KR20200139768A - Photosensitive resin composition and method of forming resist pattern - Google Patents

Abstract

There is provided a photosensitive resin composition that has good sensitivity, adhesion, line width reproducibility, and resolution when developing after heating after exposure, and in particular, realizing good adhesion even when the time from exposure to development is long. One aspect of the present invention is (A) Alkali-soluble polymer: 10% by mass to 90% by mass; (B) Compound having ethylenically unsaturated double bond: 5% by mass to 70% by mass; (C) Photoinitiator: 0.01 mass%-20 mass %; And (D) a phenolic polymerization inhibitor: 1 ppm to 300 ppm; As a photosensitive resin composition containing, it provides the said photosensitive resin composition whose light transmittance in at least one of 375 nm and 405 nm is 58%-95%.

Description

Photosensitive resin composition and method of forming resist pattern

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

In electronic devices such as PCs and mobile phones, printed wiring boards or the like are used to mount components, semiconductors, and the like. As a resist for manufacturing such as a printed wiring board, conventionally, a photosensitive resin layer is laminated on a support film and a protective film is laminated on the photosensitive resin layer as necessary, a so-called dry film photoresist (hereinafter , Sometimes called DF) is used. As the photosensitive resin layer, at present, an alkali developing type using a weak alkaline aqueous solution as a developer is generally used.

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

After forming the resist pattern, the process of forming a circuit is largely divided into two methods. The first method is a method (etching method) of removing the resist pattern portion with an alkaline aqueous solution stronger than a developer after etching away the substrate surface that is not covered by the resist pattern (for example, the copper surface of the copper clad laminate).

In the second method, after plating treatment of copper, solder, nickel, tin, or the like on the substrate surface, the resist pattern portion is removed in the same manner as in the first method, and the surface of the substrate (e.g., copper coating It is a method (plating method) of etching the copper surface of the laminated plate). For etching, cupric chloride, ferric chloride, copper ammonia complex solution or the like is used.

In recent years, with the miniaturization and weight reduction of electronic devices, miniaturization and high density of printed wiring boards are in progress, and high-performance DFs that provide high resolution and high adhesion are required in the above manufacturing process. In order to realize such high resolution, Patent Document 1 describes a photosensitive resin composition in which the resolution is improved by a specific thermoplastic resin, a monomer, and a photopolymerizable initiator.

Japanese Patent Laid-Open Publication No. 2010-249884

After the exposure step, in some cases, a heating step is performed on the photosensitive resin layer, and then development may be performed. By performing this heating step, further improvement in resolution and adhesion (that is, adhesion between the resist pattern and the substrate) becomes possible. However, even if a heating step is applied after exposure, in the conventional photosensitive resin composition, adhesion and resolution are further insufficient, or there is a problem that good adhesion is not obtained when the time from exposure to development is prolonged.

The present invention has been proposed in view of such a conventional situation, and an object of an aspect of the present invention is that the sensitivity, adhesion, line width reproducibility, and resolution are good when developed after heating after exposure, and in particular, exposure It is to provide a photosensitive resin composition that realizes good adhesion even when the time from development to development is long.

The present invention includes the following aspects.

[1] (A) Alkali-soluble polymer: 10% by mass to 90% by mass

(B) Compound having ethylenically unsaturated double bond: 5% by mass to 70% by mass

(C) Photopolymerization initiator: 0.01% by mass to 20% by mass, and

(D) Phenolic polymerization inhibitor: 1 ppm to 300 ppm;

As a photosensitive resin composition comprising a,

The photosensitive resin composition, wherein the light transmittance in at least one of 375 nm and 405 nm is 58% to 95%.

[2] The photosensitive resin composition according to the first aspect, comprising metoquinone as the (D) phenolic polymerization inhibitor.

[3] The photosensitive resin composition according to Embodiment 1 or 2, comprising dibutylhydroxytoluene as the (D) phenol polymerization inhibitor.

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

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

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

[7] The (C) photopolymerization initiator described in any one of the above aspects 1 to 6, comprising 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 Embodiment 7, wherein the (C) photopolymerization initiator contains an anthracene and/or an anthracene derivative.

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

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

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

[13] The photosensitive resin composition according to any one of Aspects 1 to 12, for obtaining a cured exposure resin product 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.

[14] The photosensitive resin composition according to any one of Aspects 1 to 13, wherein the center wavelength of the first laser light is 350 nm 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.

[15] The following steps:

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 in any one of said aspects 1-14 which can form a pattern by this.

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

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

[18] The following steps:

Exposure process of exposing the photosensitive resin composition in any one of said aspects 1-17;

A heating step of heating the exposed photosensitive resin composition; And

A developing step of developing the heated photosensitive resin composition;

A method of forming a resist pattern comprising a.

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

[20] The method for forming a resist pattern according to Aspect 18 or 19, wherein the heating step is performed within 15 minutes from exposure.

[21] The resist pattern according to any one of Aspects 18 to 20, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens. Formation method.

[22] The method for forming a resist pattern according to Embodiment 21, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern.

[23] The method for forming a resist pattern according to Embodiment 22, wherein the exposure step is performed 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.

[24] The method for forming a resist pattern according to Embodiment 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.

[25] A resist pattern forming step of forming a resist pattern on a substrate by the method according to any one of aspects 18 to 24; And

A circuit board forming step of forming a circuit board by etching or plating the substrate having the resist pattern; Containing a circuit board manufacturing method.

According to the present invention, it is possible to provide a photosensitive resin composition that has good sensitivity, adhesion, line width reproducibility, and resolution when developing after heating after exposure, and in particular, realizing good adhesion even when the time from exposure to development is long. I can.

Hereinafter, exemplary embodiments for carrying out the present invention (hereinafter, abbreviated as "embodiment") will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist. In addition, the various measurement values in this specification are measured according to the method described in the [Example] section of the present disclosure or a method understood by those skilled in the art to be equivalent to this, unless otherwise noted.

<Photosensitive resin composition>

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

The photosensitive resin composition of the present embodiment may be a photosensitive resin composition for obtaining a cured resin product by exposing with a first active light having a center wavelength of less than 390 nm and a second active light having a center wavelength of 390 nm or more. The actinic light is, for example, laser light. In this aspect, the photosensitive resin composition has photosensitivity to both the first active light having a center wavelength of less than 390 nm and the second active light having a center 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 is soluble in an alkaline substance. (A) The alkali-soluble polymer is preferably a copolymer having a carboxyl group from the viewpoint of alkali developability, and more preferably a copolymer containing a carboxyl group-containing monomer as a copolymerization component. (A) The alkali-soluble polymer may be thermoplastic.

It is preferable that the photosensitive resin composition contains a copolymer having an aromatic group as (A) alkali-soluble polymer from the viewpoint of high resolution of a resist pattern and a skirt shape. The photosensitive resin composition is particularly preferably (A) an alkali-soluble polymer containing a copolymer having an aromatic group in the side chain. As such an aromatic group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted aralkyl group are mentioned, for example. The proportion of the aromatic group-containing copolymer 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, and more preferably 70% by mass or more. , More preferably 80% by mass or more. The ratio may be 100% by mass, but from the viewpoint of maintaining good alkali solubility, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass.

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

As the comonomer having the above aromatic group, for example, styrene, a polymerizable styrene derivative (eg, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene Trimer, etc.), a monomer having an aralkyl group, and the like. Among them, styrene and a styrene derivative are more preferable.

(A) The proportion of the constituent units of styrene and/or styrene derivatives in the whole alkali-soluble polymer in these sums can significantly improve the adhesion when developed after heating after exposure, especially developed from exposure. From the viewpoint of obtaining good adhesion even when the time to reach is prolonged, 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 It is above, more preferably 35 mass% or more, and more preferably 40 mass% or more. Since the styrene skeleton is hydrophobic, it is possible to suppress the swelling property to a developer, and to express good adhesion. However, when the content of the styrene skeleton is large, the mobility of the polymer tends to be low, so that the reactivity tends to be low, whereby the adhesion tends to be low. In addition, as the time from exposure to development increases, the radicals in the system become deactivated, so the effect of improving the adhesion by heating after exposure is lowered. In the present invention, by heating after exposure and then developing, the mobility of the polymer is improved by heating even in a system with a large content of the styrene skeleton, and the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly compatible, As a result, it is thought that good adhesion can be realized. Further, it is considered that by this, good adhesion can be obtained even when the time from exposure to development is prolonged. (A) The proportion of the constituent units of the styrene and/or the styrene derivative in the entire alkali-soluble polymer in these sums is preferably 90% by mass or less from the viewpoint of obtaining favorable advantages due to the presence of other constituent units. , More preferably, it may be 80 mass% or less, More preferably, it may be 70 mass% or less.

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

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

(A) The alkali-soluble polymer can remarkably improve the adhesiveness when it is developed after heating after exposure, and in particular, from the viewpoint of realizing good adhesiveness even when the time from exposure to development is prolonged, benzyl as a monomer component It is preferable to include a structural unit of (meth)acrylate. (A) The proportion of the constituent units 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, It is more preferably 20 to 40 mass%, and still more preferably 20 to 30 mass%. In addition, from the same viewpoint, it is preferable that the (A) alkali-soluble polymer has both a structural unit of styrene and/or a styrene derivative and a structural unit of benzyl (meth)acrylate.

