TW202309103A - Photosensitive resin composition and method for forming resist pattern - Google Patents

Abstract

Provided is a photosensitive resin composition having excellent sensitivity, adhesiveness, line-width reproducibility and resolution when heated after exposure, and then developed. In particular, thiscomposition exhibits excellent adhesiveness even if the length of time between exposure and development is long. According to one embodiment, the photosensitive resin composition includes: (A) an alkali-soluble polymer: 10 to 90 mass%; (B) a compound having an ethylenic unsaturated double bond: 5 to 70 mass%; (C) a photo polymerization initiator: 0.01 to 20 mass%; and (D) a phenolic polymerization inhibitor: 1 to 300 ppm. The light transmittance at 375 nm and/or 405 nm is 58 to 95%.

Description

Photosensitive resin composition and method for forming resist pattern

The invention relates to a photosensitive resin composition, a method for forming a resist pattern, and the like.

In electronic equipment such as personal computers and mobile phones, printed wiring boards, etc. are used for mounting components, semiconductors, etc. As a resist for the manufacture of printed wiring boards, the so-called dry film of a photosensitive resin laminate formed by laminating a photosensitive resin layer on a support film and optionally laminating a protective film on the photosensitive resin layer has been used in the industry. Photoresist (hereinafter, sometimes also referred to as DF). As a photosensitive resin layer, conventionally, it is an alkali-developing type which uses weak alkaline aqueous solution as a developing solution normally.

When producing a printed wiring board or the like using DF, the following steps are performed, for example. When DF has a protective film, first peel off the protective film. Thereafter, DF is laminated on a substrate for permanent circuit production such as a copper foil laminate or a flexible substrate using a laminating machine or the like, and exposed through a wiring pattern mask or the like. Next, if necessary, peel off the support film, use a developer solution to dissolve or disperse the photosensitive resin layer of the unhardened part (if it is a negative type, the unexposed part), and form a hardened resist pattern on the substrate (hereinafter, sometimes referred to as referred to as the 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 part of the resist pattern by using an alkaline aqueous solution stronger than the developing solution after etching and removing the substrate surface not covered by the resist pattern (such as the copper surface of the copper foil laminate) (etching method). ). The second method is to remove the resist pattern part in the same way as the first method after plating copper, solder, nickel, tin, etc. on the above-mentioned substrate surface, and then to expose the substrate surface (such as copper foil The method of etching (plating method) on the copper surface of laminated boards). Copper chloride, ferric chloride, cuproammonia complex solution, etc. can be used for etching.

In recent years, with the miniaturization and weight reduction of electronic equipment, the miniaturization and high density of printed wiring boards have been continuously developed. In the above-mentioned manufacturing steps, high-performance DF with high resolution and high adhesion is required. As a means for achieving such high resolution, Patent Document 1 describes a photosensitive resin composition that improves resolution by using a specific thermoplastic resin, a monomer, and a photopolymerizable initiator. [Prior Art Literature] [Patent Document]

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

[Problem to be solved by the invention]

After the exposure process, a heating process may be performed on the photosensitive resin layer as the case may be, and image development may be performed thereafter. By performing this heating step, resolution or adhesion (that is, the adhesion between the resist pattern and the substrate) can be further improved. However, even if the heating step is increased after exposure, the conventional photosensitive resin composition may not have sufficient adhesion and resolution, or if the time from exposure to development becomes longer, good adhesion may not be obtained. topic.

The present invention has been proposed in view of such prior circumstances, and an object of one aspect of the present invention is to provide a film with good sensitivity, adhesion, line width reproducibility, and resolution when developing after heating after exposure. , especially a photosensitive resin composition that realizes good adhesion even when the time from exposure to image development is long. [Technical means to solve the problem]

The present invention includes the following aspects. [1] A photosensitive resin composition comprising the following components: (A) Alkali-soluble polymer: 10% by mass to 90% by mass; (B) Compounds with ethylenically unsaturated double bonds: 5% by mass to 70% by mass; (C) photopolymerization initiator: 0.01% by mass to 20% by mass; and (D) Phenolic polymerization inhibitor: 1 ppm to 300 ppm; and The light transmittance of at least one of 375 nm and 405 nm is 58% to 95%. [2] The photosensitive resin composition described in the above aspect 1, which contains p-methoxyphenol as the above-mentioned (D) phenolic polymerization inhibitor. [3] The photosensitive resin composition according to the above aspect 1 or 2, which contains dibutylhydroxytoluene as the above-mentioned (D) phenolic polymerization inhibitor. [4] The photosensitive resin composition as described in the above-mentioned aspect 3, wherein the content of the above-mentioned dibutylhydroxytoluene is 1 to 200 ppm. [5] The photosensitive resin composition as described in the above-mentioned aspect 3, wherein the content of the above-mentioned dibutylhydroxytoluene is 10 to 150 ppm. [6] The photosensitive resin composition according to any one of the above aspects 1 to 5, wherein the (A) alkali-soluble polymer has an I/O value of 0.600 or less. [7] The photosensitive resin composition as described in any one of the above-mentioned aspects 1 to 6, wherein the above-mentioned (C) photopolymerization initiator comprises an anthracene, pyrazoline, triphenylamine, coumarin , and one or more of the group consisting of their derivatives. [8] The photosensitive resin composition as described in the above-mentioned aspect 7, wherein the above-mentioned (C) photopolymerization initiator contains anthracene and/or anthracene derivatives. [9] The photosensitive resin composition according to any one of the above-mentioned aspects 1 to 8, wherein the structural unit of styrene and/or styrene derivatives in the above-mentioned (A) alkali-soluble polymer is 26% by mass above. [10] The photosensitive resin composition according to any one of the above-mentioned aspects 1 to 9, wherein the above-mentioned (A) alkali-soluble polymer contains a structural unit of benzyl (meth)acrylate as a monomer component. [11] The photosensitive resin composition according to any one of the above aspects 1 to 10, wherein the glass transition temperature of the above (A) alkali-soluble polymer is 120°C or lower. [12] The photosensitive resin composition according to any one of the above aspects 1 to 11, wherein the above-mentioned (B) compound having an ethylenically unsaturated double bond contains a solid content relative to the entire photosensitive resin composition 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 as described in 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. Exposure to light to obtain hardened resin. [14] The photosensitive resin composition according to any one of the above aspects 1 to 13, wherein the center wavelength of the first laser light is 350 nm to 380 nm, and the center wavelength of the second laser light is 400 nm or more and 410 nm or less. [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 exposing step of exposing the photosensitive resin composition; a heating step of heating the exposed photosensitive resin composition; and A developing step of developing the heated photosensitive resin composition. [16] The photosensitive resin composition according to any one of the above aspects 1 to 15, wherein the heating temperature in the heating step is in the range of 30°C to 150°C. [17] The photosensitive resin composition according to any one of aspects 1 to 16 above, wherein the heating step is performed within 15 minutes after exposure. [18] A method for forming a resist pattern, comprising the following steps: an exposing step of exposing the photosensitive resin composition as described in any one of the above aspects 1 to 17; a heating step of heating the exposed photosensitive resin composition; and A developing step of developing the heated photosensitive resin composition. [19] The method for forming a resist pattern according to the above aspect 18, wherein the heating temperature in the heating step is in the range of 30°C to 150°C. [20] The method for forming a resist pattern according to the above-mentioned aspect 18 or 19, wherein the above-mentioned heating step is performed within 15 minutes after the exposure. [21] The method for forming a resist pattern according to any one of the above aspects 18 to 20, wherein the exposure method using the direct drawing of the drawn pattern or the exposure method of projecting the image of the mask through the lens Instead, the exposure step described above is carried out. [22] The method for forming a resist pattern as described in the above aspect 21, wherein the above exposure step is performed by an exposure method using direct drawing of a drawing pattern. [23] The method for forming a resist pattern as described in Aspect 22 above, wherein the exposure is performed by using the first laser light with a central wavelength of less than 390 nm and the second laser light with a central wavelength of 390 nm or more Instead, the exposure step described above is carried out. [24] The method for forming a resist pattern according to the above-mentioned aspect 23, wherein the center wavelength of the first laser beam is 350 nm to 380 nm, and the center wavelength of the second laser beam is 400 nm or more and Below 410 nm. [25] A method for manufacturing a circuit substrate, comprising the following steps: a resist pattern forming step of forming a resist pattern on the substrate by the method described in any one of aspects 18 to 24 above; and A circuit substrate forming step of forming a circuit substrate by etching or plating the substrate having the above-mentioned resist pattern. [Effect of Invention]

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

Hereinafter, exemplary forms (hereinafter, simply referred to as "embodiments") for implementing the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various changes can be implemented within the range of the summary. Moreover, unless otherwise specified, the various measured values in this specification were measured according to the method described in the item of [Example] of this invention, or the method understood by those skilled in the art as being equivalent to it.

＜Photosensitive resin composition＞ In this embodiment, the photosensitive resin composition includes: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a phenolic polymer Inhibitors. Moreover, in this embodiment, a photosensitive resin layer can be formed by arbitrarily applying a photosensitive resin composition to a support body. The above composition of the photosensitive resin composition of the present embodiment is useful for obtaining a cured resin by heating after exposure and then developing.

The photosensitive resin composition of this embodiment may be a photosensitive resin composition for obtaining a cured resin by exposing the first active light with a central wavelength of less than 390 nm and the second active light with a central wavelength of 390 nm or more . Active light is, for example, laser light. In this aspect, the photosensitive resin composition has the photosensitivity to both the 1st active light whose center wavelength is less than 390 nm, and the 2nd active light whose center wavelength is 390 nm or more. The central wavelength of the first active light is preferably 350-380 nm, more preferably 355-375 nm, especially preferably 375 nm. The central wavelength of the second active light is preferably 400-410 nm, more preferably 402-408 nm, and most preferably 405 nm (line h). Hereinafter, each component contained in the photosensitive resin composition is demonstrated.

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

The photosensitive resin composition preferably contains a copolymer having an aromatic group as (A) an alkali-soluble polymer from the viewpoint of high resolution and a skirt shape of the resist pattern. The photosensitive resin composition preferably contains a copolymer having an aromatic group in a side chain as (A) an alkali-soluble polymer. As such an aromatic group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aralkyl group is mentioned, for example. The proportion of the copolymer having an aromatic group in the component (A) is preferably at least 30% by mass, more preferably at least 40% by mass, more preferably at least 50% by mass, more preferably at least 70% by mass, and 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 standpoint of the high resolution of the resist pattern and the shape of the skirt, the copolymerization ratio of the comonomer having an aromatic group in (A) the alkali-soluble polymer is preferably 40% by mass or more, preferably 50% by mass % or more, preferably more than 60% by mass, preferably more than 70% by mass, preferably more than 80% by mass. The upper limit of the copolymerization ratio is not particularly limited, but is preferably at most 95% by mass, more preferably at most 90% by mass, from the viewpoint of maintaining good alkali solubility.

Examples of the above-mentioned comonomers having an aromatic group include: styrene, 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 preferable.

