JP7170723B2 - Photosensitive resin composition and method for forming resist pattern - Google Patents

Description

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

2. Description of the Related Art Printed wiring boards and the like are used in electronic devices such as personal computers and mobile phones to mount parts, semiconductors, and the like. Conventionally, as a resist for manufacturing printed wiring boards, etc., a photosensitive resin laminate obtained by laminating a photosensitive resin layer on a support film and further laminating a protective film on the photosensitive resin layer as necessary, A so-called dry film photoresist (hereinafter also referred to as DF) is used. At present, the photosensitive resin layer is generally of an alkali development type using a weak alkaline aqueous solution as a developer.

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

The process of forming a circuit after forming a resist pattern is roughly divided into two methods. The first method is to etch away the substrate surface not covered by the resist pattern (for example, the copper surface of a copper-clad laminate), and then remove the resist pattern portion with an alkaline aqueous solution stronger than the developer (etching method). is.
In the second method, after the substrate surface is plated with copper, solder, nickel, tin, etc., the resist pattern portion is removed in the same manner as in the first method, and the exposed substrate surface (for example, It is a method (plating method) of etching the copper surface of the copper-clad laminate. Cupric chloride, ferric chloride, cuprammonium complex solution, etc. are used for etching.

In recent years, with the miniaturization and weight reduction of electronic devices, the miniaturization and density of printed wiring boards are progressing. It has been demanded. As a material for achieving such high resolution, Patent Document 1 describes a photosensitive resin composition in which resolution is enhanced by a specific thermoplastic resin, a monomer, and a photopolymerization initiator. .

JP 2010-249884 A

After the exposure step, in some cases, the photosensitive resin layer is subjected to a heating step and then developed. By carrying out this heating step, it becomes possible to further improve high resolution and high adhesion. However, even if the post-exposure heating step is added, there are problems such as insufficient improvement in adhesion with conventional photosensitive resin compositions, or failure to obtain good adhesion when the elapsed time after exposure is long. rice field.

The present invention has been proposed in view of such conventional circumstances, and an object of the present invention is to:
To provide a photosensitive resin composition capable of remarkably improving adhesion when it is developed after being heated after exposure, and realizing excellent adhesion particularly even when the elapsed time after exposure is long. It is in.

As a result of intensive studies by the present inventors, it was found that the above object can be achieved by using a specific amount of a monomer component having a specific structural unit in an alkali-soluble polymer constituting a photosensitive resin composition. I realized that it is possible, and came to complete the present invention.
Further, as a result of intensive studies by the present inventors, the above object can be achieved by using a specific photopolymerization initiator in the alkali-soluble polymer constituting the photosensitive resin composition. The present invention has been completed.
That is, the present invention is as follows.
[1]
After exposure, a photosensitive resin composition for obtaining a resin cured product by heating and then developing, wherein the photosensitive resin composition contains the following, based on the total solid mass of the photosensitive resin composition: component:
(A) alkali-soluble polymer: 10% by mass to 90% by mass;
(B) a compound having an ethylenically unsaturated double bond: 5% to 70% by mass; and (C) a photopolymerization initiator: 0.01% to 20% by mass;
including
A photosensitive resin composition, wherein the constituent unit of styrene and/or a styrene derivative is 15% by mass or more in the whole alkali-soluble polymer (A).
[2]
As the (B) compound having an ethylenically unsaturated double bond, the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol/100 g or more is equal to the solid content of the photosensitive resin composition. The photosensitive resin composition according to [1], which is 0 or more and 18% by mass or less with respect to.
[3]
The photosensitive resin composition according to [1] or [2], further comprising (D) an inhibitor.
[4]
The photosensitive resin composition according to any one of [1] to [3], further comprising (E) a benzotriazole derivative.
[5]
The (B) compound having an ethylenically unsaturated double bond includes a (meth)acrylate compound having 3 or more ethylenically unsaturated double bonds. elastic resin composition.
[6]
The photosensitive resin composition according to [5], wherein the (B) compound having an ethylenically unsaturated double bond includes a (meth)acrylate compound having 4 or more ethylenically unsaturated double bonds.
[7]
The photosensitive resin composition according to [6], wherein the (B) compound having an ethylenically unsaturated double bond includes a (meth)acrylate compound having 6 or more ethylenically unsaturated double bonds.
[8]
Any of [1] to [7], wherein the value of [(A) content of alkali-soluble polymer]/[content of compound having ethylenically unsaturated double bond] is 0.94 or more The photosensitive resin composition according to 1.
[9]
The photosensitive resin according to [8], wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 1.04 or more. Composition.
[10]
The photosensitive resin according to [9], wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 1.11 or more. Composition.
[11]
The photosensitive resin according to [10], wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 1.21 or more. Composition.
[12]
The photosensitive resin according to [11], wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 1.30 or more. Composition.
[13]
Any of [1] to [12], wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 5 or less The photosensitive resin composition described.
[14]
The photosensitive resin composition according to [13], wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 4 or less. .
[15]
The photosensitive resin composition according to [14], wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 3 or less. .
[16]
The photosensitive resin composition according to [15], wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 2 or less. .
[17]
The photosensitive resin according to [16], wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 1.5 or less. Composition.
[18]
After exposure, a photosensitive resin composition for obtaining a resin cured product by heating and then developing, wherein the photosensitive resin composition contains the following, based on the total solid mass of the photosensitive resin composition: component:
(A) alkali-soluble polymer: 10% by mass to 90% by mass;
(B) a compound having an ethylenically unsaturated double bond: 5% to 70% by mass; and (C) a photopolymerization initiator: 0.01% to 20% by mass;
including
The photosensitive resin composition, wherein the photopolymerization initiator (C) contains anthracene and/or an anthracene derivative.
[19]
The anthracene derivative has an optionally substituted alkoxy group having 1 to 40 carbon atoms and/or an aryl group having 6 to 40 carbon atoms which may have a substituent at the 9-position and/or 10-position. The photosensitive resin composition according to [18], which has a group.
[20]
The anthracene derivative has an optionally substituted alkoxy group having 1 to 40 carbon atoms and/or an aryl group having 6 to 40 carbon atoms which may have a substituent at the 9 and 10 positions. , [18] or the photosensitive resin composition according to [19].
[21]
The photosensitive resin composition according to [20], wherein the (C) photopolymerization initiator contains 9,10-diphenylanthracene.
[22]
The photosensitive resin composition according to [20], wherein the (C) photopolymerization initiator contains 9,10-dialkoxyanthracene.
[23]
The photosensitive resin composition according to any one of [18] to [22], wherein the (C) photopolymerization initiator contains an anthracene derivative having a halogen atom.
[24]
The photosensitive resin composition according to [23], wherein the (C) photopolymerization initiator contains a halogen-substituted 9,10-dialkoxyanthracene.
[25]
[24], wherein the (C) photopolymerization initiator includes a compound in which the 9- and/or 10-position alkoxy groups of 9,10-dialkoxyanthracene are modified with one or more halogen atoms. A photosensitive resin composition.
[26]
The photosensitive resin composition according to any one of [18] to [25], wherein the (C) photopolymerization initiator contains a compound having a halogen atom directly bonded to an anthracene skeleton.
[27]
The photosensitive resin composition according to any one of [18] to [26], wherein the constituent units of styrene and/or styrene derivatives in the alkali-soluble polymer (A) are 15% by mass or more.
[28]
The photosensitive resin composition according to any one of [1] to [27], wherein the constituent units of styrene and/or styrene derivatives in (A) the alkali-soluble polymer are 25% by mass or more.
[29]
The photosensitive resin composition according to [28], wherein the constituent unit of styrene and/or a styrene derivative in the alkali-soluble polymer (A) is 30% by mass or more.
[30]
The photosensitive resin composition according to [29], wherein the constituent unit of styrene and/or a styrene derivative in the alkali-soluble polymer (A) is 35% by mass or more.
[31]
The photosensitive resin composition according to [30], wherein the constituent unit of styrene and/or a styrene derivative in the alkali-soluble polymer (A) is 40% by mass or more.
[32]
The photosensitive resin composition according to any one of [1] to [31], wherein the constituent units of styrene and/or styrene derivatives in (A) the alkali-soluble polymer are 90% by mass or less.
[33]
The photosensitive resin composition according to any one of [1] to [32], wherein (A) the alkali-soluble polymer further contains benzyl (meth)acrylate as a monomer component.
[34]
A step of exposing the photosensitive resin composition according to any one of [1] to [33], a heating step of heating the exposed photosensitive resin composition, and a heated photosensitive resin composition. and a developing step of developing.
[35]
The method for forming a resist pattern according to [34], wherein the heating temperature in the heating step is in the range of 30°C to 150°C.
[36]
The method of forming a resist pattern according to [34] or [35], wherein the exposure step is performed by direct drawing of a drawing pattern or by an exposure method in which an image of a photomask is projected through a lens.
[37]
The method of forming a resist pattern according to [34] or [35], wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern.
[38]
The method for forming a resist pattern according to any one of [34] to [37], wherein the heating step is performed within 15 minutes after exposure.
[39]
The resist pattern according to any one of [34] to [38], wherein the exposure step is performed by a method of exposing with a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more. method of formation.
[40]
The method of forming a resist pattern according to [39], 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.
[41]
[34] A method for manufacturing a circuit board, comprising etching or plating a substrate having a resist pattern manufactured by the method according to any one of [34] to [40] to form a circuit board.
[42]
[1] to [33], which is a photosensitive resin composition for obtaining a resin cured product by exposure with a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more. The photosensitive resin composition according to any one of the above.
[43]
The photosensitive resin composition according to [42], wherein the center wavelength of the first laser beam is 350 nm or more and 380 nm or less, and the center wavelength of the second laser beam is 400 nm or more and 410 nm or less.

According to the present invention, it is possible to remarkably improve adhesion when developing after heating after exposure, and in particular, a photosensitive resin that achieves good adhesion even when the elapsed time after exposure is long. A composition can be provided.

Exemplary embodiments for carrying out the present invention (hereinafter abbreviated as "embodiments") will be described in detail below. It should be noted that the present invention is not limited to the following embodiments, and can be modified in various ways within the scope of the gist of the present invention. In addition, unless otherwise specified, the various measured values in this specification are according to the method described in the [Examples] section of the present disclosure or the equivalent method understood by those skilled in the art. measured by

[Photosensitive resin composition]
The photosensitive resin composition of the present invention is a photosensitive resin composition for obtaining a resin cured product by heating and developing after exposure, wherein the photosensitive resin composition is the photosensitive resin composition. Based on the total solid content, the following components: (A) an alkali-soluble polymer: 10% to 90% by mass; (B) a compound having an ethylenically unsaturated double bond: 5% to 70% by mass; and (C) photopolymerization initiator: 0.01% by mass to 20% by mass;
And in particular, the photosensitive resin composition of the present embodiment, when (A) the alkali-soluble polymer consists of a plurality of types of alkali-soluble polymers, It is characterized by having a constituent unit of 15% by mass or more.

