOH at 30° C. for a predetermined time. 2 CO 3 The time of the developing spray is set to be twice the shortest developing time, and the time of the water washing spray after the development is set to be three times the shortest developing time. At this time, the shortest time required for the photosensitive resin layer of the unexposed part to be completely dissolved is taken as the shortest developing time.

[0284] (3) Sample evaluation method

[0285] <Amount of p-Hydroxyanisole>

[0286] The amount of p-hydroxyanisole in the photosensitive resin composition was determined by an internal standard method using a gas chromatograph (hereinafter referred to as GC) manufactured by Shimadzu Corporation. The detector was a hydrogen flame ionization detector (hereinafter referred to as FID), and n-docosane was used as an internal standard.

[0287] <Butylated hydroxytoluene amount>

[0288] The amount of dibutylhydroxytoluene in the photosensitive resin composition was determined by GC in the same manner as the amount of p-hydroxyanisole. n-octadecane was used as an internal standard.

[0289] <Light transmittance>

[0290] The light transmittance at 375 nm and 405 nm of each resin composition was measured by the following method.

[0291] The transmittance at each wavelength of the photosensitive resin laminate from which the polyethylene film (protective layer) was peeled was measured using a spectrophotometer (Hitachi High-Tech Corporation, U-3010) at which the transmittance was measured while being set to transmit light in the film thickness direction of the photosensitive resin laminate.

[0292] <Sensitivity evaluation>

[0293] In the above exposure process, after exposure through the mask of Stauffer 41-level step exposure meter, development is performed to set the exposure dose (mJ / cm 2 ) is calculated as the sensitivity value.

[0294] <Line width reproducibility>

[0295] In the exposure step, exposure is performed using drawing data having a line pattern in which the width of the exposed portion and the unexposed portion is at a ratio of 20 μm:20 μm. Development is performed under the above-mentioned development conditions to form a cured resist line.

[0296] The line width of the cured resist line was determined as a value of line width reproducibility.

[0297] <Resolution>

[0298] In the exposure step, exposure is performed using drawing data having a line pattern in which the width of the exposed portion and the width of the unexposed portion are in a ratio of 1:1. Development is performed under the above-mentioned development conditions to form a cured resist line.

[0299] The minimum line width at which a cured resist line was normally formed was determined as the value of resolution.

[0300] <Adhesion>

[0301] In the exposure process, exposure is performed using drawing data of a line pattern having a ratio of x μm:200 μm between the width of the exposed portion and the width of the unexposed portion. Development is performed according to the above-mentioned development conditions, and the minimum line width of a normally formed cured resist line is measured by an optical microscope. This measurement is performed for 4 lines, and the average value of the 4 line widths is calculated as the value of adhesion.

[0302] Only the adhesion was evaluated in two cases: one in which heating was performed after 1 minute had passed after the exposure, and one in which heating was performed after 7 minutes had passed after the exposure.

[0303] <Minimum development time delay>

[0304] In the development step, the shortest time required for complete dissolution of the photosensitive resin layer in the unexposed portion, i.e., the shortest development time, was measured for each of the cases where development was performed without heating after exposure and when development was performed after heating 7 minutes after exposure, and the results were ranked according to the following criteria.

[0305] Good: There is no difference in the shortest development time between when heating after exposure and when not heating after exposure

[0306] Pass: The shortest development time when heated after exposure is delayed by less than 1 second compared to the time when not heated after exposure

[0307] Fail: The shortest developing time when heated after exposure is delayed by more than 1 second compared to when not heated after exposure

[0308] The results are shown in Tables 1 and 2.

[0309] The heating conditions after exposure in this embodiment are very strict conditions because they are heating after exposure for 7 minutes. For example, the adhesion of the compositions of Example 3 and Comparative Example 2 when they were developed without heating after exposure was 13.8μm. That is, in the composition of Comparative Example 1, no effect was found when heated after exposure for 7 minutes, but in Example 3, even very strict conditions can improve the adhesion. In addition, under the condition of heating after exposure for 1 minute, the adhesion of 10.8μm was obtained in the compositions of Example 7 and Comparative Example 1. From the above results, it can be seen that even if the adhesion is good under the usual heating conditions after exposure, the adhesion does not become good under the strict conditions of heating after exposure for 7 minutes, but through the present invention, the adhesion can be made good even under such strict heating conditions after exposure. When manufacturing the circuit substrate in this way, good adhesion can be obtained even if the time from exposure to development is extended, so a high-precision circuit pattern can be stably formed.

