TWI811423B - Photosensitive resin composition and method for forming resist pattern - Google Patents

Abstract

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

Description

Photosensitive resin composition and method for forming resist pattern

The present invention relates to a photosensitive resin composition and a method for forming a resist pattern.

In electronic equipment such as personal computers and mobile phones, printed wiring boards, etc., can be used to mount components, semiconductors, etc. As a resist for manufacturing printed wiring boards and the like, the industry has previously used a so-called dry film of a photosensitive resin laminate in which a photosensitive resin layer is laminated on a support film and a protective film is laminated on the photosensitive resin layer if necessary. Photoresist (hereinafter, sometimes also referred to as DF). Currently, the photosensitive resin layer is usually an alkaline development type using a weak alkaline aqueous solution as a developer.

When using DF to make printed wiring boards, etc., the following steps are taken, for example. When DF has a protective film, peel off the protective film first. Thereafter, DF is laminated on a permanent circuit manufacturing substrate such as a copper foil laminated board or a flexible substrate using a laminating machine, and exposed through a wiring pattern mask or the like. Secondly, if necessary, peel off the support film, use a developer to dissolve or disperse the photosensitive resin layer in the unhardened part (unexposed part if it is a negative type), and form a hardened resist pattern (hereinafter, sometimes also Referred to as resist pattern).

After the resist pattern is formed, the process of forming the circuit is roughly divided into two methods. The first method is to remove the resist pattern part by using an alkaline aqueous solution that is stronger than the developer after etching and removing the substrate surface that is not covered by the resist pattern (such as the copper surface of the copper foil laminate) (etching method) ). The second method is to perform plating treatment with copper, solder, nickel, tin, etc. on the above-mentioned substrate surface, remove the resist pattern part in the same manner as the first method, and then plating the exposed substrate surface (such as copper foil The copper surface of the laminated board) is etched (plating method). Copper chloride, ferric chloride, cupro-ammonium complex solution, etc. can be used in etching.

In recent years, as electronic equipment has been miniaturized and lightweighted, printed wiring boards have been increasingly miniaturized and densified. In the above-mentioned manufacturing steps, high-performance DF with high resolution and high adhesion is required. As one that achieves such high resolution, Patent Document 1 describes a photosensitive resin composition that improves resolution using a specific thermoplastic resin, a monomer, and a photopolymerizable initiator. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2010-249884

[Problem to be solved by the invention]

After the exposure step, the photosensitive resin layer may be subjected to a heating step as appropriate, and then developed. By performing this heating step, resolution or adhesion (ie, the adhesion between the resist pattern and the substrate) can be further improved. However, even if a heating step is added after exposure, the adhesion and resolution of the conventional photosensitive resin composition may still be insufficient, or if the time from exposure to development becomes longer, good adhesion may not be obtained. subject.

The present invention was proposed in view of this previous actual situation, and the object of one aspect of the present invention is to provide a method that has good sensitivity, adhesion, line width reproducibility, and resolution when developing after heating after exposure. , in particular, a photosensitive resin composition that achieves good adhesion even when the time from exposure to development is long. [Technical means to solve problems]

The present invention includes the following aspects. [1] A photosensitive resin composition containing the following components: (A) Alkali-soluble polymer: 10% by mass to 90% by mass; (B) Compounds with ethylenically unsaturated double bonds: 5% to 70% by mass; (C) Photopolymerization initiator: 0.01 mass% to 20 mass%; and (D) Phenolic polymerization inhibitor: 1 ppm ~ 300 ppm; and The light transmittance under at least one of 375 nm and 405 nm is 58% to 95%. [2] The photosensitive resin composition according to the above aspect 1, which contains p-methoxyphenol as the (D) phenolic polymerization inhibitor. [3] The photosensitive resin composition according to the above aspect 1 or 2, which contains dibutylhydroxytoluene as the (D) phenolic polymerization inhibitor. [4] The photosensitive resin composition according to the above aspect 3, wherein the content of the dibutylhydroxytoluene is 1 to 200 ppm. [5] The photosensitive resin composition according to the above aspect 3, wherein the content of the dibutylhydroxytoluene is 10 to 150 ppm. [6] The photosensitive resin composition according to any one of aspects 1 to 5 above, wherein the I/O value of the alkali-soluble polymer (A) is 0.600 or less. [7] The photosensitive resin composition according to any one of aspects 1 to 6 above, wherein the (C) photopolymerization initiator contains anthracene, pyrazoline, triphenylamine, and coumarin. , and one or more of the group consisting of such derivatives. [8] The photosensitive resin composition according to the above aspect 7, wherein the (C) photopolymerization initiator contains anthracene and/or anthracene derivatives. [9] The photosensitive resin composition according to any one of aspects 1 to 8 above, wherein the structural unit of styrene and/or styrene derivative in the alkali-soluble polymer (A) is 26% by mass. above. [10] The photosensitive resin composition according to any one of aspects 1 to 9 above, wherein the alkali-soluble polymer (A) contains a structural unit of benzyl (meth)acrylate as a monomer component. [11] The photosensitive resin composition according to any one of aspects 1 to 10 above, wherein the glass transition temperature of the alkali-soluble polymer (A) is 120°C or lower. [12] The photosensitive resin composition according to any one of aspects 1 to 11 above, wherein the compound (B) having an ethylenically unsaturated double bond contains a solid content relative to the entire photosensitive resin composition. It is a compound having 3 or more methacrylate groups in the molecule in an amount of 5% by mass or more. [13] The photosensitive resin composition according to any one of the above aspects 1 to 12, which is used for utilizing the first laser light with a center wavelength of less than 390 nm and the second laser light with a center wavelength of 390 nm or more. The exposed resin cured product is obtained by irradiating light. [14] The photosensitive resin composition according to any one of aspects 1 to 13 above, wherein the center wavelength of the first laser light is 350 nm or more and 380 nm or less, and the center wavelength of the second laser light is Above 400 nm and below 410 nm. [15] The photosensitive resin composition according to any one of the above aspects 1 to 14, wherein the pattern can be formed by the following steps: an exposure step, which exposes the photosensitive resin composition; a heating step that heats the exposed photosensitive resin composition; and A development step is to develop the heated photosensitive resin composition. [16] The photosensitive resin composition according to any one of aspects 1 to 15 above, wherein the heating temperature in the heating step is in the range of 30°C to 150°C. [17] The photosensitive resin composition according to any one of aspects 1 to 16 above, wherein the heating step is performed within 15 minutes after exposure. [18] A method of forming a resist pattern, which includes the following steps: An exposure step, which exposes the photosensitive resin composition as described in any one of the above aspects 1 to 17; a heating step that heats the exposed photosensitive resin composition; and A development step is to develop the heated photosensitive resin composition. [19] The resist pattern forming method as described in aspect 18, wherein the heating temperature in the heating step is in a range of 30°C to 150°C. [20] The method for forming a resist pattern as described in aspect 18 or 19 above, wherein the heating step is performed within 15 minutes after exposure. [21] The method of forming a resist pattern according to any one of the above aspects 18 to 20, wherein the method is an exposure method of direct drawing using a drawing pattern or an exposure method of projecting a mask image through a lens And carry out the above-mentioned exposure steps. [22] The resist pattern forming method as described in aspect 21 above, wherein the exposure step is performed by an exposure method using direct drawing of a drawing pattern. [23] The method of forming a resist pattern as described in Aspect 22 above, wherein exposure is performed with a first laser light having a center wavelength less than 390 nm and a second laser light having a center wavelength not less than 390 nm. And carry out the above-mentioned exposure steps. [24] The method of forming a resist pattern as described in aspect 23 above, wherein the central wavelength of the first laser light is 350 nm or more and 380 nm or less, and the second laser light has a central wavelength of 400 nm or more and Below 410 nm. [25] A method of manufacturing a circuit substrate, which includes the following steps: a resist pattern forming step, which forms a resist pattern on the substrate by the method described in any one of aspects 18 to 24 above; and The circuit substrate forming step is to form the circuit substrate by etching or plating the substrate having the above-mentioned resist pattern. [Effects of the invention]

According to the present invention, it is possible to provide a product that is excellent in sensitivity, adhesion, line width reproducibility, and resolution when developing after heating after exposure, especially when the time from exposure to development is long. Photosensitive resin composition that achieves good adhesion.

Hereinafter, exemplary embodiments for implementing the present invention (hereinafter simply referred to as “embodiments”) will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the spirit. In addition, various measured values in this specification are measured according to the method described in the "Examples" of the present invention or a method understood by those skilled in the art to be equivalent thereto, unless otherwise specified.

＜Photosensitive resin composition＞ In this 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) phenolic polymerization Inhibitors. Moreover, in this embodiment, a photosensitive resin layer can be formed by applying the photosensitive resin composition arbitrarily to a support. The above-mentioned composition of the photosensitive resin composition of this embodiment is useful for obtaining a resin cured product by heating after exposure and then developing.

The photosensitive resin composition of the present embodiment can be a photosensitive resin composition for obtaining a resin cured product by exposing the first active light with a center wavelength of less than 390 nm and the second active light with a center wavelength of 390 nm or more. . The active light is, for example, laser light. In this aspect, the photosensitive resin composition has photosensitivity to both the first active light with a center wavelength of less than 390 nm and the second active light with a center wavelength of 390 nm or more. The center wavelength of the first active light is preferably 350-380 nm, more preferably 355-375 nm, and particularly preferably 375 nm. The center wavelength of the second active light is preferably 400 to 410 nm, more preferably 402 to 408 nm, and particularly preferably 405 nm (h line). Each component contained in the photosensitive resin composition is explained below.

(A)Alkali-soluble polymer (A) Alkali-soluble polymers are polymers that are soluble in alkaline substances. (A) The alkali-soluble polymer preferably has a carboxyl group from the viewpoint of alkaline developability, and further preferably is a copolymer containing a carboxyl group-containing monomer as a copolymer component. (A) The alkali-soluble polymer may be thermoplastic.

From the viewpoint of high resolution and string shape of the resist pattern, the photosensitive resin composition preferably contains a copolymer having an aromatic group as (A) the alkali-soluble polymer. The photosensitive resin composition preferably contains a copolymer having an aromatic group in a side chain as the (A) alkali-soluble polymer. Examples of such aromatic groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The proportion of the copolymer having an aromatic group in component (A) is preferably 30 mass% or more, more preferably 40 mass% or more, more preferably 50 mass% or more, more preferably 70 mass% or more, and further Preferably it is 80 mass % or more. The above ratio may 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 still more preferably 85% by mass.

From the viewpoint of high resolution and string shape of the resist pattern, the copolymerization ratio of the comonomer having an aromatic group in (A) the alkali-soluble polymer is preferably 40 mass % or more, more preferably 50 mass % % or more, preferably 60 mass% or more, preferably 70 mass% or more, preferably 80 mass% or more. The upper limit of the copolymerization ratio is not particularly limited, but from the viewpoint of maintaining good alkali solubility, it is preferably 95 mass% or less, more preferably 90 mass% or less.

Examples of the comonomer having an aromatic group include styrene and polymerizable styrene derivatives (such as methylstyrene, vinyltoluene, tert-butoxystyrene, acetyloxystyrene). , 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.), monomers with aralkyl groups, etc. Among them, styrene and styrene derivatives are more preferred.