Regarding the total ratio of the structural units of styrene and/or styrene derivatives in all (A) alkali-soluble polymers, the adhesiveness during development after heating after exposure can be significantly improved, especially From the viewpoint of obtaining good adhesion even when the time from exposure to development becomes longer, it is preferably at least 15% by mass, more preferably at least 25% by mass, more preferably at least 26% by mass, and even more preferably at least 26% by mass. It is 30 mass % or more, More preferably, it is 35 mass % or more, More preferably, it is 40 mass % or more. Since the styrene skeleton is hydrophobic, it can suppress swelling to the developer and exhibit good adhesion. Among them, when the content of the styrene skeleton is large, the fluidity of the polymer tends to be low and the reactivity tends to decrease, so the adhesiveness tends to decrease. In addition, when the time from exposure to development becomes longer, radicals in the system are gradually inactivated, so the effect of improving adhesion 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 can be improved by heating, and the styrene skeleton can be realized at the same time to a high degree. As a result of the hydrophobicity and the reactivity of the carbon-carbon double bond, it is considered that good adhesion can be achieved. Moreover, it is thought that favorable adhesiveness can be acquired also when the time from exposure to image development becomes long by this. Regarding the total ratio of the structural units of styrene and/or styrene derivatives in all (A) alkali-soluble polymers, from the viewpoint of obtaining the advantages caused by the presence of other structural units well, the Preferably, it is 90 mass % or less, More preferably, it is 80 mass % or less, More preferably, it is 70 mass % or less.

As comonomers having an aralkyl group, monomers having a substituted or unsubstituted benzyl group, monomers having a substituted or unsubstituted phenylalkyl group (excluding benzyl), etc., are preferred. 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 Examples include vinylbenzyl chloride, vinylbenzyl alcohol, and the like.

(A) Alkali-soluble polymers can remarkably improve the adhesion when developing after heating after exposure, especially when the time from exposure to development becomes longer. It is preferable to contain a structural unit of benzyl (meth)acrylate as a monomer component. (A) The ratio of the structural unit of benzyl (meth)acrylate in the alkali-soluble polymer is preferably from 5 to 85% by mass, more preferably from 10 to 80% by mass, more preferably from 15 to 60% by mass, still more preferably It is 20-40 mass %, More preferably, it is 20-30 mass %. Also, from the same viewpoint, (A) the alkali-soluble polymer preferably has both structural units of styrene and/or styrene derivatives and structural units of benzyl (meth)acrylate.

Phenylethyl (meth)acrylate etc. are mentioned as a comonomer which has a phenylalkyl group (except a benzyl group).

The copolymer having an aromatic group (preferably benzyl group) in the side chain is preferably obtained by making (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.

The (A) 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 esters etc. Among these, (meth)acrylic acid is preferable. Furthermore, in this specification, the so-called "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, the so-called "(meth)acryl" refers to acryl or methacryl, and the so-called " (Meth)acrylate" means "acrylate" or "methacrylate".

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

The second monomer system is a non-acidic monomer having at least one polymerizable unsaturated group in its molecule. As the second monomer, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, Butyl, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ring (meth)acrylate (meth)acrylates such as hexyl ester and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile, etc. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferable.

(A) The alkali-soluble polymer can be prepared by polymerizing a single or plural monomers described above by a known polymerization method, preferably addition polymerization, more preferably radical polymerization. From the viewpoint of chemical resistance, adhesiveness, high resolution, or frame shape of the resist pattern, it is preferable that the monomer contains an aralkyl-containing monomer and/or styrene. As the (A) alkali-soluble polymer, copolymers containing methacrylic acid, benzyl methacrylate, and styrene, and copolymers containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene are particularly preferred. 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), which is based on the organic concept map to evaluate the polarity of various organic compounds, and is a functional group contribution method that sets parameters for the functional groups in the compound. one of a kind. About the I/O value, for example, in the non-patent literature (Organic Concept Map (Koda Yoshio, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Items 1-16 (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)) etc. It demonstrates in detail. The concept of I/O value is to divide the properties of compounds into organic groups showing covalent bonding and inorganic groups showing ionic bonding, and all organic compounds are named organic axes and Expressed by positioning in the form of points on the coordinates of the orthogonal axes of the inorganic axes. The closer the above I/O value is to 0, the more non-polar (ie, hydrophobic or organic) organic compound is, and the larger it is, the more polar (ie, hydrophilic or inorganic) organic compounds.

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

Regarding the glass transition temperature of the (A) alkali-soluble polymer, the value obtained by the Fox formula (in the case where the (A) 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, more preferably 120° C. from the viewpoint of chemical resistance, adhesion, high resolution, or sheath shape of the resist pattern. Below, below 110°C, below 100°C, below 95°C, below 90°C, or below 80°C. (A) The lower limit of the glass transition temperature (Tg) of the alkali-soluble polymer is not limited, but it is preferably 30°C or higher, more preferably 50°C or higher, and still more preferably Above 60°C. In addition, as the glass transition temperature of a homopolymer containing the same monomer as one or plural monomers constituting the (A) alkali-soluble polymer, it was determined using the non-patent literature (Brandrup, J. Immergut, EH edited "Polymer handbook, Third edition John wiley & sons, 1989, p.209 Chapter VI "Glass transition temperatures of polymers"") expressed value.

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

(A) The weight average molecular weight of an alkali-soluble polymer (when (A) component contains several types of copolymers, the weight average molecular weight with respect to the whole mixture) is preferably 5,000-500,000. (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 or more from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to a developing solution. From the viewpoint of the developability of the etchant, the high resolution and skirt shape of the resist pattern, and 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 10,000-200,000, further preferably 20,000-100,000, and most preferably 30,000-70,000. (A) The degree of dispersion of the molecular weight of the alkali-soluble polymer is preferably from 1.0 to 6.0, more preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0.

The content of the (A) alkali-soluble polymer in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified, the same applies to each component), and is 10 mass % - 90 mass %, Preferably it is 20 mass % - 80 mass %, More preferably, it exists in the range of 40 mass % - 60 mass %. The content of the (A) alkali-soluble polymer 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 and the skirt shape of the resist pattern, and the viewpoint of the chemical resistance of the resist pattern, it is preferably at most 90% by mass, more preferably 80 mass % or less, More preferably, it is 70 mass % or less, More preferably, it is 60 mass % or less.

(B) Compounds with ethylenically unsaturated bonds (B) The compound having an ethylenically unsaturated bond is a compound having 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. (B) The compound having an ethylenically unsaturated bond preferably has an alkylene oxide structure having 3 or more carbon atoms from the viewpoint of adhesiveness and the viewpoint of suppressing foaming properties of the developer. The number of carbon atoms in the alkylene oxide structure is more preferably 3-6, further preferably 3-4.

Examples of the compound (B) having one (meth)acryl group as an ethylenically unsaturated bond include: compounds obtained by adding (meth)acrylic acid to one terminal of polyalkylene oxide; or A compound obtained by adding (meth)acrylic acid to one end of polyalkylene oxide and etherifying or allyl etherifying the other end; phthalic acid-based compounds, etc. From a point of view it is better.

As such a compound, for example, phenoxyhexaethylene glycol mono(meth)acrylate is a (meth)acrylate of a compound obtained by adding polyethylene glycol to a phenyl group; 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 (meth)acrylate is 4 -n-nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate; polypropylene glycol added with an average of 1 mole of propylene oxide and an average of 5 moles of ethylene oxide added The (meth)acrylate of the compound formed by adding polyethylene glycol to nonylphenol is 4-n-nonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate; the addition will have an average of 8 The acrylate of the compound formed by adding polyethylene glycol of mole's ethylene oxide to nonylphenol is 4-n-nonylphenoxy octaethylene glycol (meth)acrylate (such as Dongya Synthetic Co., Ltd. Co., Ltd., M-114), etc. Also, if γ-chloro-β-hydroxypropyl-β'-methacryloxyethyl-phthalate is included, in addition to the above-mentioned viewpoints, from the viewpoints of sensitivity, resolution, and adhesion Words are also better.

Examples of compounds having two (meth)acryloyl groups in the molecule include: compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain, or compounds having (meth)acryloyl groups at both ends of an oxirane chain and epoxy A compound having (meth)acryloyl groups at both ends of an alkylene oxide chain formed by randomly or block-bonded propane chains, etc.

Such compounds include, for example, tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, and heptaethylene glycol di(meth)acrylate. base) acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, ethylene oxide in 12 moles In addition to compounds having (meth)acryloyl groups at both ends of the chain, polyethylene glycol (meth)acrylate, etc., polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, etc. Acrylic etc. As a polyalkylene oxide di(meth)acrylate compound containing an oxirane group and a propylene oxide group in the compound, for example, two of polypropylene glycol to which an average of 12 moles of propylene oxide has been added The dimethacrylate of the diol obtained by adding an average of 3 moles of ethylene oxide to the ends respectively, and the addition of an average of 15 moles of propylene oxide to both ends of polypropylene glycol. Diol dimethacrylate formed from mole's ethylene oxide, FA-023M, FA-024M, FA-027M (product name, manufactured by Hitachi Chemical Industry), etc. These are preferable from viewpoints, such as flexibility, resolution, and adhesiveness.

{式中，R ₁及R ₂分別獨立地表示氫原子或甲基，A為C ₂H ₄，B為C ₃H ₆，n ₁及n ₃分別獨立地為0～39之整數，且n ₁＋n ₃為0～40之整數，n ₂及n ₄分別獨立地為0～29之整數，且n ₂＋n ₄為0～30之整數，-(A-O)-及-(B-O)-之重複單元之排列可為無規亦可為嵌段；並且，於嵌段之情形時，-(A-O)-與-(B-O)-之任一者可為雙苯基側}。 例如，就解像性、密接性之方面而言，較佳為於雙酚A之兩端分別加成有平均各5莫耳之環氧乙烷之聚乙二醇之二甲基丙烯酸酯、於雙酚A之兩端分別加成有平均各2莫耳之環氧乙烷之聚乙二醇之二甲基丙烯酸酯、於雙酚A之兩端分別加成有平均各1莫耳之環氧乙烷之聚乙二醇之二甲基丙烯酸酯。 又，可使用上述通式(I)中之芳香環具有雜原子及/或取代基之化合物。 As another example of a compound having two (meth)acryloyl groups in the molecule, from the viewpoint of resolution and adhesion, it is preferable to modify bisphenol A with alkylene oxide on both sides. A compound having a (meth)acryloyl group at the end. Specifically, compounds represented by the following general formula (I) can be used: [Chem. 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 independently an integer of 0 to 39, and n ₁ + n ₃ is an integer of 0 to 40, n ₂ and n ₄ are each independently an integer of 0 to 29, and n ₂ + n ₄ is an integer of 0 to 30, repetition of -(AO)- and -(BO)- The arrangement of the units may be random or block; and, in the case of a block, either of -(AO)- and -(BO)- may be a biphenyl side}. For example, in terms of resolution and adhesiveness, polyethylene glycol dimethacrylate to which an average of 5 moles of ethylene oxide is added to both ends of bisphenol A, Dimethacrylate of polyethylene glycol with an average of 2 moles of ethylene oxide added to both ends of bisphenol A, and an average of 1 mole of ethylene oxide added to both ends of bisphenol A Polyethylene glycol dimethacrylate of ethylene oxide. Moreover, the compound which has a heteroatom and/or a substituent in the aromatic ring in the said general formula (I) can be used.