A dry film resist obtained from a photosensitive resin composition usually cannot obtain an effect of improving adhesion unless it is heated immediately after exposure. Good adhesion (that is, thin resist) can be exhibited even when the subsequent elapsed time is long. The photosensitive resin composition of the present invention has a composition suitable for this property.

In the photosensitive resin composition of the present embodiment, when (A) the alkali-soluble polymer contains a plurality of types of alkali-soluble polymers, (A) the structural unit of styrene and/or a styrene derivative in the entire alkali-soluble polymer is 15% by mass or more, it is possible to remarkably improve adhesion when developing after heating after exposure, and in particular to obtain good adhesion even when the elapsed time after exposure is long. can be done.
Each component will be described in order below.

<(A) Alkali-soluble polymer>
In the present disclosure, (A) alkali-soluble polymers include polymers that are readily soluble in alkaline substances. More specifically, the amount of carboxyl groups contained in (A) the alkali-soluble polymer is 100 to 600, preferably 250 to 450 in acid equivalent. The acid equivalent refers to the mass (unit: gram) of a polymer having one equivalent of carboxyl groups in its molecule. (A) The carboxyl group in the alkali-soluble polymer is necessary to give the photosensitive resin layer developability and peelability with respect to an alkaline aqueous solution. An acid equivalent of 100 or more is preferable from the viewpoint of improving development resistance, resolution, and adhesion. It is more preferable to set the acid equivalent to 250 or more. On the other hand, setting the acid equivalent to 600 or less is preferable from the viewpoint of improving developability and releasability. It is more preferable to set the acid equivalent to 450 or less. In the present disclosure, the acid equivalent is a value measured by potentiometric titration using a potentiometric titrator with a 0.1 mol/L NaOH aqueous solution.

(A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. A weight average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, even more preferably 70,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, setting the weight-average molecular weight to 5,000 or more is from the viewpoint of controlling the properties of development aggregates and the properties of unexposed films such as edge-fuse properties and cut-chip properties when formed into photosensitive resin laminates. preferred from More preferably, the weight average molecular weight is 10,000 or more, and even more preferably 20,000 or more. Edge fuseability refers to the extent to which a photosensitive resin layer (that is, a layer made of a photosensitive resin composition) protrudes easily from the end face of the roll when wound into a roll as a photosensitive resin laminate. . The cut chip property refers to the degree of easiness of chip flying when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive resin laminate, etc., it will be transferred to the mask in the subsequent exposure process or the like, resulting in defective products. (A) The dispersity of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and more preferably 1.0 to 4.0. More preferably, it is still more preferably 1.0 to 3.0.

In the present embodiment, the photosensitive resin composition can significantly improve the adhesion when it is developed after being heated after exposure, and in particular, even when the elapsed time after exposure is long, the adhesion is good. (A) the alkali-soluble polymer preferably contains a monomer component having an aromatic hydrocarbon group. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of the monomer component having an aromatic hydrocarbon group in the alkali-soluble polymer (A) is preferably 20% by mass or more, preferably 40% by mass, based on the total mass of all monomer components. It is more preferably 50% by mass or more, particularly preferably 55% by mass or more, and most preferably 60% by mass or more. Although the upper limit is not particularly limited, it is preferably 95% by mass or less, more preferably 80% by mass or less. The content ratio of the monomer component having an aromatic hydrocarbon group in the case of containing a plurality of types of (A) the alkali-soluble polymer was obtained as a weight average value.

Examples of the aromatic hydrocarbon group-containing monomer include aralkyl group-containing monomers, styrene, and polymerizable styrene derivatives. Among them, a monomer having an aralkyl group or styrene is preferred.

The aralkyl group includes a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group, and the like, and a substituted or unsubstituted benzyl group is preferred.
A comonomer having a phenylalkyl group includes phenylethyl (meth)acrylate and the like.
Examples of comonomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. is mentioned. Among them, benzyl (meth)acrylate is preferred.

The (A) alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group and at least one of the first monomers described later and/or It is preferably obtained by polymerizing at least one second monomer to be described later.
The (A) alkali-soluble polymer that does not contain a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described below, and the first monomer More preferably, it is obtained by copolymerizing at least one of the monomers and at least one of the second monomers described below.

A 1st monomer is a monomer which has a carboxyl group in a molecule|numerator. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred.
In the present 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”.

The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. The copolymerization ratio of 10% by mass or more is preferable from the viewpoint of developing good developability and controlling edge fuse properties, more preferably 15% by mass or more, and even more preferably 20% by mass or more. . The copolymerization ratio of 50% by mass or less is preferable from the viewpoint of high resolution and groove shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern. The following is more preferable, 32% by mass or less is even more preferable, and 30% by mass or less is particularly preferable.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and other (meth)acrylates; vinyl acetate esters of vinyl alcohol such as; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred.
Containing a monomer having an aralkyl group and/or styrene as a monomer can remarkably improve the adhesion when developing after heating after exposure, especially after the elapsed time after exposure. It is preferable from the viewpoint of exhibiting good adhesion even when it is long. For example, a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, and the like are preferable.

(A) The alkali-soluble polymer can be used singly or in combination of two or more. When two or more types are used in combination, two types of alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group are mixed, or a monomer component having an aromatic hydrocarbon group is used. It is preferable to use a mixture of an alkali-soluble polymer containing and an alkali-soluble polymer containing no monomer component having an aromatic hydrocarbon group. In the latter case, the ratio of use of the alkali-soluble polymer containing the monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more, based on the total amount of (A) the alkali-soluble polymer. It is more preferably at least 80% by mass, more preferably at least 90% by mass, and most preferably at least 95% by mass.

The (A) alkali-soluble polymer of the present embodiment is an alkali-soluble polymer (A-1) containing 52% by mass or more of structural units of styrene and/or styrene derivatives as a monomer component in a photosensitive resin composition. It is preferable to contain 3% by mass or more with respect to the solid content of. As a result, it is possible to remarkably improve the adhesion when the film is developed after being heated after exposure, and in particular, it is possible to obtain good adhesion even when the elapsed time after exposure is long. From the same point of view, the alkali-soluble polymer (A) more preferably contains the alkali-soluble polymer (A-1) in an amount of 10% by mass or more relative to the solid content in the photosensitive resin composition, and more preferably 15% by mass. More preferably, it contains 20% by mass or more, particularly preferably 20% by mass or more, and most preferably 30% by mass or more.
Examples of styrene derivatives include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer and styrene trimer.

In particular, in the present embodiment, when (A) the alkali-soluble polymer is composed of a plurality of types of alkali-soluble polymers, (A) the constituent unit of styrene and/or a styrene derivative in the entire alkali-soluble polymer is 15% by mass. That's it. As a result, it is possible to remarkably improve the adhesion when the film is developed after being heated after exposure, and in particular, it is possible to obtain good adhesion even when the elapsed time after exposure is long. Since the styrene skeleton is hydrophobic, it is possible to suppress swelling with respect to a developer and to exhibit good adhesion. (A) The constituent unit of styrene and/or a styrene derivative in the alkali-soluble polymer is preferably 25% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass or more. It is preferably 40% by mass or more, and particularly preferably 40% by mass or more.

However, if the content of the styrene skeleton is high, the mobility of the resin is lowered, so that the reactivity cannot be fully increased and the desired adhesion cannot be obtained. In addition, as the elapsed time after exposure becomes longer, the radicals in the system are deactivated, so the effect of improving adhesion by heating after exposure is reduced. (A) The upper limit of the constituent units of styrene and/or styrene derivatives in the alkali-soluble polymer is preferably 90% by mass or less, more preferably 80% by mass or less, and 75% by mass or less. is more preferable, and 70% by mass or less is particularly preferable.

Thus, in the present invention, (A) the constituent unit of styrene and/or a styrene derivative in the entire alkali-soluble polymer is 15% by mass or more, and the styrene skeleton-containing polymer is obtained by heating after exposure and development. Even in a system with a large amount, heating improves the mobility of the resin, making it possible to achieve a high degree of compatibility between the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond, resulting in a significant improvement in adhesion. It seems that it was possible. In addition, it is believed that due to the remarkable improvement in adhesion, good adhesion could be obtained even when the elapsed time after exposure was long.

In addition, the alkali-soluble polymer can remarkably improve the adhesion when it is developed after being heated after exposure, and in particular, from the viewpoint of expressing good adhesion even when the elapsed time after exposure is long. (A-1) preferably contains 25% by mass or more, more preferably 26% by mass or more, more preferably 27% by mass or more of a (meth)acrylic acid structural unit as a monomer component, It is particularly preferably contained in an amount of 28% by mass or more, and most preferably in an amount of 29% by mass or more. From the same point of view, it preferably contains 35% by mass or less, more preferably 32% by mass or less, and even more preferably 30% by mass or less.

(A) Alkali-soluble polymer is synthesized by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, adding benzoyl peroxide, azoisobutyronitrile, or the like. It is preferable to carry out by adding an appropriate amount of a radical polymerization initiator and heating and stirring. In some cases, the synthesis is performed while part of the mixture is added dropwise to the reaction solution. After completion of the reaction, a solvent may be further added to adjust the desired concentration. As a means of synthesis, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

(A) The weight average value Tg ^total of the glass transition temperature Tg of the alkali-soluble polymer is preferably 30° C. or higher and 150° C. or lower. Tg ^total is calculated by the method described in Examples described later. By using (A) an alkali-soluble polymer having a Tg ^total of 150° C. or less in the photosensitive resin composition, it is possible to remarkably improve adhesion when developing after heating after exposure, particularly Good adhesion can be exhibited even when the elapsed time after exposure is long. From this point of view, the Tg ^total of (A) the alkali-soluble polymer is preferably 135° C. or lower, more preferably 130° C. or lower, and even more preferably 125° C. or lower. 110° C. or less is particularly preferable. In addition, it is preferable to use (A) an alkali-soluble polymer having a Tg ^total of 30° C. or higher from the viewpoint of improving edge fuse resistance. From this point of view, the Tg ^total of (A) the alkali-soluble polymer is more preferably 40° C. or higher, still more preferably 50° C. or higher, and particularly preferably 60° C. or higher.

(A) the ratio of the alkali-soluble polymer to the total solid mass of the photosensitive resin composition is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, More preferably, it is 40% by mass to 60% by mass. It is preferable from the viewpoint of controlling the developing time that the ratio of (A) the alkali-soluble polymer to the photosensitive resin composition is 90% by mass or less. On the other hand, it is preferable from the viewpoint of improving the edge fuse resistance that the ratio of (A) the alkali-soluble polymer to the photosensitive resin composition is 10% by mass or more.

