WO2020032133A1 - 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, this composition 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 present invention relates to a photosensitive resin composition, a method for forming a resist pattern, and the like.

電子 In electronic devices such as personal computers and mobile phones, printed wiring boards and the like are used to mount components, semiconductors, and the like. As a resist for manufacturing a printed wiring board or the like, conventionally, a photosensitive resin laminate obtained by laminating a photosensitive resin layer on a support film, and further laminating a protective film as necessary on the photosensitive resin layer, A so-called dry film photoresist (hereinafter sometimes referred to as DF) is used. At present, the photosensitive resin layer is generally of an alkali developing type using a weak alkaline aqueous solution as a developing solution.

In order to manufacture a printed wiring board or the like using DF, for example, the following steps are performed. When the DF has a protective film, the protective film is first peeled off. Thereafter, the DF is laminated on a substrate for producing a permanent circuit such as a copper-clad laminate or a flexible substrate using a laminator or the like, and is exposed through a wiring pattern mask film or the like. Next, if necessary, the support film is peeled off, and the photosensitive resin layer of an uncured portion (for example, an unexposed portion in a negative type) is dissolved or dispersed and removed with a developer, and a cured resist pattern (hereinafter, simply referred to as (Sometimes called a resist pattern).

After the formation of the resist pattern, the process of forming a circuit is roughly divided into two methods. The first method is a method in which a substrate surface not covered with a resist pattern (for example, a copper surface of a copper-clad laminate) is removed by etching, and then the resist pattern portion is removed with an alkaline aqueous solution stronger than a developing solution (etching method). It is.
In a second method, after performing a plating treatment on the substrate surface with copper, solder, nickel, tin, or the like, the resist pattern portion is removed in the same manner as the first method, and further, a substrate surface (for example, This is a method (plating method) for etching the copper surface of the copper-clad laminate. For the etching, cupric chloride, ferric chloride, a copper-ammonia complex solution or the like is used.

In recent years, with the miniaturization and weight reduction of electronic devices, the fineness and density of printed wiring boards have been advanced, and high-performance DFs that provide high resolution and high adhesion in the above manufacturing process have been developed. It has been demanded. To realize such high resolution, Patent Document 1 describes a photosensitive resin composition in which the resolution is enhanced by a specific thermoplastic resin, a monomer, and a photopolymerizable initiator. .

JP 2010-249888 A

(4) After the exposure step, a heating step may be performed on the photosensitive resin layer, followed by development, if necessary. By performing this heating step, it is possible to further improve resolution and adhesion (that is, adhesion between the resist pattern and the substrate). However, even if a post-exposure baking step is added, the conventional photosensitive resin composition still has insufficient adhesion and resolution, or does not provide good adhesion when the time from exposure to development is long. There was a problem that.

The present invention has been proposed in view of such conventional circumstances, and an object of one embodiment of the present invention is to provide sensitivity when heated and developed after exposure, adhesion, line width reproducibility, and It is an object of the present invention to provide a photosensitive resin composition which has good resolution and particularly achieves good adhesion even when the time from exposure to development is long.

The present invention includes the following embodiments.
[1] (A) Alkali-soluble polymer: 10% to 90% by mass;
(B) a compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass;
(C) a photopolymerization initiator: 0.01% by mass to 20% by mass; and (D) a phenolic polymerization inhibitor: 1 ppm to 300 ppm;
A photosensitive resin composition containing
The above photosensitive resin composition, wherein the light transmittance at at least one of 375 nm and 405 nm is 58% to 95%.
[2] The photosensitive resin composition according to the above aspect 1, comprising (D) methoquinone as a phenolic polymerization inhibitor.
[3] The photosensitive resin composition according to the above aspect 1 or 2, further comprising (D) dibutylhydroxytoluene as a phenolic polymerization inhibitor.
[4] The photosensitive resin composition according to the above aspect 3, wherein the content of the dibutylhydroxytoluene is 1 to 200 ppm.
[5] The photosensitive resin composition according to the above aspect 3, wherein the content of the dibutylhydroxytoluene is from 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 mode according to any one of the above aspects 1 to 6, wherein the photopolymerization initiator (C) includes at least one selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof. Photosensitive resin composition.
[8] The photosensitive resin composition according to the above aspect 7, wherein the photopolymerization initiator (C) contains anthracene and / or an anthracene derivative.
[9] The photosensitive resin composition according to any one of Aspects 1 to 8, wherein the constituent unit of (A) styrene and / or a styrene derivative in the alkali-soluble polymer is 26% by mass or more.
[10] The photosensitive resin composition according to any one of Aspects 1 to 9, wherein (A) the alkali-soluble polymer contains a benzyl (meth) acrylate structural unit as a monomer component.
[11] The photosensitive resin composition according to any one of Aspects 1 to 10, wherein the alkali-soluble polymer (A) has a glass transition temperature of 120 ° C. or lower.
[12] The compound (B) having an ethylenically unsaturated double bond is a compound having three or more methacrylate groups in a molecule in an amount of 5% by mass or more based on the solid content of the entire photosensitive resin composition. 12. The photosensitive resin composition according to any one of the above aspects 1 to 11, comprising:
[13] The photosensitive resin according to any one of the above aspects 1 to 12, for obtaining an exposed resin cured product using a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more. Composition.
[14] The photosensitive material according to any one of Aspects 1 to 13, wherein the center wavelength of the first laser light is 350 nm or more and 380 nm or less, and the center wavelength of the second laser light is 400 nm or more and 410 nm or less. Resin composition.
[15] The following steps:
An exposure step of exposing the photosensitive resin composition;
A heating step of heating the exposed photosensitive resin composition; and a developing step of developing the heated photosensitive resin composition;
15. The photosensitive resin composition according to any one of the above aspects 1 to 14, which can be formed into a pattern by the following.
[16] The photosensitive resin composition according to any of the above aspects 1 to 15, wherein the heating temperature in the heating step is in a range of 30 ° C to 150 ° C.
[17] The photosensitive resin composition according to any one of aspects 1 to 16, wherein the heating step is performed within 15 minutes after exposure.
[18] The following steps:
An exposing step of exposing the photosensitive resin composition according to 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;
A method for forming a resist pattern, comprising:
[19] The method for forming a resist pattern according to the above aspect 18, wherein a heating temperature in the heating step is in a range of 30 ° C. to 150 ° C.
[20] The method for forming a resist pattern according to the above aspect 18 or 19, wherein the heating step is performed within 15 minutes after exposure.
[21] The method of forming a resist pattern according to any of aspects 18 to 20, wherein the exposing step is performed by an exposing method by direct drawing of a drawing pattern or an exposing method of projecting an image of a photomask through a lens.
[22] The method for forming a resist pattern according to the above aspect 21, wherein the exposure step is performed by an exposure method based on direct writing of a writing pattern.
[23] The method of forming a resist pattern according to aspect 22, wherein the exposing step is performed by a method of exposing with a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more.
[24] The method of forming a resist pattern according to the above aspect 23, wherein a center wavelength of the first laser light is 350 nm or more and 380 nm or less, and a center wavelength of the second laser light is 400 nm or more and 410 nm or less.
[25] A resist pattern forming step of forming a resist pattern on a substrate by the method according to any of aspects 18 to 24; and etching or plating of the substrate having the resist pattern to form a circuit board. A circuit board forming step of forming a circuit board.

According to the present invention, the sensitivity, adhesion, line width reproducibility, and resolution when heated and developed after exposure are good, and even when the time from exposure to development is long, good adhesion is obtained. The photosensitive resin composition which realizes the property can be provided.

Hereinafter, exemplary embodiments for implementing the present invention (hereinafter, abbreviated as “embodiments”) will be described in detail. The present invention is not limited to the embodiments described below, and can be implemented with various modifications within the scope of the gist. In addition, various measured values in the present specification are based on the method described in the section of [Examples] of the present disclosure or a method understood by those skilled in the art to be equivalent thereto unless otherwise specified. Measured.

<Photosensitive resin composition>
In this embodiment, the photosensitive resin composition comprises (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a phenol-based polymerization inhibitor. Agent. In the present embodiment, the photosensitive resin composition can be applied to an arbitrary support to form a photosensitive resin layer. The above-described composition of the photosensitive resin composition of the present embodiment is useful for obtaining a cured resin by heating and developing after exposure.

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

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

(4) The photosensitive resin composition preferably contains (A) a copolymer having an aromatic group as the alkali-soluble polymer, from the viewpoints of high resolution of the resist pattern and sushi shape. It is particularly preferable that the photosensitive resin composition contains (A) a copolymer having an aromatic group in a side chain as the alkali-soluble polymer. Examples of such an aromatic group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The proportion of the copolymer having an aromatic group in the component (A) is preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass or more. It is preferably at least 80% by mass. 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 even more preferably 85% by mass.

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

Examples of the comonomer having an aromatic group include styrene and polymerizable styrene derivatives (eg, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). And a monomer having an aralkyl group. Among them, styrene and styrene derivatives are more preferred.

(A) The ratio of the total of the constituent units of styrene and / or styrene derivative in the entire alkali-soluble polymer can significantly improve the adhesiveness when heated and developed after exposure, and particularly from exposure to exposure. From the viewpoint of obtaining good adhesion even when the time until development is long, preferably 15% by mass or more, more preferably 25% by mass or more, more preferably 26% by mass or more, and more preferably 30% by mass or more. % By mass, more preferably 35% by mass or more, more preferably 40% by mass or more. Since the styrene skeleton is hydrophobic, the swelling property with respect to a developer can be suppressed, and good adhesion can be exhibited. However, when the content of the styrene skeleton is large, the mobility of the polymer tends to be low and the reactivity tends to be low, whereby the adhesion tends to be low. Further, as the time from exposure to development becomes longer, radicals in the system are deactivated, and the effect of improving the adhesion by heating after exposure is reduced. In the present invention, by heating after exposure and then developing, even in a system having a high styrene skeleton content, the mobility of the polymer is improved by heating, and the hydrophobicity of the styrene skeleton and the carbon-carbon double bond It is considered that reactivity can be highly compatible, and as a result, good adhesion can be realized. It is also believed that good adhesion can be obtained even when the time from exposure to development becomes longer. (A) The total ratio of the constituent units of styrene and / or styrene derivative in the whole alkali-soluble polymer is preferably 90% by mass or less, from the viewpoint of favorably obtaining the advantage of the presence of other constituent units. Preferably it is 80 mass% or less, more preferably 70 mass% or less.