Examples of heteroatoms include halogen atoms, and examples of substituents include alkyl groups having 1 to 20 carbons, cycloalkyl groups having 3 to 10 carbons, aryl groups having 6 to 18 carbons, and benzyl groups. Acylmethyl group, amino group, alkylamino group with 1 to 10 carbons, dialkylamino group with 2 to 20 carbons, nitro, cyano, carbonyl, mercapto, alkylmercapto with 1 to 10 carbons, Aryl, hydroxyl, hydroxyalkyl with 1 to 20 carbons, carboxy, carboxyalkyl with 1 to 10 carbons in alkyl, acyl with 1 to 10 carbons in alkyl, 1 to 20 carbons Alkoxy, alkoxycarbonyl with 1 to 20 carbons, alkylcarbonyl with 2 to 10 carbons, alkenyl with 2 to 10 carbons, N-alkylaminoformyl with 2 to 10 carbons or containing A heterocyclic group, or an aryl group substituted with these substituents, etc. These substituents may form condensed rings, or hydrogen atoms in these substituents may be substituted 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.

As (B) a compound having an ethylenically unsaturated double bond, it is possible to remarkably improve the adhesiveness during development after heating after exposure, especially when the time from exposure to development becomes longer. From the viewpoint of adhesiveness, it is preferable to contain (meth)acrylate compounds having 3 or more ethylenically unsaturated double bonds (that is, more than trifunctional). From the same viewpoint, it is more preferable to include (meth)acrylate compounds having 4 or more ethylenically unsaturated double bonds, and further preferably to include (meth)acrylate compounds having 5 or more ethylenically unsaturated double bonds. base) acrylate compound, especially a (meth)acrylate compound having 6 or more ethylenically unsaturated double bonds. Also, 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 crosslinking density during polymerization by exposure, but in most cases due to the large number of functional groups Due to the influence of steric hindrance, the desired crosslink density cannot be obtained. In the present invention, it is 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 more preferably having 5 Compounds with more than one ethylenically unsaturated double bond, especially a compound with more than six ethylenically unsaturated double bonds, are also heat-treated after exposure to improve 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. As a compound having preferably 3 or more ethylenically unsaturated double bonds, more preferably a compound having 4 or more ethylenically unsaturated double bonds, still more preferably having 5 or more ethylenically unsaturated double bonds The content of the compound, especially the compound having 6 or more ethylenically unsaturated double bonds, is preferably 3% by mass or more, more preferably 5% by mass or more, relative to the solid content of the above-mentioned photosensitive resin composition, Furthermore, it is preferably at least 7% by mass, and particularly preferably at least 10% by mass. In addition, the upper limit of the content is preferably at most 30% by mass, more preferably at most 25% by mass, still more preferably at most 20% by mass, especially from the viewpoint of expressing the effect of heat treatment after exposure. Preferably, it is 15% by mass or less.

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

(b1) The (meth)acrylate compound having 3 or more ethylenically unsaturated bonds has a weight of preferably 500 or more, more preferably 700 or more, still more preferably 900 or more, from the viewpoint of suppressing bleeding average molecular weight.

As tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate is preferable. As pentaerythritol tetra(meth)acrylate, the tetra(meth)acrylate which added 1-40 mol of alkylene oxides in total to the four terminals of pentaerythritol, etc. are preferable.

{式中，R ₃～R ₆分別獨立地表示氫原子或甲基，X表示碳數2～6之伸烷基，m ₁、m ₂、m ₃及m ₄分別獨立地為0～40之整數，於m ₁＋m ₂＋m ₃＋m ₄為1～40，並且m ₁＋m ₂＋m ₃＋m ₄為2以上之情形時，複數個X相互可相同亦可不同}。 Tetra(meth)acrylate is more preferably a tetra(meth)acrylate compound represented by the following general formula (II): [Chemical 2]

{In the formula, R ₃ to R ₆ independently represent a hydrogen atom or a methyl group, X represents an alkylene group with 2 to 6 carbons, and m ₁ , m ₂ , m ₃ and m ₄ are independently between 0 and 40 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}.

Although not wishing to be bound by theory, it is believed that the tetramethacrylate compound represented by the general formula (II) has groups R ₃ to R ₆ , and four of the moieties having H ₂ C=CH-CO-O- Compared with acrylate, it inhibits the hydrolysis in alkaline solution. From the point of view of significantly improving the adhesion when developing after heating after exposure, and especially achieving good adhesion even when the time from exposure to development becomes longer, it is preferable to use the formula containing (II) The photosensitive resin composition of the tetramethacrylate compound represented.

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

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

Regarding the resist pattern, from the viewpoint of obtaining the required resolution, skirt 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 of 1-20, more preferably an integer of 2-10. More preferably, in the general formula (II), m ₁ +m ₂ +m ₃ +m ₄ is 1-36 or 4-36.

As a compound represented by General formula (II), pentaerythritol (poly) alkoxy tetramethacrylate etc. are mentioned, for example. Also, in the present invention, "pentaerythritol (poly) alkoxytetramethacrylate" is included in the above-mentioned general formula (II), and "pentaerythritol alkoxytetramethylacrylate" in which m ₁ + m ₂ + m ₃ + m ₄ = 1 Acrylate" and "pentaerythritol polyalkoxytetramethacrylate" in which m ₁ +m ₂ +m ₃ +m ₄ = 2 to 40. As a compound represented by general formula (II), the compound listed in Unexamined-Japanese-Patent No. 2013-156369, such as pentaerythritol (poly) alkoxy tetramethacrylate, etc. are mentioned.

As the hexa(meth)acrylate compound, a hexa(meth)acrylate in which a total of 1 to 24 moles of ethylene oxide is added to the 6 ends of dipentaerythritol is preferred. A total of 1 to 10 moles of ε-caprolactone hexa(meth)acrylate was added.

The photosensitive resin of the present embodiment can remarkably improve the adhesion when developing after heating after exposure, especially when the time from exposure to development becomes longer, it can achieve good adhesion. It is more preferable that a composition contains the (meth)acrylate compound which has 4 or more ethylenically unsaturated bonds and has an alkylene oxide chain as (B) the compound which has an ethylenically unsaturated bond. In this case, the ethylenically unsaturated bond is more preferably derived from a methacryl group, and the alkylene oxide chain is more preferably an ethylene oxide chain.

In the present embodiment, from the viewpoint of significantly improving the adhesion when developing after heating after exposure, especially when the time from exposure to development becomes longer, it is possible to achieve good adhesion. The permanent resin composition preferably contains a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton as (B) a compound having an ethylenically unsaturated bond. As an alkylene oxide chain, an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, a pentylene oxide chain, a hexylene oxide chain etc. are mentioned, for example. When the photosensitive resin composition contains a plurality of alkylene oxide chains, these may be the same as or different from each other. In view of the above, the alkylene oxide chain is more preferably an ethylene oxide chain, a propylene oxide chain, and a butylene oxide chain, further preferably an ethylene oxide chain, and a propylene oxide chain, especially Preferred are ethylene oxide chains.

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

The (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton is an ester of (meth)acrylic acid and a dipentaerythritol compound modified by at least one alkyleneoxy group having a plurality of hydroxyl groups. The 6 hydroxyl groups of the dipentaerythritol skeleton can be modified by alkoxyl groups. The number of ester bonds in one molecule of the ester should just be 1-6, 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. Hexa(meth)acrylate of alkylene oxide.

{式中，R分別獨立地表示氫原子或甲基，且n為0～30之整數，且全部n之合計值為1以上}。於通式(III)中，較佳為全部n之平均值為4以上，或n分別為1以上。作為R，較佳為甲基。 Specifically, as a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, the adhesiveness during development after heating after exposure can be significantly improved, especially from exposure to development. From the viewpoint of realizing good adhesion even when the time becomes longer, the compound represented by the following general formula (III) is preferred: [Chem. 3]

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

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% by mass to 50% by mass relative to the total solid content It is more preferably within the range of 5% by mass to 40% by mass, and still more preferably within the range of 7% by mass to 30% by mass.

(b1) A (meth)acrylate compound having 3 or more ethylenically unsaturated bonds (that is, a compound having 3 or more (meth)acrylate groups) relative to the total solid content of the photosensitive resin composition compound) is preferably more than 0% by mass and 50% by mass or less. If the content is more than 0% by mass, the aspect of adhesiveness during development after heating after exposure is remarkably improved, especially when the time from exposure to development becomes longer, good adhesion is achieved. More advantageously, if it is 50% by mass or less, the flexibility of the cured resist is improved and the peeling time tends to be shortened. The content is more preferably from 2% by mass to 40% by mass, and still more preferably from 4% by mass to 35% by mass. In a more preferable aspect, (B) the compound having an ethylenically unsaturated double bond is preferably contained in an amount of at least 5% by mass, more preferably at least 9% by mass, and further Preferably at least 13% by mass, more preferably at least 20% by mass, and preferably at most 40% by mass, more preferably at most 35% by mass, and still more preferably at most 30% by mass. The above methacrylate-based compounds.

From the viewpoint of adhesion and the viewpoint of suppressing the foaming property of the developer, the photosensitive resin composition preferably contains (b2) having a butylene oxide chain or a propylene oxide chain and 1 or 2 (methyl ) a compound having an acryl group as (B) a compound having an ethylenically unsaturated bond. Regarding (b2) a compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryloyl groups, from the viewpoint of suppressing bleed-out, it is preferably 500 or more, more preferably 700 or more. Above, more preferably 1000 or above molecular weight.

Examples of (b2) compounds having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryl 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)acryl groups may also contain an ethylene oxide chain in addition to a butylene oxide chain or a propylene oxide chain .

Specifically, (b2) compounds having a butylene oxide chain or a propylene oxide chain and 1 or 2 (meth)acryl groups preferably have 1 to 20, more preferably 4 to 15 , and more preferably 6 to 12 (meth)acrylates or di(meth)acrylates of C ₄ H ₈ O or C ₃ H ₆ O.

Relative to the total solid content of the photosensitive resin composition, the content of (b2) the compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryl groups is preferably more than 0 % by mass and not more than 20% by mass.

In this embodiment, in order to suppress exudation of the constituents of the dry film resist and improve storage stability, it is preferably 70% by mass based on the total solid content of the compound having an ethylenically unsaturated bond (B). % or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, most preferably 100% by mass are compounds having a weight average molecular weight of 500 or more. The weight average molecular weight of (B) the compound having an ethylenically unsaturated bond is preferably at least 760, more preferably at least 800, and still more preferably at least 830, from the viewpoint of suppression of bleeding and chemical resistance of the resist pattern. Above, preferably above 900. (B) The weight average molecular weight of the compound which has an ethylenically unsaturated bond can be calculated|required as the molecular weight calculated from the molecular structure of the compound which has (B) ethylenically unsaturated bond. When there are plural kinds of (B) compounds having an ethylenically unsaturated bond, it can be obtained by weighting the molecular weight of each compound by content.