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

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

(A) alkali-soluble polymer other than the copolymer having an aromatic group in the side chain is preferably obtained by polymerizing at least one of the first monomers described later, and at least one of the first monomers described later and the second monomer described later It is more preferable that it is obtained by copolymerizing at least 1 type of.

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 preferable.

In addition, in this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acryloyl group" means an acryloyl group or a methacryloyl group, and "(meth) "Acrylate" means "acrylate" or "methacrylate".

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

The second monomer is non-acidic and is a monomer having at least one polymerizable unsaturated group in its molecule. As the second monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethyl (Meth)acrylates such as hexyl (meth)acrylate; Esters of vinyl alcohol such as vinyl acetate; And (meth)acrylonitrile, etc. are mentioned. Among them, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate are preferred.

(A) The alkali-soluble polymer can be prepared by polymerizing the above-described single or multiple monomers by a known polymerization method, preferably addition polymerization, and more preferably radical polymerization.

It is preferable that the monomer contains a monomer having an aralkyl group and/or styrene from the viewpoint of chemical resistance, adhesion, high resolution, or skirt 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 the ratio of (inorganic value)/(organic value), and is a value for evaluating the polarity of various organic compounds based on the organic conceptual diagram, and is a functional group contribution method that sets parameters for each functional group in the compound. Is one. Regarding the I/O value, for example, non-patent literature (organic conceptual diagram (manufactured by Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, paragraphs 1 to 16 (1954); domain of chemistry) , Vol. 11, Nos. 10, 719-725 (1957); Fragrance Journal, Nos. 34, 97-111 (1979); Fragrance Journal, Nos. 50, 79-82 (1981) )); It is described in detail in the literature of et al. The concept of the I/O value is the coordinates of an orthogonal axis that divides the properties of a compound into an organic group that exhibits covalent bonding and an inorganic group that exhibits ionic bonding, and all organic compounds are labeled organic and inorganic axes, respectively. It is indicated by placing it as a point on the image. The I/O value indicates that the closer to 0 is the nonpolar (i.e., hydrophobic, or organic compound) organic compound, and the larger the I/O value is, the more polar (i.e., hydrophilic or inorganic) organic compound is Show.

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

(A) The glass transition temperature of the alkali-soluble polymer is a value obtained by the Fox equation ((A) When the alkali-soluble polymer contains a plurality of polymers, the glass transition temperature Tg for the entire mixture, that is, glass transition The weight average value of temperature Tg _total ) is preferably 130°C or less, and 120°C or less, 110°C or less, 100°C or less, 95°C or less, from the viewpoint of chemical resistance, adhesion, high resolution, or skirt shape of the resist pattern, It is more preferably 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 from the viewpoint of controlling the edge fuse property, it is preferably 30° C. or higher, more preferably 50° C. or higher, still more preferably 60 It is above ℃. In addition, as the glass transition temperature of a homopolymer consisting of the same monomer as each of (A) one or more monomers constituting the alkali-soluble polymer, non-patent literature (Brandrup, J. Immergut, EH edited "Polymer handbook," Third edition, John Wiley & Sons, 1989, p. 209 Chapter VI "Glass transition temperatures of polymers").

(A) Acid equivalent of the alkali-soluble polymer (when component (A) contains a plurality of copolymers, the acid equivalent of the entire mixture) Silver, development resistance of the photosensitive resin layer, and resolution of the resist pattern And from the viewpoint of adhesion, it is preferably 100 or more, and from the viewpoint of developability and peelability of the photosensitive resin layer, it is preferably 600 or less. (A) It is more preferable that it is 200-500, and, as for the acid equivalent of an alkali-soluble polymer, it is still more preferable that it is 250-450.

(A) The weight average molecular weight of the alkali-soluble polymer (when the component (A) contains a plurality of types of copolymers, the weight average molecular weight with respect to 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 uniformly and obtaining resistance to a developer, and from the viewpoint of maintaining the developability of the dry film resist, It is preferably 500,000 or less from the viewpoint of high resolution of the resist pattern and the shape of the skirt, and further from the viewpoint of 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, still more preferably 20,000 to 100,000, and particularly preferably 30,000 to 70,000. (A) The dispersion degree of the molecular weight of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 4.0, and more preferably 1.0 to 3.0.

The content of the alkali-soluble polymer (A) in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified, the same in each containing component), 10% by mass to 90% by mass, It is preferably in the range of 20% by mass to 80% by mass, more preferably 40% by mass 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 from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist material, the resist pattern It is preferably 90% by mass or less, more preferably 80% by mass or less, more preferably 70% by mass or less, and 60% by mass from the viewpoint of the high resolution of the resist pattern and the skirt shape of the resist pattern, and furthermore, from the viewpoint of the chemical resistance of the resist pattern. It is more preferable that it is% or less.

(B) a compound having an ethylenically unsaturated bond

(B) A compound having an ethylenically unsaturated bond is a compound having polymerizable properties by having an ethylenically unsaturated bond (ie, a double bond) in its structure. The ethylenically unsaturated bond is more preferably derived from a methacryloyl group. From the viewpoint of adhesiveness and suppression of developer foamability, (B) the compound having an ethylenically unsaturated bond preferably has an alkylene oxide structure having 3 or more carbon atoms. The number of carbon atoms in the alkylene oxide structure is more preferably 3 to 6, and still more preferably 3 to 4.

As the compound (B) having one (meth)acryloyl group as an ethylenically unsaturated bond, for example, a compound obtained by adding (meth)acrylic acid to one end of a polyalkylene oxide, or a polyalkylene oxide A compound obtained by adding (meth)acrylic acid to one end of the and the other end is alkyl etherified or allyl etherified, a phthalic acid compound, and the like, and is preferable from the viewpoint of peelability and cured film flexibility.

As such a compound, for example, 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, and , 4-normal nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound in which polyethylene glycol to which an average of 7 moles of ethylene oxide is added to nonylphenol is added, and an average of 1 mole of propylene oxide 4-Normalnonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate of a compound obtained by adding polypropylene glycol to which is added and polyethylene glycol to which an average of 5 mol of ethylene oxide is added to nonylphenol , 4-normal nonylphenoxyoctaethylene glycol (meth)acrylate, which is an acrylate of a compound in which polyethylene glycol to which an average of 8 moles of ethylene oxide is added is added to nonylphenol (for example, manufactured by Toa Synthesis Co., Ltd., M- 114) and the like.

Further, when γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-о-phthalate is included, in addition to the above viewpoint, it is preferable from the viewpoint of sensitivity, resolution, and adhesion.

As a compound having two (meth)acryloyl groups in the molecule, for example, a compound having a (meth)acryloyl group at both ends of an alkylene oxide chain, or a random or block ethylene oxide chain and a propylene oxide chain And compounds having a (meth)acryloyl group at both ends of the alkylene oxide chain bonded to each other.

Such compounds include, for example, tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, hepta ethylene glycol di (meth) acrylate, Octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, compounds having (meth)acryloyl groups at both ends of 12 moles of ethylene oxide chain, etc. In addition to polyethylene glycol (meth) acrylate and the like, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate and the like can be mentioned. As a 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 moles of ethylene at both ends of the polypropylene glycol to which an average of 12 moles of propylene oxide is added Dimethacrylate of glycol to which oxide is additionally added, and dimethacrylate of glycol to which an average of 15 moles of ethylene oxide is additionally added to both ends of polypropylene glycol to which an average of 18 moles of propylene oxide is added, FA- 023M, FA-024M, and FA-027M (product name, manufactured by Hitachi Chemical Industries), and the like. These are preferable from the viewpoint of flexibility, resolution, adhesiveness, and the like.

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

Specifically, the following general formula (I):

[Formula 1]

{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 , n ¹ and n ³ are each independently 0 to 39 And n ¹ + n ³ is an integer of 0 to 40, n ² and n ⁴ are each independently an integer of 0 to 29, and n ² + n ⁴ is an integer of 0 to 30, -( The arrangement of the repeating units of AO)- and -(BO)- may be random or block. And, in the case of a block, any of -(AO)- and -(BO)- may be on the side of the bisphenyl group.} A compound represented by} can be used.