The total ratio of the structural units of styrene and/or styrene derivatives in the entire alkali-soluble polymer (A) can significantly improve the adhesion during development after heating after exposure, especially From the viewpoint of obtaining good adhesion even when the time from exposure to development becomes longer, it is preferably 15 mass% or more, more preferably 25 mass% or more, more preferably 26 mass% or more, still more preferably It is 30 mass % or more, more preferably 35 mass % or more, more preferably 40 mass % or more. Since the styrene skeleton is hydrophobic, it can inhibit swelling with the developer and exhibit good adhesion. Among them, when the content of the styrene skeleton is high, the fluidity of the polymer tends to be low and the reactivity tends to decrease, so the adhesion tends to decrease. In addition, if the time from exposure to development becomes longer, the free radicals in the system are gradually deactivated, so the adhesion improvement effect caused by heating after exposure is reduced. In the present invention, by heating after exposure and then developing, even in a system with a large content of styrene skeleton, the fluidity of the polymer is improved by heating, and a high degree of simultaneous realization of the styrene skeleton can be achieved The hydrophobicity and the reactivity of the carbon-carbon double bond result in good adhesion. Furthermore, it is thought that good adhesion can be obtained even when the time from exposure to development becomes long. The ratio of the total of the structural units of styrene and/or styrene derivatives in the entire alkali-soluble polymer (A) is relatively high from the viewpoint of well obtaining the advantages arising from the presence of other structural units. Preferably, it is 90 mass % or less, More preferably, it is 80 mass % or less, Still more preferably, it is 70 mass % or less.

Examples of the comonomer having an aralkyl group include monomers having a substituted or unsubstituted benzyl group, monomers having a substituted or unsubstituted phenylalkyl group (excluding benzyl), etc., and preferred examples are It is a monomer having a substituted or unsubstituted benzyl group.

Examples of comonomers having a benzyl group include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group For example, vinyl benzyl chloride, vinyl benzyl alcohol, etc.

(A) Alkali-soluble polymer can significantly improve the adhesion during development after heating after exposure, and in particular, can achieve good adhesion even when the time from exposure to development becomes longer. Preferably, it contains a structural unit of benzyl (meth)acrylate as a monomer component. (A) The ratio of the structural units of benzyl (meth)acrylate in the alkali-soluble polymer is preferably 5 to 85 mass %, more preferably 10 to 80 mass %, more preferably 15 to 60 mass %, still more preferably It is 20-40 mass %, and it is more preferable that it is 20-30 mass %. Furthermore, from the same viewpoint, (A) the alkali-soluble polymer preferably has both a structural unit of styrene and/or a styrene derivative and a structural unit of benzyl (meth)acrylate.

Examples of the comonomer having a phenylalkyl group (excluding benzyl group) include phenylethyl (meth)acrylate.

The copolymer having an aromatic group (preferably a benzyl group) in the side chain is preferably produced by combining (i) a monomer having an aromatic group and (ii) at least one of the following first monomers and/or It is obtained by polymerizing at least one of the following second monomers.

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

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 etc. Among these, (meth)acrylic acid is preferred. In addition, in this specification, the term "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, the term "(meth)acrylyl group" refers to an acrylyl group or a methacrylic acid group, and the term "(meth)acrylic acid" refers to acrylic acid or methacrylic acid. (Meth)acrylate" means "acrylate" or "methacrylate".

The copolymerization ratio of the first monomer is preferably 10 to 50 mass % based on the total mass of all monomer components of the polymer obtained by polymerizing at least one of the first monomers. From the viewpoint of exhibiting good developability and controlling edge meltability, the copolymerization ratio is preferably 10% by mass or more. From the viewpoint of high resolution and string shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, the copolymerization ratio is preferably 50 mass% or less, more preferably 30 mass% or less. , more preferably 25 mass% or less, particularly preferably 22 mass% or less, most preferably 20 mass% or less.

The second monomer system is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (methyl)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, and n-propyl(meth)acrylate. Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid ring (Meth)acrylates such as hexyl ester and 2-ethylhexyl (meth)acrylate; 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.

(A) The alkali-soluble polymer can be produced by polymerizing the singular or plural monomers described above using a known polymerization method, preferably addition polymerization, more preferably radical polymerization. From the viewpoint of chemical resistance, adhesion, high resolution, or string shape of the resist pattern, it is preferable that the monomer contains a monomer having an aralkyl group and/or styrene. (A) The alkali-soluble polymer is particularly preferably a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, or a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene. Things etc.

(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). It is a value that evaluates the polarity of various organic compounds based on the organic concept diagram. It is a functional group contribution method that sets parameters for the functional groups in the compound. One of a kind. Regarding the I/O value, for example, non-patent literature (Organic Concept Diagram (written by Zeno Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Items 1 to 16 (1954); Chemical Field, No. 11 Volume, No. 10, Items 719-725 (1957); Fragrancejournal, No. 34, Items 97-111 (1979); Fragrancejournal, No. 50, Items 79-82 (1981)) and other documents Explain in detail. The concept of I/O value is to divide the properties of compounds into organic groups showing covalent bonding properties and inorganic groups showing ionic bonding properties, and all organic compounds are named organic axes and It is positioned and expressed in the form of points on the coordinates of the orthogonal axis of the inorganic axis. The closer the above I/O value is to 0, the more non-polar (i.e., the more hydrophobic or organic) the organic compound is, and the larger the value is, the more polar (i.e., the more hydrophilic or inorganic) the organic compound is. organic compounds.

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

Regarding the glass transition temperature of (A) the alkali-soluble polymer, the value calculated by the Fox equation (when (A) the alkali-soluble polymer contains a plurality of polymers, the glass transition temperature Tg related to the entire mixture, That is, the weight average value of the glass transition temperature Tg _total ) is preferably 130°C or lower, and more preferably 120°C from the viewpoint of chemical resistance, adhesion, high resolution, or train shape of the resist pattern. below, below 110℃, below 100℃, below 95℃, below 90℃, or below 80℃. (A) The lower limit of the glass transition temperature (Tg) of the alkali-soluble polymer is not limited, but from the viewpoint of controlling edge meltability, it is preferably 30°C or higher, more preferably 50°C or higher, and still more preferably Above 60℃. In addition, as the glass transition temperature of a homopolymer containing the same monomer as one or a plurality of monomers constituting the alkali-soluble polymer (A), the non-patent document (Brandrup, J. The value expressed by I mmergut, EH editor "Polymer handbook, Third edition John wiley & sons, 1989, p.209 Chapter VI "Glass transition temperatures of polymers").

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

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 related to the entire mixture) is preferably 5,000 to 500,000. The weight average molecular weight of (A) the alkali-soluble polymer is preferably 5,000 or more from the viewpoint of maintaining a uniform thickness of the dry film resist and obtaining resistance to the developer. From the viewpoint of the developability of the etchant, the high resolution and string shape of the resist pattern, and further the chemical resistance of the resist pattern, it is preferably 500,000 or less. (A) The weight average molecular weight of the alkali-soluble polymer is more preferably 10,000 to 200,000, further preferably 20,000 to 100,000, particularly preferably 30,000 to 70,000. (A) The molecular weight dispersion of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 4.0, even more preferably 1.0 to 3.0.

The content of (A) alkali-soluble polymer in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise stated, the same applies to each contained component): 10 mass % to 90 mass %, preferably 20 mass % to 80 mass %, further preferably 40 mass % to 60 mass %. 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 so that the resist pattern formed by exposure can fully function as a resist From the viewpoint of the performance of the resist material, the high resolution of the resist pattern, the train shape of the resist pattern, and further the chemical resistance of the resist pattern, it is preferably 90 mass % or less, and more preferably 80 mass% or less, more preferably 70 mass% or less, still more preferably 60 mass% or less.

(B) Compounds with ethylenically unsaturated bonds (B) The compound having an ethylenically unsaturated bond is a compound that has polymerizability by having an ethylenically unsaturated bond (that is, a double bond) in its structure. The ethylenically unsaturated bond is more preferably derived from a methacryl group. From the viewpoint of adhesiveness and suppression of developer foaming properties, the compound having an ethylenically unsaturated bond (B) is preferably an alkylene oxide structure having 3 or more carbon atoms. The number of carbon atoms in the alkylene oxide structure is more preferably 3 to 6, and still more preferably 3 to 4.

Examples of the compound (B) having one (meth)acrylyl group as an ethylenically unsaturated bond include: a compound in which (meth)acrylic acid is added to one terminal of polyalkylene oxide; or Compounds in which (meth)acrylic acid is added to one end of a polyalkylene oxide and the alkyl group on the other end is etherified or allyl etherified; phthalic acid-based compounds, etc., with regard to peelability or softness of the cured film Better from that point of view.

Examples of such compounds include: phenoxyhexaethylene glycol mono(meth)acrylate, a (meth)acrylate compound obtained by adding polyethylene glycol to a phenyl group; The (meth)acrylate ester of a compound in which polypropylene glycol with an average of 2 moles of propylene oxide and polyethylene glycol with an average of 7 moles of ethylene oxide added to nonylphenol is 4 - n-nonylphenoxy heptaethylene glycol dipropylene glycol (meth)acrylate; polypropylene glycol added with an average of 1 mole of propylene oxide, and polypropylene glycol with an average addition of 5 moles of ethylene oxide The (meth)acrylate of the compound formed by adding polyethylene glycol to nonylphenol is 4-n-nonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate; the addition has an average of 8 The acrylate ester of a compound formed by adding molar polyethylene glycol to nonylphenol, namely 4-n-nonylphenoxy octaethylene glycol (meth)acrylate (such as Toa Gosei Co., Ltd. Co., Ltd., M-114), etc. Moreover, if γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-phthalate is included, in addition to the above-mentioned viewpoints, the viewpoints of sensitivity, resolution, and adhesion are Words are also better.

Examples of compounds having two (meth)acrylyl groups in the molecule include compounds having (meth)acrylyl groups at both ends of an alkylene oxide chain, or compounds having an ethylene oxide chain and an epoxy group. Compounds having (meth)acrylyl groups at both ends of an alkylene oxide chain formed by randomly or block-bonded propane chains.

Examples of such compounds include tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, and heptaethylene glycol di(meth)acrylate. acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, in 12 moles of ethylene oxide In addition to compounds having (meth)acrylyl groups at both ends of the chain, such as polyethylene glycol (meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, etc. Acrylic etc. Examples of polyalkylene oxide di(meth)acrylate compounds containing an ethylene oxide group and a propylene oxide group include polypropylene glycol to which an average of 12 moles of propylene oxide has been added. Dimethacrylate of a glycol to which an average of 3 moles of ethylene oxide was added to each end, and polypropylene glycol to which an average of 18 moles of propylene oxide was added to both ends were added to an average of 15 moles. Dimethacrylate of diol made from mole of ethylene oxide, FA-023M, FA-024M, FA-027M (product name, manufactured by Hitachi Chemical Industry), etc. These are better from the viewpoints of flexibility, resolution, adhesion, etc.