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

Examples of the comonomer having a benzyl group include (meth) acrylates having a benzyl group, such as benzyl (meth) acrylate and chlorobenzyl (meth) acrylate; vinyl monomers having a benzyl group, such as vinyl benzyl chloride and vinyl benzyl alcohol Is mentioned.

(A) The alkali-soluble polymer can significantly improve the adhesion when heated and developed after exposure, and achieves good adhesion even when the time from exposure to development is prolonged. From the viewpoint, it is preferable to include 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 5 to 85% by mass, more preferably 10 to 80% by mass, more preferably 15 to 60% by mass, and more preferably Is 20 to 40% by mass, more preferably 20 to 30% by mass. From the same viewpoint, it is preferable that the alkali-soluble polymer (A) has both a structural unit of styrene and / or a styrene derivative and a structural unit of benzyl (meth) acrylate.

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

The copolymer having an aromatic group (preferably a benzyl group) in the side chain includes (i) a monomer having an aromatic group, and (ii) at least one kind of a first monomer described below and / or a second monomer described below. Is preferably obtained by polymerizing at least one of the above.

The alkali-soluble polymer (A) other than the copolymer having an aromatic group in the side chain is preferably obtained by polymerizing at least one kind of a first monomer described later, and is preferably obtained by polymerizing at least one of the first monomers described later. More preferably, it is obtained by copolymerizing the species with at least one of the second monomers described below.

The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is preferred.
In this specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, “(meth) acryloyl group” means acryloyl group or methacryloyl group, and “(meth) acrylate "" Means "acrylate" or "methacrylate".

The copolymerization ratio of the first monomer is preferably from 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 developing good developability and controlling the edge fusing property. The copolymerization ratio is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 30% by mass or less, from the viewpoints of high resolution and swelling shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern. It is at most 25% by mass, particularly preferably at most 22% by mass, most preferably at most 20% by mass.

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

(A) The alkali-soluble polymer can be prepared by polymerizing one or more monomers described above by a known polymerization method, preferably by addition polymerization, more preferably by radical polymerization.
It is preferable that the monomer contains a monomer having an aralkyl group and / or styrene from the viewpoints of chemical resistance, adhesion, high resolution, and swell shape of the resist pattern. (A) As the alkali-soluble polymer, a copolymer composed of methacrylic acid, benzyl methacrylate and styrene, a copolymer composed of methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, and the like are particularly preferable.

(A) The I / O value of the alkali-soluble polymer is preferably 0.600 or less. The I / O value represents a ratio of (inorganic value) / (organic value), and is a value for evaluating the polarity of various organic compounds based on an organic conceptual diagram. A parameter is assigned to each of the functional groups in the compound. This is one of the functional group contribution methods to be set. Regarding the I / O value, for example, Non-Patent Documents (Organic Conceptual Diagram (by Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Paragraphs 1 to 16 (1954); Vol. 11, No. 10, pp. 719-725 (1957); Fragrance Journal, No. 34, No. 97-111 (1979); Fragrance Journal, No. 50, No. 79-82 (1981) ); And the like. The concept of the I / O value divides the properties of the compound into an organic group representing a covalent bond and an inorganic group representing an ionic bond, and all organic compounds are named as an organic axis and an inorganic axis, respectively. It is shown as a point on the coordinates with respect to the orthogonal axis. The I / O value closer to 0 indicates a non-polar (ie, hydrophobic or organic) organic compound, and a larger I / O value indicates a more polar (ie, hydrophilic or inorganic) compound. Large) organic compound.

(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 heated and developed after exposure. Hereinafter, more preferably 0.520 or less, particularly preferably 0.490 or less, from the viewpoint of resolution and peelability when heated and developed after exposure, preferably 0.300 or more, more preferably Preferably it is 0.400 or more, more preferably 0.450 or more.

(A) The glass transition temperature of the alkali-soluble polymer is a value determined by the Fox equation ((A) When the alkali-soluble polymer contains a plurality of types of polymers, the glass transition temperature Tg of the entire mixture thereof, that is, The weight average value (Tg _total ) of the glass transition temperature is preferably 130 ° C. or lower, and more preferably 120 ° C. or lower and 110 ° C. or lower, from the viewpoints of chemical resistance, adhesion, high resolution, and swelling shape of the resist pattern. , 100 ° C or less, 95 ° C or less, 90 ° C or less, or 80 ° C or less. (A) The lower limit of the glass transition temperature (Tg) of the alkali-soluble polymer is not limited, but is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, and still more preferably 60 ° C., from the viewpoint of controlling the edge fusing property. That is all. The glass transition temperature of (A) a homopolymer composed of the same monomer as one or more of the monomers constituting the alkali-soluble polymer is disclosed in Non-patent Document (Brandrup, J. Imergutt, EH Edit. "Polymer handbook, Third edition, John Wiley & sons, 1989, p. 209 Chapter VI" Glass transition temperatures of polymers ").

(A) The acid equivalent of the alkali-soluble polymer (if the component (A) contains a plurality of copolymers, the acid equivalent of the entire mixture) is determined by the development resistance of the photosensitive resin layer and the resolution of the resist pattern. It is preferably 100 or more from the viewpoints of imageability and adhesion, and preferably 600 or less from the viewpoints of developability and peelability of the photosensitive resin layer. (A) The acid equivalent of the alkali-soluble polymer is more preferably from 200 to 500, further preferably from 250 to 450.

(A) The weight average molecular weight of the alkali-soluble polymer (when the component (A) contains a plurality of copolymers, the weight average molecular weight of the entire mixture) is preferably 5,000 to 500,000. . (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 uniform and obtaining resistance to a developing solution. It is preferably 500,000 or less from the viewpoints of maintaining the resist pattern, the high resolution of the resist pattern and the lithography shape, and further, the chemical resistance of the resist pattern. (A) The weight average molecular weight of the alkali-soluble polymer is more preferably 10,000 to 200,000, further preferably 20,000 to 100,000, and particularly preferably 30,000 to 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, and even 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), 10 mass % To 90% by mass, preferably 20% to 80% by mass, more preferably 40% to 60% by mass. (A) The content of the alkali-soluble polymer is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and the resist pattern formed by light exposure has a performance as a resist material. It is preferably 90% by mass or less, and more preferably 80% by mass or less, from the viewpoint of exerting the effect sufficiently, the high resolution of the resist pattern and the swelling shape of the resist pattern, and further from the viewpoint of the chemical resistance of the resist pattern. Is more preferably 70% by mass or less, further preferably 60% by mass or less.

(B) Compound having an ethylenically unsaturated bond (B) The compound having an ethylenically unsaturated bond is a compound having a polymerizable property by having an ethylenically unsaturated bond (that is, a double bond) in its structure. . The ethylenically unsaturated bond is more preferably derived from a methacryloyl group. From the viewpoints of adhesion and suppression of developer foamability, the compound (B) having an ethylenically unsaturated bond preferably has an alkylene oxide structure having 3 or more carbon atoms. The alkylene oxide structure preferably has 3 to 6 carbon atoms, and more preferably 3 to 4 carbon atoms.

Examples of the (B) compound having one (meth) acryloyl group as an ethylenically unsaturated bond include, for example, a compound in which (meth) acrylic acid is added to one end of a polyalkylene oxide or one of a polyalkylene oxide (Meth) acrylic acid is added to the terminal of the compound, and the other terminal is alkyl-etherified or allyl-etherified, or a phthalic acid-based compound, which is preferable from the viewpoint of peelability and flexibility of the cured film.

Examples of such a compound include phenoxyhexaethylene glycol mono (meth) acrylate, which is a (meth) acrylate of a compound in which polyethylene glycol is added to a phenyl group, polypropylene glycol to which an average of 2 mol of propylene oxide is added, Mole of polyethylene glycol to which ethylene oxide has been added, and 4-normal-nonylphenoxyheptaethylene glycol dipropylene glycol (meth) acrylate which is a (meth) acrylate of a compound having nonylphenol added thereto, and polypropylene having an average of 1 mole of propylene oxide added. (Meth) acrylate, which is a compound obtained by adding glycol and polyethylene glycol having an average of 5 moles of ethylene oxide added to nonylphenol. Normal nonyl phenoxy pentaethylene glycol monopropylene glycol (meth) acrylate, 4-normal nonyl phenoxy octa ethylene glycol (meth) acrylate which is an acrylate of a compound obtained by adding polyethylene glycol having an average of 8 moles of ethylene oxide to nonyl phenol (eg, Toa) M-114, manufactured by Synthetic Co., Ltd.).
Further, when γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-о-phthalate is contained, it is preferable from the viewpoints of sensitivity, resolution and adhesion in addition to the above viewpoints.

Examples of the compound having two (meth) acryloyl groups in the molecule include a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain, or an alkylene in which an ethylene oxide chain and a propylene oxide chain are bonded randomly or in a block. Compounds having (meth) acryloyl groups at both ends of the oxide chain can be exemplified.

Examples of such a compound include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, and octaethylene glycol di ( Polyethylene glycol (meth) acrylates such as (meth) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and compounds having (meth) acryloyl groups at both ends of a 12-mol ethylene oxide chain And polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and the like. As the polyalkylene oxide di (meth) acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound, for example, an average of 3 mol of ethylene oxide is further added to both ends of polypropylene glycol having an average of 12 mol of propylene oxide. Dimethacrylate of glycol, and dimethacrylate of glycol in which an average of 15 moles of ethylene oxide is further added to both ends of polypropylene glycol having an average of 18 moles of propylene oxide added, FA-023M, FA-024M, FA-027M (product name) And Hitachi Chemical Co., Ltd.). These are preferred from the viewpoint of flexibility, resolution, adhesion and the like.