For example, dimethacrylate of polyethylene glycol in which an average of 5 moles of ethylene oxide is added to both ends of bisphenol A, dimethacrylate of polyethylene glycol in which an average of 2 moles of ethylene oxide is added to both ends of bisphenol A, Dimethacrylate of polyethylene glycol obtained by adding an average of 1 mol of ethylene oxide to both ends of bisphenol A is preferable from the viewpoint 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 examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, and a carbon number. 1 to 10 alkylamino group, C 2 to C 20 dialkyl amino group, nitro group, cyano group, carbonyl group, mercapto group, C 1 to C 10 alkyl mercapto group, aryl group, hydroxyl group, C 1 to C 20 hydroxy An alkyl group, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms of the alkyl group, an acyl group having 1 to 10 carbon atoms of 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, A C2-C10 alkenyl group, a C2-C10 N-alkylcarbamoyl group or a group containing a heterocycle, or an aryl group substituted with 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 General Formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

(B) A compound having an ethylenically unsaturated double bond, which contains a (meth)acrylate compound having three or more ethylenically unsaturated double bonds (i.e., having three or more functionalities), adhesion when developed after heating after exposure Can be remarkably improved, and is particularly preferable from the viewpoint of obtaining good adhesion even when the time from exposure to development is prolonged. From the same viewpoint, it is more preferable to include a (meth)acrylate compound having 4 or more ethylenically unsaturated double bonds, and even more preferably a (meth)acrylate compound having 5 or more ethylenically unsaturated double bonds. And, it is particularly preferable to include a (meth)acrylate compound having 6 or more ethylenically unsaturated double bonds. Further, from the same viewpoint, it is preferable that these are methacrylate compounds. Compounds having 3 or more, 4 or more, 5 or more, 6 or more ethylenically unsaturated double bonds are considered to have an effect of increasing the crosslinking density during polymerization by exposure, but the number of functional groups is large. Due to the effect of steric hindrance, a desired crosslinking density cannot be obtained in many cases. In the present invention, preferably a compound having 3 or more ethylenically unsaturated double bonds, more preferably a compound having 4 or more ethylenically unsaturated double bonds, more preferably 5 or more ethylenically unsaturated double bonds. A compound, particularly preferably a compound having 6 or more ethylenically unsaturated double bonds, is used, and heat treatment is also performed after exposure to improve mobility in the system, thereby reducing the effect of steric hindrance even when the number of functional groups is large, resulting in high adhesion. I figured out what I could do. Preferably, a compound having 3 or more ethylenically unsaturated double bonds, more preferably a compound having 4 or more ethylenically unsaturated double bonds, more preferably a compound having 5 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, and still more preferably 7% by mass or more, based on the solid content of the photosensitive resin composition. , 10 mass% or more is particularly preferred. In addition, as the upper limit of the content, from the viewpoint of expressing the effect of the heat treatment after exposure, 30% by mass or less is preferable, 25% by mass or less is more preferable, 20% by mass or less is still more preferable, and 15% by mass or less. Is particularly preferred.

(b1) As a (meth)acrylate compound having 3 or more ethylenically unsaturated bonds:

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 (for example, as a preferred example from the viewpoint of flexibility, adhesion, and bleed-out inhibition, tri(meth)acrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane, and trimethylolpropane Tri(meth)acrylate) in which an average of 30 moles of ethylene oxide was added to;

Tetra(meth)acrylate, such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.;

Penta(meth)acrylate, for example, dipentaerythritol penta(meth)acrylate, etc.;

Hexa(meth)acrylate, for example, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

Among these, tetra, penta, or hexa(meth)acrylate is preferable.

(b1) The (meth)acrylate compound having three or more ethylenically unsaturated bonds is preferably 500 or more, more preferably 700 or more, and even more preferably 900 or more weight average molecular weight from the viewpoint of suppression of bleed out. Has.

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

Tetra (meth) acrylate is the following general formula (II):

[Formula 2]

{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 are 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 X is, It is more preferable that it is a tetra(meth)acrylate compound represented by mutually same or may be different.

Although not wishing to be bound by theory, the tetramethacrylate compound represented by the general formula (II), by having groups R ₃ to R ₆ , to a tetraacrylate having a H ₂ C = CH-CO-O- moiety In contrast, it is thought that the hydrolysis property in an alkaline solution is suppressed. The use of the photosensitive resin composition containing the tetramethacrylate compound represented by the general formula (II) can significantly improve the adhesion when developed after heating after exposure, and in particular, the time from exposure to development is long. Even when it is lost, it is preferable from the viewpoint of realizing good adhesion.

In the formula (II), at least one group of R ₃ ~ R ₆ is a methyl group is preferable, and the group R ₃ ~ R ₆ in all, more preferably a methyl group.

From the viewpoint of obtaining the desired resolution, skirt shape, and film residual rate with respect to the resist pattern, in the general formula (II), X is preferably -CH ₂ -CH ₂ -.

From the viewpoint of obtaining the desired resolution, skirt shape, and film residual rate with respect to 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. It is preferable and it is more preferable that it is an integer of 2-10. In addition, in General Formula (II), it is preferable that m ₁ + m ₂ + m ₃ + m ₄ is 1 to 36 or 4 to 36.

As a compound represented by general formula (II), pentaerythritol (poly) alkoxy tetramethacrylate etc. are mentioned, for example. In addition, in the present disclosure, "pentaerythritol (poly) alkoxytetramethacrylate" is, in the general formula (II), m ₁ + m ₂ + m ₃ + m ₄ = 1 "pentaerythritol alkoxy. Tetramethacrylate" and both of "pentaerythritol polyalkoxytetramethacrylate" in which m ₁ + m ₂ + m ₃ + m ₄ = 2 to 40 are included. As the compound represented by the general formula (II), compounds listed in JP 2013-156369 A, for example, pentaerythritol (poly) alkoxytetramethacrylate and the like can be given.

As a hexa(meth)acrylate compound, a total of 1 to 6 ends of hexa(meth)acrylate and dipentaerythritol in which 1 to 24 moles of ethylene oxide are added to the six ends of dipentaerythritol Hexa(meth)acrylate to which 10 moles of ε-caprolactone is added is preferable.

From the viewpoint of realizing good adhesion even when the time from exposure to development is prolonged, the adhesiveness when developing after heating after exposure can be remarkably improved, and the photosensitive resin composition according to the present embodiment is (B ) As the compound having an ethylenically unsaturated bond, it is particularly preferable to include a (meth)acrylate compound having 4 or more ethylenically unsaturated bonds and having an alkylene oxide chain. In this case, the ethylenic unsaturated bond is more preferably derived from a methacryloyl group, and the alkylene oxide chain is more preferably an ethylene oxide chain.

In this embodiment, from the viewpoint of realizing good adhesion even when the time from exposure to development and then heating after exposure to development can be remarkably improved, and particularly when the time from exposure to development is prolonged, the photosensitive resin composition comprises (B ) As the compound having an ethylenically unsaturated bond, it is preferable to include a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton. As the alkylene oxide chain, an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, a pentylene oxide chain, a hexylene oxide chain, etc. are mentioned, for example. When the photosensitive resin composition contains a plurality of alkylene oxide chains, they may be the same as or different from each other. From the above point of view, 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. .

In the photosensitive resin composition, (A) an alkali-soluble polymer and a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton are used in combination to maintain the balance of chemical resistance, adhesion, and resolution of the resist pattern. There is a tendency.

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 has been modified with an alkyleneoxy group, and (meth)acrylic acid. The six hydroxyl groups of the dipentaerythritol skeleton may be modified with an alkyleneoxy group. The number of ester bonds in one ester molecule may be 1-6, and it is preferable that it is 6.

As the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, for example, an average of 4 to 30 moles of an alkylene oxide in dipentaerythritol, an average of 6 to 24 moles, or an average of 10 to Hexa(meth)acrylate added by 14 moles is mentioned.

Specifically, as a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, it is possible to remarkably improve the adhesion when developed after heating after exposure. In particular, the time from exposure to development is reduced. From the viewpoint of realizing good adhesion even when it is lengthened, the following general formula (III):

[Formula 3]

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

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

With respect to the total solid content of the photosensitive resin composition, the content of (b1) a (meth)acrylate compound having 3 or more ethylenically unsaturated bonds (that is, a compound having 3 or more (meth)acrylate groups) is 0% by mass. It exceeds, and it is preferable that it is 50 mass% or less. If this content exceeds 0% by mass, it is more advantageous in that the adhesion after heating after exposure to development is remarkably improved, and in particular, good adhesion is achieved even when the time from exposure to development is prolonged. If it is 50 mass% or less, the flexibility of the cured resist tends to be improved and the peeling time tends to be shortened. It is more preferable that it is 2 mass% or more and 40 mass% or less, and, as for this content, it is still more preferable that it is 4 mass% or more and 35 mass% or less. In a more preferred embodiment, (B) the compound having an ethylenically unsaturated double bond contains a compound having 3 or more methacrylate groups in the molecule, preferably 5% by mass or more, based on the solid content of the entire photosensitive resin composition. Preferably 9% by mass or more, more preferably 13% by mass or more, particularly preferably 20% by mass or more, and more preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30 It contains in an amount of not more than mass%.

From the viewpoint of adhesion and from the viewpoint of suppressing the foamability of the developer, the photosensitive resin composition is a compound having (B) an ethylenically unsaturated bond, (b2) a butylene oxide chain or a propylene oxide chain, and one or two (meth) It is preferable to include a compound having an acryloyl group.

(b2) the compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryloyl groups, from the viewpoint of suppressing bleed-out, preferably 500 or more, more preferably 700 or more, More preferably, it has a molecular weight of 1000 or more.

(b2) As a 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, poly Tetramethylene glycol (meth)acrylate, polytetramethylene glycol di(meth)acrylate, etc. are mentioned. (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, (b2) a butylene oxide chain or a propylene oxide chain, and a compound having one or two (meth)acryloyl groups is preferably 1 to 20, more preferably 4 to 15, More preferably, it is a (meth)acrylate or di(meth)acrylate 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 with respect to the total solid content of the photosensitive resin composition exceeds 0 mass%, and further 20 mass It is preferable that it is% or less.