As another example of a compound having two (meth)acrylyl groups in the molecule, from the viewpoint of resolution and adhesion, it is preferable to modify bisphenol A with an alkylene oxide. A compound with a (meth)acrylyl group at the end. Specifically, a compound represented by the following general formula (I) can be used: [Chemical 1] {In the formula, R ₁ and R ₂ independently represent 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 independently an integer from 0 to 29, and n ₂ + n ₄ is an integer from 0 to 30, the repetition of -(AO)- and -(BO)- The arrangement of the units may be random or block; and, in the case of block, either -(AO)- or -(BO)- may be a biphenyl side}. For example, in terms of resolution and adhesion, polyethylene glycol dimethacrylate, in which an average of 5 moles of ethylene oxide is added to both ends of bisphenol A, is preferred. Polyethylene glycol dimethacrylate has an average of 2 moles of ethylene oxide added to both ends of bisphenol A, and an average of 1 mole of ethylene oxide is added to both ends of bisphenol A. Ethylene oxide polyethylene glycol dimethacrylate. In addition, compounds in which the aromatic ring in the above general formula (I) has a heteroatom and/or a substituent can be used.

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, and benzyl. Methyl group, amino group, alkylamino group with 1 to 10 carbon atoms, dialkylamino group with 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkyl mercapto group with 1 to 10 carbon atoms, Aryl group, hydroxyl group, hydroxyalkyl group with 1 to 20 carbon atoms, carboxyl group, carboxyalkyl group with 1 to 10 carbon atoms in the alkyl group, hydroxyl group with 1 to 10 carbon atoms in the alkyl group, hydroxyalkyl group with 1 to 20 carbon atoms in the alkyl group Alkoxy group, alkoxycarbonyl group with 1 to 20 carbon atoms, alkylcarbonyl group with 2 to 10 carbon atoms, alkenyl group with 2 to 10 carbon atoms, N-alkylamine methyl group with 2 to 10 carbon atoms may include Heterocyclic groups, or aryl groups substituted by such substituents, etc. These substituents may form a condensed ring, or the hydrogen atoms in these substituents may be replaced by 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.

(B) A compound having an ethylenically unsaturated double bond can significantly improve the adhesion when developing after heating after exposure. In particular, good adhesion can be obtained even when the time from exposure to development becomes longer. From the viewpoint of adhesiveness, it is preferable to include a (meth)acrylate compound having three or more ethylenically unsaturated double bonds (that is, trifunctional or more). From the same viewpoint, a (meth)acrylate compound having 4 or more ethylenically unsaturated double bonds is more preferred, and a (meth)acrylate compound having 5 or more ethylenically unsaturated double bonds is even more preferred. (meth)acrylate compound, preferably a (meth)acrylate compound having 6 or more ethylenically unsaturated double bonds. Moreover, from the same viewpoint, these are preferably methacrylate compounds. It is believed that compounds with 3 or more, 4 or more, 5 or more, or 6 or more ethylenically unsaturated double bonds have the effect of increasing the cross-linking density when exposed to polymerization, but in most cases due to the large number of functional groups Due to the influence of steric hindrance, the required cross-linking density cannot be obtained. In the present invention, it was found that by using a compound preferably having 3 or more ethylenically unsaturated double bonds, more preferably a compound having 4 or more ethylenically unsaturated double bonds, and still more preferably 5 Compounds with more than 4 ethylenically unsaturated double bonds, especially compounds with 6 or more ethylenically unsaturated double bonds, are also heated after exposure to improve the fluidity in the system. Even if the number of functional groups is large, It can also reduce the influence of steric hindrance and obtain higher adhesion. A compound having three or more ethylenically unsaturated double bonds is preferred, a compound having four or more ethylenically unsaturated double bonds is more preferred, and a compound having five or more ethylenically unsaturated double bonds is still more preferred. The content of the compound, particularly a compound having 6 or more ethylenically unsaturated double bonds, is preferably 3 mass% or more, more preferably 5 mass% or more, based on the solid content of the photosensitive resin composition. Furthermore, it is more preferable that it is 7 mass % or more, and it is especially preferable that it is 10 mass % or more. In addition, the upper limit of the content is preferably 30 mass% or less, more preferably 25 mass% or less, and further preferably 20 mass% or less from the viewpoint of expressing the effect of heat treatment after exposure. Preferably, it is 15 mass % or less.

Examples of (b1) (meth)acrylate compounds having three or more ethylenically unsaturated bonds include: Tri(meth)acrylates such as ethoxylated glyceryl tri(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and trihydroxy Methylpropane tri(meth)acrylate (for example, as a suitable example from the viewpoint of flexibility, adhesion, and bleeding inhibition, an average of 21 moles of ethylene oxide is added to trimethylolpropane Tris(meth)acrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane, etc.; Tetra(meth)acrylate such as di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.; Penta(meth)acrylate such as dipentaerythritol penta(meth)acrylate, etc.; Hexa(meth)acrylate includes dipentaerythritol hexa(meth)acrylate and the like. Among these, tetra, penta or hexa(meth)acrylate is preferred.

From the viewpoint of inhibiting bleeding, the (b1) (meth)acrylate compound having three or more ethylenically unsaturated bonds has a weight of preferably 500 or more, more preferably 700 or more, and still more preferably 900 or more. average molecular weight.

As the tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate is preferred. As pentaerythritol tetra(meth)acrylate, 1 to 40 moles of alkylene oxide tetra(meth)acrylate in total added to the four terminal ends of pentaerythritol is preferred.

Tetrakis(meth)acrylate is more preferably a tetrakis(meth)acrylate compound represented by the following general formula (II): [Chemical 2] {In the formula _, R _{3 to} R _{6 each} independently represent a hydrogen atom or a _methyl group, Integer, when m ₁ + m ₂ + m ₃ + m ₄ is 1 to 40, and m ₁ + m ₂ + m ₃ + m ₄ is 2 or more, the plural Xs may be the same or different from each other}.

Without wishing to be bound by theory, it is thought that the tetramethacrylate compound represented by the general formula (II) has groups R ₃ to R ₆ and has H ₂ C=CH-CO-O- moiety tetra Compared with acrylates, it inhibits hydrolysis in alkaline solutions. From the viewpoint of significantly improving the adhesion during development after heating after exposure, and in particular achieving good adhesion even when the time from exposure to development becomes longer, it is preferable to use the general formula (II) Photosensitive resin composition of the represented tetramethacrylate compound.

In the general formula (II), it is preferable that at least one of the groups R ₃ to R ₆ is a methyl group, and more preferably, all of the groups R ₃ to R ₆ are methyl groups.

Regarding the resist pattern, from the viewpoint of obtaining desired resolution, string shape, and residual film rate, it is preferable that in the general formula (II), X is -CH ₂ -CH ₂ -.

Regarding the resist pattern, from the viewpoint of obtaining the required resolution, frame shape and residual film rate, it is preferable that in the general formula (II), m ₁ , m ₂ , m ₃ and m ₄ are each independently It is an integer from 1 to 20, more preferably, it is an integer from 2 to 10. Furthermore, in the general formula (II), m ₁ + m ₂ + m ₃ + m ₄ is preferably 1 to 36 or 4 to 36.

Examples of the compound represented by the general formula (II) include pentaerythritol (poly)alkoxytetramethacrylate and the like. Moreover, in the present invention, "pentaerythritol (poly)alkoxytetramethacrylate" is included in the above-mentioned general formula (II), and "pentaerythritol alkoxytetramethylacrylate" where m ₁ + m ₂ + m ₃ + m ₄ =1 Both of "acrylate" and "pentaerythritol polyalkoxytetramethacrylate" with 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 Japanese Patent Application Laid-Open No. 2013-156369, such as pentaerythritol (poly)alkoxytetramethacrylate.

As the hexa(meth)acrylate compound, a hexa(meth)acrylate having a total of 1 to 24 moles of ethylene oxide added to the 6 terminals of dipentaerythritol is preferred. The total addition is 1 to 10 moles of ε-caprolactone hexa(meth)acrylate.

The photosensitive resin of this embodiment can significantly improve the adhesion when developing after heating after exposure, and in particular, can achieve good adhesion even when the time from exposure to development becomes longer. The photosensitive resin of this embodiment The composition preferably contains a (meth)acrylate compound having four or more ethylenically unsaturated bonds and an alkylene oxide chain as (B) the compound having ethylenically unsaturated bonds. In this case, the ethylenically unsaturated bond is preferably derived from a methacrylyl group, and the alkylene oxide chain is more preferably an ethylene oxide chain.

In this embodiment, from the viewpoint of significantly improving the adhesion during development after heating after exposure, and in particular achieving good adhesion even when the time from exposure to development becomes longer, the photosensitivity The resin composition preferably contains a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton as (B) the compound having an ethylenically unsaturated bond. Examples of the alkylene oxide chain include an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, an epoxypentane chain, and an epoxyhexane chain. When the photosensitive resin composition contains a plurality of alkylene oxide chains, they may be the same or different from each other. From the above point of view, the alkylene oxide chain is more preferably an ethylene oxide chain, a propylene oxide chain, and a butylene oxide chain, and further preferably an ethylene oxide chain, and a propylene oxide chain, especially Preferably it is an ethylene oxide chain.

By using (A) an alkali-soluble polymer in combination with a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton in a photosensitive resin composition, the chemical resistance and adhesion of the resist pattern can be maintained And the tendency of interpretive balance.

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

Examples of the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton include an average of 4 to 30 moles, an average of 6 to 24 moles, or an average of 10 to 14 moles added to dipentaerythritol. Alkylene oxide hexa(meth)acrylate.

Specifically, a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton can significantly improve the adhesion during development after heating after exposure, especially from exposure to development. From the viewpoint of achieving good adhesion even over a long period of time, a compound represented by the following general formula (III) is preferred: [Chemical 3] {In the formula, R each independently represents a hydrogen atom or a methyl group, and n is an integer from 0 to 30, and the total value of all n is 1 or more}. In general formula (III), it is preferable that the average value of all n is 4 or more, or that each n is 1 or more. As R, methyl is preferred.

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

(b1) A (meth)acrylate compound having three or more ethylenically unsaturated bonds (that is, a compound having three or more (meth)acrylate groups) relative to the total solid content of the photosensitive resin composition The content of the compound) is preferably more than 0% by mass and 50% by mass or less. If the content exceeds 0% by mass, the adhesion during development after heating after exposure is significantly improved, and in particular, good adhesion can be achieved even when the time from exposure to development becomes longer. More advantageously, when the content is 50% by mass or less, the flexibility of the hardened resist tends to be improved and the peeling time tends to be shortened. The content is more preferably 2 mass% or more and 40 mass% or less, and still more preferably 4 mass% or more and 35 mass% or less. In a more preferred aspect, (B) the compound having an ethylenically unsaturated double bond is preferably 5 mass % or more, more preferably 9 mass % or more, based on the solid content of the entire photosensitive resin composition. It is 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, and still more preferably 30% by mass or less. There are 3 molecules in the amount. The above methacrylate-based compounds.