From the viewpoint of chemical resistance, adhesion, high resolution, and frame shape of the resist pattern, the concentration of the methacryl group in the compound having an ethylenically unsaturated bond in (B) is preferably 0.20 mol/100 g or more, more preferably 0.30 mol/100 g or more, still more 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 alkali developability are ensured, and may be, for example, 0.90 mol/100 g or less or 0.80 mol/100 g or less.

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

The (meth)acrylate compound demonstrated above can be used independently or in combination, respectively. The photosensitive resin composition may contain another compound as (B) the compound which has an ethylenically unsaturated bond. Examples of other compounds include (meth)acrylates having urethane bonds, compounds obtained by reacting α,β-unsaturated carboxylic acids with polyhydric alcohols, 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) It is preferable that the ratio of the compound which has an ethylenically unsaturated double bond with respect to the mass of the total solid content of a photosensitive resin composition is 5 mass % - 70 mass %. From the viewpoint of sensitivity, resolution, and adhesiveness, it is preferable to make this ratio 5 mass % or more. The ratio is more preferably at least 10 mass %, more preferably at least 20 mass %, further preferably at least 30 mass %. On the other hand, from the viewpoint of suppressing edge melting and peeling delay of the hardened resist, it is preferable to make this ratio 70% by mass or less. More preferably, this ratio is 50 mass % or less.

(C) Photopolymerization initiator (C) The photoinitiator is a compound which polymerizes a monomer using light. From the point of view that the adhesiveness during development after heating after exposure can be significantly improved, especially good adhesion can be obtained even when the time from exposure to development becomes longer, (C) photopolymerization The initiator preferably contains at least one selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and their derivatives, more preferably contains anthracene and/or anthracene derivatives , and further preferably contains an anthracene derivative. In addition, anthracene, pyrazoline, triphenylamine, coumarin, and their derivatives, especially anthracene and/or anthracene derivatives have a central wavelength of less than 390 nm for the first active light and a central wavelength of 390 nm. The second active light of nm or more absorbs light, and functions well as a polymerization initiator. Therefore, in one aspect, the photosensitive resin composition can have photosensitivity to the first active light and the second active light, and can also be used for two-wavelength exposure. (C) The photopolymerization initiator can also be selected so as to have a plurality of absorption maxima in the wavelength range of the first active light and the second active light.

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

Anthracene and anthracene derivatives are advantageous in that they can remarkably improve the adhesiveness when developing after heating after exposure, and are particularly advantageous in that they can achieve good adhesiveness even when the time from exposure to development becomes longer. From the same point of view, the anthracene derivative is preferably at the 9-position and/or 10-position, more preferably at the 9 and 10-position, an alkoxy group having 1 to 40 carbon atoms which may have a substituent and/or may be An aryl group having 6 to 40 carbon atoms as a substituent.

In one aspect, from the viewpoint of significantly improving the adhesiveness when developing after heating after exposure, especially when the time from exposure to development becomes longer, anthracene 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-position or the 10-position, and more preferably has an alkoxy group that may have a substituent on at least one of the 9-position or the 10-position. An alkoxy group having 1 to 30 carbon atoms as a substituent. From the viewpoint of obtaining good adhesion and resolution, it is preferable to have an alkoxy group having 1 to 40 carbon atoms that may have a substituent at the 9 and 10 positions, and it is more preferable to have an alkoxy group that may have a substituent at the 9 and 10 positions. An alkoxy group having 1 to 30 carbon atoms as a substituent. The carbon numbers of the bases at the 9th and 10th positions 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, nor-rhexyloxy, tricyclodecanyloxy, tetracyclododecyloxy, adamantyloxy, methyladamantyloxy, ethyladamantyloxy, and butyl adamantyloxy; Halogen-modified alkoxy such as chlorobutoxy, chloropropoxy; Alkoxy groups with hydroxyl groups added, such as hydroxybutoxy groups; Alkoxy groups with cyano added such as cyanobutoxy; An alkoxy group with an epoxy group added such as methoxybutoxy; Alkoxy groups added with aryl groups include phenoxybutoxy groups and the like. Among them, n-butoxy is more preferable.

In one aspect, from the viewpoint of significantly improving the adhesiveness when developing after heating after exposure, especially when the time from exposure to development becomes longer, anthracene 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-position or the 10-position, and more preferably has a substituent that may have a substituent on at least one of the 9-position or the 10-position. An aryl group with 6 to 30 carbon atoms.

From the point of view of significantly improving the adhesion when developing after heating after exposure, and especially achieving good adhesion even when the time from exposure to development becomes longer, it is preferably at 9 or 10 An aryl group having 6 to 40 carbon atoms which may have a substituent at the position, more preferably an aryl group having 6 to 30 carbon atoms which may have a substituent at the 9 and 10 positions. The carbon numbers of the bases at the 9th and 10th positions may be the same or different. Also, the groups at the 9th and 10th positions may be the same or different. For example, the group at the 9th position is an alkoxy group having 1 to 40 carbon atoms which may have a substituent, and the group at the 10th position may be an aryl group having 6 to 40 carbon atoms which may have a substituent.

基、壬基苯基；加成有鹵素之芳基例如氯苯基；加成有羥基之芳基例如羥基苯基等。其中，更佳為苯基。Examples of aryl groups having 6 to 40 carbon atoms that may have substituents include: phenyl, biphenyl, naphthyl, anthracenyl; aryl groups to which alkoxy groups are added such as methoxyphenyl, ethoxy Phenyl; aryl with alkyl added such as tolyl, xylyl,

Base, nonylphenyl; aryl group with halogen addition, such as chlorophenyl; aryl group with hydroxyl addition, such as hydroxyphenyl, etc. Among them, phenyl is more preferable.

R ¹獨立地表示氫原子、碳數1～40之經取代或未經取代之烷基、碳數3～20之經取代或未經取代之脂環族基、碳數2～4之烯基、經取代或未經取代之芳基、經取代或未經取代之雜芳基或N(R') ₂基，2個以上之R ¹可相互鍵結而形成環狀結構，該環狀結構可含有雜原子。 The anthracene derivative is preferably represented by the following general formula (IV). [chemical 4]

^R1 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group with 1 to 40 carbons, a substituted or unsubstituted alicyclic group with 3 to 20 carbons, or an alkenyl group with 2 to 4 carbons , substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl or N(R') ₂ groups, two or more R ¹ may be bonded to each other to form a ring structure, the ring structure May contain heteroatoms.

X independently represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, a -N(R')- group, a -CO-O- group, a -CO-S- group, a -SO ₂ -O- group, _-SO2 -S-group, _-SO2 -N(R')-group, -O-CO-group, -S-CO-group, -O- _SO2 -group or S- _SO2 -group. Wherein, X is a single bond, and R ¹ is a combination of hydrogen atoms (ie unsubstituted anthracene) except.

The above R' represents a hydrogen atom, a substituted or unsubstituted alkyl group with 1 to 40 carbons, a substituted or unsubstituted alicyclic group with 3 to 20 carbons, an alkenyl group with 2 to 4 carbons, In a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms, R' may bond with each other to form a ring structure, and the ring structure may contain heteroatoms.

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

As the substituted or unsubstituted alkyl group having 1 to 40 carbon atoms in ^R1 and R', specifically, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-eicosyl, iso Propyl, isobutyl, second butyl and third butyl, etc.

Specific examples of substituted or unsubstituted alicyclic groups having 3 to 20 carbon atoms in R ^and R' include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and carbon Bridged alicyclic hydrocarbon groups with a number of 6 to 20 (for example, Noryl, Tricyclodecanyl, 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.

基、壬基苯基、氯苯基、羥基苯基。 Specific examples of substituted or unsubstituted aryl groups having 6 to 40 carbon atoms in R ^and R' include: phenyl, biphenyl, naphthyl, anthracenyl, methoxyphenyl, Ethoxyphenyl, tolyl, xylyl,

phenyl, nonylphenyl, chlorophenyl, hydroxyphenyl.

As the substituted or unsubstituted heteroaryl group in the above-mentioned ^R1 and R', those containing one or more heteroatoms such as a sulfur atom, an oxygen atom, and a nitrogen atom in the substituted or unsubstituted aryl group can be mentioned. Groups such as pyridyl, imidazolyl, morpholinyl, piperidinyl, pyrrolidinyl and the like.

In addition, each hydrocarbon group of the aforementioned R ¹ and R' may be substituted with a substituent. Examples of such substituents include: hydroxyl group, carboxyl group, hydroxyalkyl group having 1 to 4 carbon atoms (such as hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, etc.) group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc.), alkoxy group with 1 to 4 carbons (such as methoxy, ethyl Oxygen, n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, tert-butoxy, etc.), cyano, carbon number 2 to 5 cyanoalkyl (such as cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, etc.), alkoxycarbonyl (such as methoxycarbonyl, ethoxycarbonyl , tertiary butoxycarbonyl, etc.), alkoxycarbonylalkoxy (such as methoxycarbonylmethoxy, ethoxycarbonylmethoxy, tertiary butoxycarbonylmethoxy, etc.), halogen atoms ( For example, fluorine, chlorine, etc.) and fluoroalkyl groups (such as fluoromethyl, trifluoromethyl, pentafluoroethyl, etc.) and the like. Each of the above-mentioned hydrocarbon groups of R ¹ and R' is preferably substituted with a halogen atom. Especially 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 group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- Heptyl, n-octyl, cyclopentyl, cyclohexyl, camphoryl, northyl, p-toluyl, benzyl, methylbenzyl, phenyl and 1-naphthyl.

Preferable specific examples of the aforementioned 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, northyl or benzyl.

Examples of compounds represented by the above-mentioned 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, anthracenol, 1,4,9,10-tetrahydroxyanthracene, 9-anthracenemethanol, 1-aminoanthracene, 2-aminoanthracene Anthracene, 9-(methylaminomethyl)anthracene, 9-acetyl anthracene, 9-anthracene, 10-methyl-9-anthracene, 1,8,9-triacetyloxyanthracene, etc. Among these, 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10- Dibutoxyanthracene, 9,10-bis(2-ethylhexyloxy)anthracene, 9,10-bis-(3-chloropropoxy)anthracene, especially after exposure and heating Adhesiveness at the time of development, especially from the viewpoint of achieving good adhesion even when the time from exposure to development becomes longer, 9,10-diethoxyanthracene, 9,10-diethoxyanthracene, Butoxyanthracene and 9,10-diphenylanthracene, 9,10-bis-(3-chloropropoxy)anthracene, especially 9,10-dibutoxyanthracene and 9,10-diphenylanthracene Anthracene, 9,10-bis-(3-chloropropoxy)anthracene. The compound represented by the said general formula (IV) may be used individually or in combination of 2 or more types.