<(B) a compound having an ethylenically unsaturated double bond>
(B) The compound having an ethylenically unsaturated double bond preferably contains a compound having a (meth)acryloyl group in the molecule from the viewpoint of curability and (A) compatibility with the alkali-soluble polymer. (B) The number of (meth)acryloyl groups in the compound may be 1 or more.

(B) A compound having an ethylenically unsaturated bond is a compound having polymerizability due to having an ethylenically unsaturated group in its structure. The ethylenically unsaturated bonds are more preferably derived from methacryloyl groups. From the viewpoint of adhesion and suppression of developer foaming, (B) the compound having an ethylenically unsaturated bond preferably has an alkylene oxide structure with 3 or more carbon atoms. The number of carbon atoms in the alkylene oxide structure is more preferably 3-6, more preferably 3-4.

As the (B) compound having one (meth) acryloyl group, for example, a compound obtained by adding (meth) acrylic acid to one end of a polyalkylene oxide, or a (meth) acrylic Compounds in which an acid is added and the other terminal is alkyl-etherified or allyl-etherified, phthalic acid-based compounds, and the like can be mentioned, and they are preferable from the viewpoint of releasability and cured film flexibility.

Such compounds include, for example, phenoxyhexaethylene glycol mono(meth)acrylate which is a (meth)acrylate of a compound obtained by adding polyethylene glycol to a phenyl group, polypropylene glycol obtained by adding an average of 2 mol of propylene oxide, and an average of 7 4-Normal nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound obtained by adding 1 mole of ethylene oxide to polyethylene glycol and nonylphenol, and polypropylene to which an average of 1 mole of propylene oxide is added. 4-Normal nonylphenoxypentaethylene glycol, which is a (meth)acrylate of a compound obtained by adding glycol and polyethylene glycol to which an average of 5 mol of ethylene oxide is added to nonylphenol, monopropylene glycol (meth)acrylate, an average of 8 mol of ethylene Examples thereof include 4-normal nonylphenoxyoctaethylene glycol (meth)acrylate (eg, M-114, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol to which an oxide is added to nonylphenol.
Further, if γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate is contained, it is preferable from the viewpoints of sensitivity, resolution and adhesion in addition to the above viewpoints.

The compound having two (meth)acryloyl groups in the molecule includes, for example, a compound having (meth)acryloyl groups at both ends of an alkylene oxide chain, or an alkylene in which an ethylene oxide chain and a propylene oxide chain are randomly or block-bonded. Examples include compounds having (meth)acryloyl groups at both ends of the oxide chain.

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

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

{Wherein, R1 and R2 each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n1 and n3 each independently represent from 1 to 39 an integer, and n1+n3 is an integer of 2 to 40, n2 and n4 are each independently an integer of 0 to 29, and n2+n4 is an integer of 0 to 30, -(AO)- and - The arrangement of the repeating units of (BO)- may be random or block. In the case of a block, either -(AO)- or -(B-O)- may be on the side of the biphenyl group. } can be used.
For example, dimethacrylate of polyethylene glycol obtained by adding an average of 5 mol each of ethylene oxide to both ends of bisphenol A, and polyethylene glycol obtained by adding an average of 2 mol each of ethylene oxide to both ends of bisphenol A. Polyethylene glycol dimethacrylate obtained by adding an average of 1 mol each of ethylene oxide to each end of bisphenol A is preferred from the viewpoint of resolution and adhesion.
A compound in which the aromatic ring in the general formula (I) has a heteroatom and/or a substituent may also be used.

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

A compound having 3 or more (meth)acryloyl groups in the molecule has 3 mol or more of a group capable of adding an alkylene oxide group in the molecule as a central skeleton, and an ethyleneoxy group, a propyleneoxy group, It is obtained by converting an alcohol obtained by adding an alkyleneoxy group such as a butyleneoxy group into a (meth)acrylate. In this case, examples of compounds that can serve as the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings. These compounds include tri(meth)acrylates such as ethoxylated glycerin tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate (e.g. Trimethacrylate obtained by adding an average of 21 mol of ethylene oxide to trimethylolpropane, and trimethacrylate obtained by adding an average of 30 mol of ethylene oxide to trimethylolpropane are preferred from the viewpoint of flexibility, adhesion, and bleedout suppression), etc.; (meth)acrylates, such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate; penta(meth)acrylates, such as dipentaerythritol penta(meth)acrylate; etc.; hexa(meth)acrylates such as dipentaerythritol hexa(meth)acrylate and the like. A compound having 3 or more (meth)acryloyl groups can remarkably improve adhesion when heated and then developed after exposure, and in particular, good adhesion even when the elapsed time after exposure is long. and more preferably a compound having 3 or more methacryl groups.

Pentaerythritol tetra(meth)acrylate is preferred as the tetra(meth)acrylate. The pentaerythritol tetra(meth)acrylate may be a tetra(meth)acrylate in which a total of 1 to 40 mol of alkylene oxide is added to the four terminals of pentaerythritol.
As the hexa(meth)acrylate, hexa(meth)acrylate in which a total of 1 to 40 mol of ethylene oxide is added to the six ends of dipentaerythritol, and a total of 1 to 20 mol of ε to the six ends of dipentaerythritol. - Hexa(meth)acrylates to which caprolactone is added are preferred.

As the compound having an ethylenically unsaturated double bond (B), a (meth)acrylate compound having 3 or more ethylenically unsaturated double bonds is included, so that the adhesiveness when heated after exposure and then developed. can be remarkably improved, and in particular it is preferable from the viewpoint that good adhesion can be obtained even when the elapsed time after exposure is long. From the same point of view, it is more preferable to contain a (meth)acrylate compound having 4 or more ethylenically unsaturated double bonds, and it is possible to contain a (meth)acrylate compound having 5 or more ethylenically unsaturated double bonds. More preferably, it particularly preferably contains a (meth)acrylate compound having 6 or more ethylenically unsaturated double bonds. Moreover, from the same point of view, these are preferably methacrylate compounds.

Compounds having 3 or more, 4 or more, 5 or more, 6 or more ethylenically unsaturated double bonds are considered to have the effect of increasing the crosslink density during polymerization by exposure, but the number of functional groups is Due to the effect of steric hindrance due to the large amount, the desired crosslink density is often not obtained. In the present invention, compounds preferably have 3 or more ethylenically unsaturated double bonds, more preferably compounds having 4 or more ethylenically unsaturated double bonds, still more preferably 5 ethylenically unsaturated double bonds. A compound having 6 or more ethylenically unsaturated double bonds, particularly preferably a compound having 6 or more ethylenically unsaturated double bonds, is also subjected to heat treatment after exposure to improve the mobility in the system, so that even if the number of functional groups is large, the effect of steric hindrance can be reduced and high adhesion can be obtained.

Compounds preferably having 3 or more ethylenically unsaturated double bonds, more preferably compounds having 4 or more ethylenically unsaturated double bonds, still more preferably compounds 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, preferably 5% by mass or more, based on the solid content of the photosensitive resin composition. is more preferably 7% by mass or more, and particularly preferably 10% by mass or more. In addition, the upper limit of the content is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and 15% by mass or less, from the viewpoint of expressing the effect of heat treatment after exposure. is particularly preferred.

(b1) As the (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 (e.g. flexibility, Preferred examples from the viewpoint of adhesion and bleed-out suppression include tri(meth)acrylate obtained by adding an average of 21 mol of ethylene oxide to trimethylolpropane, and tri(meth)acrylate obtained by adding an average of 30 mol of ethylene oxide to trimethylolpropane. (meth) acrylate) and the like;
Tetra(meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.;
penta(meth)acrylates, such as dipentaerythritol penta(meth)acrylate;
Hexa(meth)acrylates such as dipentaerythritol hexa(meth)acrylate and the like can be mentioned.
Among these, tetra-, penta- or hexa(meth)acrylates are preferred.

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

Pentaerythritol tetra(meth)acrylate is preferred as the tetra(meth)acrylate. As the pentaerythritol tetra(meth)acrylate, a tetra(meth)acrylate in which a total of 1 to 40 mol of alkylene oxide is added to four terminals of pentaerythritol is preferable.

｛式中、Ｒ₃～Ｒ₆は、それぞれ独立に、炭素数１～４のアルキル基を表し、Ｘは、炭素数２～６のアルキレン基を表し、ｍ₁、ｍ₂、ｍ₃及びｍ₄は、それぞれ独立に、０～４０の整数であり、ｍ₁＋ｍ₂＋ｍ₃＋ｍ₄は、１～４０であり、そしてｍ₁＋ｍ₂＋ｍ₃＋ｍ₄が２以上である場合には、複数のＸは、互いに同一であるか、又は異なっていてよい｝で表されるテトラメタクリレート化合物であることがより好ましい。Tetra (meth) acrylate has the following general formula (II):

{wherein R ₃ to R ₆ each independently represent an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, m ₁ , m ₂ , m ₃ and m ₄ is each independently 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, multiple may be the same or different}.

Without wishing to be bound by theory, it is believed that the tetramethacrylate compounds of general formula (II) have the groups R ₃ to R ₆ to form the H ₂ C═CH—CO—O— moiety. It is considered that the hydrolyzability in an alkaline solution is suppressed compared to the tetraacrylate having. The use of a photosensitive resin composition containing a tetramethacrylate compound represented by the general formula (II) can significantly improve adhesion when heated after exposure and then developed, particularly after exposure. It is preferable from the viewpoint of achieving good adhesion even when the elapsed time is long.

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

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

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

Examples of compounds represented by general formula (II) include pentaerythritol (poly)alkoxytetramethacrylate and the like. In addition, in the present disclosure, “pentaerythritol (poly)alkoxytetramethacrylate” means “pentaerythritolalkoxytetramethacrylate” where m ₁ +m ₂ +m ₃ +m ₄ =1 and m ₁ +m ₂ in general formula (II) above. It includes both "pentaerythritol polyalkoxytetramethacrylates" where +m ₃ +m ₄ =2-40. Examples of the compound represented by the general formula (II) include compounds listed in JP-A-2013-156369, such as pentaerythritol (poly)alkoxytetramethacrylate.

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

The photosensitivity according to the present embodiment can remarkably improve the adhesion when developing after heating after exposure, and in particular, from the viewpoint of realizing good adhesion even when the elapsed time after exposure is long. It is particularly preferable that the resin composition contains, as (B) the compound having an ethylenically unsaturated bond, a (meth)acrylate compound having four or more ethylenically unsaturated bonds and an alkylene oxide chain. In this case, the ethylenically unsaturated bonds are more preferably derived from methacryloyl groups and the alkylene oxide chains are more preferably ethylene oxide chains.