｛式中、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子又はメチル基を表し、ＡはＣ_２Ｈ_４であり、ＢはＣ_３Ｈ_６であり、ｎ１及びｎ３は各々独立に０～３９の整数であり、かつｎ１＋ｎ３は０～４０の整数であり、ｎ２及びｎ４は各々独立に０～２９の整数であり、かつｎ２＋ｎ４は０～３０の整数であり、－（Ａ－Ｏ）－及び－（Ｂ－Ｏ）－の繰り返し単位の配列は、ランダムであってもブロックであってもよい。そして、ブロックの場合、－（Ａ－Ｏ）－と－（Ｂ－Ｏ）－とのいずれがビスフェニル基側でもよい。｝で表される化合物を使用することができる。
　例えば、ビスフェノ－ルＡの両端にそれぞれ平均５モルずつのエチレンオキサイドを付加したポリエチレングリコ－ルのジメタクリレ－ト、ビスフェノ－ルＡの両端にそれぞれ平均２モルずつのエチレンオキサイドを付加したポリエチレングリコ－ルのジメタクリレ－ト、ビスフェノ－ルＡの両端にそれぞれ平均１モルずつのエチレンオキサイドを付加したポリエチレングリコ－ルのジメタクリレ－トが、解像性、密着性の点で好ましい。
　また、上記一般式（Ｉ）中の芳香環が、ヘテロ原子及び／又は置換基を有する化合物を用いてもよい。 As another example of a compound having two (meth) acryloyl groups in a molecule, a compound having (meth) acryloyl groups at both terminals by modifying bisphenol A with an alkylene oxide has improved resolution and adhesion. It is preferable from the viewpoint of.
Specifically, the following general formula (I):

In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , and n1 and n3 each independently represent 0 to An integer of 39, n1 + n3 is an integer of 0 to 40, n2 and n4 are each independently an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30,-(A-0)- And the sequence of-(BO)-repeating units may be random or block. In the case of a block, either-(A-0)-or-(BO)-may be on the bisphenyl group side. Compounds represented by｝ can be used.
For example, dimethacrylate of polyethylene glycol having an average of 5 moles of ethylene oxide added to both ends of bisphenol A, and polyethylene glycol having an average of 2 moles of ethylene oxide added to both ends of bisphenol A Polymethacrylate dimethacrylate in which an average of 1 mole of ethylene oxide is added to both ends of dimethacrylate and bisphenol A, respectively, is preferred in terms of resolution and adhesion.
Further, a compound in which the aromatic ring in the general formula (I) has a hetero atom and / or a substituent may be used.

Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group. , Amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group A hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, An alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, 2 to 10 carbon atoms N- alkylcarbamoyl group or a group containing a heterocyclic ring, or an aryl group substituted by these substituents. These substituents may form a condensed ring, or a hydrogen atom in these substituents may be substituted with a hetero atom such as a halogen atom. When the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

(B) As a compound having an ethylenically unsaturated double bond, a (meth) acrylate compound having three or more ethylenically unsaturated double bonds (that is, trifunctional or more) may be contained after heating after exposure. Adhesion at the time of development can be remarkably improved, and it is particularly preferable from the viewpoint that good adhesion can be obtained even when the time from exposure to development becomes long. From the same viewpoint, it is more preferable to include a (meth) acrylate compound having four or more ethylenically unsaturated double bonds, and to include a (meth) acrylate compound having five or more ethylenically unsaturated double bonds. More preferably, it is particularly preferable to include a (meth) acrylate compound having 6 or more ethylenically unsaturated double bonds. From the same viewpoint, these are preferably methacrylate compounds. Compounds having 3 or more, 4 or more, 5 or more, and 6 or more ethylenically unsaturated double bonds are considered to have an effect of increasing the crosslink density at the time of polymerization by exposure, but the number of functional groups is In many cases, a desired crosslink density cannot be obtained due to steric hindrance due to the large number. In the present invention, a compound having three or more ethylenically unsaturated double bonds is preferable, a compound having four or more ethylenically unsaturated double bonds is more preferable, and a compound having five or more ethylenically unsaturated double bonds is more preferable. Compounds having at least six ethylenically unsaturated double bonds, particularly preferably a compound having at least six ethylenically unsaturated double bonds, and performing heat treatment after exposure to improve the mobility in the system, so that steric hindrance may occur even if the number of functional groups is large. It has been found that the influence can be reduced and high adhesion can be obtained. Preferably a compound having three or more ethylenically unsaturated double bonds, more preferably a compound having four or more ethylenically unsaturated double bonds, even more preferably a compound having five or more ethylenically unsaturated double bonds, Particularly preferably, the content of the compound having 6 or more ethylenically unsaturated double bonds is preferably 3% by mass or more, more preferably 5% by mass or more, based on the solid content of the photosensitive resin composition. It is more preferably at least 10 mass%, particularly preferably at least 10 mass%. In addition, the upper limit of the content is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and further preferably 15% by mass or less, from the viewpoint of exhibiting the effect of the heat treatment after exposure. Is particularly preferred.

(B1) Examples of the (meth) acrylate compound having three or more ethylenically unsaturated bonds include:
Tri (meth) acrylates, such as ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylolpropane tri (meth) acrylate (eg, flexible, As preferable examples from the viewpoint of adhesion and bleed-out suppression, tri (meth) acrylate obtained by adding an average of 21 mol of ethylene oxide to trimethylolpropane, and trimethyl acrylate obtained by adding an average of 30 mol of ethylene oxide to trimethylolpropane (Meth) acrylate) and the like;
Tetra (meth) acrylate, for example, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and the like;
Penta (meth) acrylate, such as dipentaerythritol penta (meth) acrylate;
Hexa (meth) acrylate, for example, dipentaerythritol hexa (meth) acrylate and the like.
Among these, tetra, penta or hexa (meth) acrylate is preferred.

(B1) The (meth) acrylate compound having three or more ethylenically unsaturated bonds preferably has a weight average molecular weight of 500 or more, more preferably 700 or more, and still more preferably 900 or more, from the viewpoint of suppressing bleed-out. .

ペ ン タ As the tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate is preferable. As pentaerythritol tetra (meth) acrylate, tetra (meth) acrylate in which a total of 1 to 40 moles of alkylene oxide is added to four terminals of pentaerythritol is preferable.

｛式中、Ｒ₃～Ｒ₆は、それぞれ独立に、水素原子又はメチル基を表し、Ｘは、炭素数２～６のアルキレン基を表し、ｍ₁、ｍ₂、ｍ₃及びｍ₄は、それぞれ独立に、０～４０の整数であり、ｍ₁＋ｍ₂＋ｍ₃＋ｍ₄は、１～４０であり、そしてｍ₁＋ｍ₂＋ｍ₃＋ｍ₄が２以上である場合には、複数のＸは、互いに同一であるか、又は異なっていてよい｝で表されるテトラ（メタ）アクリレート化合物であることがより好ましい。 Tetra (meth) acrylate has the following general formula (II):

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

Without wishing to be bound by theory, the tetramethacrylate compound represented by the general formula (II) can form an H ₂ CＲCH—CO—O— moiety by having groups R ₃ to R _6. It is considered that the hydrolyzability in an alkaline solution is suppressed as compared with the tetraacrylate. The use of the photosensitive resin composition containing the tetramethacrylate compound represented by the general formula (II) can significantly improve the adhesion when heated and developed after exposure, and particularly from exposure to development. This is preferable from the viewpoint of realizing good adhesion even when the time is long.

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.

In the general formula (II), X is preferably —CH ₂ —CH ₂ — from the viewpoint of obtaining desired resolution, swell shape, and remaining film ratio of the resist pattern.

In the general formula (II), m ₁ , m ₂ , m ₃ and m ₄ are each independently an integer of 1 to 20 from the viewpoint of obtaining desired resolution, swell shape and residual film ratio of the resist pattern. And more preferably an integer of 2 to 10. Further, in the general formula (II), m ₁ + m ₂ + m ₃ + m ₄ is preferably from 1 to 36 or from 4 to 36.

Examples of the compound represented by the general formula (II) include pentaerythritol (poly) alkoxytetramethacrylate and the like. Further, in the present disclosure, “pentaerythritol (poly) alkoxytetramethacrylate” refers to “pentaerythritol alkoxytetramethacrylate” and m ₁ + m _{2 where} m ₁ + m ₂ + m ₃ + m ₄ = 1 in the general formula (II). + M ₃ + m ₄ = 2 to 40, including both “pentaerythritol polyalkoxytetramethacrylate”. Examples of the compound represented by the general formula (II) include compounds listed in JP-A-2013-156369, for example, pentaerythritol (poly) alkoxytetramethacrylate and the like.

The hexa (meth) acrylate compound includes hexa (meth) acrylate in which 1 to 24 moles of ethylene oxide is added to 6 terminals of dipentaerythritol, and 1 to 10 moles of total in 6 terminals of dipentaerythritol. Hexa (meth) acrylate to which ε-caprolactone is added is preferred.

From the viewpoint of realizing good adhesion even when the time from exposure to development can be significantly improved, it is possible to significantly improve the adhesion when heated and then developed after exposure. It is particularly preferable that the conductive resin composition contains, as the compound (B) having an ethylenically unsaturated bond, a (meth) acrylate compound having four or more ethylenically unsaturated bonds and having an alkylene oxide chain. In this case, the ethylenically unsaturated bond is more preferably derived from a methacryloyl group, and the alkylene oxide chain is more preferably an ethylene oxide chain.

In the present embodiment, it is possible to significantly improve the adhesion when heated and then developed after exposure, and from the viewpoint of realizing good adhesion even when the time from exposure to development is prolonged, The conductive resin composition preferably contains (B) a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton as a compound having an ethylenically unsaturated bond. Examples of the alkylene oxide chain include an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, a pentylene oxide chain, a hexylene oxide chain, and the like. When the photosensitive resin composition contains a plurality of alkylene oxide chains, they may be the same or different. In view of the above, as the alkylene oxide chain, an ethylene oxide chain, a propylene oxide chain, and a butylene oxide chain are more preferable, an ethylene oxide chain and a propylene oxide chain are more preferable, and an ethylene oxide chain is particularly preferable.

By using (A) an alkali-soluble polymer and a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton in a photosensitive resin composition, the chemical resistance, adhesion and resolution of a resist pattern are obtained. Gender balance tends to be maintained.

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

Examples of the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton include, for example, hexapentadierythritol to which alkylene oxide is added to an average of 4 to 30 mol, an average of 6 to 24 mol, or an average of 10 to 14 mol. (Meth) acrylates.

｛式中、Ｒは、それぞれ独立に、水素原子又はメチル基を表し、かつｎは、０～３０の整数であり、かつ全てのｎの合計値が１以上である｝で表される化合物が好ましい。一般式（ＩＩＩ）において、全てのｎの平均値が４以上であるか、又はｎがそれぞれ１以上であることが好ましい。Ｒとしてはメチル基が好ましい。 Specifically, as a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, adhesion after heating and development after exposure can be significantly improved, and particularly, the time from exposure to development can be improved. From the viewpoint of realizing good adhesion even when the length becomes longer, the following general formula (III):

Wherein R is each independently 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. preferable. In the general formula (III), it is preferable that the average value of all n is 4 or more, or that n is 1 or more. R is preferably a methyl group.