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

From the viewpoint of chemical resistance, adhesion, high resolution, and skirt shape of the resist pattern, (B) the concentration of the methacryloyl group in the compound having an ethylenically unsaturated bond is preferably 0.20 mol/100 g or more, It is more preferably 0.30 mol/100 g or more, and still more preferably 0.35 mol/100 g or more. The upper limit of the concentration of the methacryloyl group is not limited as long as polymerization and 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, (B) the value of the concentration of methacryloyl group/(concentration of methacryloyl group + concentration of acryloyl group) in the compound having an ethylenically unsaturated bond is preferably 0.50 or more, more It is preferably 0.60 or more, more preferably 0.80 or more, particularly preferably 0.90 or more, and most preferably 0.95 or more.

The (meth)acrylate compounds described above may be used independently or in combination. The photosensitive resin composition is a compound having an ethylenically unsaturated bond (B), and may also contain other compounds. 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 glycidyl group-containing compound with an α,β-unsaturated carboxylic acid. The obtained compound, 1,6-hexanediol di(meth)acrylate, etc. are mentioned.

(B) The ratio of the compound having an ethylenically unsaturated double bond to the total solids mass of the photosensitive resin composition is preferably 5% by mass to 70% by mass. It is preferable from the viewpoint of sensitivity, resolution, and adhesiveness to make this ratio 5 mass% or more. This ratio is more preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more. On the other hand, setting this ratio to 70% by mass or less is preferable from the viewpoint of suppressing the delay in peeling of the edge fuse and the cured resist. It is more preferable to make this ratio 50 mass% or less.

(C) photopolymerization initiator

(C) A photoinitiator is a compound which polymerizes a monomer by light. (C) The photopolymerization initiator can remarkably improve the adhesiveness when developing after heating after exposure, and particularly from the viewpoint of obtaining good adhesiveness even when the time from exposure to development is prolonged, preferably , Anthracene, pyrazoline, triphenylamine, coumarin, and one or more selected from the group consisting of derivatives thereof, more preferably, anthracene and/or anthracene derivative, more preferably, anthracene It includes derivatives. In addition, anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof, particularly anthracene and/or anthracene derivatives, absorb 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. It functions well as a polymerization initiator. Accordingly, in one aspect, the photosensitive resin composition can have photosensitivity to the first active light and the second active light, and can also be used for two-wavelength exposure. (C) The photoinitiator may be selected so as to have a plurality of absorption maximums 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% by mass to 10% by mass, still more preferably 0.1% by mass to 7% by mass, particularly preferably It is in the range of 0.1 mass% to 6 mass%. (C) The total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and preferably 20% by mass or less from the viewpoint of sufficiently transmitting light to the bottom of the resist and obtaining good high resolution. .

The anthracene and anthracene derivatives are advantageous in that they can remarkably improve the adhesiveness when developed after heating after exposure, and in particular, realize good adhesiveness even when the time from exposure to development is prolonged. The anthracene derivative, from the same viewpoint, preferably at the 9 position and/or the 10 position, more preferably at the 9,10 position, an alkoxy group having 1 to 40 carbon atoms which may have a substituent and/or the number of carbon atoms which may have a substituent It has 6-40 aryl groups.

In one aspect, the anthracene derivative can remarkably improve the adhesiveness when developed after heating after exposure, and in particular, from the viewpoint of realizing good adhesiveness even when the time from exposure to development is prolonged, the 9 position or It is preferable to have an alkoxy group having 1 to 40 carbon atoms which may have a substituent in at least one of the 10 positions, and more preferably an alkoxy group having 1 to 30 carbon atoms which may have a substituent in at least one of the 9 or 10 positions. Do. 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 positions 9,10, and an alkoxy group having 1 to 30 carbon atoms which may have a substituent at position 9,10 It is more preferable to have. The number of carbon atoms in the groups at the 9-position and 10-position may be the same or different.

As an alkoxy group which may have a substituent:

Methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, n-pentyloxy group, isoamyl Oxy group, n-hexyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tetradecyloxy group, hexadecyloxy group, eicosyloxy group, cyclohexyloxy group , Norbornyloxy group, tricyclodecanyloxy group, tetracyclododecyloxy group, adamantyloxy group, methyladamantyloxy group, ethyladamantyloxy group, and butyladamantyloxy group;

Alkoxy groups modified with halogen, such as a chlorobutoxy group and a chloropropoxy group;

An alkoxy group added by a hydroxyl group, such as a hydroxybutyloxy group;

An alkoxy group added by a cyano group, such as a cyanobutoxy group;

An alkoxy group added by an alkylene oxide group, such as a methoxybutoxy group;

An alkoxy group added by an aryl group, for example, a phenoxybutoxy group,

And the like. Among these, n-butoxy group is more preferable.

In one aspect, the anthracene derivative can remarkably improve the adhesiveness when developed after heating after exposure, and in particular, from the viewpoint of realizing good adhesiveness even when the time from exposure to development is prolonged, the 9 position or It is preferable to have an aryl group having 6 to 40 carbon atoms which may have a substituent in at least one of the 10 position, and more preferably have an aryl group having 6 to 30 carbon atoms which may have a substituent in at least one of the 9 or 10 position Do.

The number of carbon atoms that may have substituents at positions 9 and 10 can be remarkably improved when the adhesion is developed after heating after exposure, and particularly from the viewpoint of realizing good adhesion even when the time from exposure to development is prolonged. It is preferable to have an aryl group of 6 to 40, and it is more preferable to have an aryl group having 6 to 30 carbon atoms which may have a substituent at positions 9 and 10. The number of carbon atoms in the groups at the 9-position and 10-position may be the same or different. In addition, the groups at the 9-position and 10-position may be the same or different contributions. For example, the group at position 9 may be an alkoxy group having 1 to 40 carbon atoms which may have a substituent, and the group at position 10 may be an aryl group having 6 to 40 carbon atoms which may have a substituent.

Examples of 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 was added, such as a methoxyphenyl group and an ethoxyphenyl group; An aryl group added by an alkyl group, for example, tolyl group, xylyl group, mesityl group, nonylphenyl group; An aryl group added by halogen, such as a chlorophenyl group; An aryl group added with a hydroxyl group, such as a hydroxyphenyl group, etc. are mentioned. Among these, a phenyl group is more preferable.

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

[Formula 4]

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, a substituted or unsubstituted aryl group, a substituted or unsubstituted A ring heteroaryl group or a group N(R') _{2 may be} represented, and two or more R ¹ may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a hetero atom.

X is independently a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, -N(R')- group, -CO-O- group, -CO-S- group, -SO ₂ -O- group, -SO ₂ -S- _{group, -SO 2 -N (R ')} - represents an - group, -O-CO- group, -S-CO- group, -O-SO ₂ - group or a S-SO _2. However, the combination of X is a single bond and R ¹ is a hydrogen atom (unsubstituted anthracene) is excluded.

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, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms Alternatively, a substituted or unsubstituted heteroaryl group may be represented, and R′ may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a hetero atom.

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

Specific examples of the substituted or unsubstituted alkyl group having 1 to 40 carbon atoms in R ¹ and R′ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-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, t-butyl group, etc. are mentioned.

Specific examples of the substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms in the above R ¹ and R′ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cross-linked alicyclic group having 6 to 20 carbon atoms. Formula hydrocarbon groups (eg, norbornyl group, tricyclodecanyl group, tetracyclododecyl group, adamantyl group, methyladamantyl group, ethyladamantyl group, and butyladamantyl group, etc.), and the like.

As specific examples of the alkenyl group having 2 to 4 carbon atoms in the above R ¹ and R′, vinyl and propenyl groups and the like may be mentioned.

Specific examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms in the above R ¹ and R′ include phenyl group, biphenyl group, naphthyl group, anthracenyl group, methoxyphenyl group, ethoxyphenyl group, tolyl group, xyl A reel group, a mesityl group, a nonylphenyl group, a chlorophenyl group, and a hydroxyphenyl group are mentioned.

The substituted or unsubstituted heteroaryl group for R ¹ and R′ is a group containing at least one hetero atom such as a sulfur atom, an oxygen atom, or a nitrogen atom in the substituted or unsubstituted aryl group, for example, pyri A diyl group, an imidazolyl group, a morpholinyl group, a piperidyl group, a pyrrolidyl group, etc. are mentioned.

Further, each of the hydrocarbon groups of R ¹ and R'may be substituted with a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, and a hydroxyalkyl group having 1 to 4 carbon atoms (e.g., hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2- Hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc.), alkoxyl group having 1 to 4 carbon atoms ( For example, 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 , C2-C5 cyanoalkyl group (e.g., cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group , Ethoxycarbonyl group, t-butoxycarbonyl group, etc.), alkoxycarbonylalkoxy group (e.g., methoxycarbonylmethoxy group, ethoxycarbonylmethoxy group, t-butoxycarbonylmethoxy group, etc.), halogen atom (For example, fluorine, chlorine, etc.) and a fluoroalkyl group (for example, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, etc.), etc. are mentioned. It is preferable that each of the hydrocarbon groups of R ¹ and R'is substituted with a halogen atom. In particular, it is preferable that an anthracene derivative has an alkoxy group substituted by a halogen atom at the 9 position and/or the 10 position.