In this embodiment, it is possible to significantly improve the adhesion when developing after heating after exposure, especially from the viewpoint of realizing good adhesion even when the elapsed time after exposure is long. The resin composition preferably contains a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton as (B) the compound having an ethylenically unsaturated bond. Examples of alkylene oxide chains include ethylene oxide chains, propylene oxide chains, butylene oxide chains, pentylene oxide chains, and hexylene oxide chains. When the photosensitive resin composition contains a plurality of alkylene oxide chains, they may be the same or different. From the above viewpoint, the alkylene oxide chain is more preferably an ethylene oxide chain, a propylene oxide chain, or a butylene oxide chain, more preferably an ethylene oxide chain or a propylene oxide chain, and particularly preferably an ethylene oxide chain.

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

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

The (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton includes, for example, a hexadecalylate having an average of 4 to 30 mol, an average of 6 to 24 mol, or an average of 10 to 14 mol of an alkylene oxide added to dipentaerythritol. (Meth)acrylates are mentioned.

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

{wherein each R 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} 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 point of view, the content of the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton with respect to the total solid content in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 5% by mass. % to 40% by mass, more preferably 7% to 30% by mass.

The content of (b1) a (meth)acrylate compound having 3 or more ethylenically unsaturated bonds is more than 0% by mass and 40% by mass or less with respect to the total solid content of the photosensitive resin composition. is preferred. When this content exceeds 0% by mass, it is possible to remarkably improve adhesion when developing after heating after exposure, and in particular, good adhesion even when the elapsed time after exposure is long. When the amount is 40% by mass or less, the flexibility of the cured resist tends to be improved and the peeling time tends to be shortened. This content is more preferably 2% by mass or more and 30% by mass or less, and even more preferably 4% by mass or more and 25% by mass or less.

From the viewpoint of adhesion and the viewpoint of suppressing developer foaming, the photosensitive resin composition contains (B) a compound having an ethylenically unsaturated bond, (b2) a butylene oxide chain or a propylene oxide chain, and one or It preferably contains compounds having two (meth)acryloyl groups.
(b2) A compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryloyl groups is preferably 500 or more, more preferably 700 or more, still more preferably 700 or more, from the viewpoint of suppressing bleed out. has a molecular weight of 1000 or more.

(b2) Compounds having a butylene oxide chain or propylene oxide chain and one or two (meth)acryloyl groups include polypropylene glycol (meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol ( meth)acrylate, polytetramethylene glycol di(meth)acrylate, and the like. (b2) The compound having a butylene oxide chain or propylene oxide chain and one or two (meth)acryloyl groups may contain an ethylene oxide chain in addition to the butylene oxide chain or propylene oxide chain.

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

The content of (b2) a compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryloyl groups, relative to the total solid content of the photosensitive resin composition, exceeds 0% by mass. , and 20% by mass or less.

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

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

From the same point of view, the value of methacryloyl group concentration/(methacryloyl group concentration + acryloyl group concentration) in the compound having an ethylenically unsaturated bond (B) is preferably 0.50 or more, more preferably 0. 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 can be used individually or in combination. The photosensitive resin composition may also contain other compounds as (B) the compound having an ethylenically unsaturated bond. Other compounds include (meth)acrylates having urethane bonds, compounds obtained by reacting α,β-unsaturated carboxylic acids with polyhydric alcohols, and α,β-unsaturated carboxylic acids with glycidyl group-containing compounds. and 1,6-hexanediol di(meth)acrylate.

(B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid weight of the photosensitive resin composition is preferably 5% by mass to 70% by mass. A ratio of 5% by mass or more is preferable from the viewpoint of sensitivity, resolution and adhesion. This ratio is more preferably 20% by mass or more, and even 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 peeling delay of the edge fuse and the hardened resist. It is more preferable to make this ratio 50% by mass or less.

(B) As a compound having an ethylenically unsaturated double bond, the content of a compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol/100 g or more is added to the solid content of the photosensitive resin composition. It is preferably 0 or more and 18 mass % or less. As a result, it is possible to remarkably improve the adhesion when developing after heating after exposure, and in particular, it is possible to obtain good adhesion even when the elapsed time after exposure is long. A compound having an ethylenically unsaturated double bond with a high concentration of the bisphenol A skeleton generally improves adhesion due to its hydrophobicity in some cases.

In the present invention, it was found that due to the rigid skeleton of bisphenol A, the mobility is not improved even if heating is performed after exposure, and the effect of improving adhesion is small. Therefore, in the present invention, from the above viewpoint, the content of compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol/100 g or more as (B) a compound having an ethylenically unsaturated double bond is , The solid content of the photosensitive resin composition is preferably 18% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and 6% by mass or less. It is more preferably 3% by mass or less, and most preferably 1% by mass or less. From the same point of view, the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.20 mol/100 g or more as the compound having an ethylenically unsaturated double bond (B) is It is preferably 18% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and more preferably 6% by mass or less relative to the solid content of the product, It is particularly preferably 3% by mass or less, most preferably 1% by mass or less.

In particular, in the present embodiment, the value of [(A) the content of the alkali-soluble polymer]/[the content of the (B) compound having an ethylenically unsaturated double bond] is preferably 0.94 or more. . As a result, it is possible to remarkably improve the adhesion when developing after heating after exposure, and in particular, it is possible to obtain good adhesion even when the elapsed time after exposure is long. From the same point of view, [(A) the content of the alkali-soluble polymer]/[(B) the content of the compound having an ethylenically unsaturated double bond] is preferably 1.04 or more. It is more preferably 1.11 or more, particularly preferably 1.21 or more, still more preferably 1.30 or more, and most preferably 1.35 or more.
Increasing the value of [(A) content of alkali-soluble polymer]/[content of compound having an ethylenically unsaturated double bond] is generally alkali-soluble, that is, hydrophilic increases, the Tg in the system increases, the mobility decreases, the double bond reaction rate decreases, and as a result, the adhesiveness generally decreases. However, in the present invention, the value of [(A) the content of the alkali-soluble polymer]/[the content of the (B) compound having an ethylenically unsaturated double bond] is large, and heat treatment is also performed after exposure. Therefore, even if the value of [(A) the content of the alkali-soluble polymer] / [the content of the compound having an ethylenically unsaturated double bond] is large, the mobility in the system is improved and the double bond It is believed that the effect of the present invention was realized because the reaction rate was improved and furthermore, the effect of improving the adhesion due to the interaction of the carboxyl group of the alkali-soluble polymer with copper was added.

The value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is preferably 5 or less, more preferably 4 or less. , is more preferably 3 or less, particularly preferably 2 or less, and most preferably 1.5 or less.

<(C) Photoinitiator>
(C) A photopolymerization initiator is a compound that polymerizes a monomer by light.
(C-1) Photopolymerization initiator The photosensitive resin composition of the present embodiment contains a compound generally known in the technical field as (C-1) photopolymerization initiator ((C) photopolymerization initiator). include.

The total content of the photopolymerization initiator (C-1) in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05% to 10% by mass, still more preferably 0.05% by mass to 10% by mass. It is in the range of 1% to 7% by weight, particularly preferably 0.1% to 6% by weight. (C-1) The total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and allows light to sufficiently pass through to the bottom of the resist, resulting in a good high resolution. From the viewpoint of obtaining image quality, it is preferably 20% by mass or less.

(C-1) Photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkylketals, thioxanthones, dialkylaminobenzoates, and oximes. Esters and acridines (e.g., 9-phenylacridine, bisacridinylheptane, 9-(p-methylphenyl)acridine, and 9-(m-methylphenyl)acridine are preferred from the viewpoints of sensitivity, resolution, and adhesion. ), and further hexaarylbiimidazoles, pyrazoline compounds, and anthracene compounds (for example, 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene improve sensitivity, resolution, and adhesion. in terms of sensitivity), coumarin compounds (for example, 7-diethylamino-4-methylcoumarin is preferred in terms of sensitivity, resolution, and adhesion), N-arylamino acids or their ester compounds (for example, N-phenylglycine is preferred in terms of sensitivity and resolution). preferred from the viewpoint of image quality and adhesion), and halogen compounds (eg, tribromomethylphenylsulfone). These can be used individually by 1 type or in combination of 2 or more types. Other, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzo Ilu-diphenyl-phosphine oxide, triphenylphosphine oxide may also be used.

Examples of aromatic ketones include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. can be done. These can be used individually by 1 type or in combination of 2 or more types. Among these, 4,4'-bis(diethylamino)benzophenone is preferable from the viewpoint of adhesion.

Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3% by mass. It is within the range of % by mass.

Examples of hexaarylbiimidazoles 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) fluorophenyl)-4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2′-bis-(2,3,4,5-tetrafluorophenyl)-4,4 ',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'- Tetrakis-(3-methoxyphenyl)-biimidazole , and 2,2′-bis-(2,3,4,5,6-pentafluorophenyl)-4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole and the like. These can be used singly or in combination of two or more. From the viewpoint of high sensitivity, resolution and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

In the present embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass to 7% by mass from the viewpoint of improving the peeling properties and/or sensitivity of the photosensitive resin layer. %, more preferably 0.1% by mass to 6% by mass, still more preferably 1% by mass to 5% by mass.

From the viewpoint of peeling properties, sensitivity, resolution, and adhesion of the photosensitive resin layer, the photosensitive resin composition contains pyrazoline compounds and anthracene compounds (e.g., 9,10-diphenylanthracene, 9,10 -dibutoxyanthracene, 9,10-diethoxyanthracene and other sialkoxyanthracenes are preferred from the viewpoints of sensitivity, resolution and adhesion).
Examples of pyrazoline compounds include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzoxazol-2-yl) Phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl- Phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropyl Phenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5 -dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)- 5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2, 3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, etc. It is preferable from the point of view, and it is mentioned. Among these, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferred.

In the present embodiment, the content of the photosensitizer in the photosensitive resin composition is preferably 0.5 from the viewpoint of transmittance and from the viewpoint of improving the release property and/or sensitivity of the photosensitive resin layer. 05% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass, still more preferably 0.1% by mass to 1% by mass, particularly preferably 0.1% by mass to 0.7% by mass is within.

(C-2) Photopolymerization initiator In the present embodiment, the photosensitive resin composition contains anthracene and/or anthracene derivative as (C-2) photopolymerization initiator ((C) photopolymerization initiator). can be used.