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

The content of (b1) a (meth) acrylate compound having three or more ethylenically unsaturated bonds (that is, a compound having three or more (meth) acrylate groups) is based on the total solid content of the photosensitive resin composition. , 0 mass% and 50 mass% or less. When the content exceeds 0% by mass, the adhesion after heating and development after exposure is significantly improved, and good adhesion is achieved even when the time from exposure to development is prolonged. When the content is 50% by mass or less, the flexibility of the cured resist is improved, and the peeling time tends to be shortened. This content is more preferably 2% by mass or more and 40% by mass or less, and still more preferably 4% by mass or more and 35% by mass or less. In a more preferred embodiment, (B) the compound having an ethylenically unsaturated double bond is a compound having three or more methacrylate groups in the molecule, preferably 5% by mass based on the solid content of the entire photosensitive resin composition. Above, more preferably 9% by mass or more, still more preferably 13% by mass or more, particularly preferably 20% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less. In the amount of

From the viewpoints of adhesion and suppression of foaming property of the developer, the photosensitive resin composition contains (B2) a butylene oxide chain or a propylene oxide chain as one compound having an ethylenically unsaturated bond, It is preferable to include a compound having two (meth) acryloyl groups.
(B2) The compound having a butylene oxide chain or a propylene oxide chain and one or two (meth) acryloyl groups is preferably 500 or more, more preferably 700 or more, and still more preferably, from the viewpoint of suppressing bleed-out. Has a molecular weight of 1000 or more.

(B2) As the compound having a butylene oxide chain or a propylene oxide chain and one or two (meth) acryloyl groups, polypropylene glycol (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol ( (Meth) acrylate, polytetramethylene glycol di (meth) acrylate, and the like. (B2) The compound having a butylene oxide chain or a propylene oxide chain and one or two (meth) acryloyl groups may contain an ethylene oxide chain in addition to the butylene oxide chain or the propylene oxide chain.

Specifically, the compound (b2) having a butylene oxide chain or a propylene oxide chain and one or two (meth) acryloyl groups is preferably 1 to 20, more preferably 4 to 15, and Preferred are (meth) acrylates or di (meth) acrylates having 6 to 12 C ₄ H ₈ O or C ₃ H ₆ O.

The content of the compound having (b2) a butylene oxide chain or a propylene oxide chain and one or two (meth) acryloyl groups is more than 0% by mass based on the total solid content of the photosensitive resin composition. And 20% by mass or less.

In the present embodiment, in order to suppress the bleed-out of the components of the dry film resist and to improve the storage stability, (B) preferably 70 mass% based on the total solid content of the compound having an ethylenically unsaturated bond. %, More preferably 80% by weight or more, still more preferably 90% by weight or more, particularly preferably 100% by weight, is a compound having a weight average molecular weight of 500 or more. In light of suppression of bleed-out and chemical resistance of the resist pattern, the weight-average molecular weight of the compound (B) having an ethylenically unsaturated bond is preferably 760 or more, more preferably 800 or more, and still more preferably 830 or more. Preferably it is 900 or more. The weight average molecular weight of the compound (B) having an ethylenically unsaturated bond can be determined as the molecular weight calculated from the molecular structure of the compound (B) having an ethylenically unsaturated bond. When a plurality of types of (B) compounds having an ethylenically unsaturated bond are present, the weight can be determined by weighting the molecular weight of each compound by the content.

From the viewpoints of chemical resistance, adhesion, high resolution, and semi-shape of the resist pattern, the concentration of the methacryloyl group in the compound (B) having an ethylenically unsaturated bond is preferably 0.20 mol / 100 g or more. , More preferably at least 0.30 mol / 100 g, even more preferably at least 0.35 mol / 100 g. The upper limit of the concentration of the methacryloyl group is not limited as long as the polymerizability and the alkali developability are ensured, but 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 (methacryloyl group concentration / (methacryloyl group concentration + acryloyl group concentration)) in the compound (B) having an ethylenically unsaturated bond is preferably 0.50 or more, more preferably 0 or more. It is at least 0.60, more preferably at least 0.80, particularly preferably at least 0.90, most preferably at least 0.95.

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

割 合 (B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid content of the photosensitive resin composition is preferably 5% by mass to 70% by mass. It is preferable to set this ratio to 5% by mass or more from the viewpoints of sensitivity, resolution and adhesion. This ratio is more preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. On the other hand, it is preferable to set this ratio to 70% by mass or less from the viewpoint of suppressing edge fuse and delay of peeling of the cured resist. It is more preferable that this ratio be 50% by mass or less.

(C) Photopolymerization initiator (C) The photopolymerization initiator is a compound that polymerizes a monomer by light. (C) The photopolymerization initiator can significantly improve the adhesiveness when heated and developed after exposure, and can obtain good adhesiveness even when the time from exposure to development is prolonged. From the viewpoint that can be obtained, preferably contains one or more selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof, more preferably contains anthracene and / or anthracene derivative, more preferably Include anthracene derivatives. In addition, anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof, particularly anthracene and / or anthracene derivative, absorb first active light having a central wavelength of less than 390 nm and second active light having a central wavelength of 390 nm or more. And functions well as a polymerization initiator. Therefore, in one embodiment, the photosensitive resin composition can have sensitivity to the first active light and the second active light, and can 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 the photopolymerization initiator (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and further preferably 0.1% by mass. % To 7% by weight, particularly preferably 0.1% to 6% by weight. (C) The total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining a sufficient sensitivity, and sufficiently transmits light to the bottom of the resist to obtain good high resolution. Is preferably 20% by mass or less from the viewpoint of obtaining

Anthracene and anthracene derivatives can significantly improve the adhesion when heated and developed after exposure, and are particularly advantageous in that they achieve good adhesion even when the time from exposure to development is long. It is. From the same viewpoint, the anthracene derivative is preferably an alkoxy group having 1 to 40 carbon atoms and / or a substituent which may have a substituent at the 9-position and / or 10-position, more preferably the 9,10-position. And an aryl group having 6 to 40 carbon atoms which may have

In one embodiment, the anthracene derivative can significantly improve the adhesiveness when heated and developed after exposure, and particularly achieves good adhesiveness even when the time from exposure to development is long. It is preferable that at least one of the 9-position and the 10-position has an optionally substituted alkoxy group having 1 to 40 carbon atoms, and at least one of the 9-position and the 10-position has a substituent. It is more preferred to have an optionally substituted alkoxy group having 1 to 30 carbon atoms. From the viewpoint of obtaining good adhesion and resolution, it is preferable to have an alkoxy group having 1 to 40 carbon atoms which may have a substituent at the 9 and 10 positions, and to have a substituent at the 9 and 10 positions. It is more preferred to have an optionally substituted alkoxy group having 1 to 30 carbon atoms. The carbon numbers of the 9-position and the 10-position group may be the same or different.

Examples of the alkoxy group which may have a substituent include:
Methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, 2-methylpropoxy, 1-methylpropoxy, n-pentyloxy, isoamyloxy, n- Hexyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tetradecyloxy group, hexadecyloxy group, eicosyloxy group, cyclohexyloxy group, norbornyloxy group, A tricyclodecanyloxy group, a tetracyclododecyloxy group, an adamantyloxy group, a methyladamantyloxy group, an ethyladamantyloxy group, and a butyladamantyloxy group;
A halogen-modified alkoxy group such as a chlorobutoxy group or a chloropropoxy group;
An alkoxy group having a hydroxyl group added thereto, for example, a hydroxybutyloxy group;
An alkoxy group to which a cyano group has been added, for example, a cyanobutoxy group;
An alkoxy group to which an alkylene oxide group has been added, for example, a methoxybutoxy group;
An alkoxy group to which an aryl group has been added, for example, a phenoxybutoxy group,
And the like. Among these, an n-butoxy group is more preferred.

In one embodiment, the anthracene derivative can significantly improve the adhesiveness when heated and developed after exposure, and particularly achieves good adhesiveness even when the time from exposure to development is long. It is preferable that at least one of the 9-position and the 10-position has an optionally substituted aryl group having 6 to 40 carbon atoms, and at least one of the 9-position and the 10-position has a substituent. It is more preferred to have an optionally substituted aryl group having 6 to 30 carbon atoms.

Adhesion when heated and developed after exposure can be significantly improved, and from the viewpoint of realizing good adhesion even when the time from exposure to development is prolonged, from the viewpoint of ninth and tenth, It is preferable to have an aryl group having 6 to 40 carbon atoms which may have a substituent, and to have an aryl group having 6 to 30 carbon atoms which may have a substituent at the 9th and 10th positions. More preferred. The carbon numbers of the 9-position and the 10-position group may be the same or different. Further, the groups at the 9-position and the 10-position may be the same group or different groups. For example, the group at the 9-position is an alkoxy group having 1 to 40 carbon atoms which may have a substituent, and the group at the 10-position is an aryl group having 6 to 40 carbon atoms which may have a substituent. There may be.

Examples of the aryl group having 6 to 40 carbon atoms which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group and an anthracenyl group; an aryl group to which an alkoxy group is added, such as a methoxyphenyl group and an ethoxyphenyl group; An aryl group to which an alkyl group is added, for example, a tolyl group, a xylyl group, a mesityl group, a nonylphenyl group; an aryl group to which a halogen is added, for example, a chlorophenyl group; an aryl group to which a hydroxyl group is added, such as a hydroxyphenyl group. Can be Of these, a phenyl group is more preferred.

　Ｒ¹は、独立に水素原子、炭素数１～４０の置換若しくは非置換のアルキル基、炭素数３～２０の置換若しくは非置換の脂環族基、炭素数２～４のアルケニル基、置換若しくは非置換のアリール基、置換若しくは非置換のヘテロアリール基又はＮ（Ｒ’）₂基を示し、２以上のＲ¹が互いに結合して環状構造を形成してもよく、該環状構造はヘテロ原子を含んでもよい。 The anthracene derivative is preferably represented by the following general formula (IV).

R ¹ is independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, Represents an unsubstituted aryl group, a substituted or unsubstituted heteroaryl group or an N (R ′) ₂ group, and two or more R ¹ may be bonded to each other to form a cyclic structure, wherein the cyclic structure is a heteroatom May be included.

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 , —SO ₂ —S—, —SO ₂ —N (R ′) —, —O—CO—, —S—CO—, —O—SO ₂ — or S—SO ₂ — Show. However, X excludes a single bond and R ¹ excludes a combination of hydrogen atoms (that is, unsubstituted anthracene).