Preferred specific examples of R ¹ and R′ include hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, cyclopentyl group, cyclohexyl group, camporoyl 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 a -N(R')- group, R'is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a cyclopentyl group, a cyclohexyl group, Camporoyl groups, norbornyl groups or benzyl groups are preferred.

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-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di(2-ethylhexyloxy)anthracene, 1,2-benz Anthracene, anthrol, 1,4,9,10-tetrahydroxyanthracene, 9-anthracenemethanol, 1-aminoanthracene, 2-aminoanthracene, 9-(methylaminomethyl)anthracene, 9-acetylanthracene, 9-anthracene Aldehyde, 10-methyl-9-anthraaldehyde, 1,8,9-triacetoxyanthracene, etc. are mentioned. 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, and in particular, the adhesion when developed after heating after exposure can be remarkably improved, especially developed from exposure. 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene, 9,10-bis-(3-chloro Propoxy) anthracene is more preferable, and 9,10-dibutoxyanthracene and 9,10-diphenylanthracene and 9,10-bis-(3-chloropropoxy) anthracene are particularly preferable. The compound represented by the general formula (IV) may be used alone or in combination of two or more.

From the viewpoint of obtaining good adhesion even when the time from exposure to development is prolonged, the adhesiveness when developed after heating after exposure can be remarkably improved. (C) The photopolymerization initiator is preferably And (1) 9,10-diphenylanthracene; (2) 9,10-dialkoxyanthracene is included; (3) containing an anthracene derivative having a halogen atom; (4) a halogen substituent of 9,10-dialkoxyanthracene is included; (5) The 9,10-dialkoxyanthracene contains a compound in which the alkoxy group at the 9 and/or 10 positions 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 adhesion when developed after heating after exposure, and is particularly advantageous from the viewpoint of obtaining good adhesion even when the time from exposure to development is prolonged. In addition, it can be used for two-wavelength exposure using a first active light having a center wavelength of less than 390 nm and a second active light having a wavelength of 390 nm or more as a center wavelength, and showing excellent sensitivity, adhesion and resolution. It is also advantageous in that it can provide a resin composition.

In one aspect, it is preferable that the (C) photoinitiator contains an anthracene derivative having a halogen atom. A preferred example of an anthracene derivative having a halogen atom is a halogen substituent of 9,10-dialkoxyanthracene. A preferable example of the halogen substituent is a compound in which the alkoxy group at the 9 and/or 10 positions of the 9,10-dialkoxyanthracene is modified with one or more halogens. As a preferable alkoxy group, what was illustrated above as a C1-C40 alkoxy group is mentioned.

In one aspect, 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 anthracene and 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, more preferably 0.1 to 3% by mass with respect to the total solid content of the photosensitive resin composition. %, particularly preferably 0.1 to 1.0 mass%.

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

As a pyrazoline derivative, for example, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzooxa Zol-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)- 5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-( 4-Isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1 -Phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5- (3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3 -(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3 -Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, etc. are preferable from the above viewpoint, 1 -Phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferred.

Examples of the coumarin derivatives include 7-diethylamino-4-methylcoumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, and the like. Among them, 7-diethylamino-4-methylcoumarin is preferable 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, dialkylaminobenzoic acid esters. Compounds, oxime esters, acridines (for example, 9-phenylacridine, bisacridinylheptane, 9-(p-methylphenyl)acridine, 9-(m-methylphenyl)acridine, It is preferable from the viewpoint of resolution and adhesion), hexaarylbiimidazole, N-arylamino acid or an ester compound thereof (for example, N-phenylglycine is preferable from the viewpoint of sensitivity, resolution, and adhesion), and Halogen compounds (for example, tribromomethylphenyl sulfone), etc. are mentioned. These may be used alone or in combination of two or more. Others, 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, or the like may be used.

As aromatic ketones, for example, benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4 '-Dimethylaminobenzophenone. These may be used alone or in combination of two or more. Among these, 4,4'-bis(diethylamino)benzophenone is preferable from the viewpoint of adhesiveness. In addition, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably in the range of 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3% 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',5,5'-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-tetra Fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-penta Fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, etc., and these may be used alone or in combination of two or more.I can. From the viewpoint of sensitivity, resolution, and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

The content of hexaarylbisimidazole in the photosensitive resin composition is preferably 0.05% by mass to 8% by mass, more preferably 0.1% by mass to 7% by mass, from the viewpoint of improving the peeling properties and/or sensitivity of the photosensitive resin layer. %, more preferably in the range of 1% by mass 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, the (D) phenolic polymerization inhibitor is a compound having one or more phenolic hydroxyl groups. The phenolic polymerization inhibitor has a characteristic of inhibiting a polymerization reaction caused by heat or the like, thereby improving storage stability. The phenolic polymerization inhibitor is a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, a substituted or unsubstituted You may have one or more substituents selected from the group consisting of an aryl group and a substituted or unsubstituted heteroaryl group. In a preferred embodiment, the (D) phenolic polymerization inhibitor is a monohydric phenol (that is, a compound having one phenolic hydroxyl group in the molecule). (D) More specific preferred examples of the phenolic polymerization inhibitor are metoquinone, dibutylhydroxytoluene, hydroquinone, tetrakis(3-(3',5'-di-tert-butyl-4'-hydroxy Phenyl) propionic acid) pentaerythritol, 2,2'-thiodiethylbis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 3-(3,5-di -tert-butyl-4-hydroxyphenyl) stearyl propionate, N,N'-hexamethylenebis(3-(3,5-di-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)mesitylene, 2, 4-bis(dodecylthiomethyl)-6-methylphenol, 2,4-bis(octylthiomethyl)-6-methylphenol, bis(3-(3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propionic acid) (ethylenebis(oxyethylene)), 1,6-hexanediolbis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 1,3,5- Tris((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione , 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol, etc., and in particular, metoquinone and dibutyl Hydroxytoluene is preferable from the viewpoint that the difference in the shortest development time between the presence and absence of heating after exposure does not occur easily.

(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 1 ppm or more, preferably from the viewpoint of obtaining a desired polymerization inhibitory effect on the photosensitive resin composition. Is 5 ppm or more, more preferably 10 ppm or more, even more preferably 15 ppm or more, particularly preferably 20 ppm or more, and when developing after heating after exposure, especially when the time from exposure to development is prolonged From the viewpoint of realizing a good adhesion of 300 ppm or less, preferably 200 ppm or less, more preferably 150 ppm or less, still more preferably 100 ppm or less, still more preferably 75 ppm or less, even more preferably 50 ppm, particularly preferably 40 ppm or less. When the photosensitive resin composition contains (D) a phenolic polymerization inhibitor, but the amount thereof is small, after exposure, heating and subsequent development are performed, the polymerization reaction in the photosensitive resin composition during exposure is favorable. And, it is advantageous in that both the reaction acceleration of the polymer (and hence the improvement of adhesion) can be achieved due to the favorable effect of improving the mobility by heating the polymer. For example, in a system in which the polymer has a bulky molecular structure (e.g., a relatively large amount of styrene skeleton), when heating after exposure intended to improve adhesion, the mobility improvement effect by heating the polymer is low. (Therefore, the effect of improving adhesion is low), but according to the photosensitive resin composition of the present embodiment, since the amount of the (D) phenolic polymerization inhibitor is in the above range, even when such a bulky polymer is present, After exposure, the effect of improving adhesion by heating is obtained satisfactorily.

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

[Optional ingredient]

In addition to the components of the above (A) to (D), the photosensitive resin composition may further contain optional components as desired. Examples of the optional component include (d) (D) additional polymerization inhibitors other than the phenolic polymerization inhibitor, dyes, coloring substances, plasticizers, antioxidants, stabilizers, and the like. For example, additives listed in Japanese Unexamined Patent Application Publication No. 2013-156369 may be used.

((d) additional polymerization inhibitor)

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

Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosoamine. Since the sensitivity of the photosensitive resin composition is not impaired, a nitrosophenylhydroxyamine aluminum salt is preferred.

As benzotriazoles, for example, 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.

As carboxybenzotriazoles, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2- Ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzo Triazole, etc. are mentioned.

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

(Dyes and coloring substances)

In the present embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of dyes (for example, leuco dyes, fluorane dyes, etc.) and colored substances, as desired.

As a coloring substance, for example, fuxine, phthalocyanine green, oramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (e.g., Eisen manufactured by Hodogaya Chemical Co., Ltd. (Registered trademark) MALACHITE GREEN), basic blue 20, diamond green (for example, Hodogaya Chemical Co., Ltd. Aizen (registered trademark) DIAMOND GREEN GH) can be mentioned. The content of the colored substance in the photosensitive resin composition is preferably from 0.001% by mass to 1% by mass, when the total solid content mass of the photosensitive resin composition is 100% by mass. It is preferable to make the content 0.001 mass% or more from the viewpoint of improving the handleability of the photosensitive resin composition. On the other hand, it is preferable from the viewpoint of maintaining the storage stability of the photosensitive resin composition to make the content 1 mass% or less.

Since the photosensitive resin composition contains a dye, the exposed portion is colored, so it is preferable in terms of visibility.In addition, when an inspection device or the like reads a positioning marker for exposure, it is recognized that the contrast between the exposed portion and the unexposed portion is large. Easy and advantageous. As preferable dyes from this viewpoint, a leuco dye and a fluorane dye are mentioned.