(C-2) The use of at least anthracene and/or anthracene derivative as the photopolymerization initiator can significantly improve the adhesiveness when the photopolymerization initiator is heated after exposure and then developed. It is advantageous from the viewpoint that good adhesion can be obtained even when the length is long. In addition, anthracene and/or anthracene derivative can function as a polymerization initiator by absorbing the first actinic light having a center wavelength of less than 390 nm and the second actinic light having a center wavelength of 390 nm or more. The activating light is, for example, laser light.

Therefore, in one aspect, the photosensitive resin composition can have photosensitivity to the first actinic light and the second actinic light, and can be used for two-wavelength exposure. The anthracene and/or anthracene derivative can also be selected to have multiple absorption maxima in the wavelength range of the first actinic light and the second actinic light. The central wavelength of the first activating light is preferably 350-380 nm, more preferably 355-375 nm, and particularly preferably 375 nm. The central wavelength of the second activating light is preferably 400-410 nm, more preferably 402-408 nm, and particularly preferably 405 nm (h-line).

The total content of the photopolymerization initiator (C-2) in the photosensitive resin composition is preferably 0.01 to 20 mass%, more preferably 0.05 to 10 mass%, still more preferably 0.05 mass% to 10 mass%. It is in the range of 1% to 7% by weight, particularly preferably 0.1% to 6% by weight. (C-2) The total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and allows light to sufficiently pass through to the bottom of the resist to achieve a good high resolution. From the viewpoint of obtaining image quality, it is preferably 20% by mass or less.

Anthracene and anthracene derivatives can remarkably improve adhesion when heated and then developed after exposure, and are particularly advantageous in terms of realizing good adhesion even when the elapsed time after exposure is long. is. From the same point of view, the anthracene derivative preferably has an alkoxy group having 1 to 40 carbon atoms and/or a substituent at the 9- and/or 10-positions, more preferably at the 9- and 10-positions. It has an aryl group having 6 to 40 carbon atoms which may have

In one aspect, the anthracene derivative can remarkably improve adhesion when it is developed after being heated after exposure, and in particular from the viewpoint of realizing good adhesion even when the elapsed time after exposure is long. Therefore, at least one of 9-position or 10-position preferably has an alkoxy group having 1 to 40 carbon atoms, which may have a substituent, and at least one of 9-position or 10-position has a substituent. It is more preferable to have an alkoxy group having 1 to 30 carbon atoms which may be substituted. From the viewpoint of obtaining good adhesion and resolution, it is preferable to have an optionally substituted alkoxy group having 1 to 40 carbon atoms at the 9 and 10 positions, and a substituent at the 9 and 10 positions. It is more preferable to have an alkoxy group having 1 to 30 carbon atoms which may be substituted. The number of carbon atoms in the 9- and 10-position groups may be the same or different.
Examples of optionally substituted alkoxy groups include:
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, isoamyloxy 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, a tricyclodecanyloxy group, a tetracyclododecyloxy group, an adamantyloxy group, a methyladamantyloxy group, an ethyladamantyloxy group, and a butyladamantyloxy group;
alkoxy groups modified with halogens, such as chlorobutoxy groups and chloropropoxy groups;
an alkoxy group attached with a hydroxyl group, such as a hydroxybutyloxy group;
an alkoxy group attached with a cyano group, such as a cyanobutoxy group;
an alkoxy group attached with an alkylene oxide group, such as a methoxybutoxy group;
an alkoxy group attached with an aryl group, such as a phenoxybutoxy group,
etc. Among these, an n-butoxy group is more preferred.

In one aspect, the anthracene derivative can remarkably improve adhesion when it is developed after being heated after exposure, and in particular from the viewpoint of realizing good adhesion even when the elapsed time after exposure is long. Therefore, at least one of the 9- and 10-positions preferably has an optionally substituted aryl group having 6 to 40 carbon atoms, and at least one of the 9- and 10-positions has a substituent. It is more preferable to have an aryl group having 6 to 30 carbon atoms which may be substituted.

From the viewpoint of being able to remarkably improve the adhesion when developing after heating after exposure, and particularly from the viewpoint of achieving good adhesion even when the elapsed time after exposure is long, 9th and 10th, It preferably has an aryl group having 6 to 40 carbon atoms which may have a substituent, and may have an aryl group having 6 to 30 carbon atoms which may have a substituent at the 9th and 10th positions. more preferred. The number of carbon atoms in the 9- and 10-position groups may be the same or different. Moreover, the groups at the 9-position and the 10-position may be the same group or different groups. For example, the 9-position group is an optionally substituted C1-40 alkoxy group, and the 10-position group is an optionally substituted C6-40 aryl group. There may be.

Examples of optionally substituted aryl groups having 6 to 40 carbon atoms include phenyl group, biphenyl group, naphthyl group and anthracenyl group; aryl groups to which alkoxy groups are added, such as methoxyphenyl group and ethoxyphenyl group; aryl groups to which alkyl groups are added, such as tolyl, xylyl, mesityl, and nonylphenyl; aryl groups to which halogens are added, such as chlorophenyl; and aryl groups to which hydroxyl is added, such as hydroxyphenyl. be done. Among these, a phenyl group is more preferred.

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

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 represents an unsubstituted aryl group, a substituted or unsubstituted heteroaryl group or an N(R') ₂ group, two or more of R ¹ may be bonded together to form a cyclic structure, the cyclic structure being a heteroatom; may include

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')- group, -O-CO- group, -S-CO- group, -O-SO ₂ - group or S-SO ₂ - group show. However, the combination of X being a single bond and R ¹ being a hydrogen atom (that is, unsubstituted anthracene) is excluded.

The above 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, and 6 carbon atoms. ~40 substituted or unsubstituted aryl groups or substituted or unsubstituted heteroaryl groups, and R' may be bonded to each other to form a cyclic structure, which may contain a heteroatom. .

p is an integer of 1-10, preferably 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 and t-butyl group.

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

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

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

The substituted or unsubstituted heteroaryl group for R ¹ and R' includes groups containing one or more heteroatoms such as a sulfur atom, an oxygen atom, and a nitrogen atom in the substituted or unsubstituted aryl group, such as a pyridyl group. , imidazolyl group, morpholinyl group, piperidyl group, pyrrolidyl group and the like.

Further, each of the hydrocarbon groups of R ¹ and R' may be substituted with a substituent. Such substituents include a hydroxyl group, a carboxyl group, a hydroxyalkyl group having 1 to 4 carbon atoms (e.g., a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2- hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc.), alkoxyl groups having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, etc.), cyano group, cyanoalkyl group having 2 to 5 carbon atoms ( For example, 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 ( For example, methoxycarbonylmethoxy group, ethoxycarbonylmethoxy group, t-butoxycarbonylmethoxy group, etc.), halogen atoms (e.g., fluorine, chlorine, etc.) and fluoroalkyl groups (e.g., fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, etc.). Each hydrocarbon group of R ¹ and R' is preferably substituted with a halogen atom. In particular, the anthracene derivative preferably has an alkoxy group substituted with a halogen atom at the 9- and/or 10-position.

Preferable specific examples of R ¹ and R′ are hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group and n-hexyl. n-heptyl, n-octyl, cyclopentyl, cyclohexyl, camphoroyl, norbornyl, p-toluyl, benzyl, methylbenzyl, phenyl and 1-naphthyl groups.

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

Examples of compounds represented by the general formula (IV) include 1-methylanthracene, 2-methylanthracene, 2-ethylanthracene, 2-t-butylanthracene, 9-methylanthracene, 9,10-dimethylanthracene, 9-vinylanthracene, 9-phenylanthracene, 9,10-diphenylanthracene, 2-bromo-9,10-diphenylanthracene, 9-(4-bromophenyl)-10-phenylanthracene, 9-(1-naphthyl)anthracene , 9-(2-naphthyl)anthracene, 2-bromo-9,10-bis(2-naphthyl)anthracene, 2,6-dibromo-9,10-bis(2-naphthyl)anthracene, 9,10-diethoxy Anthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di(2-ethylhexyloxy)anthracene, 1,2-benzanthracene, anthrobin, 1,4,9,10-tetra hydroxyanthracene, 9-anthracenemethanol, 1-aminoanthracene, 2-aminoanthracene, 9-(methylaminomethyl)anthracene, 9-acetylanthracene, 9-anthraldehyde, 10-methyl-9-anthraldehyde, 1,8, 9-triacetoxyanthracene and the like. Among these are 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 can significantly improve the adhesion, particularly when the product is developed after being heated after exposure, particularly after the elapsed time from exposure. 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene, 9,10-bis-(3-chloro Propoxy)anthracene is more preferred, and 9,10-dibutoxyanthracene, 9,10-diphenylanthracene and 9,10-bis-(3-chloropropoxy)anthracene are particularly preferred. The compounds represented by the general formula (IV) may be used alone or in combination of two or more.

From the viewpoint that it is possible to significantly improve the adhesion when developing after heating after exposure, and in particular that good adhesion can be obtained even when the elapsed time after exposure is long, (C-2 ) The photoinitiator preferably contains (1) 9,10-diphenylanthracene; (2) 9,10-dialkoxyanthracene; (3) an anthracene derivative having a halogen atom; 9,10-dialkoxyanthracene including halogen-substituted products; (5) 9,10-dialkoxyanthracene including compounds in which the 9- and/or 10-position alkoxy groups are modified with one or more halogen atoms; and/or (6) compounds having a halogen atom directly bonded to the anthracene skeleton.

The compound represented by the general formula (IV) can remarkably improve the adhesion when the compound is heated after exposure and then developed. Further, 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 Used for two-wavelength exposure using It is also advantageous in that it is possible to provide a photosensitive resin composition that exhibits excellent sensitivity, adhesion and resolution.

In one aspect, (C-2) the photopolymerization initiator preferably contains an anthracene derivative having a halogen atom. A preferred example of an anthracene derivative having a halogen atom is a halogen-substituted 9,10-dialkoxyanthracene. A preferred example of the halogen-substituted compound is a compound in which the 9- and/or 10-position alkoxy groups of 9,10-dialkoxyanthracene are modified with one or more halogens. Preferred alkoxy groups include those exemplified above as alkoxy groups having 1 to 40 carbon atoms.

In one embodiment, the anthracene derivative is also preferably a compound having a halogen atom directly bonded to the anthracene skeleton. Examples of such anthracene compounds include 9-bromo-10-phenylanthracene, 9-chloro-10-phenylanthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl) Anthracene, 9-(2-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 relative to the total solid content of the photosensitive resin composition, More preferably 0.1 to 3% by mass, particularly preferably 0.1 to 1.0% by mass.