R ′ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, Represents up to 40 substituted or unsubstituted aryl groups or substituted or unsubstituted heteroaryl groups, and R's may be mutually bonded to form a cyclic structure, and the cyclic structure may include a heteroatom .

P is an integer of 1 to 10, preferably 2 to 4.

Specific examples of the substituted or unsubstituted alkyl group having 1 to 40 carbon atoms for R ¹ and R ′ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-pentyl group, -Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-eicosyl group, i -Propyl group, i-butyl group, sec-butyl group and t-butyl group.

Specific examples of the substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms for R ¹ and R ′ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a bridged group having 6 to 20 carbon atoms. And alicyclic hydrocarbon groups (for example, norbornyl group, tricyclodecanyl group, tetracyclododecyl group, adamantyl group, methyladamantyl group, ethyladamantyl group, butyladamantyl group and the like).

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

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

Examples of the substituted or unsubstituted heteroaryl group for R ¹ and R ′ include a group containing one or more hetero atoms such as a sulfur atom, an oxygen atom, and a nitrogen atom in a substituted or unsubstituted aryl group, for example, a pyridyl group. , Imidazolyl group, morpholinyl group, piperidyl group, pyrrolidyl group and the like.

Further, each hydrocarbon group of R ¹ and R ′ may be substituted with a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a hydroxyalkyl group having 1 to 4 carbon atoms (eg, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, A hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, etc., an alkoxyl group having 1 to 4 carbon atoms (eg, a methoxy group, Ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, etc.), cyano group, cyanoalkyl group having 2 to 5 carbon atoms ( For example, a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group, etc.) Alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, etc.), alkoxycarbonylalkoxy group (eg, methoxycarbonylmethoxy group, ethoxycarbonylmethoxy group, t-butoxycarbonylmethoxy group, etc.), halogen atom (Eg, fluorine, chlorine, etc.) and fluoroalkyl groups (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, etc.). It is preferable that each hydrocarbon group of R ¹ and R ′ is substituted by a halogen atom. In particular, the anthracene derivative preferably has an alkoxy group substituted by a halogen atom at the 9-position and / or the 10-position.

Preferred examples of R ¹ and R ′ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl. Groups, n-heptyl group, n-octyl group, cyclopentyl group, cyclohexyl group, camphoroyl group, norbornyl group, p-toluyl group, benzyl group, methylbenzyl group, phenyl group and 1-naphthyl group.

Preferred specific examples of X include a single bond, an oxygen atom, a sulfur atom, a —N (R ′) — group, a —O—CO— group, and an O—SO ₂ — group. Here, when X is —N (R ′) — group, R ′ is hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, cyclopentyl group, cyclohexyl. Groups, camphoroyl groups, norbornyl groups or benzyl groups.

Examples of the compound represented by the general formula (IV) include, for example, 1-methylanthracene, 2-methylanthracene, 2-ethylanthracene, 2-t-butylanthracene, 9-methylanthracene, 9,10-dimethylanthracene, 9-vinylanthracene, 9-phenylanthracene, 9,10-diphenylanthracene, 2-bromo-9,10-diphenylanthracene, 9- (4-bromophenyl) -10-phenylanthracene, 9- (1-naphthyl) anthracene , 9- (2-naphthyl) anthracene, 2-bromo-9,10-bis (2-naphthyl) anthracene, 2,6-dibromo-9,10-bis (2-naphthyl) anthracene, 9,10-diethoxy Anthracene, 9,10-dipropoxyanthracene, 9,10- Butoxyanthracene, 9,10-di (2-ethylhexyloxy) anthracene, 1,2-benzanthracene, anthrobin, 1,4,9,10-tetrahydroxyanthracene, 9-anthracenemethanol, 1-aminoanthracene, 2- Examples include aminoanthracene, 9- (methylaminomethyl) anthracene, 9-acetylanthracene, 9-anthraldehyde, 10-methyl-9-anthaldehyde, 1,8,9-triacetoxyanthracene, and the like. Among these, 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di (2 -Ethylhexyloxy) anthracene and 9,10-bis- (3-chloropropoxy) anthracene are preferred. Particularly, the adhesion after heating and development after exposure can be remarkably improved, and especially the time from exposure to development. From the viewpoint of realizing good adhesion even when the length of the resin becomes longer, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene, 9,10-bis- (3-chloro- Propoxy) anthracene is more preferred, and 9,10-dibutoxyanthracene Beauty 9,10-diphenyl anthracene, 9,10-bis - (3-chloropropoxy) anthracene is particularly preferable. The compound represented by the general formula (IV) may be used alone or in combination of two or more.

From the viewpoint that adhesion after heating and development after exposure can be significantly improved, and in particular from the viewpoint that good adhesion can be obtained even when the time from exposure to development is long, The polymerization initiator preferably includes (1) 9,10-diphenylanthracene; (2) includes 9,10-dialkoxyanthracene; (3) includes an anthracene derivative having a halogen atom; (4) 9, (5) including a compound wherein the 9- and / or 10-position alkoxy group of 9,10-dialkoxyanthracene is modified with one or more halogen atoms; And / or (6) a compound having a halogen atom directly bonded to the anthracene skeleton.

The compound represented by the general formula (IV) can remarkably improve the adhesiveness when heated and developed after exposure, and has good adhesiveness even when the time from exposure to development is prolonged. And is used for two-wavelength exposure using a first active light having a central wavelength of less than 390 nm and a second active light having a central wavelength of 390 nm or more. It is also advantageous in that a photosensitive resin composition exhibiting excellent sensitivity, adhesion and resolution can be provided.

に お い て In one embodiment, it is preferable that the photopolymerization initiator (C) includes an anthracene derivative having a halogen atom. A preferred example of the anthracene derivative having a halogen atom is a halogen-substituted 9,10-dialkoxyanthracene. A preferred example of the halogen substituent is a compound in which the 9- and / or 10-position alkoxy group of 9,10-dialkoxyanthracene is modified with one or more halogens. Preferred alkoxy groups include those exemplified above as alkoxy groups having 1 to 40 carbon atoms.

In one embodiment, as the anthracene derivative, a compound having a halogen atom directly bonded to the anthracene skeleton is also preferable. Examples of such anthracene compounds include 9-bromo-10-phenylanthracene, 9-chloro-10-phenylanthracene, 9-bromo-10- (2-naphthyl) anthracene, and 9-bromo-10- (1-naphthyl) Anthracene, 9- (2-biphenylyl) -10-bromoanthracene, 9- (4-biphenylyl) -10-bromoanthracene, 9-bromo-10- (9-phenanthryl) anthracene, 2-bromoanthracene, 9-bromoanthracene , 2-chloroanthracene and 9,10-dibromoanthracene.

The total amount of the anthracene and the anthracene derivative, or in a preferred embodiment, the amount of the compound represented by the general formula (IV) is preferably 0.05 to 5% by mass based on the total solid content of the photosensitive resin composition, It is more preferably in the range of 0.1 to 3% by mass, and particularly preferably in the range of 0.1 to 1.0% by mass.

(4) Pyrazolin and pyrazoline derivatives are preferred from the viewpoints of the peeling properties, sensitivity, resolution, and adhesion of the photosensitive resin layer.

Examples of the pyrazoline derivative include, for example, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazolin, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropyl Phenyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3 (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,6-dimethoxystyryl) -5- (2,6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,5-dimethoxystyryl) -5- (2,5- Dimethoxyphenyl) -pyrazolin, 1-phenyl-3- (2,3-dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,4-dimethoxystyryl) -5 -(2,4-Dimethoxyphenyl) -pyrazoline and the like are preferable from the above viewpoint, and 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) is preferred. Yl) - pyrazoline is more preferable.

Examples of the coumarin derivative include 7-diethylamino-4-methylcoumarin, 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin and the like. Among them, 7-diethylamino-4-methylcoumarin is preferred in terms of sensitivity, resolution, and adhesion.

(C) Further examples of the photopolymerization initiator include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, and dialkylaminobenzoates. , Oxime esters, and acridines (eg, 9-phenylacridine, bisacridinylheptane, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine are sensitive, Preferred), hexaarylbiimidazole, N-arylamino acids or ester compounds thereof (eg, N-phenylglycine is preferred in terms of sensitivity, resolution, and adhesion), and halogen compounds (eg, tribromomethylphenylsulfone) ). These can be used alone or in combination of two or more. In addition, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl -Diphenyl-phosphine oxide, triphenylphosphine oxide and the like may be used.

Examples of aromatic ketones include benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. Can be. These can be used alone or in combination of two or more. Among these, 4,4'-bis (diethylamino) benzophenone is preferable from the viewpoint of adhesion. Further, from the viewpoint of transmittance, the content of the aromatic ketone in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3% by mass. % By mass.

Examples of hexaarylbiimidazole include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl ) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2′-bis- (2-fluorophenyl) -4,4 ′ , 5,5'-Tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4 ', , 5'-Tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -Biimidazole, 2,2'-bis- (2,5-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- ( 2,6-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4-trifluorophenyl) -4 , 4 ', 5,5'-Tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4', 5,5'- Tetrakis- (3-methoxyphenyl -Biimidazole, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'- Bis- (2,4,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,4,6- (Trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4,5-tetrafluorophenyl) -4 4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4', 5,5 ' -Tetrakis- (3-methoxyphenyl) -biimidazo And 2,2′-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole These can be used alone or in combination of two or more. From the viewpoints of sensitivity, resolution and adhesion, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferred.

The content of the hexaarylbisimidazole in the photosensitive resin composition is preferably 0.05% by mass to 8% by mass, more preferably 0% by mass, from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin layer. It is in the range of 0.1 to 7% by mass, more preferably 1 to 6% by 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 disclosure, (D) a phenolic polymerization inhibitor is a compound having one or more phenolic hydroxyl groups. A phenolic polymerization inhibitor has a property of inhibiting a polymerization reaction caused by heat or the like and improving storage stability. The phenolic polymerization inhibitor includes a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, and a substituted or unsubstituted 3 to 20 carbon atoms. It may have one or more substituents selected from the group consisting of an alicyclic group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. In a preferred embodiment, the (D) phenol polymerization inhibitor is a monohydric phenol (that is, a compound having one phenolic hydroxyl group in the molecule). More specific preferred examples of the (D) phenolic polymerization inhibitor include methoquinone, dibutylhydroxytoluene, hydroquinone, and tetrakis (3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionic acid. ) Pentaerythritol, 2,2′-thiodiethylbis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) stearyl propionate, N, N′-hexamethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide), octyl-3,5-di-tert-butyl-4 -Hydroxy-hydrocinnamic acid, 2,4,6-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) mesitile 2,4-bis (dodecylthiomethyl) -6-methylphenol, 2,4-bis (octylthiomethyl) -6-methylphenol, bis (3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) propionic acid) (ethylene bis (oxyethylene)), 1,6-hexanediol bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 1,3,5- Tris ((3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 4- ((4,6-bis (octylthio) -1,3,5-triazin-2-yl) amino) -2,6-di-tert-butylphenol and the like, in particular, methoquinone and dibutyl Hydroxytoluene is preferred from the viewpoint that a difference in the shortest development time with and without heating after exposure hardly occurs.