Examples of the leuco dye include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leuco malachite green], and the like. In particular, from the viewpoint of improving the contrast, it is preferable to use leucocrystal violet as the leuco dye. It is preferable that the content of the leuco dye in the photosensitive resin composition is 0.1% by mass to 10% by mass with respect to the total solid content mass of the photosensitive resin composition. It is preferable to make this content 0.1 mass% or more from the viewpoint of improving the contrast between an exposed part and an unexposed part. As for this content, it is more preferable to set it as 0.2 mass% or more, and it is especially preferable to set it as 0.4 mass% or more. On the other hand, it is preferable to make this content into 10 mass% or less from a viewpoint of maintaining storage stability. This content is more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

In addition, it is preferable from the viewpoint of optimizing adhesion and contrast to use in combination with a leuco dye and the above-described halogen compound in the photopolymerization initiator (C) in the photosensitive resin composition. 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 to 3% by mass when the total solid content of the photosensitive resin composition is 100% by mass. It is preferable from the viewpoint of maintaining the storage stability of the hue.

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

In this embodiment, the photosensitive resin composition may further contain a plasticizer. As a plasticizer, for example, phthalic acid esters (e.g., diethylphthalate), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri acetyl citrate -n-propyl, tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like. In addition, adecanol SDX-1569, adecanol SDX-1570, adecanol SDX-1571, adecanol SDX-479 (manufactured by Asahi Telephone Co., Ltd.), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, Newpol BPE-20T, Newpol BPE-60, Newpol BPE-100, Newpol BPE-180 (manufactured by Sanyo Chemical Co., Ltd.), Uniall DB-400, Uniall DAB-800, Uniall DA-350F , Uniol DA-400, Uniol DA-700 (manufactured by Nippon Oil Co., Ltd.), BA-P4U glycol, BA-P8 glycol (manufactured by Nippon Emulsifier Co., Ltd.), and other compounds having a bisphenol skeleton have.

The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, and more preferably 1% by mass to 30% by mass with respect to the total solid content mass of the photosensitive resin composition. It is preferable that the content is 1% by mass or more from the viewpoint of suppressing the delay in development time and providing 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 hardening and cold flow.

When the moisture content in the photosensitive resin composition is large, local plasticization of the photosensitive resin composition is rapidly accelerated, and an edge fuse is generated. From the viewpoint of suppressing the edge fuse, the water content in the photosensitive resin composition is preferably 0.7% or less, based on the photosensitive resin composition after coating and drying the photosensitive resin composition on a supporting film. The moisture content in the photosensitive resin composition is preferably 0.65% or less, preferably 0.6% or less, preferably 0.55% or less, preferably 0.5% or less, preferably 0.45% or less, preferably 0.4% or less, and 0.35% It is preferable that it is below, it is preferable that it is 0.3% or less, it is preferable that it is 0.25% or less, and it is preferable that it is 0.2% or less.

[solvent]

The photosensitive resin composition can be dissolved in a solvent and used in the manufacture of a photosensitive resin laminate in the form of a photosensitive resin composition combination liquid. Ketones, alcohols, etc. are mentioned as a solvent. The ketones are represented by methyl ethyl ketone (MEK) and acetone. The alcohols are represented by methanol, ethanol, and isopropanol. The solvent is in an amount such that the viscosity at 25°C of the photosensitive resin composition combination liquid applied on the support film in the production of the photosensitive resin laminate is 500 mPa·s to 4,000 mPa·s, and the photosensitive resin It is preferably added to the composition.

[Light transmittance of photosensitive resin composition]

The light transmittance in 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 developing after heating after exposure, especially developed from exposure. From the viewpoint of providing a photosensitive resin composition that realizes good adhesion even when the time until it is long, it is 58% to 95%. 375 nm and 405 nm correspond to typical exposure wavelengths in the photosensitive resin composition of the present embodiment. The light transmittance is 58% or more, preferably 60% or more, from the viewpoint of obtaining good sensitivity, adhesion, line width reproducibility and resolution by reaching a deeper region of the photosensitive resin composition during exposure. It is preferably 62% or more, more preferably 64% or more, even more preferably 65% or more, and from the viewpoint of obtaining a good skirt shape by suppressing diffused light from the substrate surface, 95% or less, preferably It is 85% or less, more preferably 80% or less, more preferably 75% or less, and still more preferably 70% or less.

The means for controlling the light transmittance in at least one of 375 nm and 405 nm within the above range is not limited to these, but examples include controlling the amount of addition of a photoinitiator, a dye, or a colored substance.

[Photosensitive resin laminate]

This embodiment also provides the photosensitive resin layered product which has the photosensitive resin layer which consists of the photosensitive resin composition mentioned above, and a support film. As the supporting film, a transparent supporting film that transmits light emitted from an exposure light source is preferable. As such a supporting 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 A composite film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, etc. are mentioned. As these films, those stretched as necessary can be used.

As the haze of the support film, from the viewpoint of suppressing light scattering at the time of exposure, 5% or less is preferable, 2% or less is more preferable, 1.5% or less is still more preferable, and 1.0% or less is particularly preferable. 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 to improve the image formability and economic efficiency. 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. It is preferable that the size of fine particles such as a lubricant contained in the support film is less than 5 µm.

The supporting 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, an antistatic layer may be provided. 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 side A, and on the other side B, (1) fine particles are added in the same manner as the surface A. Containing, (2) containing a small amount of fine particles than the surface A, (3) containing finer particles than the surface A, (4) containing no fine particles, the same structure can be taken. In the case of the structures of (2), (3), and (4), it is preferable to form a photosensitive resin layer on the side B side. At this time, if there is a resin layer containing fine particles on the side A side, it is preferable from the viewpoint of sliding properties of the film. It is preferable that the size of the fine particles at this time is less than 1.5 µm. In addition, the size of the fine particles is a value obtained by measurement with a scanning electron microscope calibrated using a standard sample.

An important characteristic of the protective layer used in the photosensitive resin layered product is that the adhesive force with the photosensitive resin layer is sufficiently smaller than that of the supporting film and can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as a protective layer. In addition, a film having excellent peelability shown in Japanese Laid-Open Patent Publication No. 59-202457 may be used. The thickness of the protective layer is preferably 10 µm to 100 µm, more preferably 10 µm to 50 µm.

A gel called fish eye may exist on the surface of the polyethylene film. When a polyethylene film having a fish eye is used as a protective layer, the fish eye may be transferred to the photosensitive resin layer. When the fish eye is transferred to the photosensitive resin layer, air may be mixed during lamination to form voids, leading to defects in the resist pattern. From the viewpoint of preventing fish eye, the material of the protective layer is preferably oriented polypropylene. As a specific example, Oji Paper Co., Ltd. product Alpan E-200A is mentioned.

The thickness of the photosensitive resin layer in the photosensitive resin layered product is different in use, 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 it is 10 micrometers-30 micrometers. As for the thickness of the photosensitive resin layer, the thinner the resolution is improved, and the thicker the film strength is improved.

The light transmittance of the laminate of the supporting film and the photosensitive resin layer at a wavelength of 630 nm is an index of discoloration of the dye, and a high light transmittance at a wavelength of 630 nm indicates that the dye is discolored. The light transmittance at a wavelength of 630 nm of the laminate of the supporting film and the photosensitive resin layer is preferably 80% or less, preferably 78% or less, preferably 75% or less, preferably 72% or less, and 70% or less. It is preferably 68% or less, preferably 65% or less, preferably 62% or less, preferably 60% or less, preferably 58% or less, preferably 55% or less, and 52% or less It is preferable and it is preferable that it is 50% or less. This light transmittance is a value of a laminate of a supporting film and a photosensitive resin layer (that is, a protective layer is not included).

Next, a method of manufacturing a 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 that dissolves it to obtain a homogeneous solution, first applied on a support film using a bar coater or roll coater, and then dried to prepare the solvent. By removing, a photosensitive resin layer made of a photosensitive resin composition can be laminated on the support film. Then, if necessary, by laminating a protective layer on the photosensitive resin layer, a photosensitive resin laminate can be produced.

<Method of forming a resist pattern>

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

As a resist pattern, for example, a printed wiring board, a semiconductor element, a printing board, 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, Patterns, such as a wiring for liquid crystal TFT, and an electrode for PDP (plasma display panel), are mentioned. As an example, the manufacturing method of a printed wiring board is demonstrated as follows.

The printed wiring board is manufactured through each of the following steps.

(1) Lamination process

First, in a lamination process, 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, and then the photosensitive resin layer is heated and press-bonded to the substrate surface with a laminator to laminate. Examples of the material of the substrate include copper, stainless steel (SUS), glass, and indium tin oxide (ITO).

In this embodiment, the photosensitive resin layer may be laminated only on one side of the substrate surface, or may be laminated on both sides as necessary. The heating temperature at the time of lamination is generally 40°C to 160°C. Further, by performing heat compression bonding at the time of lamination two or more times, the adhesion of the obtained resist pattern to the substrate can be improved. At the time of heat-compression bonding, a two-stage laminator provided with two rolls may be used, or a laminate of a substrate and a photosensitive resin layer may be repeatedly passed through a roll several times to press bonding.