(C-2) The photopolymerization initiator may further contain compounds other than anthracene and anthracene derivatives. Such compounds include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or Benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters, acridines (e.g. 9-phenylacridine, bisacridinylheptane, 9-(p-methylphenyl)acridine, 9-( m-methylphenyl)acridine is preferred in terms of sensitivity, resolution, and adhesion), hexaarylbiimidazole, pyrazoline compounds, coumarin compounds (for example, 7-diethylamino-4-methylcoumarin is preferred in terms of sensitivity, resolution, and adhesion). preferred in terms of adhesion), N-arylamino acids or ester compounds thereof (for example, N-phenylglycine is preferred in terms of sensitivity, resolution, and adhesion), halogen compounds (for example, tribromomethylphenylsulfone), etc. is mentioned. These can be used individually by 1 type or in combination of 2 or more types. Other, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl -diphenyl-phosphine oxide, triphenylphosphine oxide and the like may also be used.

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

Examples of hexaarylbiimidazoles 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) fluorophenyl)-4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2′-bis-(2,3,4,5-tetrafluorophenyl)-4,4 ',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'- Tetrakis-(3-methoxyphenyl)-biimidazole , and 2,2′-bis-(2,3,4,5,6-pentafluorophenyl)-4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole and the like. These can be used singly or in combination of two or more. From the viewpoint of sensitivity, resolution and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

The content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably from 0.05% by mass to 8% by mass, more preferably from the viewpoint of improving the peeling properties and/or sensitivity of the photosensitive resin layer. It is in the range of 0.1% to 7% by mass, more preferably 1% to 6% by mass.

From the viewpoint of peeling properties, sensitivity, resolution, and adhesion of the photosensitive resin layer, the photosensitive resin composition contains one or more pyrazoline compounds as (C-2) a photopolymerization initiator. is preferred.

Examples of pyrazoline compounds include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzoxazol-2-yl) Phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl- Phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropyl Phenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5 -dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)- 5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2, 3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, etc. From this point of view, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferred.

<(D) inhibitor>
In the present embodiment, it is preferable that the photosensitive resin composition further contains (D) an inhibitor from the viewpoint that the shortest development time of the unexposed portion is not extended even if heating is performed after exposure. From the same point of view, the inhibitor (D) is preferably a radical polymerization inhibitor or a phenol derivative, more preferably a phenol derivative. (D) The inhibitor may be originally contained in the raw material components to be used, or may be added at the time of preparation of the photosensitive resin composition preparation liquid. When the inhibitor is originally contained in the raw material components used, the content of the inhibitor can be quantified by GC-MS analysis or the like after the photosensitive resin laminate is produced.

Examples of radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. A nitrosophenylhydroxyamine aluminum salt is preferred so as not to impair the sensitivity of the photosensitive resin composition.

Examples of phenol derivatives include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis(4-methyl-6-tert-butylphenol ), 2,2′-methylenebis(4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2,5- Di-tert-butylhydroquinone, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), bis(2-hydroxy-3-t-butyl-5-ethylphenyl)methane, triethylene glycol-bis[ 3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] , pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl- 4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-t-butyl-4 -hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5- di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 4,4′-thiobis(6-tert-butyl-m- cresol), 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrenated phenol ( Examples include Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.), tribenzylphenol (eg, TBP, manufactured by Kawaguchi Chemical Industry Co., Ltd., phenol having 1 to 3 benzyl groups), biphenol, and the like.

The ratio of (D) inhibitor to the total solid mass of the photosensitive resin composition is preferably 0.001% by mass to 10% by mass. This ratio is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, from the viewpoint of not extending the shortest development time of the unexposed portion even if heating is performed after exposure. It is more preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. On the other hand, this ratio is preferably 10% by mass or less, more preferably 2% by mass or less, and 1% by mass or less in terms of less sensitivity reduction and improved resolution. is more preferable, 0.5% by mass or less is particularly preferable, and 0.3% by mass or less is most preferable.

<(E) benzotriazole derivative>
Furthermore, (E) containing a benzotriazole derivative is preferable from the viewpoint that discoloration is not observed on the copper surface after the photosensitive resin composition layer is developed and removed even if heating is performed after exposure. (E) The benzotriazole derivative preferably contains at least one compound selected from the group consisting of benzotriazoles and carboxybenzotriazoles.
Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole and the like.
Carboxybenzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole and the like.
Among these, carboxybenzotriazoles are particularly preferred.

(E) The content of the benzotriazole derivative is preferably 0.001% by mass to 3% by mass when the total solid content of the photosensitive resin composition is 100% by mass. The content of 0.001% by mass or more is preferable from the viewpoint that no discoloration is observed on the copper surface after the photosensitive resin composition layer has been removed by development even after heating after exposure. 02% by mass or more is more preferable, and 0.05% by mass or more is even more preferable. On the other hand, the content is preferably 3% by mass or less from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye, more preferably 2% by mass or less, further preferably 1% by mass or less, and 0.5% by mass. % or less is particularly preferable, and 0.3 mass % or less is most preferable.

Decolorization of the dye can be measured by transmittance at a wavelength of 630 nm. A high transmittance at a wavelength of 630 nm indicates that the dye is decolorized. The transmittance of the laminate of the support film and the photosensitive resin composition layer at a wavelength of 630 nm is preferably 80% or less, preferably 78% or less, preferably 75% or less, and 72% or less. preferably 70% or less, preferably 68% or less, preferably 65% or less, preferably 62% or less, preferably 60% or less, It is preferably 58% or less, preferably 55% or less, preferably 52% or less, and preferably 50% or less. This transmittance is the transmittance of the laminate of the support film and the photosensitive resin composition layer, and does not include the protective layer.

<Additive>
The photosensitive resin composition may optionally contain additives such as dyes, plasticizers, antioxidants and stabilizers. For example, additives listed in JP-A-2013-156369 may be used.
(Dyes and coloring substances)
In the present embodiment, the photosensitive resin composition may optionally further contain at least one selected from the group consisting of dyes (eg, leuco dyes, fluorane dyes, etc.) and coloring substances.

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

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

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

(Other additives)
In the present embodiment, the photosensitive resin composition may further contain epoxy compounds of bisphenol A. Epoxy compounds of bisphenol A include, for example, compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the ends.
In this embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of plasticizers include phthalates (e.g., diethylflate, etc.), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl triethyl citrate, -n-propyl, tri-n-butyl acetylcitrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether and the like. In addition, ADEKA NOL SDX-1569, ADEKA NOL SDX-1570, ADEKA NOL SDX-1571, ADEKA NOL SDX-479 (manufactured by Asahi Denka Co., Ltd.), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, Newpol Paul BPE-20T, Nieupol BPE-60, Nieupol BPE-100, Nieupol BPE-180 (manufactured by Sanyo Kasei Co., Ltd.), Uniol DB-400, Uniol DAB-800, Uniol DA-350F, Uniol DA- 400, Uniol DA-700 (manufactured by NOF Corporation), BA-P4U glycol, BA-P8 glycol (manufactured by Nippon Nyukazai Co., Ltd.) and other compounds having a bisphenol skeleton.

The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, based on the total solid mass of the photosensitive resin composition. is. The content of 1% by mass or more is preferable from the viewpoint of suppressing the development time delay and imparting flexibility to the cured film. On the other hand, setting the content to 50% by mass or less is preferable from the viewpoint of suppressing insufficient curing and cold flow.
If the water content in the photosensitive resin composition is large, the local plasticization of the photosensitive resin composition is rapidly accelerated, causing edge fuses. From the viewpoint of suppressing edge fuse, the water content in the photosensitive resin composition should be 0.7% or less based on the photosensitive resin composition after the photosensitive resin composition preparation is applied to the support film and dried. is preferred. The water content in the photosensitive resin composition is preferably 0.65% or less, preferably 0.6% or less, preferably 0.55% or less, and 0.5% or less. preferably 0.45% or less, preferably 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, and 0.4% or less. It is preferably 25% or less, preferably 0.2% or less.

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

[Photosensitive resin laminate]
As the support film, a transparent support film that transmits light emitted from the exposure light source is preferable. Examples of such support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, A polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film and the like can be mentioned. These films can also be used in a stretched form, if desired.
The support film preferably has a haze of 5% or less, more preferably 2% or less, even more preferably 1.5% or less, and particularly 1.0% or less, from the viewpoint of suppressing light scattering during exposure. preferable. From the same point of view, 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. As for the thickness of the film, the thinner the film, the more advantageous it is in terms of improving the image forming property and economic efficiency. The size of fine particles such as lubricant contained in the support film is preferably less than 5 μm.

Moreover, the support film may have a single-layer structure, or may have a multi-layer structure in which resin layers formed from a plurality of compositions are laminated. In the case of multilayer structures, there may be an antistatic layer. In the case of a multilayer structure such as a two-layer structure or a three-layer structure, for example, a resin layer containing fine particles is formed on one surface A, and on the other surface B, (1) fine particles in the same manner as on surface A (2) contains a smaller amount of fine particles than the surface A, (3) contains finer particles than the surface A, and (4) does not contain fine particles. In the case of structures (2), (3), and (4), it is preferable to form a photosensitive resin layer on the surface B side. At this time, it is preferable to have a resin layer containing fine particles on the surface A side from the viewpoint of the slipperiness of the film. The size of the fine particles at this time is preferably less than 1.5 μm from the viewpoint of the effects of the present invention.

An important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesive force to the photosensitive resin layer is sufficiently smaller than that of the support layer, so that the protective layer can be easily peeled off. For example, a polyethylene film or a polypropylene film can preferably be used as protective layer. In addition, a film having excellent releasability disclosed in JP-A-59-202457 can also be used. The film thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

A gel called fish eye may be present on the surface of the polyethylene film. When a polyethylene film having fisheyes is used as the protective layer, the fisheyes may be transferred to the photosensitive resin layer. If the fisheye is transferred to the photosensitive resin layer, air may be entrapped during lamination to form voids, leading to defects in the resist pattern. From the viewpoint of preventing fish eyes, oriented polypropylene is preferable as the material for the protective layer. A specific example is Alphan E-200A manufactured by Oji Paper Co., Ltd.

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

Next, a method for manufacturing a photosensitive resin laminate will be described.
A known method can be adopted as a method for sequentially laminating a support layer, a photosensitive resin layer, and, if necessary, a protective layer to produce a photosensitive resin laminate. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves it to form a uniform solution, first applied onto the support layer using a bar coater or roll coater, and then dried to remove the solvent. can be laminated on the support layer by removing the photosensitive resin layer composed of the photosensitive resin composition. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

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

A printed wiring board is manufactured through the following steps.
(1) Lamination step First, in the lamination step, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed onto the substrate surface by a laminator to laminate. Examples of substrate materials 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 required. The heating temperature during lamination is generally 40°C to 160°C. Further, by performing the thermocompression bonding at the time of lamination two or more times, the adhesion of the obtained resist pattern to the substrate can be improved. During thermocompression bonding, a two-stage laminator equipped with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the rolls several times.