(D) The amount of the phenolic polymerization inhibitor on a mass basis when the total solid content of the photosensitive resin composition is 100% by mass is from the viewpoint of obtaining a desired polymerization inhibiting effect on the photosensitive resin composition. 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, still more preferably 15 ppm or more, particularly preferably 20 ppm or more, when developed after heating after exposure, particularly when the time from exposure to development is prolonged. From the viewpoint of realizing good adhesion, it is 300 ppm or less, preferably 200 ppm or less, more preferably 150 ppm or less, further preferably 100 ppm or less, further preferably 75 ppm or less, further preferably 50 ppm, particularly preferably 40 ppm or less. is there. The fact that the photosensitive resin composition contains (D) a phenolic polymerization inhibitor but the amount thereof is small means that the polymerization reaction of the photosensitive resin composition at the time of exposure to light in the photosensitive resin composition in the case where heating, then development is performed after exposure. This is advantageous in that both good progress and promotion of the reaction of the polymer (and thus improvement in adhesion) due to good mobility improvement effect by heating the polymer can be achieved. For example, in a system in which a polymer has a bulky molecular structure (for example, a relatively large amount of a styrene skeleton), when heating is performed after exposure intended to improve the adhesiveness, the effect of improving the mobility by heating the polymer is low (therefore, the adhesiveness is low). Although the improvement effect may be low), according to the photosensitive resin composition of the present embodiment, such a bulky polymer is present because the amount of the (D) phenolic polymerization inhibitor is in the above range. Also in this case, the effect of improving adhesion by heating after exposure can be favorably obtained.

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

[Optional component]
The photosensitive resin composition may further contain optional components, if desired, in addition to the components (A) to (D). Optional components include (d) additional polymerization inhibitors other than the (D) phenolic polymerization inhibitor, dyes, coloring substances, plasticizers, antioxidants, stabilizers, and the like. For example, the additives listed in JP-A-2013-156369 may be used.

((D) additional polymerization inhibitor)
Additional polymerization inhibitors include radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles that are not the phenolic polymerization inhibitors.

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

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like can be mentioned.

Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene Carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like can be mentioned.

In one embodiment, the total amount of the additional polymerization inhibitor is preferably from 0.001 to 3% by mass, more preferably from 0.01% by mass to 100% by mass of the total solid content of the photosensitive resin composition. 1% by mass. Making the total amount 0.001% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, setting the total amount to 3% by mass or less is preferable from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye.

(Dyes and coloring substances)
In the present embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of a dye (for example, a leuco dye, a fluoran dye or the like) and a coloring substance, if desired.

Examples of the coloring substance include fuchsin, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, and malachite green (for example, Eizen (registered trademark) MALACHITE @ GREEN manufactured by Hodogaya Chemical Co., Ltd.), Basic Blue 20 and Diamond Green (for example, Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). The content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass when the total solid content of the photosensitive resin composition is 100% by mass. Making the content 0.001% by mass or more is preferable from the viewpoint of improving the handleability of the photosensitive resin composition. On the other hand, setting the content to 1% by mass or less is preferable from the viewpoint of maintaining the storage stability of the photosensitive resin composition.

The photosensitive resin composition is preferable from the viewpoint of visibility because the exposed portion develops a color by containing a dye, and when an inspection machine or the like reads an alignment marker for exposure, an exposed portion and an unexposed portion are used. Is more advantageous because it is easier to recognize. Preferred dyes in this respect include leuco dyes and fluoran dyes.
Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green]. In particular, from the viewpoint of improving contrast, it is preferable to use leuco crystal violet as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass based on the total solid mass of the photosensitive resin composition. Making the content 0.1% by mass or more is preferable from the viewpoint of improving the contrast between the exposed portion and the unexposed portion. This content is more preferably at least 0.2% by mass, particularly preferably at least 0.4% by mass. On the other hand, it is preferable to set the content to 10% by mass or less from the viewpoint of maintaining storage stability. This content is more preferably 5% by mass or less, particularly preferably 2% by mass or less.

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

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

で は In the present embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalic acid esters (for example, diethyl phthalate and the like), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, triacetyl citrate -N-propyl, tri-n-butyl acetylcitrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether and the like. Also, ADEKANOL SDX-1569, ADEKANOL SDX-1570, ADEKANOL SDX-1571, ADEKANOL SDX-479 (all manufactured by Asahi Denka Co., Ltd.), Newpole BP-23P, Newpole BP-3P, Newpole BP-5P, New Pole BPE-20T, New Pole BPE-60, New Pole BPE-100, New Pole BPE-180 (manufactured by Sanyo Chemical Co., Ltd.), Uniall DB-400, Uniall DAB-800, Uniall DA-350F, Uniall DA- Compounds having a bisphenol skeleton such as 400, Uniol DA-700 # (all manufactured by Nippon Oil & Fats Co., Ltd.), BA-P4U glycol and BA-P8 glycol (all manufactured by Nippon Emulsifier Co., Ltd.) are also included.

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 mass of the photosensitive resin composition. It is. Setting the content to 1% by mass or more is preferable from the viewpoints of suppressing a delay in the development time and imparting flexibility to the cured film. On the other hand, setting the content to 50% by mass or less is preferable from the viewpoint of suppressing insufficient curing and cold flow.

(4) If the amount of water in the photosensitive resin composition is large, local plasticization of the photosensitive resin composition is rapidly promoted, and an edge fuse is generated. From the viewpoint of suppressing the edge fuse, the photosensitive resin composition preparation liquid is applied to the support film, and the moisture content in the photosensitive resin composition is 0.7% by mass based on the photosensitive resin composition after drying. The following is preferred. The water content in the photosensitive resin composition is preferably 0.65% or less, more preferably 0.6% or less, preferably 0.55% or less, and 0.5% or less. It is preferably 0.45% or less, more preferably 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, and 0.1% or less. It is preferably at most 25%, more preferably at most 0.2%.

[solvent]
The photosensitive resin composition can be used in the production of a photosensitive resin laminate in the form of a solution prepared by dissolving the photosensitive resin composition in a solvent. Examples of the solvent include ketones and alcohols. The ketones are represented by methyl ethyl ketone (MEK) and acetone. The alcohols are represented by methanol, ethanol, and isopropanol. The solvent is used in an amount such that the viscosity at 25 ° C. of the photosensitive resin composition preparation liquid applied on the support film in the production of the photosensitive resin laminate is 500 mPa · s to 4,000 mPa · s. It is preferably added to the resin composition.

[Light transmittance of photosensitive resin composition]
The light transmittance of at least one of 375 nm and 405 nm of the photosensitive resin composition of the present embodiment is good in sensitivity, adhesion, line width reproducibility, and resolution when heated and developed after exposure. In particular, the content is 58% to 95% from the viewpoint of providing a photosensitive resin composition that achieves good adhesion even when the time from exposure to development is long. 375 nm and 405 nm correspond to typical exposure wavelengths in the photosensitive resin composition of the present embodiment. The light transmittance is preferably 58% or more, more preferably 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. Is 60% or more, more preferably 62% or more, more preferably 64% or more, and still more preferably 65% or more. From the viewpoint of obtaining a good swelling shape by suppressing irregularly reflected light from the substrate surface, 95% Or less, preferably 85% or less, more preferably 80% or less, more preferably 75% or less, and still more preferably 70% or less.

Means for controlling the light transmittance at at least one of ｎｍ375 nm and 405 nm within the above range is not limited thereto, and includes, for example, control of the addition amount of a photopolymerization initiator, a dye, or a coloring substance.

[Photosensitive resin laminate]
The present embodiment also provides a photosensitive resin laminate having a photosensitive resin layer made of the above-described photosensitive resin composition and a support film. As the support film, a transparent support film that transmits light emitted from an exposure light source is preferable. As such a support film, for example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, those stretched as necessary can be used.

か ら The haze of the support film is preferably 5% or less, more preferably 2% or less, still more preferably 1.5% or less, and particularly preferably 1.0% or less, 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 30 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less. The thinner the film is, the more advantageous it is for improving the image formability and economy. However, in order to maintain the strength of the photosensitive resin laminate, a film having a thickness of 10 μm to 30 μm is preferably used. The size of the fine particles such as a lubricant contained in the support film is preferably less than 5 μm.

The support film may have a single-layer structure or a multilayer structure in which a plurality of resin layers having different compositions are laminated. In the case of a multilayer structure, there may be an antistatic layer. In the case of a multilayer structure such as a two-layer structure or a three-layer structure, for example, a resin layer containing fine particles is formed on one surface A, and fine particles are formed on the other surface B in the same manner as (1) Surface A. , (2) fine particles smaller than surface A, (3) fine particles finer than surface A, and (4) no fine particles. In the case of the structures (2), (3) and (4), it is preferable to form a photosensitive resin layer on the surface B side. At this time, it is preferable that there is a resin layer containing fine particles on the surface A side from the viewpoint of the slipperiness of the film. At this time, the size of the fine particles is preferably less than 1.5 μm. The size of the fine particles is a value obtained by measurement with a scanning electron microscope calibrated using a standard sample.

重要 An important property of the protective layer used in the photosensitive resin laminate is that the adhesion to the photosensitive resin layer is sufficiently smaller than that of the support film, and the protective layer can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. Further, a film having excellent releasability as disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably from 10 μm to 100 μm, more preferably from 10 μm to 50 μm.

ゲ ル A gel called fisheye may be present on the polyethylene film surface. When a polyethylene film having fish eyes is used as the protective layer, the fish eyes may be transferred to the photosensitive resin layer. When the fish eyes are transferred to the photosensitive resin layer, air may be entrained during lamination to form voids, leading to loss of the resist pattern. From the viewpoint of preventing fish eyes, the material of the protective layer is preferably stretched polypropylene. Specific examples include Alphan E-200A manufactured by Oji Paper Co., Ltd.