From the viewpoint of adhesiveness and developer foaming suppression, the photosensitive resin composition preferably contains (b2) having a butylene oxide chain or a propylene oxide chain and one or two (methyl ) acrylyl compound as (B) a compound having an ethylenically unsaturated bond. Regarding the compound (b2) having a butylene oxide chain or a propylene oxide chain and one or two (meth)acrylyl groups, from the viewpoint of inhibiting bleeding, the compound has preferably 500 or more, more preferably 700. The molecular weight is more than 1000 and more preferably 1000 or more.

Examples of (b2) compounds having a butylene oxide chain or a propylene oxide chain and one or two (meth)acrylyl groups include: polypropylene glycol (meth)acrylate, polypropylene glycol di(methyl) Acrylate, polytetramethylene glycol (meth)acrylate, polytetramethylene glycol di(meth)acrylate, etc. (b2) Compounds having a butylene oxide chain or a propylene oxide chain and one or two (meth)acrylyl groups may also contain an ethylene oxide chain in addition to a butylene oxide chain or a propylene oxide chain. .

Specifically, the compound (b2) having a butylene oxide chain or a propylene oxide chain and 1 or 2 (meth)acrylyl groups has preferably 1 to 20, more preferably 4 to 15 , and more preferably 6 to 12 C ₄ H ₈ O or C ₃ H ₆ O (meth)acrylate or di(meth)acrylate.

The content of (b2) the compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acrylyl groups is preferably more than 0 relative to the total solid content of the photosensitive resin composition. mass% and less than 20 mass%.

In this embodiment, in order to suppress the bleeding of the constituent components of the dry film resist and improve the storage stability, the total solid content of the compound having an ethylenically unsaturated bond (B) is preferably 70% by mass. % or more, more preferably 80 mass % or more, further preferably 90 mass % or more, especially 100 mass %, is a compound having a weight average molecular weight of 500 or more. From the viewpoint of suppression of bleeding and chemical resistance of the resist pattern, (B) the weight average molecular weight of the compound having an ethylenically unsaturated bond is preferably 760 or more, more preferably 800 or more, and still more preferably 830 Above, preferably above 900. (B) The weight average molecular weight of the compound having an ethylenically unsaturated bond can be determined as a molecular weight calculated from the molecular structure of the compound having (B) an ethylenically unsaturated bond. When there are a plurality of compounds (B) having an ethylenically unsaturated bond, it can be determined by weighting the molecular weight of each compound by its content.

From the viewpoint of chemical resistance, adhesion, high resolution, and string shape of the resist pattern, the concentration of the methacryl group in (B) the compound having an ethylenically unsaturated bond is preferably 0.20 mol/100 g or more, more preferably 0.30 mol/100 g or more, further preferably 0.35 mol/100 g or more. The upper limit of the concentration of the methacryl group is not particularly limited as long as polymerizability and alkaline developability are ensured. For example, it may be 0.90 mol/100 g or less or 0.80 mol/100 g or less.

From the same viewpoint, (B) the value of the concentration of methacryl group/(concentration of methacryl group + concentration of acryl group) in the compound having an ethylenically unsaturated bond is preferably 0.50 or more , more preferably 0.60 or more, still more preferably 0.80 or more, particularly preferably 0.90 or more, most preferably 0.95 or more.

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

(B) The ratio of the compound having an ethylenically unsaturated double bond to the mass of the total solid content of the photosensitive resin composition is preferably 5 to 70 mass %. From the viewpoint of sensitivity, resolution and adhesion, it is preferable to set the ratio to 5 mass % or more. The ratio is more preferably 10 mass% or more, more preferably 20 mass% or more, and still more preferably 30 mass% or more. On the other hand, from the viewpoint of suppressing edge melting and peeling delay of the hardened resist, it is preferable to set the ratio to 70 mass % or less. More preferably, the ratio is 50% by mass or less.

(C) Photopolymerization initiator (C) The photopolymerization initiator is a compound that polymerizes monomers using light. (C) Photopolymerization can significantly improve the adhesion during development after heating after exposure, and in particular, good adhesion can be obtained even when the time from exposure to development becomes longer. The starting agent preferably contains at least one selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof, and more preferably contains anthracene and/or anthracene derivatives. , and further preferably contains anthracene derivatives. In addition, anthracene, pyrazoline, triphenylamine, coumarin, and their derivatives, especially anthracene and/or anthracene derivatives, are sensitive to the first active light with a center wavelength less than 390 nm and a center wavelength of 390 nm. The second active light above nm absorbs light and functions well as a polymerization initiator. Therefore, in one aspect, the photosensitive resin composition may have photosensitivity to the first active light and the second active light, and may be used for two-wavelength exposure. (C) The photopolymerization initiator can also be selected so as to have a plurality of absorption maximum values within the wavelength range of the first active light and the second active light.

The total content of (C) photopolymerization initiator in the photosensitive resin composition is preferably in the range of 0.01 to 20 mass%, more preferably in the range of 0.05 to 10 mass%, and further preferably 0.1 mass% % to 7% by mass, particularly preferably 0.1% to 6% by mass. The total content of (C) photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, so that light can be fully transmitted to the resist bottom surface and good high resolution can be obtained. From the viewpoint of sex, it is preferably 20% by mass or less.

Anthracene and anthracene derivatives are advantageous in that they can significantly improve the adhesion when developing after heating after exposure, and in particular, can achieve good adhesion even when the time from exposure to development becomes longer. From the same point of view, the anthracene derivative preferably has an alkoxy group having 1 to 40 carbon atoms that may have a substituent at the 9-position and/or 10-position, and more preferably has an optional substituent at the 9 or 10-position. A substituent-containing aryl group having 6 to 40 carbon atoms.

In one aspect, anthracene can significantly improve the adhesion during development after heating after exposure, and in particular, can achieve good adhesion even when the time from exposure to development becomes longer. The derivative is preferably an alkoxy group having 1 to 40 carbon atoms that may have a substituent on at least one of the 9- or 10-positions, and further preferably has an alkoxy group on at least one of the 9- or 10-positions that may have a substituent. The substituent is an alkoxy group having 1 to 30 carbon atoms. From the viewpoint of obtaining good adhesion and resolution, an alkoxy group having 1 to 40 carbon atoms that may have a substituent at the 9 or 10 positions is preferred, and it is more preferred that the alkoxy group has an optional substituent at the 9 or 10 positions. An alkoxy group having 1 to 30 carbon atoms having a substituent. The number of carbon atoms in the base at position 9 and position 10 may be the same or different.

Examples of the alkoxy group which may have a substituent include: Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, 2-methylpropoxy, 1-methylpropoxy, n-pentoxy, Isopentyloxy, n-hexyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, di Decyloxy, cyclohexyloxy, nordecyloxy, tricyclodecyloxy, tetracyclododecyloxy, adamantyloxy, methyladamantyloxy, ethyladamantyloxy, and butyloxy Adamantane alkoxy; Halogen-modified alkoxy groups such as chlorobutoxy and chloropropoxy; Alkoxy groups with added hydroxyl groups such as hydroxybutoxy groups; Alkoxy groups with added cyano groups such as cyanobutoxy groups; Alkoxy groups with added epoxyalkyl groups such as methoxybutoxy groups; Alkoxy groups to which aryl groups are added include phenoxybutoxy groups, etc. Among them, n-butoxy is more preferred.

In one aspect, anthracene can significantly improve the adhesion during development after heating after exposure, and in particular, can achieve good adhesion even when the time from exposure to development becomes longer. The derivative is preferably an aryl group having 6 to 40 carbon atoms that may have a substituent on at least one of the 9- or 10-positions, and more preferably has an optional substituent on at least one of the 9- or 10-positions. An aryl group with 6 to 30 carbon atoms.

From the viewpoint of significantly improving the adhesion during development after heating after exposure, and in particular achieving good adhesion even when the time from exposure to development becomes longer, 9 and 10 are preferred. An aryl group having a carbon number of 6 to 40 that may have a substituent at the 9th or 10th position is more preferred. The number of carbon atoms in the base at position 9 and position 10 may be the same or different. In addition, the bases of the 9th and 10th positions may be the same base or different bases. For example, the group at position 9 is an alkoxy group having 1 to 40 carbon atoms which may have a substituent, and the group at position 10 may be an aryl group having 6 to 40 carbon atoms which may have a substituent.

Examples of aryl groups having 6 to 40 carbon atoms that may have a substituent include phenyl, biphenyl, naphthyl, and anthracenyl; aryl groups having an alkoxy group added such as methoxyphenyl and ethoxy Phenyl; aryl groups with an alkyl group added such as tolyl, xylyl, base, nonylphenyl; aryl groups with halogen added such as chlorophenyl; aryl groups with hydroxyl added such as hydroxyphenyl, etc. Among them, phenyl is more preferred.

The anthracene derivative is preferably represented by the following general formula (IV). [Chemical 4] R ¹ independently 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, or an alkenyl group having 2 to 4 carbon atoms. , substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group or N(R') ₂ group, two or more R ¹ can be bonded to each other to form a cyclic structure. May contain heteroatoms.

X independently indicates that single bonds, oxygen atoms, sulfur atoms, cymbal bases, sulfonal bases, -N (R ') -B, -CO-O-base, -CO-S-base, -SO _2-O -base, base, base, base, base, base, base, base, base, base, base, base, base, base, basal -SO ₂ -S- group, -SO ₂ -N(R')- group, -O-CO- group, -S-CO- group, -O-SO ₂ - group or S-SO ₂ - group. Among them, except for the combination of X being a single bond and R ¹ being a hydrogen atom (i.e. unsubstituted anthracene).

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, R' may be bonded to each other to form a cyclic structure, and the cyclic structure may contain heteroatoms.

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

Specific examples of the substituted or unsubstituted alkyl group having 1 to 40 carbon atoms in R ¹ and R′ include: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-eicosyl, iso Propyl, isobutyl, second butyl and third butyl, etc.

Specific examples of the substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms in R ¹ and R′ include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and carbon Bridged alicyclic hydrocarbon groups with numbers 6 to 20 (such as nordecyl, tricyclodecyl, tetracyclododecyl, adamantyl, methyladamantyl, ethyladamantyl, and butyladamantyl) base etc.) etc.

Specific examples of the alkenyl group having 2 to 4 carbon atoms in R ¹ and R′ include vinyl and propenyl groups.

Specific examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms in R ¹ and R′ include: phenyl group, biphenyl group, naphthyl group, anthracenyl group, methoxyphenyl group, Ethoxyphenyl, tolyl, xylyl, base, nonylphenyl, chlorophenyl, hydroxyphenyl.

Examples of the substituted or unsubstituted heteroaryl group in R ¹ and R′ include one or more heteroatoms such as a sulfur atom, an oxygen atom, and a nitrogen atom in the substituted or unsubstituted aryl group. Examples of the group include pyridyl, imidazolyl, morpholinyl, piperidinyl, pyrrolidinyl, etc.

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

Preferable specific examples of the above-mentioned R1 ^and R' include: hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n- Heptyl, n-octyl, cyclopentyl, cyclohexyl, camphoryl, norbenzyl, p-toluyl, benzyl, methylbenzyl, phenyl and 1-naphthyl.

Preferable specific examples of the above-mentioned X include a single bond, an oxygen atom, a sulfur atom, an -N(R')- group, an -O-CO- group, and an O-SO ₂ - group. Here, when the above-mentioned X is a -N(R')-group, the above-mentioned R' is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, Cyclohexyl, camphoryl, norbenyl or benzyl.