From the point of view that the adhesiveness during development after heating after exposure can be significantly improved, especially good adhesion can be obtained even when the time from exposure to development becomes longer, (C) photopolymerization 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 9- and/or 10-position alkoxy groups of 9,10-dialkoxyanthracene modified with more than one halogen atom; and/ Or (6) a compound containing a halogen atom directly bonded to the anthracene skeleton.

The compound represented by the above-mentioned general formula (IV) can remarkably improve the adhesiveness during development after heating after exposure, especially when the time from exposure to development becomes longer, good adhesion can be obtained. It is advantageous from a point of view, and can be used for two-wavelength exposure using the first active light having a central wavelength of less than 390 nm and the second active light having a wavelength of 390 nm or more as a central wavelength, and can provide excellent performance. It is also advantageous in terms of sensitivity, adhesion and resolution of the photosensitive resin composition.

In one aspect, the (C) photopolymerization initiator preferably comprises an anthracene derivative having a halogen atom. Suitable examples of anthracene derivatives having a halogen atom are halogen-substituted 9,10-dialkoxyanthracene. A suitable example of the halogen substituent is a compound in which the alkoxy group at the 9-position and/or 10-position of 9,10-dialkoxyanthracene is modified with one or more halogens. As a preferable alkoxy group, what was illustrated above as an alkoxy group with 1-40 carbon atoms is mentioned.

In one aspect, the anthracene derivative is also preferably a compound having a halogen atom directly bonded to the anthracene skeleton. 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-biphenylyl)-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 a preferred embodiment, the amount of the compound represented by the above general formula (IV) is preferably 0.05 to 0.05 to the total solid content of the photosensitive resin composition. The range of 5% by mass, more preferably the range of 0.1 to 3% by mass, most preferably the range of 0.1 to 1.0% by mass.

Pyrazoline and pyrazoline derivatives are preferable from the viewpoint of peeling properties, sensitivity, resolution, and adhesiveness 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 preferable. -pyrazoline, 1-(4-(benzoxazol-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-tertoctyl-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-dimethoxystyryl)-5-(2,6-di Methoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline , 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2 ,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, etc., 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), 3-benzyl Acyl-7-diethylaminocoumarin, etc. Among them, 7-diethylamino-4-methylcoumarin is preferred in terms of sensitivity, resolution, and adhesiveness.

類、二烷基胺基苯甲酸酯類、肟酯類、吖啶類(例如，就感度、解像性、及密接性之方面而言，較佳為9-苯基吖啶、雙吖啶基庚烷、9-(對甲基苯基)吖啶、9-(間甲基苯基)吖啶)、六芳基聯咪唑、N-芳基胺基酸或其酯化合物(例如，就感度、解像性、及密接性之方面而言，較佳為N-苯基甘胺酸)、及鹵素化合物(例如三溴甲基苯基碸)等。該等可單獨使用一種或組合兩種以上而使用。除此以外，亦可使用2,2-二甲氧基-1,2-二苯乙烷-1-酮、2-甲基-1-(4-甲基噻吩基)-2-嗎啉基丙烷-1-酮、2,4,6-三甲基苯甲醯基-二苯基氧化膦、三苯基氧化膦等。As further examples of (C) photopolymerization initiators, quinones, aromatic ketones, acetophenones, acyl phosphine oxides, benzoin or benzoin ethers, dialkyl ketals, 9 -Oxysulfur 𠮿

Classes, dialkylaminobenzoic acid esters, oxime esters, acridines (for example, in terms of sensitivity, resolution, and adhesion, preferably 9-phenylacridine, bisacridine Heptane, 9-(p-methylphenyl)acridine, 9-(m-methylphenyl)acridine), hexaarylbiimidazole, N-aryl amino acid or its ester compound (for example, on In terms of sensitivity, resolution, and adhesion, N-phenylglycine) and halogen compounds (such as tribromomethylphenylsulfone) 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-diphenylethane-1-one, 2-methyl-1-(4-methylthienyl)-2-morpholinyl Propan-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, triphenylphosphine oxide, etc.

Examples of aromatic ketones include benzophenone, michelerone [4,4'-bis(dimethylamino)benzophenone], 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 them, 4,4'-bis(diethylamino)benzophenone is preferable from the viewpoint of adhesiveness. 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 %, more preferably in the range of 0.02 mass % to 0.3 mass % Inside.

As an example of hexaarylbiimidazole, 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tri-(o-chlorophenyl)-4-( 3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl )-diphenylbiimidazole, 2,4,5-tri-(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'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetra -(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) -biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2 ,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2' -bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis -(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, etc., which can be used alone Or use it in combination of 2 or more types. From the viewpoints of sensitivity, resolution and adhesiveness, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferable.

The content of hexaarylbiimidazole in the photosensitive resin composition is preferably in the range of 0.05% by mass to 8% by mass, more preferably from the viewpoint of improving the release properties and/or sensitivity of the photosensitive resin layer It exists in the range of 0.1 mass % - 7 mass %, More preferably, it exists 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, the (D) phenolic polymerization inhibitor is a compound having one or more phenolic hydroxyl groups. Phenolic polymerization inhibitors have the characteristics of hindering the polymerization reaction caused by heat, etc., and improving the storage stability. The phenolic polymerization inhibitor may have one or more members selected from substituted or unsubstituted alkyl groups with 1 to 40 carbons, alkoxy groups with 1 to 40 carbons, alkenyl groups with 2 to 4 carbons, alkenyl groups with 2 to 4 carbons, Substituents 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-tert-butyl Base-4'-hydroxyphenyl) propionate) pentaerythritol ester, 2,2'-thiodiethylbis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, N,N'-hexamethylenebis(3-(3,5-di-tertiary Butyl-4-hydroxyphenyl) propionamide), 3,5-di-tert-butyl-4-hydroxy-octylhydrocinnamate, 2,4,6-tris(3',5'-di- tert-butyl-4'-hydroxybenzyl) mesitylene, 2,4-bis(dodecylthiomethyl)-6-methylphenol, 2,4-bis(octylthiomethyl) -6-methylphenol, bis(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid)(ethylenylbis(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-trione-2,4,6(1H,3H,5H)-trione, 4-((4,6-bis(octyl Sulfuryl)-1,3,5-tri-(2-yl)amino)-2,6-di-tert-butylphenol, etc., especially it is not easy to produce the difference of the shortest developing time under heating after exposure From this point of view, p-methoxyphenol and dibutylhydroxytoluene are preferable.

Regarding (D) the amount of the phenolic polymerization inhibitor based on the mass basis when the total solid content of the photosensitive resin composition is 100% by mass, the desired polymerization inhibition for the photosensitive resin composition can be obtained. From the viewpoint of the effect, it is 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, further preferably 15 ppm or more, and especially preferably 20 ppm or more. , 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, further preferably 100 ppm or less , and more preferably 75 ppm or less, further preferably 50 ppm, especially preferably 40 ppm or less. Although the photosensitive resin composition contains (D) a phenolic polymerization inhibitor, the amount is a small amount, and when the exposure is followed by heating and then developing, the polymerization reaction of the photosensitive resin composition during exposure can be simultaneously realized. It is advantageous in terms of good progress, and acceleration of the reaction of the polymer due to the good effect of improving the fluidity of the polymer by heating (thereby improving the adhesion). For example, in a system where the polymer has a bulky molecular structure (such as a relatively large number of styrene skeletons), when post-exposure heating intended to improve adhesion is performed, there is a low effect of improving fluidity by heating of the polymer. (Therefore, the effect of improving the adhesion is low), according to the photosensitive resin composition of this embodiment, by (D) the amount of the phenolic polymerization inhibitor is in the above range, in the case where there is such a fluffy polymer In this case, the effect of improving the adhesion by heating after exposure can also be obtained favorably.

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

[optional ingredient] The photosensitive resin composition can further contain an arbitrary component other than the said (A)-(D) component as needed. Examples of optional components include additional polymerization inhibitors other than (d) (D) phenolic polymerization inhibitors, dyes, coloring substances, plasticizers, antioxidants, stabilizers, and the like. For example, additives listed in JP-A-2013-156369 can be used.

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

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

Examples of benzotriazoles include: 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminoethylene 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)aminoethylenylcarboxybenzotriazole and the like.

In one aspect, when the total solid content of the photosensitive resin composition is set as 100% by mass, the total amount of the polymerization inhibitor added is preferably 0.001 to 3% by mass, more preferably 0.01% by mass to 1% by mass. From the viewpoint of providing storage stability to the photosensitive resin composition, it is preferable to set the total amount to 0.001% by 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 the present 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 as needed.

Examples of coloring substances include magenta, phthalocyanine green, auretamine, 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), basic blue 20, diamond green (for example, Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). When 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. It is preferable to make this content into 0.001 mass % or more from a viewpoint of improving the handleability of a photosensitive resin composition. On the other hand, it is preferable to make this content into 1 mass % or less from a viewpoint of maintaining the storage stability of a photosensitive resin composition.

The photosensitive resin composition is preferable in terms of visibility because it contains a dye to make the exposed part develop color, and when an inspection machine or the like reads an alignment mark for exposure, the exposed part and the unexposed part are separated. It is advantageous that the contrast ratio of the exposed portion is higher for easier identification. From this point of view, preferred dyes include leuco dyes and fluorescent yellow matrix dyes. Examples of the leuco dye include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)benzenemethane [leuco malachite green], and the like. In particular, it is preferable to use leuco crystal violet as a leuco dye from the point of view that contrast becomes favorable. It is preferable that content of the leuco dye in a photosensitive resin composition is 0.1 mass % - 10 mass % with respect to the mass of the whole solid content of a photosensitive resin composition. It is preferable to make this content into 0.1 mass % or more from a viewpoint of making the contrast of an exposed part and a non-exposed part favorable. The content is more preferably at least 0.2% by mass, and particularly preferably at least 0.4% by mass. On the other hand, it is preferable to make this content into 10 mass % or less from a viewpoint of maintaining storage stability. The content is more preferably at most 5% by mass, particularly preferably at most 2% by mass.

Also, from the viewpoint of optimizing adhesion and contrast, it is preferable to use a combination of a leuco dye and the above-mentioned halogen compound described in (C) photopolymerization initiator in the photosensitive resin composition. . When the 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 of the photosensitive resin composition is 100% by mass. From the viewpoint of the storage stability of the hue in the photosensitive layer, it is preferably 0.01% by mass to 3% by mass.

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

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, triethyl citrate , Acetyl triethyl citrate, Acetyl tri-n-propyl citrate, Acetyl tri-n-butyl citrate, Polyethylene glycol, Polypropylene glycol, Polyethylene glycol alkyl ether, Polypropylene glycol alkyl ether, etc. Also, ADEKA NOL SDX-1569, ADEKA NOL SDX-1570, ADEKA NOL SDX-1571, ADEKA NOL SDX-479 (manufactured by Asahi Denka Co., Ltd. above), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, Newpol BPE-20T, Newpol BPE-60, Newpol BPE-100, Newpol BPE-180 (manufactured by Sanyo Chemical Co., Ltd.), Uniol DB-400, Uniol DAB-800, Uniol DA-350F, Compounds having a bisphenol skeleton such as Uniol DA-400, Uniol DA-700 (manufactured by NOF Co., Ltd.), BA-P4U Glycol, and BA-P8 Glycol (manufactured by Nippon Emulsifier Co., Ltd. above).