(4) The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, but is preferably 1 μm to 300 μm, more preferably 3 μm to 100 μm, particularly preferably 5 μm to 60 μm, and most preferably 10 μm to 30 μm. As the thickness of the photosensitive resin layer is smaller, the resolution is improved, and as the thickness is larger, the film strength is improved.

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

Next, a method for manufacturing the photosensitive resin laminate will be described.
As a method for producing a photosensitive resin laminate by sequentially laminating a support film, a photosensitive resin layer, and, if necessary, a protective layer, a known method can be employed. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent for dissolving the same to form a uniform solution, first coated on a support film using a bar coater or a roll coater, and then dried to dry the solvent. By removing the above, a photosensitive resin layer composed of a photosensitive resin composition can be laminated on the support film. Next, if necessary, a protective layer is laminated on the photosensitive resin layer, whereby a photosensitive resin laminate can be produced.

<Method of forming resist pattern>
Next, an example of a method for manufacturing a resist pattern using the photosensitive resin laminate of the present embodiment will be described. The method can include an exposure step of exposing the photosensitive resin composition, a heating step of heating the exposed photosensitive resin composition, and a development step of developing the photosensitive resin composition.
Examples of the resist pattern include a printed wiring board, a semiconductor element, a printing plate, a liquid crystal display panel, a touch panel, a flexible substrate, a lead frame substrate, a COF (chip-on-film) substrate, a semiconductor package substrate, a liquid crystal transparent electrode, and a liquid crystal. Pattern for a TFT wiring, a PDP (plasma display panel) electrode, and the like. As an example, a method for manufacturing a printed wiring board will be described as follows.

The printed wiring board is manufactured through the following steps.
(1) Laminating Step First, in a laminating step, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is laminated on the surface of the substrate by heating and pressing with a laminator. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like.
In this embodiment, the photosensitive resin layer may be laminated on only one side of the substrate surface, or may be laminated on both sides as needed. The heating temperature during lamination is generally between 40 ° C and 160 ° C. In addition, by performing the thermocompression bonding at least twice during lamination, the adhesion of the obtained resist pattern to the substrate can be improved. At the time of thermocompression bonding, a two-stage laminator provided with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly pressed several times to pass through the rolls.

(2) Exposure Step In this step, an exposure method in which a mask film having a desired wiring pattern is brought into close contact with a support film using an active light source, an exposure method by directly drawing a drawing pattern as a desired wiring pattern, or The photosensitive resin layer is exposed by an exposure method by projecting an image of a photomask through a lens.

The exposure step is preferably performed by an exposure method by directly drawing a drawing pattern, or by an exposure method of projecting an image of a photomask through a lens, and more preferably by an exposure method by directly drawing a drawing pattern. The advantages of the photosensitive resin composition according to the present embodiment are more prominent in an exposure method by direct drawing of a drawing pattern, or an exposure method of projecting an image of a photomask through a lens, and an exposure method by direct drawing of a drawing pattern. Is particularly remarkable.

(4) In the case where the exposure step is an exposure method by direct writing, it is preferable to use laser light having a center wavelength of less than 390 nm or laser light having a center wavelength of 390 nm or more. More preferably, the laser light has a center wavelength of 350 nm or more and 380 nm or less, or has a center wavelength of 400 nm or more and 410 nm or less. It is more preferable to perform exposure by a method of exposing with a first laser light having a center wavelength of less than 390 nm and a second laser light having a center wavelength of 390 nm or more. It is more preferable that the center wavelength of the first laser light be 350 nm or more and 380 nm or less, and the center wavelength of the second laser light be 400 nm or more and 410 nm or less.

(3) Heating Step In this step, the exposed photosensitive resin composition is preferably subjected to a heating step at about 30 ° C. to about 200 ° C., more preferably in the range of 30 ° C. to 150 ° C. More preferably, it is in the range of 60 ° C to 120 ° C. By performing this heating step, resolution and adhesion can be improved. For heating, a heating furnace, a thermostat, a hot plate, a hot-air dryer, an infrared dryer, a hot roll, or the like of a hot air, infrared or far-infrared method can be used. It is preferable that the heating method is a hot roll in that processing can be performed in a short time, and it is more preferable that the number of hot rolls is two or more.

In particular, in the present invention, by using (D) a phenolic polymerization inhibitor and using a small amount thereof, and controlling the light transmittance of the resin composition at a specific wavelength to a specific range, heating after exposure is performed. After the development, the mobility of the polymer is improved by heating. For example, even in a system having a relatively high content of a styrene skeleton, the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond are improved. Can be highly compatible. As a result, the sensitivity, adhesion, line width reproducibility, and resolution can be significantly improved. Then, since the adhesion is remarkably improved, good adhesion can be obtained even when the time from exposure to development is long. In addition, it is preferable that the heating step is performed within 15 minutes after exposure, from the viewpoint of the effect of the present invention, and it is more preferable that the heating step is performed 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 portion is developed and removed using a developing solution of an alkaline aqueous solution, so that the resist pattern is formed on the substrate. Form.
As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but is preferably a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2% by weight to about 2% by weight and a temperature of about 20 ° C. to about 40 ° C.
In an exemplary embodiment, the time from exposure to development (ie, the time from the end of exposure to the start of development) may be 5 minutes or more, or 60 minutes or more, or 180 minutes or more, and 1440 minutes or less, or 720 minutes. Minutes or less, or 300 minutes or less.
Through the above steps (1) to (4), a resist pattern can be obtained.

In the method for manufacturing a circuit board according to the present invention, a circuit board is formed by etching or plating a substrate having a resist pattern manufactured by the above method.

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

(6) Stripping Step Thereafter, the resist pattern is stripped from the substrate using an appropriate stripping solution, if necessary. Examples of the stripping solution include an aqueous alkali solution and an amine-based stripping solution. However, the resist pattern formed from the photosensitive resin composition of the present invention through post-exposure baking exhibits good releasability with respect to an amine-based release liquid, and the release pieces are not excessively miniaturized. It has the advantage that. Therefore, it is preferable to use an amine-based stripping solution as the stripping solution because the advantageous effects of the present invention can be further exhibited.

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

Examples of the organic amine include ethanolamine, propanolamine, alkylamine, cyclic amine, and quaternary ammonium salt. Specific examples of these include:
Examples of the ethanolamine include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, aminoethoxyethanol and the like;
As propanolamine, for example, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol and the like;
Examples of the alkylamine include monomethylamine, dimethylamine, trimethylamine, ethyleneamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, tetraethylenepentamine and the like;
Cyclic amines such as, for example, choline, morpholine and the like;
As the quaternary ammonium salt, for example, 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 and the like;
Each can be exemplified.

The amine-based stripping solution may be an aqueous solution containing one or more of the amines exemplified above. The concentration of the amine in the aqueous solution may be appropriately set depending on the purpose, the composition of the photosensitive resin layer, the development conditions, and the like.
The amine-based stripping solution may further contain additives usually used for the stripping agent, for example, a surfactant, an antifoaming agent, a pH adjuster, a preservative, and an anti-redeposition agent.
The peeling step is performed at a temperature of, for example, 0 ° C. or more and 100 ° C. or less, preferably room temperature (23 ° C.) or more and 50 ° C. or less, for example, for 1 second or more and 1 hour or less, preferably 10 seconds or more and 10 minutes or less.

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

The photosensitive resin laminate of the present embodiment includes a printed wiring board, a flexible substrate, a lead frame substrate, a touch panel substrate, a COF substrate, a semiconductor package substrate, a liquid crystal transparent electrode, a liquid crystal TFT wiring, a PDP electrode, and the like. It is a photosensitive resin laminate suitable for producing a conductor pattern.
The above-described various parameters are measured according to a measurement method in the examples described later or a method understood by those skilled in the art to be equivalent thereto, unless otherwise specified.

Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless departing from the gist thereof. The physical properties in the examples were measured by the following methods.
The method of measuring the physical properties of the polymer and the method of preparing the evaluation samples of the examples and comparative examples will be described. In addition, an evaluation method and an evaluation result of the obtained sample will be described.

(1) Measurement and calculation of physical properties <Measurement of weight average molecular weight or number average molecular weight of polymer>
The weight average molecular weight or number average molecular weight of the polymer is determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK) KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve with Shodex STANDARD SM-105 manufactured by Showa Denko KK) It was determined in terms of polystyrene.
Further, the degree of dispersion of the polymer was calculated as a 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 disclosure, the acid equivalent means the mass (gram) of a polymer having one equivalent of a carboxyl group in a molecule. Using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., the acid equivalent was measured by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution.

<I / O value>
The I / O value of the alkali-soluble polymer was derived by the following method. First, Non-Patent Documents (Organic Conceptual Diagram (Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, Nos. 1, 1-16 (1954); Chemistry, Vol. 11, No. 10 , 719-725 (1957); Fragrance Journal, No. 34, 97-111 (1979); Fragrance Journal, No. 50, 79-82 (1981)) each comonomers calculates the I value and the O value, then give _{I average} value and _{O average} value by averaging the respective molar ratio of the comonomers of the IO values and O values. Then, the I / O value was derived by dividing the obtained I _average value by the O _average value.

｛式中、Ｗ_ｉは、各々のアルカリ可溶性高分子の固形重量であり、Ｔｇ_ｉは、各々のアルカリ可溶性高分子のＦｏｘ式で求められるガラス転移温度であり、Ｗ_{ｔｏｔａｌ}は、各々のアルカリ可溶性高分子の合計固形重量であり、かつｎは、感光性樹脂組成物に含まれるアルカリ可溶性高分子の種類の数である｝ <Glass transition temperature Tg>
The glass transition temperature Tg of the alkali-soluble polymer was determined by the Fox equation. When obtaining the glass transition temperature Tg, a non-patent document (Brandrup, J. Imergutt, EH, edited by Polymer Handbook, Third) is used as a glass transition temperature of a homopolymer composed of a comonomer that forms a corresponding alkali-soluble polymer. edition, John Wiley & sons, 1989, p. 209 Chapter VI "Glass transition tempera- tures of polymers"). Table 1 shows the glass transition temperature of the homopolymer composed of each comonomer used in the calculation in the examples. When the alkali-soluble polymer is composed of two or more kinds of polymers, the value determined by the following equation is the glass transition temperature of the alkali-soluble polymer.

{Wherein, _{W i} is the solid weight of each of the alkali-soluble polymer, Tg _i is the glass transition temperature determined by the Fox equation of each of the alkali-soluble _{polymer, W total,} each of the alkali-soluble It is the total solid weight of the polymer, and n is the number of types of alkali-soluble polymer contained in the photosensitive resin composition.