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

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

When the exposure process is an exposure method by direct drawing, laser light with a center wavelength of less than 390 nm or laser light with a center wavelength of 390 nm or more is preferable. Laser light with a center wavelength of 350 nm or more and 380 nm or less or laser light with a center wavelength of 400 nm or more and 410 nm or less is more preferable. A method of exposing with a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more is preferable. More preferably, 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 step In this step, the exposed photosensitive resin composition is preferably subjected to a heating step at about 30°C to about 200°C, more preferably in the range of 30°C to 150°C. It is more preferably in the range of 60°C to 120°C. By performing this heating step, it is possible to improve resolution and adhesion. For heating, a heating furnace using hot air, infrared rays, or far infrared rays, a constant temperature bath, a hot plate, a hot air dryer, an infrared dryer, a hot roll, or the like can be used. It is preferable that the heating method is a hot roll in that the treatment can be performed in a short time, and it is more preferable that the hot roll is two or more.

In particular, in the present invention, even if the system contains a structural unit of styrene and/or a styrene derivative in an amount of 15% by mass or more and is developed after heating after exposure, even if the system has a high styrene skeleton content, the resin can be converted by heating. The mobility is improved, and the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly compatible.

Further, in the present invention, at least anthracene and/or anthracene derivative is used as the (C-2) photopolymerization initiator ((C) photopolymerization initiator), and by heating after exposure and then developing, The mobility of the resin is improved, and, for example, even in a system having a relatively large styrene skeleton content, both the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be achieved at a high level.

As a result, adhesion can be significantly improved. Further, since the adhesion is remarkably improved, good adhesion can be obtained even when the elapsed time after exposure is long. From the viewpoint of the effects of the present invention, the heating step is preferably performed within 15 minutes after exposure, more preferably within 10 minutes, and even more preferably within 5 minutes.

(4) Development process In this process, after exposure, the support layer on the photosensitive resin layer is peeled off, and then the unexposed area is developed and removed using an alkaline aqueous developer, thereby forming the resist pattern on the substrate. Form.
As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used. The alkaline aqueous solution is appropriately selected according to the properties of the photosensitive resin layer, but a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2% by mass to about 2% by mass and a temperature of about 20°C to about 40°C is preferable.
A resist pattern can be obtained through the above steps (1) to (4).

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

(5) Etching step or plating step A substrate surface exposed by development (for example, the copper surface of a copper-clad laminate) is etched or plated to produce a conductor pattern.
(6) Stripping Step After that, the resist pattern is stripped from the substrate using a suitable stripping solution.
Examples of the stripping solution used here include an alkaline aqueous solution and an amine-based stripping solution. However, the resist pattern formed from the photosensitive resin composition of the present invention through post-exposure heating exhibits good releasability with respect to the amine stripping solution, and the exfoliated pieces are not excessively fine. It has the characteristics of Therefore, it is preferable to use an amine-based stripping solution as the stripping solution because the advantageous effects of the present invention are maximized.

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

Examples of organic amines include ethanolamine, propanolamine, alkylamines, cyclic amines, quaternary ammonium salts and the like. Specific examples of these include:
Examples of ethanolamines include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, aminoethoxyethanol and the like;
Examples of propanolamine include 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol;
Examples of alkylamines include monomethylamine, dimethylamine, trimethylamine, ethyleneamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, tetraethylenepentamine, and the like;
Cyclic amines such as choline, morpholine, etc.;
Examples of quaternary ammonium salts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, N,N,N-triethyl-N-(2-hydroxyethyl)ammonium hydroxide, N,N- diethyl-N,N-di(2-hydroxyethyl)ammonium hydroxide and the like;
Each can be exemplified.

The amine-based release agent used in the present invention may be an aqueous solution containing one or more of the amines exemplified above. The concentration of amine in the aqueous solution may be appropriately set according to the purpose, composition of the photosensitive resin layer, development conditions, and the like.
The amine-based stripping agent used in the present invention may further contain additives commonly used in stripping agents, such as surfactants, antifoaming agents, pH adjusters, preservatives, anti-redeposition agents, and the like. good.
The peeling step is performed at a temperature of, for example, 0° C. to 100° C., preferably room temperature (23° C.) to 50° C., for 1 second to 1 hour, preferably 10 seconds to 10 minutes.

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

The photosensitive resin laminate of the present embodiment can be used as a printed wiring board, a flexible substrate, a lead frame substrate, a touch panel substrate, a COF substrate, a semiconductor package substrate, a transparent electrode for liquid crystal, a wiring for TFT for liquid crystal, an electrode for PDP, or the like. It is a photosensitive resin laminate suitable for manufacturing a conductor pattern of.
Unless otherwise specified, the various parameters described above are measured according to the measurement methods in Examples described later or equivalent methods understood by those skilled in the art.

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

<<First Embodiment>>
In the first example, (A) a photosensitive resin composition in which the structural unit of styrene and/or a styrene derivative in the whole alkali-soluble polymer is 15% by mass or more was evaluated.

(1) Measurement of physical properties <Measurement of weight average molecular weight or number average molecular weight of polymer>
The weight average molecular weight or number average molecular weight of the polymer is determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko Co., Ltd. ( KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (Showa Denko Co., Ltd. Shodex STANDARD SM-105) using a calibration curve) Calculated as polystyrene equivalent.
Furthermore, the polymer dispersity 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).

(2) Method for producing evaluation samples Evaluation samples were produced as follows.
<Preparation of photosensitive resin laminate>
Components shown in Table 1-1 (Table 2-1, Table 3-1) shown below (wherein the numbers of each component indicate the amount (parts by mass) of the solid content) and the solvent are sufficiently stirred, By mixing, a photosensitive resin composition preparation liquid was obtained. The names of the components represented by abbreviations in Table 1-1 (Tables 2-1 and 3-1) are shown in Tables 1-2 (Tables 2-2 and 3-2) below. A polyethylene terephthalate film (FB-40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm was used as a support film, and the prepared liquid was uniformly applied to the surface thereof using a bar coater. After drying for a minute, a photosensitive resin composition layer was formed. The dry thickness of the photosensitive resin composition layer was 25 μm.
Next, on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film is not laminated, a 19 μm thick polyethylene film (GF-818, manufactured by Tamapoly Co., Ltd.) is laminated as a protective layer to form a photosensitive resin. A laminate was obtained.

<Board surface preparation>
As a substrate for evaluating image quality, a 0.4 mm thick copper-clad laminate laminated with 35 μm rolled copper foil was sprayed with an abrasive (#400, manufactured by Ujiden Chemical Industry Co., Ltd.) at a spray pressure of 0.2 MPa. After scrub polishing, the substrate surface was washed with a 10 mass % H ₂ SO ₄ aqueous solution.
<Lamination>
While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, a copper-clad laminate preheated to 50 ° C. is coated with a hot roll laminator (AL-700, manufactured by Asahi Kasei Co., Ltd.). Lamination was performed at a roll temperature of 105°C. The air pressure was 0.35 MPa and the lamination speed was 1.5 m/min.

<Exposure>
Two hours after lamination, the substrate for evaluation was exposed using a direct drawing exposure machine IP-8 8000H using a Stouffer 41-stage step tablet. The exposure was carried out at an exposure amount such that the maximum number of remaining film steps was 15 steps when exposed and developed using the Stouffer 41 step tablet as a mask.

Seven minutes after the exposure, the substrate for evaluation was heated with a hot roll laminator (AL-700, manufactured by Asahi Kasei Corp.). The roll temperature was 105° C., the air pressure was 0.30 MPa, and the lamination speed was 0.5 m/min. If the elapsed time after exposure is increased, the effect of heating is lost, so heating is normally performed for about 1 minute after exposure. Therefore, the heating after 7 minutes of exposure in this embodiment is a very severe condition.

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

<Adhesion evaluation>
The minimum line width at which a pattern of mask pattern L/S=X μm/200 μm is normally formed was measured with an optical microscope. This measurement was performed for eight lines, and the average value of the eight line widths was obtained as the adhesion value.

<Discoloration of copper surface>
The same steps as described above were carried out up to development, and the copper surface after the photosensitive resin composition layer was removed by development was visually observed in the unexposed area where the photosensitive resin composition layer was laminated.
〇: No discoloration △: Slight discoloration

<Delay in shortest development time>
The shortest development time was measured under the following two conditions.
(A) Ordinary Shortest Developing Time A photosensitive resin laminate was laminated on a substrate, and the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve after peeling off the support film was measured.
(B) Shortest development time after heating After laminating the photosensitive resin laminate on the substrate, it was heated with a hot roll laminator (AL-700, manufactured by Asahi Kasei Corp.). The roll temperature was 105° C., the air pressure was 0.30 MPa, and the lamination speed was 0.1 m/min.
○: (B) and (A) have the same shortest development time (no delay)
△: The shortest development time of (B) is 1 to 3 seconds longer than the shortest development time of (A) (with delay)

The above evaluation results are shown in Table 1-1 together with the components of the photosensitive resin compositions of Examples and Comparative Examples. In addition, Table 1-2 shows the names of the components represented by abbreviations in Table 1-1.

From the results of Tables 1-1 and 1-2, it was found that the examples within the scope of the constituent elements of the present invention had better image property evaluation results than the comparative examples outside the scope of the present invention. confirmed.

From the results of Tables 1-1 and 1-2, it can be seen that the examples within the scope of the constituent elements of the present invention are superior to the comparative examples, which are outside the scope of the present invention, in image quality evaluation results. was confirmed.

Note that the heating conditions after exposure in this example are very strict conditions because the heating is after 7 minutes of exposure. For example, when the compositions of Example 1 and Comparative Example 1 were developed without heating after exposure, the adhesion was 12.0 μm for both. That is, in the composition of Comparative Example 1, no effect was observed by heating after 7 minutes of exposure, but in Example 1, adhesion can be improved even under extremely severe conditions. In addition, under the condition of heating one minute after exposure, the adhesion of 10.0 μm was obtained for both the compositions of Example 1 and Comparative Example 1.

From the above results, even if the adhesion is good under general heating conditions after exposure, it does not mean that the adhesion is improved under the severe conditions of heating 7 minutes after exposure in this example. do not have. However, with the photosensitive resin composition of the present invention having a specific composition, it was possible for the first time to improve adhesion even under this severe post-exposure heating condition. As a result, when manufacturing a circuit board, good adhesion can be obtained even if the elapsed time after exposure is long, so that a high-definition circuit pattern can be stably formed.