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-bromobenzene base)-10-phenylanthracene, 9-(1-naphthyl)anthracene, 9-(2-naphthyl)anthracene, 2-bromo-9,10-bis(2-naphthyl)anthracene, 2,6- Dibromo-9,10-bis(2-naphthyl)anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10- Bis(2-ethylhexyloxy)anthracene, 1,2-benzanthracene, anthracene, 1,4,9,10-tetrahydroxyanthracene, 9-anthracenemethanol, 1-aminoanthracene, 2-aminoanthracene Anthracene, 9-(methylaminomethyl)anthracene, 9-acetyl anthracene, 9-anthracene aldehyde, 10-methyl-9-anthracene, 1,8,9-triethyl anthracene, etc. Among these, 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10- Dibutoxyanthracene, 9,10-bis(2-ethylhexyloxy)anthracene, and 9,10-bis-(3-chloropropoxy)anthracene can be significantly improved after heating after exposure. In terms of adhesion during development, especially in terms of achieving good adhesion even when the time from exposure to development becomes longer, 9,10-diethoxyanthracene and 9,10-bis are more preferred. Butoxyanthracene and 9,10-diphenylanthracene, 9,10-bis-(3-chloropropoxy)anthracene, especially 9,10-dibutoxyanthracene and 9,10-diphenyl Anthracene, 9,10-bis-(3-chloropropoxy)anthracene. The compound represented by the general formula (IV) may be used alone or in combination of two or more.

(C) Photopolymerization can significantly improve the adhesion during development after heating after exposure, and in particular, good adhesion can be obtained even when the time from exposure to development becomes longer. The starting agent is preferably (1) containing 9,10-diphenylanthracene; (2) containing 9,10-dialkoxyanthracene; (3) containing anthracene derivatives with halogen atoms; (4) containing 9, Halogen substitutes of 10-dialkoxyanthracene; (5) Compounds containing the alkoxy group at position 9 and/or 10 of 9,10-dialkoxyanthracene modified with more than one halogen atom; and/ or (6) compounds containing halogen atoms directly bonded to the anthracene skeleton.

The compound represented by the above general formula (IV) can significantly improve the adhesion when developing after heating after exposure, and in particular, good adhesion can be obtained even when the time from exposure to development becomes longer. It is advantageous from this point of view, and can be used for two-wavelength exposure using the first active light with a central wavelength less than 390 nm and the second active light with a wavelength above 390 nm as the central wavelength, thereby providing excellent display results. The photosensitive resin composition is also advantageous in terms of sensitivity, adhesion and resolution.

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

In one aspect, as the anthracene derivative, a compound having a halogen atom directly bonded to an 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-phenanthrenyl)anthracene , 2-bromoanthracene, 9-bromoanthracene, 2-chloroanthracene, 9,10-dibromoanthracene.

In the total amount of anthracene and anthracene derivatives, or in a more preferred embodiment, the amount of the compound represented by the general formula (IV) is preferably 0.05 to 0.05 with respect to the total solid content of the photosensitive resin composition. It is in the range of 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.

Pyrazoline and pyrazoline derivatives are preferable from the viewpoint of peeling characteristics, sensitivity, resolution, and adhesion of the photosensitive resin layer.

As the pyrazoline derivative, from the above viewpoint, for example, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl) is preferred. -Pyrazoline, 1-(4-(benzoethazol-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-benzene base)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4- Biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylbenzene base)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3 ,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl) )-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxyphenyl)-5-(2,6-di Methoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxyphenyl)-5-(2,5-dimethoxyphenyl)-pyrazoline , 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2 ,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, etc., more preferably 1-phenyl-3-(4-biphenyl)- 5-(4-tert-Butyl-phenyl)-pyrazoline.

Examples of coumarin derivatives include 7-diethylamino-4-methylcoumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), and 3-benzyl Cyl-7-diethylaminocoumarin, etc. Among them, 7-diethylamino-4-methylcoumarin is preferred in terms of sensitivity, resolution, and adhesion.

Further examples of (C) photopolymerization initiators include: quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, 9 -oxygen sulfur𠮿 esters, dialkylaminobenzoates, oxime esters, and acridines (for example, in terms of sensitivity, resolution, and adhesion, 9-phenylacridine and bisacridine are preferred) ylheptane, 9-(p-methylphenyl)acridine, 9-(m-methylphenyl)acridine), hexaarylbiimidazole, N-arylamino acid or its ester compound (for example, for In terms of sensitivity, resolution, and adhesion, N-phenylglycine) and halogen compounds (such as tribromomethylphenyltrilane) are preferred. These can be used individually by 1 type or in combination of 2 or more types. In addition, 2,2-dimethoxy-1,2-diphenylethan-1-one and 2-methyl-1-(4-methylthienyl)-2-morpholinyl can also be used Propan-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, triphenylphosphine oxide, etc.

Examples of aromatic ketones include benzophenone, Michelone [4,4'-bis(dimethylamino)benzophenone], and 4,4'-bis(diethylamine). base) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone. These can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of adhesiveness, 4,4'-bis(diethylamino)benzophenone is preferred. Furthermore, from the viewpoint of transmittance, the content of the aromatic ketones in the photosensitive resin composition is preferably in the range of 0.01 mass% to 0.5 mass%, and further preferably in the range of 0.02 mass% to 0.3 mass%. within.

Examples of hexaarylbimidazole 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-di Methoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'- Bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5- Difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4 ,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5 ,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis -(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methyl Oxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl) -Bimidazole, 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 use two or more types in combination. From the viewpoint of sensitivity, resolution and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

Regarding the content of hexaarylbisimidazole in the photosensitive resin composition, from the viewpoint of improving the peeling characteristics and/or sensitivity of the photosensitive resin layer, it is preferably in the range of 0.05 mass % to 8 mass %, more preferably It is in the range of 0.1 mass % - 7 mass %, and it is more preferable that it is in the range of 1 mass % - 6 mass %.

(D) Phenolic polymerization inhibitor The photosensitive resin composition contains (D) a phenolic polymerization inhibitor in order to improve thermal stability and storage stability. In the present invention, (D) the phenolic polymerization inhibitor is a compound having one or more phenolic hydroxyl groups. Phenolic polymerization inhibitors have the property of inhibiting polymerization reactions caused by heat, etc., and improving storage stability. The phenolic polymerization inhibitor may have at least one selected from 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, or an alkenyl group having 2 to 4 carbon atoms. A substituent in the group consisting of 3 to 20 substituted or unsubstituted alicyclic groups, substituted or unsubstituted aryl groups, and substituted or unsubstituted heteroaryl groups. In a preferred aspect, (D) the phenolic polymerization inhibitor is a monohydric phenol (that is, a compound having one phenolic hydroxyl group in the molecule). (D) More specific suitable examples of phenolic polymerization inhibitors include: p-methoxyphenol, dibutylhydroxytoluene, hydroquinone, tetrakis(3-(3',5'-di-tertiary butylene) Pentaerythritol-4'-hydroxyphenyl)propionate, 2,2'-thiodiethylbis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ), 3-(3,5-di-tertiary butyl-4-hydroxyphenyl) stearyl propionate, N,N'-hexamethylene bis(3-(3,5-di-tertiary Butyl-4-hydroxyphenyl)propylamide), 3,5-di-tert-butyl-4-hydroxy-octyl hydrocinnamate, 2,4,6-tris(3',5'-di- 3-Butyl-4'-hydroxybenzyl) mesitylene, 2,4-bis(dodecylthiomethyl)-6-methylphenol, 2,4-bis(octylthiomethyl) -6-methylphenol, bis(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid) (ethylidene bis(oxyethylene)), 1,6-hexanedi Alcohol bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 1,3,5-tris((3,5-bis(1,1-dimethyl) Ethyl)-4-hydroxyphenyl)methyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione, 4-((4,6-bis(octyl) (Thio)-1,3,5-Tris-2-yl)Amino)-2,6-di-tert-butylphenol, etc. In particular, it is not easy to produce a difference in the shortest development time with or without post-exposure heating. From this point of view, p-methoxyphenol and dibutylhydroxytoluene are preferred.

(D) The phenolic polymerization inhibitor is an amount based on the mass basis when the mass of the total solid content of the photosensitive resin composition is 100% by mass, so that the required polymerization inhibition for the photosensitive resin composition can be obtained. From the viewpoint of effect, it is 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, further preferably 15 ppm or more, especially 20 ppm or more, when developing after heating after exposure. , especially from the viewpoint of good adhesion even when the time from exposure to development becomes longer, it is 300 ppm or less, preferably 200 ppm or less, more preferably 150 ppm or less, and still more preferably 100 ppm or less. , more preferably 75 ppm or less, still more preferably 50 ppm, still more preferably 40 ppm or less. Although the photosensitive resin composition contains (D) a phenol-based polymerization inhibitor, the amount is small, and when the photosensitive resin composition is heated and then developed after exposure, the polymerization reaction during exposure of the photosensitive resin composition can be simultaneously realized. It is advantageous in terms of good progress and a good effect of improving fluidity by heating the polymer, thereby accelerating the reaction of the polymer (thereby improving the adhesion). For example, in systems where the polymer has a fluffy molecular structure (such as a relatively large amount of styrene skeleton), when post-exposure heating is performed to improve adhesion, the fluidity improvement effect caused by heating of the polymer is low. (Therefore, the adhesion improvement effect is low), according to the photosensitive resin composition of this embodiment, the amount of (D) phenolic polymerization inhibitor is in the above range, in the case where such a fluffy polymer is present The adhesion improvement effect caused by post-exposure heating can also be obtained well.

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

[optional ingredients] In addition to the above-mentioned components (A) to (D), the photosensitive resin composition may further contain optional components as necessary. Examples of optional components include: (d) (D) additional polymerization inhibitors other than the phenol-based polymerization inhibitor, dyes, coloring substances, plasticizers, antioxidants, stabilizers, and the like. For example, additives listed in Japanese Patent Application Laid-Open No. 2013-156369 can be used.

((d) Additional polymerization inhibitor) Examples of additional polymerization inhibitors include radical polymerization inhibitors other than the above-mentioned phenolic polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles.

Examples of radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, diphenylnitrosamine, and the like. In order not to impair the sensitivity of the photosensitive resin composition, nitrosophenylhydroxylamine aluminum salt is preferred.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis(N-2-ethylhexyl)aminotriazole. Methyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl) )Aminomethylene-1,2,3-benzotriazole, etc.

Examples of 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, N-(N,N -Di-2-ethylhexyl)aminoethylcarboxybenzotriazole, etc.

In one aspect, when the total solid component mass of the photosensitive resin composition is 100 mass %, the total amount of the additional polymerization inhibitor is preferably 0.001 to 3 mass %, more preferably 0.01 mass % to 1% by mass. From the viewpoint of providing storage stability to the photosensitive resin composition, it is preferred that the total amount be 0.001 mass % or more. On the other hand, from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye, the total amount is preferably 3% by mass or less.

(dyes and coloring substances) In this embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of dyes (such as leuco dyes, fluorescent yellow matrix dyes, etc.) and coloring substances, if necessary.