(2) Exposure process

In this step, an exposure method in which a mask film having a desired wiring pattern is in close contact on a support film and performed using an active light source, an exposure method by direct drawing of a drawing pattern that is a desired wiring pattern, or an image of a photomask is converted into a lens. The photosensitive resin layer is exposed by the exposure method by projecting through.

The exposure step is preferably performed by an exposure method by direct drawing of a drawing pattern, or an exposure method in which an image of a photomask is projected through a lens, and it is performed by an exposure method by direct drawing of a drawing pattern. More preferable. The advantage of the photosensitive resin composition according to the present embodiment is more remarkable in an exposure method by direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens, and exposure by direct drawing of a drawing pattern It is particularly remarkable in the method.

When the exposure step is an exposure method by direct drawing, it is preferable that it is laser light with a center wavelength of less than 390 nm or laser light with a center wavelength of 390 nm or more. It is more preferable that they are laser light with a center wavelength of 350 nm or more and 380 nm or less, or a laser light with 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. Further, it is more preferable that 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.

(3) heating process

In this step, it is preferable to perform a heating step of about 30°C to about 200°C, more preferably in the range of 30°C to 150°C, and in the range of 60°C to 120°C on the exposed photosensitive resin composition. It is more preferable. By performing this heating process, the resolution and adhesiveness can be improved. For heating, a hot air, infrared or far-infrared heating furnace, a thermostat, a hot plate, a hot air dryer, an infrared dryer, a hot roll, or the like can be used. If the heating method is a hot roll, it is preferable from the viewpoint of enabling a short-time treatment, and more preferably two or more hot rolls.

In particular, in the present invention, (D) a phenolic polymerization inhibitor is used and the amount thereof is reduced to a small amount, and development after heating after exposure by controlling the light transmittance at a specific wavelength of the resin composition to a specific range. In this case, the mobility of the polymer is improved by heating, and for example, even in a system having a relatively large content of the styrene skeleton, the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly compatible. As a result, sensitivity, adhesion, line width reproducibility, and resolution can be remarkably improved. And by remarkably improving the adhesiveness, even when the time from exposure to development is long, favorable adhesiveness can be obtained. In addition, it is preferable from the viewpoint of the effect of the present invention to perform the heating step within 15 minutes from exposure, and more preferably within 10 minutes.

(4) development process

In this step, after exposure, the support film on the photosensitive resin layer is peeled off, and then the unexposed portion is developed and removed using a developer of an aqueous alkali solution to form a resist pattern on the substrate.

As the aqueous alkali solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used. The aqueous alkali solution is appropriately selected in accordance with the characteristics of the photosensitive resin layer, but a concentration of about 0.2% by mass to about 2% by mass, and an aqueous Na ₂ CO ₃ solution of about 20°C to about 40°C is preferable.

In an exemplary embodiment, the time from exposure to development (that is, the time from the end of exposure to the start of development) may be 5 minutes or more, or 60 minutes or more, or 180 minutes or more, 1440 minutes or less, or 720 minutes or less. , Or 300 minutes or less.

A resist pattern can be obtained through each of the steps (1) to (4) described above.

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

(5) Etching process or plating process

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

(6) peeling process

Then, if necessary, the resist pattern is peeled from the substrate using an appropriate stripper. Examples of the stripping solution include an aqueous alkali solution and an amine stripper. However, the resist pattern formed by heating after exposure from the photosensitive resin composition of the present invention has the advantage that the peeling piece is not excessively micronized while exhibiting good peelability to an amine-based peeling solution. Therefore, when an amine-based stripping solution is used as the stripping solution, the advantageous effects of the present invention are further exerted and are preferable.

The amine contained in the amine stripper may be an inorganic amine or an organic amine.

As an inorganic amine, ammonia, hydroxylamine, hydrazine, etc. are mentioned, for example.

Examples of the organic amine include ethanolamine, propanolamine, alkylamine, cyclic amine, and quaternary ammonium salt. In these specific examples,

As ethanolamine, for example, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, amino acid Oxyethanol, etc.;

As a propanolamine, For example, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, etc.;

As the alkylamine, for example, monomethylamine, dimethylamine, trimethylamine, ethyleneamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, tetraethylenepentamine, etc.;

As a cyclic amine, for example, choline, morpholine, etc.;

As a 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, etc.;

Each can be illustrated.

The amine stripper may be an aqueous solution containing one or more of the amines illustrated 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, development conditions, and the like.

The amine-based peeling solution may further contain additives commonly used in the peeling agent, for example, a surfactant, an antifoaming agent, a pH adjusting agent, a preservative, an anti-reposition agent, and the like.

The peeling process is, for example, at a temperature of 0°C or more and 100°C or less, preferably room temperature (23°C) or more and 50°C or less, for example, 1 second or more and 1 hour or less, and preferably 10 seconds or more and 10 minutes. In the following time, it is carried out.

After the peeling step, as desired, the substrate after removing the resist pattern may be washed with pure water or the like.

The photosensitive resin laminate of this embodiment is a conductor such as 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, and a PDP electrode. It is a photosensitive resin laminate suitable for manufacture of a pattern.

In addition, the above-described various parameters are measured according to a method understood by those skilled in the art that the measurement method in Examples to be described later or equivalent thereto unless otherwise specified.

Example

Next, the present embodiment will be described more specifically with reference to Examples and Comparative Examples. However, this embodiment is not limited to the following examples, unless departing from the gist. Physical properties in Examples were measured by the following method.

The measurement of the physical properties of the polymer, and methods of preparing samples for evaluation of Examples and Comparative Examples will be described. In addition, the evaluation method and the evaluation result of the obtained sample are shown.

(1) Measurement and calculation of physical properties

<Measurement of the weight average molecular weight or number average molecular weight of the polymer>

The weight average molecular weight or number average molecular weight of the polymer is determined by Nippon Spectroscopy Co., Ltd. gel permeation chromatography (GPC) (pump: Gulliver, PU-1580 type, column: Showa Electric Co., Ltd. Shodex (registered trademark) ( KF-807, KF-806M, KF-806M, KF-802.5) 4 series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use calibration curve by Shodex STANDARD SM-105 manufactured by Showa Electric Works) It was calculated|required as polystyrene conversion by.

In addition, the degree of dispersion of the polymer was calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

<Acid equivalent>

In the present disclosure, an acid equivalent means the mass (grams) of a polymer having 1 equivalent of carboxyl group in a molecule. The acid equivalent was measured by a potentiometric titration method using a 0.1 mol/L aqueous sodium hydroxide solution using the Hiranuma Industrial Co., Ltd. product Hiranuma automatic titration apparatus (COM-555).

<I/O value>

The I/O value of the alkali-soluble polymer was derived by the following method. First, non-patent literature (organic conceptual diagram (by Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, Nos. 1, 1 to 16 (1954); Area of Chemistry, Vol. 11, No. 10, 719-725 (1957); Fragrance Journal, Nos. 34, 97-111 (1979); Fragrance Journal, Nos. 50, 79-82 (1981)) I and O values of each comonomer were calculated, and then the I _average and O _average values were obtained by averaging each of the IO and O values by the molar ratio of the comonomer. And, the I/O value was derived by dividing the obtained I _average value by the O _average value.

<Glass transition temperature Tg>

The glass transition temperature Tg of the alkali-soluble polymer was determined by the Fox equation. When determining the glass transition temperature Tg, as the glass transition temperature of a homopolymer composed of a comonomer forming the corresponding alkali-soluble polymer, non-patent literature (Brandrup, J. Immergut, EH edited "Polymer handbook, Third edition, John Wiley &amp; sons, 1989, p. 209 Chapter VI "Glass transition temperatures of polymers"). In addition, the glass transition temperature of the homopolymer composed of each comonomer used for calculation in Examples is shown in Table 1. When the alkali-soluble polymer is composed of two or more kinds of polymers, the value obtained by the following formula is the glass transition temperature of the alkali-soluble polymer.

{In the formula, W _i is the solid weight of each alkali-soluble polymer, Tg _i is the glass transition temperature obtained by the Fox formula of each alkali-soluble polymer, and W _total is the total solid of each alkali-soluble polymer Weight, and n is the number of kinds of alkali-soluble polymers contained in the photosensitive resin composition}

(2) How to prepare samples for evaluation

Samples for evaluation were prepared as follows.

<Production of photosensitive resin laminate>

Components shown in Tables 1-3 (however, the number of each component indicates the amount (part by mass) as a solid content) and a solvent were sufficiently stirred and mixed to obtain a photosensitive resin composition mixture. The details of the components shown in Tables 1 and 2 are shown in Table 3. A 16 µm-thick polyethylene terephthalate film (manufactured by Toray Co., Ltd., FB-40) was used as a supporting film, and this combination solution was uniformly applied to the surface using a bar coater, and 3 in a dryer at 95°C. It dried for a minute to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 30 µm.

Subsequently, on the surface of the side where the polyethylene terephthalate film of the photosensitive resin composition layer is not laminated, as a protective layer, a 19 μm-thick polyethylene film (manufactured by Tama Poly Co., Ltd., GF-18) is bonded to the photosensitive resin laminate. Got it.