<<Second embodiment>>
In the second example, (B) a compound having an ethylenically unsaturated double bond includes a (meth)acrylate compound having 3 or more ethylenically unsaturated double bonds, evaluation of a photosensitive resin composition did
Using the components shown in Table 2-1 below, an evaluation sample was prepared in the same manner as in the first example described above.
<Exposure>
Two hours after lamination, the substrate for evaluation was exposed using a direct drawing exposure machine (Nuvogo 1000, manufactured by Orbotech, light source: 375 nm (30%) + 405 nm (70%)) using a Stouffer 41-stage step tablet. . The exposure was carried out at an exposure amount such that the maximum number of remaining film steps was 19 steps when exposed and developed using the Stouffer 41-step tablet as a mask.

<Heating>
Seven minutes after the exposure, the substrate for evaluation was heated with a hot roll laminator (AL-700, manufactured by Asahi Kasei Corp.). The roll temperature was 105° C., the air pressure was 0.30 MPa, and the lamination speed was 1 m/min. If the elapsed time after exposure is increased, the effect of heating is lost, so heating is normally performed for about 1 minute after exposure. Therefore, the heating after 7 minutes of exposure in this embodiment is a very severe condition.

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

Evaluation was performed in the same manner as in Example 1, except that the steps from exposure to development were performed as described above.
The above evaluation results are shown in Table 2-1 together with the components of the photosensitive resin compositions of Examples and Comparative Examples. In addition, Table 2-2 shows the names of the components represented by abbreviations in Table 2-1.

From the results of Tables 2-1 and 2-2, it was found that the examples within the scope of the constituent elements of the present invention were superior in image property evaluation results to the comparative examples outside the scope of the present invention. confirmed.

Note that the heating conditions after exposure in this example are very strict conditions because the heating is after 7 minutes of exposure. For example, when the compositions of Example 1 and Comparative Example 1 were developed without heating after exposure, the adhesion was 11.8 μm for both. That is, in the composition of Comparative Example 1, no effect was observed by heating after 7 minutes of exposure, but in Example 1, adhesion can be improved even under extremely severe conditions. Moreover, under the condition of heating one minute after the exposure, the adhesiveness of 9.6 μm was obtained for both the compositions of Example 1 and Comparative Example 1.

From the above results, even if the adhesion is good under general heating conditions after exposure, it does not mean that the adhesion is improved under the severe conditions of heating 7 minutes after exposure in this example. do not have. However, according to the present invention, for the first time, it was possible to improve the adhesion even under this severe post-exposure heating condition. As a result, when manufacturing a circuit board, good adhesion can be obtained even if the elapsed time after exposure is long, so that a high-definition circuit pattern can be stably formed.

<<Third Embodiment>>
In the third example, (C-2) a photosensitive resin composition containing an anthracene and/or an anthracene derivative as a photopolymerization initiator was evaluated.
Using the components shown in Table 3-1 below, an evaluation sample was prepared in the same manner as in the first example described above.
<Exposure>
Two hours after lamination, the substrate for evaluation was exposed using a direct drawing exposure machine (Nuvogo 1000, manufactured by Orbotech, light source: 375 nm (30%) + 405 nm (70%)) using a Stouffer 41-stage step tablet. . The exposure was carried out at an exposure amount such that the maximum number of remaining film steps was 21 steps when exposed and developed using the Stouffer 41-step tablet as a mask.

<Heating>
Seven minutes after the exposure, the substrate for evaluation was heated with a hot roll laminator (AL-700, manufactured by Asahi Kasei Corp.). The roll temperature was 105° C., the air pressure was 0.30 MPa, and the lamination speed was 1 m/min. If the elapsed time after exposure is increased, the effect of heating is lost, so heating is normally performed for about 1 minute after exposure. Therefore, the heating after 7 minutes of exposure in this embodiment is a very severe condition.

<Development>
After peeling off the polyethylene terephthalate film (supporting layer), using an alkali developing machine (manufactured by Fuji Kiko, dry film developing machine), develop by spraying a 1% by mass Na ₂ CO ₃ aqueous solution at 30° C. for a predetermined time. did The development spray time was twice the shortest development time, and the washing spray time after development was three times the shortest development time. At this time, the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was taken as the shortest developing time.

Evaluation was performed in the same manner as in Example 1, except that the steps from exposure to development were performed as described above.
The above evaluation results are shown in Table 3-1 together with the components of the photosensitive resin compositions of Examples and Comparative Examples. In addition, Table 3-2 shows the names of the components represented by abbreviations in Table 3-1.

From the results of Tables 3-1 and 3-2, it can be seen that the results of evaluation of image quality are superior to those of the comparative examples, which are outside the scope of the invention, in the examples within the scope of the constituent elements of the invention. was confirmed. Note that the heating conditions after exposure in this example are very strict conditions because the heating is after 7 minutes of exposure. For example, when the compositions of Example 7 and Comparative Example 1 were developed without heating after exposure, the adhesion was 12.8 μm for both. That is, in the composition of Comparative Example 1, no effect was observed by heating after 7 minutes of exposure, but in Example 7, the adhesion can be improved even under extremely severe conditions. Moreover, under the condition of heating one minute after the exposure, the adhesion of 9.6 μm was obtained for both the compositions of Example 7 and Comparative Example 1.

From the above results, even if the adhesion is good under general heating conditions after exposure, it does not mean that the adhesion is improved under the severe condition of heating 7 minutes after exposure. It can be seen that the adhesion can be improved even under this severe post-exposure heating condition for the first time with the invention. That is, according to the composition according to the present invention, when manufacturing a circuit board, good adhesion can be obtained even if the elapsed time after exposure is long, so that a high-definition circuit pattern can be stably formed. can be formed by

Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be modified as appropriate without departing from the gist of the invention.

By using the photosensitive resin composition according to the present invention, it is possible to remarkably improve adhesion when developing after heating after exposure, and in particular, good adhesion even when the elapsed time after exposure is long. It can be widely used as a photosensitive resin composition.

Claims (30)

The following steps:
exposing the layer of the photosensitive resin composition;
A heating step of heating the exposed photosensitive resin composition layer; and a developing step of developing the heated photosensitive resin composition layer. A method for forming a resist pattern for manufacturing a circuit board ,
Without exposing the layer of the photosensitive resin composition to a reduced pressure atmosphere or a low oxygen concentration atmosphere between the exposure and the heating,
The photosensitive resin composition contains the following components, based on the total solid mass of the photosensitive resin composition:
(A) alkali-soluble polymer: 10% by mass to 90% by mass;
(B) a compound having an ethylenically unsaturated double bond: 5% to 70% by mass; and (C) a photopolymerization initiator: 0.01% to 20% by mass;
including
(A) A method of forming a resist pattern, wherein the constituent unit of styrene and/or a styrene derivative in the entire alkali-soluble polymer is 15% by mass or more. As the (B) compound having an ethylenically unsaturated double bond, the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol/100 g or more is equal to the solid content of the photosensitive resin composition. 2. The method of forming a resist pattern according to claim 1, wherein the content is 0 or more and 18% by mass or less with respect to the 3. The method of forming a resist pattern according to claim 1, further comprising (D) an inhibitor. 4. The method of forming a resist pattern according to claim 1, further comprising (E) a benzotriazole derivative. The (B) compound having an ethylenically unsaturated double bond comprises a (meth)acrylate compound having 3 or more ethylenically unsaturated double bonds. The resist according to any one of claims 1 to 4. How the pattern is formed. 6. The method of forming a resist pattern according to claim 5, wherein (B) the compound having an ethylenically unsaturated double bond includes a (meth)acrylate compound having 4 or more ethylenically unsaturated double bonds. 7. The method of forming a resist pattern according to claim 6, wherein (B) the compound having an ethylenically unsaturated double bond includes a (meth)acrylate compound having 6 or more ethylenically unsaturated double bonds. Any one of claims 1 to 7, wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 0.94 or more. A method of forming a resist pattern according to the item. The resist pattern according to claim 8, wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 1.04 or more. Forming method. The resist pattern according to claim 9, wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 1.11 or more. Forming method. The resist pattern according to claim 10, wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 1.21 or more. Forming method. The resist pattern according to claim 11, wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 1.30 or more. Forming method. The value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 5 or less, according to any one of claims 1 to 12 A method of forming a resist pattern as described. 14. The method of forming a resist pattern according to claim 13, wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 4 or less. . 15. The method of forming a resist pattern according to claim 14, wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 3 or less. . 16. The method of forming a resist pattern according to claim 15, wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 2 or less. . 17. The resist pattern according to claim 16, wherein the value of [(A) the content of the alkali-soluble polymer]/[the content of the compound having an ethylenically unsaturated double bond] is 1.5 or less. Forming method. The method of forming a resist pattern according to any one of claims 1 to 17 , wherein the constituent units of styrene and/or styrene derivatives in (A) the alkali-soluble polymer are 25% by mass or more. 19. The method of forming a resist pattern according to claim 18 , wherein the constituent unit of styrene and/or a styrene derivative in (A) the alkali-soluble polymer is 30% by mass or more. 20. The method of forming a resist pattern according to claim 19 , wherein the constituent unit of styrene and/or a styrene derivative in (A) the alkali-soluble polymer is 35% by mass or more. 21. The method of forming a resist pattern according to claim 20 , wherein the constituent units of styrene and/or styrene derivatives in (A) the alkali-soluble polymer are 40% by mass or more. The method of forming a resist pattern according to any one of claims 1 to 21 , wherein the constituent units of styrene and/or styrene derivatives in (A) the alkali-soluble polymer are 90% by mass or less. The method of forming a resist pattern according to any one of claims 1 to 22 , wherein (A) the alkali-soluble polymer further contains benzyl (meth)acrylate as a monomer component. The method of forming a resist pattern according to any one of claims 1 to 23 , wherein the heating temperature in said heating step is in the range of 30°C to 150°C. 25. The method of forming a resist pattern according to any one of claims 1 to 24 , wherein the exposure step is performed by an exposure method in which a drawing pattern is directly drawn, or an exposure method in which an image of a photomask is projected through a lens. 26. The method of forming a resist pattern according to any one of claims 1 to 25 , wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern. 27. The method of forming a resist pattern according to claim 1, wherein said heating step is performed within 15 minutes after exposure. The resist pattern according to any one of claims 1 to 27 , wherein the exposure step is performed by a method of exposing with a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more. method of formation. 29. The method of forming a resist pattern according to claim 28 , wherein the center wavelength of said first laser light is 350 nm or more and 380 nm or less, and the center wavelength of said second laser light is 400 nm or more and 410 nm or less. Etching or plating a substrate having a resist pattern manufactured by the method according to any one of claims 1 to 29 , and peeling the resist pattern from the substrate to form a circuit board. A method of manufacturing a circuit board.