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

When the amount of moisture in the photosensitive resin composition is large, the partial plasticization of the photosensitive resin composition is rapidly promoted, and edge melting occurs. From the point of view of suppressing edge melting, it is preferable to apply the photosensitive resin composition preparation solution on the support film, based on the dried photosensitive resin composition, and to measure the moisture in the photosensitive resin composition based on the mass The amount is below 0.7%. The moisture content in the photosensitive resin composition is preferably less than 0.65%, preferably less than 0.6%, preferably less than 0.55%, preferably less than 0.5%, preferably less than 0.45%, preferably less than 0.4% , preferably less than 0.35%, preferably less than 0.3%, preferably less than 0.25%, preferably less than 0.2%.

[solvent] The photosensitive resin composition can be dissolved in a solvent, and can be used in the manufacture of a photosensitive resin laminate in the form of a photosensitive resin composition preparation solution. As a solvent, ketones, alcohols, etc. are mentioned. The aforementioned ketones are represented by methyl ethyl ketone (MEK) and acetone. The aforementioned alcohols are represented by methanol, ethanol, and isopropanol. The solvent is preferably added to the substrate in such an amount that the viscosity of the photosensitive resin composition preparation solution coated on the support film at 25°C becomes 500 mPa·s to 4,000 mPa·s when the photosensitive resin laminate is produced. 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 resolution when developing after exposure and heating. The image property is good, especially from the viewpoint of the photosensitive resin composition which realizes favorable adhesiveness even if the time from exposure to image development is long, it is 58% - 95%. 375 nm and 405 nm correspond to typical exposure wavelengths of the photosensitive resin composition of this embodiment. Regarding the light transmittance, it is 58% or more from the viewpoint of obtaining good sensitivity, adhesion, line width reproducibility and resolution by the exposure light reaching a deeper region of the photosensitive resin composition during exposure , preferably more than 60%, more preferably more than 62%, more preferably more than 64%, and more preferably more than 65%, from the viewpoint of obtaining a good skirt shape by suppressing diffuse reflection light from the surface of the substrate It is 95% or less, preferably 85% or less, more preferably 80% or less, more preferably 75% or less, and more preferably 70% or less.

The method of controlling the light transmittance at least one of 375 nm and 405 nm within the above range is not limited to these, for example, control of the amount of photopolymerization initiator, dye, or coloring substance added, etc. .

[Photosensitive resin laminate] This embodiment also provides the photosensitive resin laminated body which has the photosensitive resin layer containing the said photosensitive resin composition, and a support film. The support film is preferably a transparent support film through which light emitted from a light source for exposure passes. As such a support film, for example, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. As these films, stretched ones can also be used as necessary.

The haze of the support film is preferably at most 5%, more preferably at most 2%, further preferably at most 1.5%, and most preferably at most 1.0%, from the viewpoint of suppressing light scattering during exposure. From the same viewpoint, the surface roughness Ra of the surface in contact with the photosensitive layer is preferably at most 30 nm, more preferably at most 20 nm, and most preferably at most 10 nm. The thinner the film thickness, the better the image forming performance and economical efficiency. However, in order to maintain the strength of the photosensitive resin laminate, it is preferable to use a film with a thickness of 10 μm to 30 μm. The size of fine particles such as lubricant 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 multilayer constructions, an antistatic layer may be present. In the case of a multilayer structure such as a 2-layer structure or a 3-layer structure, for example, a resin layer containing fine particles can be formed on one side A, and on the other side B, (1) contain fine particles similarly to the side A, (2) ) contains less fine particles than surface A, (3) contains finer particles than surface A, (4) does not contain fine particles, etc. In the case of the structures of (2), (3), and (4), it is preferable to form a photosensitive resin layer on the surface B side. At this time, it is preferable from the viewpoint of film slidability and the like that a resin layer containing fine particles exists on the surface A side. At this time, the size of the fine particles is preferably less than 1.5 μm. In addition, the size of the said fine particle is the value obtained by the measurement by the scanning electron microscope calibrated using the 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 can be preferably used as the protective layer. Moreover, the film excellent in peelability shown in Unexamined-Japanese-Patent No. 59-202457 can also be used. The film thickness of the protective layer is preferably from 10 μm to 100 μm, more preferably from 10 μm to 50 μm.

A gel called fisheye may exist on the surface of the polyethylene film. When using the polyethylene film which has fish eyes as a protective layer, this fish eyes may be transferred to a photosensitive resin layer. If the fisheye is transferred to the photosensitive resin layer, air may be trapped during lamination to form voids, resulting in defects in the resist pattern. From the viewpoint of preventing fish eyes, stretched polypropylene is preferable as a material of the protective layer. As a specific example, ALPHAN E-200A by Oji Paper Co., Ltd. is mentioned.

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

The light transmittance of the laminate of the support film and the photosensitive resin layer at a wavelength of 630 nm is an indicator of dye decolorization, and a higher light transmittance at a wavelength of 630 nm indicates that the dye is decolorized. The light transmittance of the laminate of the support film and the photosensitive resin layer at a wavelength of 630 nm is preferably 80% or less, preferably 78% or less, preferably 75% or less, preferably 72% or less, more preferably Below 70%, preferably below 68%, preferably below 65%, preferably below 62%, preferably below 60%, preferably below 58%, preferably below 55%, preferably below 52% % or less, preferably less than 50%. The light transmittance is the value of the laminate (that is, without the protective layer) of the support film and the photosensitive resin layer.

Next, the manufacturing method of the photosensitive resin laminate is demonstrated. Known methods can be employed as a method of sequentially laminating a support film, a photosensitive resin layer, and an optional protective layer to produce a photosensitive resin laminate. For example, the photosensitive resin composition used in the photosensitive resin layer is mixed with a solvent to dissolve it to make a uniform solution, and firstly coated on a support film using a bar coater or a roll coater , followed by drying to remove the above-mentioned solvent, whereby a photosensitive resin layer comprising a photosensitive resin composition can be laminated on the support film. Then, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer as necessary.

<Formation method of resist pattern> Next, an example of a method of producing a resist pattern using the photosensitive resin laminate of this embodiment will be described. The method may include the following steps: an exposing 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, Substrates for semiconductor packaging, transparent electrodes for liquid crystals, wiring for TFTs (Thin Film Transistors) for liquid crystals, patterns for PDP (Plasma Display Panels, electrodes for plasma display panels, etc. As an example, printed wiring boards will be described as follows The manufacturing method.

A printed wiring board is manufactured through the following steps. (1) Lamination step First, in the laminating step, a laminating machine is used to form a photosensitive resin layer on the substrate. Specifically, when the photosensitive resin laminate has a protective layer, after the protective layer is peeled off, the photosensitive resin layer is bonded and laminated by thermocompression bonding to the surface of the substrate by a laminating machine. As a material of a board|substrate, copper, stainless steel (SUS), glass, indium tin oxide (ITO), etc. are mentioned, for example. 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 as necessary. The heating temperature during lamination is usually 40°C to 160°C. Moreover, the adhesiveness of the obtained resist pattern with respect to a board|substrate can be improved by carrying out the thermocompression bonding at the time of laminating|stacking two or more times. In the heat-compression bonding, the pressure-bonding can be performed by using a two-stage laminating machine equipped with double rollers, or by repeatedly passing the laminate of the substrate and the photosensitive resin layer through the rollers several times.

(2) Exposure steps In this step, the photosensitive resin is exposed by the following exposure method: an exposure method in which a mask having the required wiring pattern is closely attached to the support film and an active light source is used; drawing of the required wiring pattern is used An exposure method of direct drawing of a pattern; or an exposure method by projecting an image of a mask 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 an image of a mask 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 an image of a mask through a lens, in the exposure method of direct drawing using a drawing pattern Especially notable.

When the exposure step is an exposure method using direct drawing, it is preferably laser light with a central wavelength of less than 390 nm or laser light with a central wavelength of 390 nm or more. More preferably, it is a laser light with a central wavelength of 350 nm to 380 nm, or a laser light with a central wavelength of 400 nm to 410 nm. Furthermore, it is preferable to carry out by the method of exposing with the 1st laser light whose center wavelength is less than 390 nm, and the 2nd laser light whose center wavelength is 390 nm or more. Moreover, it is more preferable that the center wavelength of the first laser light is not less than 350 nm and not more than 380 nm, and that the center wavelength of the second laser light be not less than 400 nm and not more than 410 nm.

(3) Heating step In this step, it is preferable to heat the exposed photosensitive resin composition at about 30°C to about 200°C, more preferably in the range of 30°C to 150°C, and more preferably in the range of 60°C to 120°C scope. By implementing this heating process, resolution and adhesiveness can be improved. For heating, 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, and it is more preferable if there are two or more heating rollers.

In particular, in the present invention, by using (D) a phenolic polymerization inhibitor in a small amount, and controlling the light transmittance of the resin composition at a specific wavelength to a specific range, heating is performed 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 of the hydrophobicity of the styrene skeleton and the carbon-carbon double bond can also be realized at the same time. sex. As a result, sensitivity, adhesion, line width reproducibility, and resolution can be remarkably improved. Furthermore, since the adhesiveness is remarkably improved, favorable adhesiveness can be acquired also when the time from exposure to image development is long. Moreover, from the viewpoint of the effect of this invention, it is preferable to perform the said heating process within 15 minutes after exposure, and it is more preferable to perform within 10 minutes.

(4) Developing step In this step, after exposure, the support film on the photosensitive resin layer is peeled off, and then the unexposed part 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 at a concentration of about 0.2% by mass to about 2% by mass and at 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 more than 5 minutes, or more than 60 minutes, or more than 180 minutes, and may be less than 1440 minutes, Or less than 720 minutes, or less than 300 minutes. The resist pattern can be obtained through the steps of (1) to (4) above.

In the manufacturing method of the circuit board of this invention, a circuit board is formed by etching or plating the board|substrate which has the resist pattern manufactured by the said method.

(5) Etching step or plating step Conductor patterns are produced by etching or plating the surface of the substrate exposed by development (for example, the copper surface of a copper-clad laminate).

(6) Stripping step Thereafter, the resist pattern is stripped from the substrate using an appropriate stripping solution as needed. As a stripping liquid, an alkaline aqueous solution, an amine-based stripping liquid, etc. are mentioned, for example. However, the resist pattern formed by heating after exposure using the photosensitive resin composition of the present invention has the following advantages: it exhibits good peelability with respect to amine-based strippers, and the peeled sheet does not become too fine. Therefore, if an amine-based stripping liquid is used as the stripping liquid, the advantageous effect of the present invention can be exhibited, which is preferable.

The amine contained in the amine-based stripping solution may be an inorganic amine or an organic amine. As an inorganic amine, ammonia, hydroxylamine, hydrazine etc. are mentioned, for example.