In addition, the amount of metoquinone and the amount of dibutylhydroxytoluene in Tables 1 and 2 mean the concentration of each component based on the total amount of solid content in the photosensitive resin composition.

＜Front of the board＞

As a substrate for evaluation of image properties, a 0.4 mm thick copper-clad laminate laminated with 35 μm rolled copper foil was subjected to jet scrub polishing with a spray pressure of 0.2 MPa (manufactured by Ujiden Chemical Industries, Ltd., #400). Thereafter, the substrate surface was washed with a 10% by mass H ₂ SO ₄ aqueous solution.

<Laminate>

Roll the photosensitive resin laminated body with a hot roll laminator (manufactured by Asahi Chemical Co., Ltd., AL-700) on a copper clad laminate preheated to 50°C while peeling the polyethylene film (protective layer) of the photosensitive resin laminate. Laminated at a temperature of 105°C. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m/min.

<Exposure>

On the evaluation substrate 2 hours after lamination, by direct drawing exposure machine (manufactured by Orvotech Co., Ltd., Nuvogo Fine 10, light source: 375 nm (30%) + 405 nm (70%)), a stopper 41 step step It was exposed using a tablet. The exposure was performed at an exposure amount of 14 stages of the highest residual film when exposed and developed using the stopper 41 stage step tablet as a mask.

<heating>

The evaluation substrate 7 minutes after exposure was heated by a hot roll laminator (Asahi Chemical Co., Ltd. make, AL-700). The roll temperature was 105°C, the air pressure was 0.30 MPa, and the lamination speed was 1 m/min. Further, if the time from exposure to development is lengthened, the effect of heating is lost, and therefore, it is usually heated in about 1 minute after exposure. Therefore, heating 7 minutes after exposure in this example is a very severe condition.

<phenomena>

After peeling off the polyethylene terephthalate film (supporting film), using an alkali developing device (manufactured by Fuji pore Co., Ltd., developing device for dry films), a 30°C 1 mass% Na ₂ CO ₃ aqueous solution was sprayed over a predetermined period of time. The development was carried out. The time of the developing spray was made twice as long as the shortest developing time, and the time of the water washing spray after development was made three times the shortest developing time. At this time, the shortest time required to completely dissolve the photosensitive resin layer in the unexposed portion was taken as the shortest development time.

(3) Sample evaluation method

<Metoquinone amount>

The amount of metoquinone 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 hydrogen flame ionization detector (hereinafter, abbreviated as FID), and n-docoic acid was used as an internal standard.

<Amount of dibutylhydroxytoluene>

The amount of dibutylhydroxytoluene in the photosensitive resin composition was determined by GC in the same manner as the amount of metoquinone. 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 in each wavelength of the photosensitive resin layered product from which the polyethylene film (protective layer) was peeled off was measured using a spectrophotometer (Hitachi High-Technologies Co., Ltd., U-3010). At that time, measurement was performed by installing so that transmitted light may pass in the film thickness direction of the photosensitive resin laminate.

<Sensitivity evaluation>

In the above-described exposure step, after exposure was performed by passing through the mask of the stopper 41-step tablet, it was developed, and the exposure amount (mJ/cm2) at which the highest number of remaining films was 14 was determined as a value of sensitivity.

<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 is a ratio of 20 µm to 20 µm. It developed in accordance with the above-described developing 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 is a ratio of 1:1. It developed in accordance with the above-described developing conditions to form a cured resist line.

The minimum line width in which the cured resist line was normally formed was determined as a value of the resolution.

<Adhesion>

In the above-described exposure step, exposure was performed using drawing data having a line pattern in which the widths of the exposed portion and the unexposed portion were x µm: 200 µm. It developed according to the above-described developing conditions, and the minimum line width in which the cured resist line was 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 obtained as a value of adhesion.

About the evaluation of adhesiveness only, evaluation was performed by two methods, the case where it heated after 1 minute elapsed after exposure, and the case where it heated after 7 minutes elapsed after exposure.

<Delay of the shortest development time>

In the above-described developing process, it is necessary for the photosensitive resin layer in the unexposed portion to be completely dissolved for each of the development without heating after exposure and after heating after 7 minutes of exposure. The shortest development time, which is the shortest time to do, was measured, and ranked according to the following criteria.

Good: There is no difference in the shortest development time between with heating after exposure and without heating after exposure

A: The shortest development time with heating after exposure is delayed within 1 second compared to without heating after exposure

Impossible: The shortest development time with heating after exposure is delayed by more than 1 second compared to without heating after exposure.

The results are shown in Tables 1 and 2.

The heating condition after exposure in this example is a very severe condition because it is heating 7 minutes after exposure. For example, the adhesiveness when the compositions of Example 3 and Comparative Example 2 were developed without heating after exposure were all 13.8 µm. In short, in the composition of Comparative Example 1, no effect was observed in heating after 7 minutes of exposure, but in Example 3, adhesion can be improved even under very severe conditions. In addition, under the conditions of heating 1 minute after exposure, adhesion of 10.8 µm was obtained also in any of the compositions of Example 7 and Comparative Example 1. As can be seen from the above results, even if the adhesion is good under general heating conditions after exposure, it does not mean that the adhesion becomes good under the harsh conditions of heating 7 minutes after exposure. Even in the heating conditions after exposure, adhesion can be improved. Thereby, when manufacturing a circuit board, even if the time from exposure to development is lengthened, good adhesion can be obtained, so that a high-definition circuit pattern can be stably formed.

Industrial availability

Since the photosensitive resin composition according to the present invention has good sensitivity, adhesion, line width reproducibility, and resolution when developed after heating after exposure, and particularly realizes good adhesion even when the time from exposure to development is long. As a photosensitive resin composition, it can be used for a wide range of applications.

Claims (25)

(A) Alkali-soluble polymer: 10 mass%-90 mass%;
(B) Compound having ethylenically unsaturated double bond: 5% by mass to 70% by mass;
(C) Photoinitiator: 0.01 mass%-20 mass %; And
(D) Phenolic polymerization inhibitor: 1 ppm to 300 ppm;
As a photosensitive resin composition comprising a,
The photosensitive resin composition, wherein the light transmittance in at least one of 375 nm and 405 nm is 58% to 95%. The method of claim 1,
The photosensitive resin composition containing metoquinone as said (D) phenol-type polymerization inhibitor. The method according to claim 1 or 2,
The photosensitive resin composition containing dibutylhydroxytoluene as said (D) phenolic polymerization inhibitor. The method of claim 3,
The photosensitive resin composition, wherein the content of the dibutylhydroxytoluene is 1 to 200 ppm. The method of claim 3,
The photosensitive resin composition, wherein the content of the dibutylhydroxytoluene is 10 to 150 ppm. The method according to any one of claims 1 to 5,
The photosensitive resin composition, wherein the (A) alkali-soluble polymer has an I/O value of 0.600 or less. The method according to any one of claims 1 to 6,
The photosensitive resin composition, wherein the (C) photopolymerization initiator contains at least one selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof. The method of claim 7,
The photosensitive resin composition, wherein the (C) photopolymerization initiator contains an anthracene and/or an anthracene derivative. The method according to any one of claims 1 to 8,
The photosensitive resin composition, wherein the structural unit of styrene and/or a styrene derivative in the alkali-soluble polymer (A) is 26% by mass or more. The method according to any one of claims 1 to 9,
The photosensitive resin composition, wherein the alkali-soluble polymer (A) contains a structural unit of benzyl (meth)acrylate as a monomer component. The method according to any one of claims 1 to 10,
The photosensitive resin composition, wherein the (A) alkali-soluble polymer has a glass transition temperature of 120°C or less. The method according to any one of claims 1 to 11,
The photosensitive resin composition, wherein the compound (B) having an ethylenically unsaturated double bond contains a compound having 3 or more methacrylate groups in the molecule in an amount of 5% by mass or more with respect to the solid content of the entire photosensitive resin composition. The method according to any one of claims 1 to 12,
A photosensitive resin composition for obtaining a cured exposure resin product 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. The method according to any one of claims 1 to 13,
The photosensitive resin composition, 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. The method according to any one of claims 1 to 14,
The following process:
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 which can form a pattern by. The method according to any one of claims 1 to 15,
The photosensitive resin composition in which the heating temperature in the said heating process is a range of 30 degreeC-150 degreeC. The method according to any one of claims 1 to 16,
The photosensitive resin composition which performs the said heating process within 15 minutes from exposure. The following process:
The exposure process of exposing the photosensitive resin composition in any one of Claims 1-17;
A heating step of heating the exposed photosensitive resin composition; And
A developing step of developing the heated photosensitive resin composition;
A method of forming a resist pattern comprising a. The method of claim 18,
The method for forming a resist pattern, wherein the heating temperature in the heating step is in the range of 30°C to 150°C. The method of claim 18 or 19,
A method for forming a resist pattern, wherein the heating step is performed within 15 minutes from exposure. The method according to any one of claims 18 to 20,
A method of forming a resist pattern, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens. The method of claim 21,
A method of forming a resist pattern, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern. The method of claim 22,
A method of forming a resist pattern, wherein the exposure step is performed 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. The method of claim 23,
The method of forming a resist pattern, 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 board forming step of forming a circuit board by etching or plating the substrate having the resist pattern; Containing a circuit board manufacturing method.