Examples of the coloring substance include magenta, phthalocyanine green, aurinine, p-magenta, crystal violet, methyl orange, Nero blue 2B, Victoria blue, and malachite green (for example, Aizen (manufactured by Hodogaya Chemical Co., Ltd.) Registered trademark) MALACHITE GREEN), alkaline blue 20, diamond green (for example, Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). When the mass of the total solid content of the photosensitive resin composition is 100% by mass, the content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass. From the viewpoint of improving the handleability of the photosensitive resin composition, it is preferable to set the content to 0.001 mass % or more. On the other hand, from the viewpoint of maintaining the storage stability of the photosensitive resin composition, it is preferable to set the content to 1 mass % or less.

The photosensitive resin composition contains a dye to color the exposed portion, so it is better in terms of visibility. In addition, when an inspection machine or the like reads the alignment mark used for exposure, the exposed portion is different from the unexposed portion. The one with a larger contrast in the exposed part is easier to identify and is more advantageous. From this point of view, preferred dyes include leuco dyes and fluorescent yellow matrix dyes. Examples of leuco dyes include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)benzenemethane [leuco malachite green], and the like. In particular, from the viewpoint of improving the contrast, it is preferable to use leuco crystal violet as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass based on the mass of the total solid content of the photosensitive resin composition. From the viewpoint of improving the contrast between the exposed portion and the unexposed portion, the content is preferably 0.1 mass % or more. The content is more preferably 0.2 mass% or more, and particularly preferably 0.4 mass% or more. On the other hand, from the viewpoint of maintaining storage stability, the content is preferably 10% by mass or less. The content is more preferably 5% by mass or less, still more preferably 2% by mass or less.

Moreover, from the viewpoint of optimizing the adhesion and contrast, it is preferred to use the leuco dye in combination with the above-mentioned halogen compound described in (C) photopolymerization initiator in the photosensitive resin composition. . When a leuco dye and the halogen compound are used together, the content of the halogen compound in the photosensitive resin composition is maintained when the total solid content mass of the photosensitive resin composition is 100% by mass. From the viewpoint of storage stability of the hue in the photosensitive layer, 0.01% by mass to 3% by mass is preferred.

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 terminals.

In this embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of plasticizers include phthalates (such as diethyl phthalate, etc.), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, and triethyl citrate. , triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, etc. Also included are: ADEKA NOL SDX-1569, ADEKA NOL SDX-1570, ADEKA NOL SDX-1571, ADEKA NOL SDX-479 (the above are manufactured by Asahi Denka Co., Ltd.), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, Newpol BPE-20T, Newpol BPE-60, Newpol BPE-100, Newpol BPE-180 (the above are manufactured by Sanyo Chemical Co., Ltd.), Uniol DB-400, Uniol DAB-800, Uniol DA-350F, Uniol DA-400, Uniol DA-700 (the above are manufactured by Nippon Oils and Fats Co., Ltd.), BA-P4U Glycol, BA-P8 Glycol (the above are manufactured by Nippon Emulsifier Co., Ltd.) and other compounds with a bisphenol skeleton.

The content of the plasticizer in the photosensitive resin composition is preferably 1 to 50 mass%, more preferably 1 to 30 mass% based on the mass of the total solid content of the photosensitive resin composition. From the viewpoint of suppressing a delay in development time and imparting flexibility to the cured film, the content is preferably 1 mass % or more. On the other hand, from the viewpoint of suppressing insufficient hardening and cold flow, the content is preferably 50 mass % or less.

If the water content in the photosensitive resin composition is large, local plasticization of the photosensitive resin composition is rapidly accelerated and edge melting occurs. From the viewpoint of suppressing edge melting, it is preferable to apply the photosensitive resin composition mixture to the support film and calculate the moisture in the photosensitive resin composition based on the mass based on the dried photosensitive resin composition. The amount is less than 0.7%. The moisture content 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.

[Solvent] The photosensitive resin composition can be dissolved in a solvent and used in the form of a photosensitive resin composition mixture to produce a photosensitive resin laminate. Examples of solvents include ketones, alcohols, and the like. The above ketones are represented by methyl ethyl ketone (MEK) and acetone. The above-mentioned alcohols are represented by methanol, ethanol, and isopropyl alcohol. The solvent is preferably added in an amount such that the viscosity of the photosensitive resin composition mixture coated on the support film becomes 500 mPa·s to 4,000 mPa·s at 25°C during the production of the photosensitive resin laminate. in photosensitive resin compositions.

[Light transmittance of photosensitive resin composition] The light transmittance of the photosensitive resin composition of this embodiment at least one of 375 nm and 405 nm provides sensitivity, adhesion, line width reproducibility, and solution when developing after heating after exposure. It is 58% to 95% from the viewpoint of the photosensitive resin composition having good imageability and achieving good adhesion especially even when the time from exposure to development is long. 375 nm and 405 nm correspond to the typical exposure wavelength of the photosensitive resin composition of this embodiment. The light transmittance is 58% or more from the viewpoint of obtaining good sensitivity, adhesion, line width reproducibility and resolution by allowing the exposure light to reach deeper areas of the photosensitive resin composition during exposure. , preferably 60% or more, more preferably 62% or more, more preferably 64% or more, further preferably 65% or more, from the viewpoint of obtaining a good train shape by suppressing diffusely reflected light from the substrate surface Specifically, it is 95% or less, preferably 85% or less, more preferably 80% or less, more preferably 75% or less, and still more preferably 70% or less.

The method of controlling the light transmittance in at least one of 375 nm and 405 nm to be within the above range is not limited to these, and examples thereof include control of the addition amount of a photopolymerization initiator, a dye, or a coloring substance. .

[Photosensitive resin laminate] This embodiment also provides a photosensitive resin laminate having a photosensitive resin layer containing the above-mentioned photosensitive resin composition, and a support film. As the support film, a transparent support film that transmits light emitted from the light source for exposure is preferred. Examples of such a support film include: polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. As such films, those that are stretched may be used if necessary.

From the viewpoint of suppressing light scattering during exposure, the haze of the support film is preferably 5% or less, more preferably 2% or less, further preferably 1.5% or less, particularly preferably 1.0% or less. From the same viewpoint, the surface roughness Ra of the surface in contact with the photosensitive layer is preferably 30 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less. A thinner film thickness is advantageous because it improves image formability and economical efficiency. However, in order to maintain the strength of the photosensitive resin laminate, 10 μm to 30 μm is preferably used. The size of the lubricant and other fine particles contained in the support film is preferably less than 5 μm.

The support film may have a single-layer structure or a multi-layer structure in which resin layers with different compositions are laminated. In the case of multi-layer construction, an antistatic layer may be present. In the case of a multi-layer structure such as a two-layer structure or a three-layer structure, for example, a resin layer containing microparticles can be formed on one side A, and the other side B can (1) contain microparticles in the same manner as surface A, (2) ) Contains fewer microparticles than surface A, (3) Contains finer particles than surface A, (4) Contains no microparticles, etc. In the case of the structures (2), (3), and (4), it is preferable to form the photosensitive resin layer on the surface B side. At this time, it is preferable from the viewpoint of the sliding property of the film if there is a resin layer containing fine particles on the surface A side. The size of the fine particles at this time is preferably less than 1.5 μm. In addition, the size of the said microparticles is the value obtained by the measurement using the scanning electron microscope calibrated using a standard sample.

An important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesive force with the photosensitive resin layer is sufficiently smaller than that of the support film and that it can be easily peeled off. For example, a polyethylene film or a polypropylene film may be preferably used as the protective layer. In addition, a film excellent in releasability shown in Japanese Patent Application Laid-Open No. Sho 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.

A gel called fisheye exists on the surface of the polyethylene film. When a polyethylene film having fish eyes is used as a protective layer, the fish eyes may be transferred to the photosensitive resin layer. If the fisheyes are transferred to the photosensitive resin layer, air may be entrained during lamination and become voids, resulting in defects in the resist pattern. From the viewpoint of preventing fish eyes, the preferred material for the protective layer is extended polypropylene. As a specific example, ALPHAN E-200A manufactured by Oji Paper Co., Ltd. can be cited.

Although the thickness of the photosensitive resin layer in the photosensitive resin laminate differs depending on the application, it is preferably 1 μm to 300 μm, more preferably 3 μm to 100 μm, particularly preferably 5 μm to 60 μm, and most preferably 1 μm to 300 μm. Preferably, it is 10 μm~30 μm. The thinner the thickness of the photosensitive resin layer, the higher the resolution, and the thicker the photosensitive resin layer, the higher the film strength.

The light transmittance at the wavelength of 630 nm of the laminate of the support film and the photosensitive resin layer is an indicator of dye decolorization. A high light transmittance at the wavelength of 630 nm indicates that the dye is decolorized. The light transmittance at a wavelength of 630 nm of the laminate of the support film and the photosensitive resin layer is preferably 80% or less, preferably 78% or less, preferably 75% or less, preferably 72% or less, and 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 light transmittance is the value of the laminate of the support film and the photosensitive resin layer (that is, excluding the protective layer).

Next, the manufacturing method of the photosensitive resin laminated body is demonstrated. As a method of sequentially laminating a support film, a photosensitive resin layer, and optionally a protective layer to produce a photosensitive resin laminate, a known method can be used. For example, the photosensitive resin composition used in the photosensitive resin layer and a solvent to dissolve the photosensitive resin composition are mixed to prepare a uniform solution, which is first coated on the support film using a rod coater or a roll coater. , and then drying to remove the solvent, whereby a photosensitive resin layer including the photosensitive resin composition can be laminated on the support film. Then, if necessary, a protective layer is laminated on the photosensitive resin layer, whereby a photosensitive resin laminate can be produced.

＜Method for forming resist pattern＞ Next, an example of a method of manufacturing a resist pattern using the photosensitive resin laminate of this embodiment will be described. The method may include the following steps: an exposure step, which exposes the photosensitive resin composition; a heating step, which heats the exposed photosensitive resin composition; and a developing step, which develops the photosensitive resin composition. . Examples of resist patterns include: printed wiring boards, semiconductor elements, printing plates, liquid crystal display panels, touch panels, flexible substrates, lead frame substrates, COF (Chip On Film, chip on film) substrates, Patterns such as substrates for semiconductor packaging, transparent electrodes for liquid crystal, wiring for TFT (Thin Film Transistor, thin film transistor) for liquid crystal, electrodes for PDP (Plasma Display Panel, plasma display panel). As an example, a printed wiring board will be described as follows manufacturing method.

The printed wiring board is manufactured through the following steps. (1)Lamination step First, in the lamination step, a photosensitive resin layer is formed on the substrate using a laminating machine. Specifically, when the photosensitive resin laminated body has a protective layer, after peeling off the protective layer, the photosensitive resin layer is heat-pressed and bonded to the substrate surface using a laminating machine to perform lamination. Examples of materials for the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like. In this embodiment, the photosensitive resin layer may be laminated on only one side of the substrate surface, or may be laminated on both sides if necessary. The heating temperature during lamination is usually 40°C to 160°C. In addition, by performing heat and pressure bonding during lamination two or more times, the adhesiveness of the obtained resist pattern to the substrate can be improved. During heat pressure bonding, pressure bonding can be performed by using a two-stage laminating machine equipped with a double roller, or by repeatedly passing the laminate of the substrate and the photosensitive resin layer through the rollers several times.