Examples of organic amines include ethanolamines, propanolamines, alkylamines, cyclic amines, quaternary ammonium salts, and the like. As a specific example of these, Examples of ethanolamine include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, aminoethoxy ethanol, etc.; Examples of propanolamine include 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, etc. ; Examples of alkylamines include: monomethylamine, dimethylamine, trimethylamine, ethylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylene Basetetramine, tetraethylenepentamine, etc.; As the cyclic amine, for example, choline, thioline, etc. can be illustrated; Examples of quaternary ammonium salts include: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, N,N,N-triethyl-N-(2-hydroxyethyl) Ammonium hydroxide, N,N-diethyl-N,N-di(2-hydroxyethyl)ammonium hydroxide, etc.

The amine-based 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 according to the purpose, the composition of the photosensitive resin layer, developing conditions, and the like. The amine-based stripping solution may further contain additives commonly used in stripping agents such as surfactants, antifoaming agents, pH regulators, preservatives, anti-reattachment agents, and the like. The peeling step is, for example, carried out 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 to 10 minutes the following time.

After the stripping step, if necessary, the substrate from which the resist pattern has been removed may be cleaned with, for example, pure water.

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, TFT wiring for liquid crystals, and PDPs Manufacturers of conductor patterns for electrodes, etc. In addition, regarding the above-mentioned various parameters, unless otherwise specified, they were measured in accordance with the measurement methods in the following examples or the methods understood by those skilled in the art to be equivalent thereto. [Example]

Next, the present embodiment will be described more specifically with reference to Examples and Comparative Examples. However, this embodiment is not limited to the following examples unless it deviates from the gist. The physical properties in the examples were measured by the following methods. The measurement of the physical property values of polymers and the preparation method of samples for evaluation in Examples and Comparative Examples will be described. In addition, evaluation methods and evaluation results of the obtained samples are shown.

(1) Determination and calculation of physical properties ＜Determination 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 obtained by using a gel permeation chromatography (GPC) manufactured by JASCO 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, mobile layer solvent: tetrahydrofuran, using polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd. ) of the calibration curve), obtained in the form of polystyrene conversion. Furthermore, the degree of dispersion of the polymer was 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 group in the molecule. The acid equivalent was determined by potentiometric titration using a 0.1 mol/L sodium hydroxide aqueous solution using a Hiranuma automatic titration device (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

<I/O value> The I/O value of the alkali-soluble polymer was derived by the following method. First, through non-patent literature (Organic Concept Map (Koda Yoshio, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Items 1-16 (1954); Chemical Field, Vol. 11, No. 10 No. 719-725 (1957); Fragrancejournal, No. 34, 97-111 (1979); Fragrancejournal, No. 50, 79-82 (1981)) to calculate the composition The I value and O value of each comonomer, and then by averaging the above-mentioned IO value and O value with the molar ratio of the comonomer, respectively, the I _average value and the O _average value are obtained. Then, the I/O value is derived by dividing the obtained I _average value by the O _average value.

{式中，W _i為各鹼可溶性高分子之固形重量，Tg _i為各鹼可溶性高分子之利用Fox式求出之玻璃轉移溫度，W _total為各鹼可溶性高分子之合計固形重量，且n為感光性樹脂組合物中所含之鹼可溶性高分子之種類之數量} <Glass transition temperature Tg> The glass transition temperature Tg of an alkali-soluble polymer was calculated|required by Fox's formula. When calculating the glass transition temperature Tg, use the non-patent literature (Brandrup, J. Immergut, EH edited "Polymer handbook, Third edition John wiley & sons, 1989, p.209 Chapter VI "Glass transition temperatures of polymers"") Values are expressed as glass transition temperatures of homopolymers comprising comonomers that form the corresponding alkali-soluble polymers. In addition, in an Example, the glass transition temperature of the homopolymer containing each comonomer used for calculation is shown in Table 1. When the alkali-soluble polymer is composed of two or more polymers, the value obtained by the following formula becomes the glass transition temperature of the alkali-soluble polymer. [number 1]

{In the formula, W _i is the solid weight of each alkali-soluble polymer, Tg _i is the glass transition temperature of each alkali-soluble polymer obtained by 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. ＜Production of photosensitive resin laminate＞ The components shown in Tables 1 to 3 disclosed below (wherein, the numbers of each component represent the formulation amount (parts by mass) in terms of solid content) and the solvent are fully stirred and mixed to obtain a photosensitive resin composition. compound liquid. Table 3 shows details of the components shown in Tables 1 and 2. Using a 16 μm thick polyethylene terephthalate film (manufactured by Toray Co., Ltd., FB-40) as a support film, the prepared liquid was evenly coated on the surface using a bar coater, and the mixture was coated at 95 ℃ drying machine for 3 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 30 μm. Then, on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film was not laminated, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-18) was bonded as a protective layer. ) to obtain a photosensitive resin laminate. Furthermore, 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 content in the photosensitive resin composition.

＜Cleaning and finishing of the surface of the substrate＞ Under the spray pressure of 0.2 MPa, use a grinding agent (manufactured by Uji Denki Chemical Industry Co., Ltd., #400) to laminate a 0.4 mm-thick 35 μm rolled copper foil as an image evaluation substrate The copper foil laminate was sandblasted, rinsed and ground, and then the surface of the substrate was cleaned with a 10% by mass H ₂ SO ₄ aqueous solution.

＜Laminated＞ While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate was laminated on the pre-coated surface at a roll temperature of 105°C using a heating roll laminating machine (manufactured by Asahi Kasei Co., Ltd., AL-700). Heat to 50 ℃ copper foil laminated board. 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 substrate for evaluation after 2 hours after lamination, using a direct drawing exposure machine (manufactured by Orbotech Co., Ltd., Nuvogo Fine 10, light source: 375 nm (30%) + 405 nm (70%)), using a Stuff ( Stouffer) 41 stage exposure meter for exposure. Exposure was carried out using the above-mentioned Steuffer 41-step exposure meter as a mask, and the maximum number of residual film steps during development was 14 steps.

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

<Development> After peeling off the polyethylene terephthalate film (support film), use an alkaline developer (manufactured by FUJI KIKO Co., Ltd., a developer for dry film) to spray 1% by mass at 30°C for a specified period of time Na ₂ CO ₃ aqueous solution for development. The time of the developing spray is set to 2 times of the shortest developing time, and the time of the washing spray after developing is set to 3 times of the shortest developing time. At this time, the shortest time required for the photosensitive resin layer in the unexposed portion to completely dissolve is set as the shortest developing 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 n-docosane is used as the internal standard. ＜Dibutylhydroxytoluene content＞ The amount of dibutylhydroxytoluene in the photosensitive resin composition was determined by GC similarly to the amount of p-methoxyphenol. The internal standard system uses n-octadecane. ＜Light transmittance＞ The light transmittance of each resin composition at 375 nm and 405 nm was measured by the following method. The transmittance at each wavelength of the photosensitive resin laminate from which the polyethylene film (protective layer) was peeled was measured using a spectrophotometer (Hitachi High-Technologies Co., Ltd., U-3010). At this time, it was installed so that transmitted light could pass through in the film thickness direction of the photosensitive resin laminate, and it measured.

<Sensitivity evaluation> In the above exposure step, after exposure through the mask of the Steuffe 41-step exposure meter, develop, and set the exposure amount (mJ/cm ² ) at which the highest residual film level is 14 levels Calculated for the value of sensitivity.

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

＜Resolution＞ In the said exposure process, exposure was performed using the drawing data of the line pattern which has the ratio of the width of an exposure part and the width of an unexposed part of 1:1. Development is performed under the above-mentioned development conditions to form hardened resist lines. The minimum line width at which hardened resist lines are normally formed is determined as the value of the resolution.

＜Adhesiveness＞ In the above-mentioned exposure step, exposure was performed using drawing data of a line pattern having a ratio of the width of the exposed portion and the unexposed portion to x μm:200 μm. Development was carried out under the above-mentioned development conditions, and the minimum line width at which hardened resist lines were normally formed was measured with an optical microscope. This measurement was performed for four lines, and the average value of the four line widths was determined as a value of adhesiveness. Only in the evaluation of the adhesiveness, two kinds of evaluations were performed: the case of heating after 1 minute after exposure and the case of heating after 7 minutes after exposure.

＜Delay of minimum developing time＞ In the above developing step, when developing without heating after exposure and heating after 7 minutes of exposure, and then developing, measure the shortest time required for the photosensitive resin layer of the unexposed part to completely dissolve, that is, the shortest The developing time is graded according to the following criteria. Good: No difference in minimum developing time between with post-exposure heating and without post-exposure heating Yes: The shortest developing time with post-exposure heating is less than 1 second compared to that without post-exposure heating Impossible: The shortest developing time with post-exposure heating is more than 1 second delayed compared with that without post-exposure heating The results are shown in Tables 1 and 2.

The post-exposure heating condition 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 13.8 μm. That is, in the composition of Comparative Example 1, the effect of heating after exposure for 7 minutes was not observed, but in Example 3, even under very severe conditions, the adhesiveness could be improved. In addition, under the condition of heating after 1 minute of exposure, the adhesion of 10.8 μm was obtained in either of the compositions of Example 7 and Comparative Example 1. From the above results, it can be seen that under the usual post-exposure heating conditions, even when the adhesion was good, the adhesion did not become good under the strict heating conditions after 7 minutes after exposure. For the first time in the present invention, good adhesion can be achieved even under such severe post-exposure heating conditions. Thereby, good adhesion can be obtained even if the time from exposure to development becomes long when manufacturing a circuit board, so that a high-definition circuit pattern can be stably formed.

[Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Component A-1 47.25 47.25 47.25 47.25 47.25 47.25 47.25 25 25 25 47.25 Component A-2 28 28 28 Component A-3 47.25 Component A-4 47.25 Component A-5 47.25 Component B-1 10 10 10 10 10 10 10 10 10 10 10 10 37 10 Component B-2 twenty one twenty one twenty one twenty one twenty one twenty one twenty one 26 twenty one twenty one 26 26 twenty one Component B-3 6 6 6 6 6 6 6 6 6 6 Component C-1 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Component D-1 0.06 0.1 0.2 0.2 0.2 0.2 0.2 0.1 0.2 0.2 0.2 0.2 Component D-2 0.1 Component D-3 0.1 Component E-1 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Component E-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Component F-1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Component G-1 0.008 0.008 0.008 0.008 0.008 0.008 0.008 0.008 0.008 0.008 0.008 0.008 0.008 0.008 Amount of p-methoxyphenol (ppm) 65 65 65 0 35 68 0 31 82 90 32 33 80 67 Dibutyl hydroxytoluene content (ppm) 75 71 80 40 57 0 82 61 96 104 75 78 90 67 Transmittance (%, 375 nm) 58.3 48.8 34.4 34.3 34.4 34.5 34.4 50.0 34.3 34.3 64.4 45.2 36.8 37.1 Transmittance (%, 405 nm) 69.4 64.9 58.2 58.1 58.2 58.3 58.2 65.5 58.1 58.1 68.7 58.1 58.1 58.5 Adhesive I/O value 0.552 0.552 0.552 0.552 0.552 0.552 0.552 0.569 0.552 0.691 0.569 0.569 0.552 0.463 Adhesive Tg(℃) 98 98 98 98 98 98 98 87 131 128 87 87 98 112 Sensitivity(mJ/cm ² ) 40 35 30 17 25 25 20 25 40 40 30 35 35 35 Line width reproducibility (μm) 23.2 23.5 23.8 23.9 24.0 24.8 24.0 23.0 24.6 24.9 24.0 24.9 24.4 24.5 Resolution (μm) 14 13 13 14 14 15 14 13 17 18 14 14 14 16 Adhesiveness when heated after exposure for 7 minutes (μm) 9.6 10.7 11.9 11.1 11.5 11.9 11.6 9.2 12.3 12.8 11.2 12.1 12.1 12.0 Adhesiveness when heated after exposure for 1 minute (μm) 7.8 8.9 10.1 10.5 10.3 10.5 10.4 8.6 10.1 10.6 10.4 11.2 11.1 9.8 Delay of minimum developing time good good good good good Can good good good good good good good good

[Table 2] Table 2 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Component A-1 47.25 47.25 47.25 47.25 Component A-2 Component A-3 Component A-4 Component A-5 Component B-1 10 10 10 10 Component B-2 twenty one twenty one twenty one twenty one Component B-3 6 6 6 6 Component C-1 5 5 5 5 Component D-1 0.4 0.2 0.2 0.2 Component D-2 Component D-3 Component E-1 0.03 0.03 0.03 0.03 Component E-2 0.5 0.5 0.5 0.5 Component F-1 0.05 0.05 0.05 0.05 Component G-1 0.008 0.008 0.008 0.008 Amount of p-methoxyphenol (ppm) 65 310 65 0 Dibutyl hydroxytoluene content (ppm) 67 80 308 0 Transmittance (%, 375 nm) 20.1 34.4 34.4 34.4 Transmittance (%, 405 nm) 45.8 58.2 58.2 58.2 Adhesive I/O value 0.552 0.552 0.552 0.552 Adhesive Tg(℃) 87 87 87 87 Sensitivity(mJ/cm ² ) 15 90 60 15 Line width reproducibility (μm) 26.0 25.5 25.7 25.8 Resolution (μm) 13 15 16 18 Adhesiveness when heated after exposure for 7 minutes (μm) 13.7 13.8 14.0 13.2 Adhesiveness when heated after exposure for 1 minute (μm) 11.7 11.6 11.6 11.2 Delay of minimum developing time good good good can't

[table 3] table 3 INGREDIENT DETAILS Component A-1 It has the composition of methacrylic acid/benzyl methacrylate/styrene (mass ratio 25/50/25), the acid equivalent is 344, the Tg of the Fox formula is 98°C, the I/O value is 0.552, and the weight average molecular weight is 50,000 , a copolymer with a dispersion of 2.3 Component A-2 It has the composition of methacrylic acid/benzyl methacrylate/methyl methacrylate (mass ratio 20/79.5/0.5), the acid equivalent is 430, the Tg of the Fox formula is 79°C, the I/O value is 0.583, and the weight average A copolymer with a molecular weight of 53000 and a dispersion of 2.2 Component A-3 It has the composition of methacrylic acid/methyl methacrylate/styrene/butyl acrylate (mass ratio 25/10/60/5), the acid equivalent is 344, the Tg of the Fox formula is 112°C, and the I/O value is 0.463 , a copolymer with a weight average molecular weight of 20,000 and a dispersion of 3.4 Component A-4 It has the composition of methacrylic acid/methyl methacrylate/styrene (mass ratio 29/19/52), the acid equivalent is 297, the Tg of the Fox formula is 131°C, the I/O value is 0.552, and the weight average molecular weight is 48000 , a copolymer with a dispersion of 4.3 Component A-5 It has the composition of methacrylic acid/methyl methacrylate/styrene (mass ratio 25/50/25), the acid equivalent is 344, the Tg of the Fox formula is 128°C, the I/O value is 0.691, and the weight average molecular weight is 65,000 , a copolymer with a dispersity of 3.5 Component B-1 Dimethacrylate of polyethylene glycol with an average of 5 moles of ethylene oxide added to both ends of bisphenol A (manufactured by Hitachi Chemical Industry FA-321M, product name) Component B-2 Tetramethacrylate with an average of 15 moles of ethylene oxide added to pentaerythritol Component B-3 Hexamethacrylate of polyethylene glycol with 13 moles of ethylene oxide added to dipentaerythritol Component C-1 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer Component D-1 9,10-Diphenylanthracene Component D-2 9,10-Dibutoxyanthracene (ANTHRACURE-UVS-1331 manufactured by Kawasaki Chemical, product name) Component D-3 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline Component E-1 diamond green Component E-2 Leuco Crystal Violet Component F-1 Carboxybenzotriazole Component G-1 Aluminum salt with addition of 3 moles of nitrosophenylhydroxylamine [Industrial availability]

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

Claims (24)

A photosensitive resin composition comprising the following components: (A) Alkali-soluble polymer: 10% by mass to 90% by mass; (B) Compounds with ethylenically unsaturated double bonds: 5% by mass to 70% by mass; (C) photopolymerization initiator: 0.01% by mass to 20% by mass; and (D) p-methoxyphenol and/or dibutylhydroxytoluene: 1 ppm to 300 ppm; and The light transmittance of at least one of 375 nm and 405 nm is 58% to 95%. A photosensitive resin composition comprising the following components: (A) Alkali-soluble polymer: 10% by mass to 90% by mass; (B) Compounds with ethylenically unsaturated double bonds: 5% by mass to 70% by mass; (C) photopolymerization initiator: 0.01% by mass to 20% by mass; and (D) Dibutylhydroxytoluene: 1 ppm to 200 ppm; and The light transmittance of at least one of 375 nm and 405 nm is 58% to 95%. The photosensitive resin composition according to claim 2, wherein the content of the above-mentioned dibutyl hydroxytoluene is 10-150 ppm. The photosensitive resin composition according to any one of claims 1 to 3, wherein the I/O value of the above-mentioned (A) alkali-soluble polymer is 0.600 or less. The photosensitive resin composition according to any one of claims 1 to 3, wherein the above-mentioned (C) photopolymerization initiator comprises an anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof One or more of the group of things. The photosensitive resin composition according to claim 5, wherein the (C) photopolymerization initiator includes anthracene and/or anthracene derivatives. The photosensitive resin composition as claimed in item 6, wherein the above-mentioned (C) photopolymerization initiator is a compound represented by general formula (IV):

In the formula, R ^{independently} represents a hydrogen atom, a substituted or unsubstituted alkyl group with 1 to 40 carbons, a substituted or unsubstituted alicyclic group with 3 to 20 carbons, a substituted or unsubstituted alicyclic group with 2 to 4 carbons Alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl or N(R') ₂ groups, two or more R ¹ can be bonded to each other to form a ring structure, the The ring structure may contain heteroatoms; X independently represents a single bond, oxygen atom, sulfur atom, carbonyl, sulfonyl, -N(R')-, -CO-O-, -CO-S-, -SO ₂ -O-group, -SO ₂ -S-group, -SO ₂ -N(R')-group, -O-CO-group, -S-CO-group, -O-SO ₂ -group or -S-SO ₂ -group, where X is a single bond and R ¹ is a combination of hydrogen atoms (ie unsubstituted anthracene); the above R' represents a hydrogen atom, a substituted or unsubstituted carbon number of 1 to 40 Substituted alkyl, substituted or unsubstituted alicyclic group with 3 to 20 carbons, alkenyl with 2 to 4 carbons, substituted or unsubstituted aryl with 6 to 40 carbons or In a substituted or unsubstituted heteroaryl group, R' may bond with each other to form a ring structure, and the ring structure may contain heteroatoms; p is an integer of 1-10. The photosensitive resin composition according to any one of claims 1 to 3, wherein the structural units of styrene and/or styrene derivatives in the (A) alkali-soluble polymer are 26% by mass or more. The photosensitive resin composition according to any one of claims 1 to 3, wherein the above-mentioned (A) alkali-soluble polymer comprises a structural unit of benzyl (meth)acrylate as a monomer component. The photosensitive resin composition according to any one of claims 1 to 3, wherein the glass transition temperature of the above-mentioned (A) alkali-soluble polymer is 120° C. or lower. The photosensitive resin composition according to any one of claims 1 to 3, wherein the above-mentioned (B) compound having an ethylenically unsaturated double bond contains 5% by mass or more of the solid content of the entire photosensitive resin composition The amount is a compound with more than 3 methacrylate groups in the molecule. The photosensitive resin composition according to any one of Claims 1 to 3, which is used to obtain an exposed resin cured product by using the first laser light with a central wavelength of less than 390 nm and the second laser light with a central wavelength of 390 nm or more . The photosensitive resin composition according to claim 12, wherein the central wavelength of the first laser light is between 350 nm and 380 nm, and the central wavelength of the second laser light is between 400 nm and 410 nm. The photosensitive resin composition according to any one of claims 1 to 3, which can be patterned by the following steps: an exposing step, which exposes the photosensitive resin composition; a heating step of heating the exposed photosensitive resin composition; and A developing step of developing the heated photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 3, wherein the heating temperature in the heating step is in the range of 30°C to 150°C. The photosensitive resin composition according to any one of claims 1 to 3, wherein the heating step is carried out within 15 minutes after exposure. A method for forming a resist pattern, comprising the steps of: an exposing step, which exposes the photosensitive resin composition according to any one of claims 1 to 16; a heating step of heating the exposed photosensitive resin composition; and A developing step of developing the heated photosensitive resin composition. The method for forming a resist pattern according to claim 17, wherein the heating temperature in the heating step is in the range of 30°C to 150°C. The method for forming a resist pattern according to claim 17 or 18, wherein the heating step is performed within 15 minutes after exposure. The method for forming a resist pattern according to claim 17 or 18, wherein the exposure step is performed by an exposure method using direct drawing of a drawing pattern, or an exposure method in which an image of a mask is projected through a lens. The method for forming a resist pattern according to claim 20, wherein the exposure step is performed by an exposure method using direct drawing of a drawing pattern. The method for forming a resist pattern according to claim 21, wherein the exposure step is performed by exposing with a first laser light with a central wavelength of less than 390 nm and a second laser light with a central wavelength of 390 nm or greater. The method for forming a resist pattern according to claim 22, wherein the center wavelength of the first laser light is not less than 350 nm and not more than 380 nm, and the center wavelength of the second laser light is not less than 400 nm and not more than 410 nm. A method of manufacturing a circuit board, comprising the steps of: A resist pattern forming step, which forms a resist pattern on the substrate by the method according to any one of claims 17 to 23; and A circuit substrate forming step of forming a circuit substrate by etching or plating the substrate having the above-mentioned resist pattern.