(2) Production method of evaluation sample The evaluation sample was produced as follows.
<Preparation of photosensitive resin laminate>
The components shown in Tables 1 to 3 below (however, the number of each component indicates the amount (parts by mass) as a solid content) and a solvent are sufficiently stirred and mixed to prepare a photosensitive resin composition preparation liquid. I got Table 3 shows details of the components shown in Tables 1 and 2. A 16 μm-thick polyethylene terephthalate film (FB-40, manufactured by Toray Industries, Inc.) was used as a support film, and the prepared solution was uniformly applied to the surface thereof using a bar coater. After drying for a minute, a photosensitive resin composition layer was formed. The dry thickness of the photosensitive resin composition layer was 30 μm.
Then, a 19 μm-thick polyethylene film (manufactured by Tamapoly Corporation, GF-18) is laminated as a protective layer on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film is not laminated. A laminate was obtained.
The amounts of methoquinone and dibutylhydroxytoluene in Tables 1 and 2 mean the concentration of each component based on the total solid content in the photosensitive resin composition.

<Board leveling>
As a substrate for evaluation of image properties, a 0.4 mm thick copper-clad laminate obtained by laminating 35 μm rolled copper foil was jetted using a grinding agent (# 400, manufactured by Uji Denka Kogyo KK) at a spray pressure of 0.2 MPa. After scrub polishing, the substrate surface was washed with a 10% by mass aqueous solution of H ₂ SO ₄ .

<Laminate>
While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate was applied to a copper-clad laminate preheated to 50 ° C. using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation). Lamination was performed at a roll temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Exposure>
A direct drawing exposure machine (Nuvogo Fine 10, manufactured by Orbotech Co., Ltd., light source: 375 nm (30%) + 405 nm (70%)) was used on the evaluation substrate 2 hours after lamination using a 41-step stofer tablet. Exposure. The exposure was performed with an exposure amount such that the maximum number of remaining film steps was 14 when exposed and developed using the 41-step stofer step tablet as a mask.

<Heating>
The evaluation substrate 7 minutes after the exposure was heated by a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation). The roll temperature was 105 ° C., the air pressure was 0.30 MPa, and the laminating speed was 1 m / min. Note that if the time from exposure to development is increased, the effect of heating is lost, so that heating is usually performed for about 1 minute after exposure. For this reason, the heating after 7 minutes of exposure in this embodiment is a very severe condition.

<Development>
After peeling off the polyethylene terephthalate film (support film), a 1% by mass aqueous solution of Na ₂ CO _{3 at} 30 ° C. is sprayed for a predetermined time using an alkali developing machine (developing machine for dry film manufactured by Fuji Kiko Co., Ltd.). And developed. The time of the developing spray was twice the shortest developing time, and the time of the water spray after the developing was three times the shortest developing time. At this time, the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was defined as the shortest development time.

(3) Sample evaluation method <Metoquinone amount>
The amount of methoquinone in the photosensitive resin composition was determined by an internal standard method using gas chromatography (hereinafter abbreviated as GC) manufactured by Shimadzu Corporation. The detector was a flame ionization detector (hereinafter abbreviated as FID), and n-docosane was used as an internal standard.
<Amount of dibutylhydroxytoluene>
The amount of dibutylhydroxytoluene in the photosensitive resin composition was determined by GC similarly to the amount of methoquinone. N-octadecane was used as an internal standard.
<Light transmittance>
The light transmittance at 375 nm and 405 nm of each resin composition was measured by the following method.
The transmittance at each wavelength of the photosensitive resin laminate from which the polyethylene film (protective layer) was removed was measured using a spectrophotometer (U-3010, Hitachi High-Technologies Corporation). At that time, measurement was performed by setting the photosensitive resin laminate so that transmitted light would pass in the thickness direction of the photosensitive resin laminate.

<Sensitivity evaluation>
In the above-mentioned exposure process, after exposing through a mask of a 41-step stofer step tablet, development was performed, and the exposure amount (mJ / cm ² ) at which the maximum remaining film number became 14 was obtained as a sensitivity value.

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

<Resolution>
In the above-described exposure step, exposure was performed using drawing data having a line pattern in which the width of the exposed portion and the unexposed portion was 1: 1. Development was performed under the above-described development conditions to form a cured resist line.
The minimum line width at which the cured resist line was normally formed was determined as the value of the resolution.

<Adhesion>
In the above-described exposure process, exposure was performed using drawing data having a line pattern in which the width of the exposed portion and the unexposed portion was x μm: 200 μm. The development was performed according to the above-described development conditions, and the minimum line width at which the cured 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 the value of adhesion.
Only the evaluation of the adhesiveness was performed in two cases, that is, when heating was performed one minute after exposure and when heating was performed seven minutes after exposure.

<Shortest development time delay>
In the above-described developing step, the time required for completely dissolving the unexposed portion of the photosensitive resin layer is the same as when developing without heating after exposure and when developing after heating 7 minutes after exposure. The shortest development time, which is a short time, was measured and ranked according to the following criteria.
Good: There is no difference in the shortest development time between the case with heating after exposure and the case without heating after exposure. Possible: The shortest development time with heating after exposure is less than 1 second compared to the case without heating after exposure. : The shortest development time with heating after exposure was more than 1 second longer than without heating after exposure. Tables 1 and 2 show the results.

加熱 The heating conditions after exposure in this example are very strict conditions because heating is performed 7 minutes after exposure. For example, when the compositions of Example 3 and Comparative Example 2 were developed without heating after exposure, the adhesion was 13.8 μm. That is, in the composition of Comparative Example 1, no effect was observed by heating after 7 minutes of exposure, but in Example 3, the adhesion could be improved even under very severe conditions. In addition, under the condition of heating after 1 minute of exposure, in each of the compositions of Example 7 and Comparative Example 1, adhesion of 10.8 μm was obtained. As can be seen from the above results, even if the adhesion is good under the general heating conditions after exposure, the adhesion does not necessarily improve under the severe condition of heating 7 minutes after exposure. However, according to the present invention, the adhesion can be improved even under the severe post-exposure heating conditions for the first time. Thereby, when manufacturing a circuit board, good adhesion can be obtained even if the time from exposure to development becomes long, so that a high-definition circuit pattern can be stably formed.

The photosensitive resin composition according to the present invention has good sensitivity, adhesion, line width reproducibility, and resolution when heated and developed after exposure, particularly when the time from exposure to development is long. Can also be used in a wide range of applications as a photosensitive resin composition to achieve good adhesion.

Claims (25)

(A) an alkali-soluble polymer: 10% to 90% by mass;
(B) a compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass;
(C) a photopolymerization initiator: 0.01% by mass to 20% by mass; and (D) a phenolic polymerization inhibitor: 1 ppm to 300 ppm;
A photosensitive resin composition containing
The above photosensitive resin composition, wherein the light transmittance at at least one of 375 nm and 405 nm is 58% to 95%. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises methoquinone as the (D) phenolic polymerization inhibitor. The photosensitive resin composition according to claim 1, wherein (D) dibutylhydroxytoluene is contained as the phenolic polymerization inhibitor. 4. The photosensitive resin composition according to claim 3, wherein the content of the dibutylhydroxytoluene is 1 to 200 ppm. 4. The photosensitive resin composition according to claim 3, wherein the content of the dibutylhydroxytoluene is from 10 to 150 ppm. 感光 The photosensitive resin composition according to any one of claims 1 to 5, wherein the (A) alkali-soluble polymer has an I / O value of 0.600 or less. The photosensitive material according to any one of claims 1 to 6, wherein the photopolymerization initiator (C) includes at least one selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof. Resin composition. The photosensitive resin composition according to claim 7, wherein the (C) photopolymerization initiator contains anthracene and / or an anthracene derivative. 感光 The photosensitive resin composition according to any one of claims 1 to 8, wherein the structural unit of styrene and / or styrene derivative in the alkali-soluble polymer (A) is 26% by mass or more. (10) The photosensitive resin composition according to any one of (1) to (9), wherein the (A) alkali-soluble polymer contains a structural unit of benzyl (meth) acrylate as a monomer component. (11) The photosensitive resin composition according to any one of (1) to (10), wherein the alkali-soluble polymer (A) has a glass transition temperature of 120 ° C. or lower. (B) the compound having an ethylenically unsaturated double bond contains a compound having three or more methacrylate groups in a molecule in an amount of 5% by mass or more based on the solid content of the entire photosensitive resin composition; The photosensitive resin composition according to any one of claims 1 to 11. (13) The photosensitive resin composition according to any one of (1) to (12), which is used to obtain an exposed resin cured product using a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more. 14. The photosensitive resin composition according to claim 1, wherein a center wavelength of the first laser light is 350 nm or more and 380 nm or less, and a center wavelength of the second laser light is 400 nm or more and 410 nm or less. . The following steps:
An exposure step of exposing the photosensitive resin composition;
A heating step of heating the exposed photosensitive resin composition; and a developing step of developing the heated photosensitive resin composition;
The photosensitive resin composition according to any one of claims 1 to 14, which is capable of forming a pattern by: The photosensitive resin composition according to any one of claims 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 claim 1, wherein the heating step is performed within 15 minutes from the exposure. The following steps:
An exposure step for exposing the photosensitive resin composition according to any one of claims 1 to 17;
A heating step of heating the exposed photosensitive resin composition; and a developing step of developing the heated photosensitive resin composition;
A method for forming a resist pattern, comprising: 19. The method of forming a resist pattern according to claim 18, wherein a heating temperature in the heating step is in a range of 30 ° C. to 150 ° C. 20. The method for forming a resist pattern according to claim 18, wherein the heating step is performed within 15 minutes after exposure. 21. The method of forming a resist pattern according to claim 18, wherein the exposing step is performed by an exposing method by direct drawing of a drawing pattern or an exposing method of projecting an image of a photomask through a lens. 22. The method for forming a resist pattern according to claim 21, wherein the exposing step is performed by an exposing method based on direct drawing of a drawing pattern. 23. The method of forming a resist pattern according to claim 22, wherein the exposing step is performed by a method of exposing with a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more. 24. The method of forming a resist pattern according to claim 23, wherein the center wavelength of the first laser light is 350 nm or more and 380 nm or less, and the center wavelength of the second laser light is 400 nm or more and 410 nm or less. A resist pattern forming step of forming a resist pattern on a substrate by the method according to any one of claims 18 to 24; and a circuit for forming a circuit board by etching or plating the substrate having the resist pattern. A substrate forming step;