(2)Exposure step In this step, the photosensitive resin is exposed by the following exposure method: a mask with the required wiring pattern is closely connected to the support film and an exposure method is performed using an active light source; using a drawing as the required wiring pattern Exposure method of direct drawing of a pattern; or exposure method by projecting a mask image through a lens.

The exposure step is preferably performed by an exposure method of direct drawing using a drawing pattern, or an exposure method of projecting a mask image through a lens, more preferably by an exposure method of direct drawing using a drawing pattern. The advantages of the photosensitive resin composition of this embodiment are more remarkable in the exposure method of direct drawing using a drawing pattern, or the exposure method of projecting a mask image through a lens, and in the exposure method of direct drawing using a drawing pattern Especially significant.

When the exposure step is a direct drawing exposure method, it is preferable to use laser light with a central wavelength less than 390 nm or laser light with a central wavelength above 390 nm. More preferably, the laser light has a central wavelength of 350 nm or more and 380 nm or less, or a laser light with a central wavelength of 400 nm or more and 410 nm or less. Furthermore, it is more preferable to perform exposure by using a first laser light with a center wavelength less than 390 nm and a second laser light with a center wavelength of 390 nm or more. Furthermore, it is more preferable that the central wavelength of the first laser light is not less than 350 nm and not more than 380 nm, and the central wavelength of the second laser light is not less than 400 nm and not more than 410 nm.

(3)Heating step In this step, the exposed photosensitive resin composition is preferably heated at about 30°C to about 200°C, more preferably in the range of 30°C to 150°C, and even more preferably in the range of 60°C to 120°C. Scope. By performing this heating step, resolution and adhesion can be improved. When heating, you can use hot air, infrared, or far infrared heating furnaces, constant temperature baths, heating plates, hot air dryers, infrared dryers, heating rollers, etc. If the heating method is a heating roller, it is preferable in that it can be processed in a short time. It is even better if there are two or more heating rollers.

In particular, in the present invention, (D) a phenol-based polymerization inhibitor is used in a small amount, and the light transmittance of the resin composition at a specific wavelength is controlled to a specific range, and is then heated after exposure. During development, the fluidity of the polymer is improved by heating. For example, in the case of a system with a relatively large content of styrene skeleton, the reaction between the hydrophobicity of the styrene skeleton and the carbon-carbon double bond can be simultaneously realized to a high degree. sex. As a result, sensitivity, adhesion, line width reproducibility, and resolution can be significantly improved. Furthermore, by significantly improving the adhesion, good adhesion can be obtained even when the time from exposure to development is long. Moreover, from the viewpoint of the effect of the present invention, it is preferable to perform the above-mentioned heating step within 15 minutes after exposure, and more preferably, it is performed within 10 minutes.

(4) Development step 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 an alkaline aqueous developer, thereby forming a resist pattern on the substrate. An aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used as the alkaline aqueous solution. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, and is preferably a Na ₂ CO ₃ aqueous solution with a concentration of about 0.2% by mass to about 2% by mass and a temperature of about 20°C to about 40°C. In the illustrated aspect, the time from exposure to development (that is, the time from the end of exposure to the start of development) may be 5 minutes or more, or 60 minutes or more, or 180 minutes or more, and may be 1440 minutes or less, Or less than 720 minutes, or less than 300 minutes. The resist pattern can be obtained through each of the steps (1) to (4) above.

In the manufacturing method of the circuit substrate of the present invention, the circuit substrate is formed by etching or plating the substrate having the resist pattern produced by the above method.

(5) Etching step or plating step The surface of the substrate exposed by development (for example, the copper surface of the copper foil laminate) is etched or plated to produce a conductor pattern.

(6) Peeling step Thereafter, if necessary, use an appropriate stripping solution to peel off the resist pattern from the substrate. Examples of the stripping liquid include alkaline aqueous solutions, amine stripping liquids, and the like. However, a resist pattern formed by heating after exposure using the photosensitive resin composition of the present invention has the advantage that it shows good releasability with respect to an amine-based stripper and that the release sheet does not become excessively fine. Therefore, it is preferable to use an amine-based stripping liquid as the stripping liquid to further exhibit the advantageous effects of the present invention.

The amine contained in the amine stripping liquid may be an inorganic amine or an organic amine. Examples of inorganic amines include ammonia, hydroxylamine, hydrazine, and the like.

Examples of organic amines include ethanolamine, propanolamine, alkylamine, cyclic amine, quaternary ammonium salt, and the like. As specific examples of this, Examples of the ethanolamine include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, and aminoethoxy ethanol, etc.; Examples of propanolamine include 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, and the like. ; Examples of the alkylamine include monomethylamine, dimethylamine, trimethylamine, ethylamine, ethylenediamine, diethyltriamine, triethyltetramine, and hexamethylene Tetraamine, tetraethylene pentamine, etc.; Examples of the cyclic amine include choline, phospholine, etc.; Examples of quaternary ammonium salts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and N,N,N-triethyl-N-(2-hydroxyethyl) Ammonium hydroxide, N,N-diethyl-N,N-di(2-hydroxyethyl)ammonium hydroxide, etc.

The amine stripping liquid may be an aqueous solution containing one or more of the amines exemplified above. The concentration of the amine in the aqueous solution can be appropriately set depending on the purpose, the composition of the photosensitive resin layer, development conditions, and the like. The amine stripping liquid may further contain additives commonly used in stripping agents, such as surfactants, defoaming agents, pH adjusters, preservatives, and re-adhesion inhibitors. The peeling step is performed, for example, at a temperature between 0°C and 100°C, preferably between room temperature (23°C) and 50°C, for example, for 1 second to 1 hour, preferably 10 seconds or more and 10 minutes. the following times.

After the stripping step, if necessary, the substrate after removing the resist pattern can be cleaned with pure water or the like.

The photosensitive resin laminate system of this embodiment is suitable for printed wiring boards, flexible substrates, lead frame substrates, touch panel substrates, COF substrates, semiconductor packaging substrates, transparent electrodes for liquid crystals, wiring for TFTs for liquid crystals, and PDPs. Manufacturer of conductor patterns using electrodes, etc. Furthermore, unless otherwise specified, the various parameters mentioned above are measured according to the measurement methods in the following examples or methods understood by those skilled in the art to be equivalent thereto. [Example]

Next, this embodiment will be explained more specifically with reference to Examples and Comparative Examples. However, this embodiment is not limited to the following examples as long as it does not deviate from the gist thereof. The physical properties in the examples were measured by the following methods. The method for measuring the physical property values of polymers and preparing samples for evaluation in Examples and Comparative Examples will be described. Furthermore, the evaluation method for the obtained sample and its evaluation results are shown.

(1) Measurement and calculation of physical property values ＜Measurement of weight average molecular weight or number average molecular weight of polymer＞ The weight average molecular weight or number average molecular weight of the polymer was determined using a gel permeation chromatography (GPC) manufactured by Nippon ASCO Co., Ltd. (Pump used: Gulliver, PU-1580 type, column: Shodex manufactured by Showa Denko Co., Ltd. (Registered Trademark) (KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, fluidized bed solvent: tetrahydrofuran, using polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd. ), calculated in polystyrene conversion form. Furthermore, the dispersion degree of a polymer is calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

＜Acid equivalent＞ In the present invention, the so-called acid equivalent refers to the mass (gram) of the polymer having 1 equivalent of carboxyl groups in the molecule. The acid equivalent was measured by potentiometric titration using a Hiranuma automatic titration device (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. and a 0.1 mol/L sodium hydroxide aqueous solution.

<I/O value> The I/O value of alkali-soluble polymers is derived by the following method. First, through non-patent literature (Organic Concept Drawing (written by Zeno Koda, published by Sankyo (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Items 1 to 16 (1954); Chemical Field, Vol. 11, No. 10 No., No. 719-725 (1957); Fragrancejournal, No. 34, No. 97-111 (1979); Fragrancejournal, No. 50, No. 79-82 (1981)) to calculate the composition. The I value and O value of each comonomer are then averaged by the molar ratio of the comonomer to obtain the I _average value and O _average value. Then, the I/O value is derived by dividing the obtained I _average value by the O _average value.

<Glass transition temperature Tg> The glass transition temperature Tg of the alkali-soluble polymer is calculated by the Fox equation. When calculating the glass transition temperature Tg, use the non-patent literature ("Polymer handbook, Third edition John wiley & sons, 1989, p.209 Chapter VI "Glass transition temperatures of polymers" edited by Brandrup, J. Immergut, EH") The values expressed are the glass transition temperatures of homopolymers containing comonomers forming the corresponding alkali-soluble polymer. In addition, in the examples, the glass transition temperature of the homopolymer including each comonomer used in the calculation is shown in Table 1. When the alkali-soluble polymer is composed of two or more types of polymers, the value determined by the following formula becomes the glass transition temperature of the alkali-soluble polymer. [Number 1] {In the formula, _Wi is the solid weight of each alkali-soluble polymer, Tg _i is the glass transition temperature of each alkali-soluble polymer calculated using the Fox formula, 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}

(2) Preparation method of samples for evaluation Samples for evaluation were prepared as follows. ＜Preparation of photosensitive resin laminate＞ The components shown in Tables 1 to 3 disclosed below (the number of each component indicates the preparation amount (parts by mass) in terms of solid content) and the solvent are sufficiently stirred and mixed to obtain a photosensitive resin combination. Material blending liquid. The details of the ingredients shown in Tables 1 and 2 are shown in Table 3. Use a 16 μm thick polyethylene terephthalate film (FB-40 manufactured by Toray Co., Ltd.) as a supporting film, and use a rod coater to evenly coat the prepared liquid on its surface. Dry in a dryer at ℃ for 3 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer is 30 μm. Then, a 19-μm-thick polyethylene film (GF-18, manufactured by Tamapoly Co., Ltd.) was bonded as a protective layer on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film was not laminated. ) to obtain a photosensitive resin laminate. In addition, the amount of p-methoxyphenol and the amount of dibutylhydroxytoluene in Tables 1 and 2 refer to the concentration of each component based on the total amount of solid components in the photosensitive resin composition.

<Substrate surface cleaning and finishing> Using abrasives (manufactured by Uji Denki Chemical Industry Co., Ltd., #400) at a spray pressure of 0.2 MPa, a 0.4 mm thick layer of 35 μm rolled copper foil was used as the evaluation substrate. The copper foil laminated board was sandblasted and polished, and then the surface of the substrate was cleaned with a 10 mass % H ₂ SO ₄ aqueous solution.

＜Lamination＞ While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, use a heated roller laminator (AL-700 manufactured by Asahi Kasei Co., Ltd.) to laminate the photosensitive resin laminate on the predetermined surface at a roller temperature of 105°C. Heat the copper foil laminate to 50°C. The air pressure system is set to 0.35 MPa, and the lamination speed system is set to 1.5 m/min.