[0310] [Table 1]

[0311]

[0312] [Table 2]

[0313]

[0314] [Table 3]

[0315]

[0316] Industrial Applicability

[0317] The photosensitive resin composition provided by the present invention has good sensitivity, adhesion, line width reproducibility and resolution when developing after heating after exposure, and particularly achieves good adhesion even when the time from exposure to development is long, so it can be widely used as a photosensitive resin composition.

Claims

1. A photosensitive resin composition comprising: (A) alkali-soluble polymer: 10% to 90% by mass; (B) Compounds having an ethylenically unsaturated double bond: 5% to 70% by mass; (C) photopolymerization initiator: 0.01% to 20% by mass; and (D) Phenol-based polymerization inhibitor: 1 ppm to 300 ppm, The (C) photopolymerization initiator contains anthracene and / or anthracene derivatives, and The (D) phenolic polymerization inhibitor contains p-hydroxyanisole and / or butylated hydroxytoluene, 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 , comprising p-hydroxyanisole as the (D) phenolic polymerization inhibitor. 3 . The photosensitive resin composition according to claim 1 , comprising dibutylhydroxytoluene as the (D) phenolic polymerization inhibitor.

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

5. The photosensitive resin composition according to claim 3, wherein The content of the butylated hydroxytoluene 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 further contains one or more selected from the group consisting of pyrazoline, triphenylamine, coumarin, and derivatives thereof.

8. 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.

9. 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.

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

11. 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 a molecule in an amount of 5% by mass or more based on the total solid content of the photosensitive resin composition. 12 . The photosensitive resin composition according to claim 1 , which is used to obtain an exposed resin cured product using a first laser beam having a central wavelength of less than 390 nm and a second laser beam having a central wavelength of 390 nm or more.

13. The photosensitive resin composition according to claim 12, wherein The center wavelength of the first laser light is greater than or equal to 350 nm and less than or equal to 380 nm, and the center wavelength of the second laser light is greater than or equal to 400 nm and less than or equal to 410 nm.

14. 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 to light; a heating step of heating the exposed photosensitive resin composition; and A developing step of developing the heated photosensitive resin composition.

15. The photosensitive resin composition according to claim 14, wherein The heating temperature in the heating step is in the range of 30°C to 150°C.

16. The photosensitive resin composition according to claim 14, wherein The heating step is performed within 15 minutes after the exposure.

17. A method for forming a resist pattern, comprising the following steps: An exposure step of exposing the photosensitive resin composition according to any one of claims 1 to 16; a heating step of heating the exposed photosensitive resin composition; and A developing step of developing the heated photosensitive resin composition.

18. The method for forming a resist pattern according to claim 17, wherein: The heating temperature in the heating step is in the range of 30°C to 150°C.

19. The method for forming a resist pattern according to claim 17 or 18, wherein: The heating step is performed within 15 minutes after the exposure.

20. The method for forming a resist pattern according to claim 17 or 18, wherein: The exposure step is performed by an exposure method using direct drawing of a drawing pattern or an exposure method using a lens to project an image of a photomask.

21. The method for forming a resist pattern according to claim 20, wherein: The exposure step is performed by a direct drawing exposure method using a drawing pattern.

22. The method for forming a resist pattern according to claim 21, wherein: The exposure step is performed by a method of exposing with a first laser beam having a central wavelength of less than 390 nm and a second laser beam having a central wavelength of 390 nm or more.

23. The method for forming a resist pattern according to claim 22, wherein: The center wavelength of the first laser light is greater than or equal to 350 nm and less than or equal to 380 nm, and the center wavelength of the second laser light is greater than or equal to 400 nm and less than or equal to 410 nm.

24. A method for manufacturing a circuit substrate, comprising the following steps: A resist pattern forming step of forming a resist pattern on a substrate by the method according to any one of claims 17 to 23; and A circuit substrate forming step of forming a circuit substrate by etching or plating the substrate having the resist pattern.

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