＜Exposure＞ On the evaluation substrate that had been 2 hours after lamination, a direct drawing exposure machine (Nuvogo Fine 10, manufactured by Orbotech Co., Ltd., light source: 375 nm (30%) + 405 nm (70%)) was used, using a Stove ( Stouffer) 41-level stage exposure meter for exposure. Exposure was performed using the above-mentioned Stuffe 41-step step exposure meter as a mask, and the exposure was performed at an exposure level at which the highest residual film level during development became 14 steps.

＜Heating＞ The evaluation substrate was heated for 7 minutes after exposure using a heating roller laminating machine (AL-700 manufactured by Asahi Kasei Co., Ltd.). The roller temperature system is set to 105°C, the air pressure system is set to 0.30 MPa, and the lamination speed system is set to 1 m/min. Furthermore, if the time from exposure to development is extended, the effect of heating will disappear, so heating is usually performed for about 1 minute after exposure. Therefore, the heating after 7 minutes of exposure in this embodiment is a very strict condition.

<Development> After peeling off the polyethylene terephthalate film (support film), use an alkaline developing machine (manufactured by FUJI KIKO Co., Ltd., a dry film developing machine) and spray 1 mass % of 30°C for a specified period of time. Na ₂ CO ₃ aqueous solution for development. The development spray time is set to 2 times the minimum development time, and the water washing spray time after development is set to 3 times the minimum development time. At this time, the shortest time required for the unexposed portion of the photosensitive resin layer to be completely dissolved is set as the shortest development time.

(3) Sample evaluation method ＜Amount of p-methoxyphenol＞ The amount of p-methoxyphenol in the photosensitive resin composition was determined by an internal standard method using a gas chromatograph (hereinafter, abbreviated as GC) manufactured by Shimadzu Corporation. The detector is a hydrogen flame ionization detector (hereinafter referred to as FID), and the internal standard uses n-docosane. <Amount of dibutylhydroxytoluene> The amount of dibutylhydroxytoluene in the photosensitive resin composition was determined by GC in the same way as the amount of p-methoxyphenol. n-octadecane was used as the internal standard. ＜Light transmittance＞ The light transmittance of each resin composition at 375 nm and 405 nm was measured by the following method. Using a spectrophotometer (Hitachi High-Technologies Co., Ltd., U-3010), the transmittance at each wavelength of the photosensitive resin laminate from which the polyethylene film (protective layer) has been peeled was measured. At this time, the photosensitive resin laminate is installed so that transmitted light can pass through in the film thickness direction, and measurement is performed.

<Sensitivity evaluation> In the above exposure step, after exposure through the mask of the Stuffe 41-level step exposure meter, development was performed, and the exposure amount (mJ/cm ² ) was set so that the highest remaining film level would be level 14. Find the value of the sensitivity.

<Line width reproducibility> In the above exposure step, exposure is performed using drawing data having a line pattern with a ratio of the width of the exposed portion and the unexposed portion of 20 μm: 20 μm. Development is performed according to the above development conditions to form hardened resist lines. The line width of the hardened resist line is determined as the line width reproducibility value.

＜Resolution＞ In the above exposure step, exposure is performed using drawing data having a line pattern with a ratio of the width of the exposed part and the unexposed part being 1:1. Development is performed according to the above development conditions to form hardened resist lines. The minimum line width at which a hardened resist line is formed normally is determined as the value of resolution.

＜Tightness＞ In the above exposure step, exposure is performed using drawing data having a line pattern with a ratio of the width of the exposed part and the unexposed part being x μm: 200 μm. Development was performed based on the above-mentioned development conditions, and the minimum line width at which a hardened resist line was normally formed was measured using an optical microscope. This measurement was performed on four lines, and the average value of the four line widths was determined as the value of adhesion. Only the adhesiveness was evaluated in two cases: heating after 1 minute after exposure and heating after 7 minutes after exposure.

＜Minimum development time delay＞ In the above development step, when developing without heating after exposure and heating after exposure for 7 minutes, and then developing, measure the shortest time required for the unexposed part of the photosensitive resin layer to completely dissolve, which is the shortest time. development time and grade based on the following criteria. Good: There is no difference in the minimum development time between the case with post-exposure heating and the case without post-exposure heating. Yes: The minimum development time with post-exposure heating is delayed within 1 second compared with that without post-exposure heating. Not allowed: The minimum development time with post-exposure heating is a delay of more than 1 second compared with that without post-exposure heating. The results are shown in Tables 1 and 2.

The heating condition after exposure in this embodiment is heating after 7 minutes of exposure, so it is a very strict condition. For example, when the compositions of Example 3 and Comparative Example 2 were developed without heating after exposure, the adhesiveness was both 13.8 μm. That is, in the composition of Comparative Example 1, no effect was observed in the heating after exposure for 7 minutes. In Example 3, the adhesiveness can be improved even under very strict conditions. Moreover, under the condition of heating after exposure for 1 minute, the adhesiveness of 10.8 μm was obtained in any of the compositions of Example 7 and Comparative Example 1. From the above results, it can be seen that under normal post-exposure heating conditions, even when the adhesion is good, under the strict conditions of heating after 7 minutes after exposure, the adhesion does not become good. For the first time, the present invention can achieve good adhesion even under such strict post-exposure heating conditions. Thereby, when manufacturing a circuit board, good adhesion can be obtained even if the time from exposure to development becomes long, and therefore a high-definition circuit pattern can be stably formed.

[Table 1] Table 1

[Table 2] Table 2

[table 3] [Industrial availability]

The photosensitive resin composition of the present invention has good sensitivity, adhesion, line width reproducibility, and resolution when it is heated after exposure and then developed, especially when the time from exposure to development is long. It also achieves good adhesion, so it can be used in a wide range of applications as a photosensitive resin composition.

Claims (26)

A photosensitive resin composition containing the following components: (A) alkali-soluble polymer: 10 mass% to 90 mass%; (B) compound with ethylenically unsaturated double bonds: 5 mass% to 70 mass% ; (C) Photopolymerization initiator: 0.01 mass% ~ 20 mass%; and (D) Monovalent phenol polymerization inhibitor: 1ppm ~ 300ppm; and the light transmittance at least one of 375nm and 405nm is 58% ~ 95%, the above-mentioned photosensitive resin composition contains at least one of p-methoxyphenol and dibutylhydroxytoluene as the above-mentioned (D) phenolic polymerization inhibitor. The photosensitive resin composition of claim 1, which contains dibutylhydroxytoluene as the (D) phenolic polymerization inhibitor. The photosensitive resin composition according to claim 1 or 2, which contains p-methoxyphenol as the (D) phenolic polymerization inhibitor. The photosensitive resin composition of claim 2, wherein the content of the above-mentioned dibutylhydroxytoluene is 1 to 200 ppm. The photosensitive resin composition of claim 2, wherein the content of the above-mentioned dibutylhydroxytoluene is 10 to 150 ppm. The photosensitive resin composition according to claim 1 or 2, wherein the I/O value of the above-mentioned (A) alkali-soluble polymer is 0.600 or less. The photosensitive resin composition of claim 1 or 2, wherein the (C) photopolymerization initiator includes an anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof. More than 1 species in the group. The photosensitive resin composition of claim 7, wherein the (C) photopolymerization initiator includes anthracene and/or anthracene derivatives. The photosensitive resin composition of claim 8, wherein the (C) photopolymerization initiator is a compound represented by the general formula (IV):

In the formula, R ¹ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group with 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group with 3 to 20 carbon atoms, or a substituted or unsubstituted alicyclic group with 2 to 4 carbon atoms. Alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group or N(R') ₂ group, two or more R ¹ can be bonded to each other to form a cyclic structure. The cyclic structure may contain heteroatoms; -SO ₂ -O-yl, -SO ₂ -S-yl, -SO ₂ -N(R')-yl, -O-CO-yl, -S-CO-yl, -O-SO ₂ -yl or ^-S -SO ₂ - group, except that Substituted alkyl group, substituted or unsubstituted alicyclic group with 3 to 20 carbon atoms, alkenyl group with 2 to 4 carbon atoms, substituted or unsubstituted aryl group with 6 to 40 carbon atoms, or For substituted or unsubstituted heteroaryl groups, R' can bond with each other to form a cyclic structure, and the cyclic structure may contain heteroatoms; p is an integer from 1 to 10. The photosensitive resin composition according to claim 1 or 2, wherein the structural unit of styrene and/or styrene derivatives in the above-mentioned (A) alkali-soluble polymer is 26 mass % or more. The photosensitive resin composition of claim 1 or 2, wherein the alkali-soluble polymer (A) contains a structural unit of benzyl (meth)acrylate as a monomer component. The photosensitive resin composition according to claim 1 or 2, wherein the glass transition temperature of the above-mentioned (A) alkali-soluble polymer is 120°C or lower. The photosensitive resin composition according to claim 1 or 2, wherein the compound having an ethylenically unsaturated double bond (B) contains an amount of 5 mass % or more in the molecule relative to the solid content of the entire photosensitive resin composition. Compounds with more than 3 methacrylate groups. The photosensitive resin composition of claim 1 or 2 is used to obtain an exposed resin cured product using a first laser light with a center wavelength less than 390 nm and a second laser light with a center wavelength of 390 nm or more. The photosensitive resin composition of claim 14, wherein the central wavelength of the first laser light is 350 nm or more and 380 nm or less, and the center wavelength of the second laser light is 400 nm or more and 410 nm or less. The photosensitive resin composition of claim 1 or 2 can form a pattern through the following steps: an exposure step, which exposes the photosensitive resin composition; and a heating step, which performs a heating step on the exposed photosensitive resin composition. Heating; and a development step, which develops the heated photosensitive resin composition. The photosensitive resin composition of claim 1 or 2, wherein the heating temperature in the above heating step is in the range of 30°C to 150°C. The photosensitive resin composition of claim 1 or 2, wherein the above heating step is performed within 15 minutes after exposure. A method for forming a resist pattern, which includes the following steps: an exposure step, which exposes the photosensitive resin composition according to any one of claims 1 to 18; and a heating step, which exposes the exposed photosensitive resin composition Heating is performed; and a development step is performed to develop the heated photosensitive resin composition. The resist pattern forming method of claim 19, wherein the heating temperature in the above heating step The temperature is in the range of 30℃~150℃. The resist pattern forming method of claim 19 or 20, wherein the above heating step is performed within 15 minutes after exposure. The resist pattern forming method of Claim 19 or 20, wherein the above exposure step is performed by an exposure method using direct drawing of a drawing pattern, or an exposure method of projecting a mask image through a lens. The resist pattern forming method of claim 22, wherein the above exposure step is performed by an exposure method using direct drawing of a drawing pattern. The method of forming a resist pattern according to claim 23, wherein the above exposure step is performed by exposing a first laser light with a center wavelength less than 390 nm and a second laser light with a center wavelength of 390 nm or more. The method of forming a resist pattern according to claim 24, wherein the central wavelength of the first laser light is not less than 350 nm and not more than 380 nm, and the central wavelength of the above second laser light is not less than 400 nm and not more than 410 nm. A manufacturing method of a circuit substrate, which includes the following steps: a resist pattern forming step, which forms a resist pattern on the substrate by the method according to any one of claims 19 to 25; and The circuit substrate forming step is to form the circuit substrate by etching or plating the substrate having the above-mentioned resist pattern.