JP7169351B2 - 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. As a resist for manufacturing printed wiring boards, etc., conventionally, it has a support layer, a photosensitive resin layer laminated on the support layer, and a protective layer laminated on the photosensitive resin layer as necessary. A photosensitive resin laminate, 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.

Examples of methods for producing printed wiring boards and the like using DF include the following methods. If the DF has a protective layer, first peel off the protective layer. After that, the DF is laminated on a substrate such as a copper clad laminate or a substrate for producing a permanent circuit such as a flexible substrate using a laminator or the like. The laminated DF is exposed through a wiring pattern mask film or the like. If necessary, the support layer is peeled off, the uncured portion (e.g., the unexposed portion in the negative type) of the photosensitive resin layer is dissolved or dispersed and removed with a developer, and a cured resist pattern (hereinafter simply referred to as (also called a “resist pattern”).

There are roughly two methods for forming a circuit after forming a resist pattern. The first method consists of etching away the substrate surface not covered by the resist pattern (for example, the copper surface of a copper-clad laminate) and removing the resist pattern portion with an alkaline aqueous solution stronger than the developer. etching methods, including In the second method, 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 (e.g., copper and etching the clad laminate (copper side). As a solution for etching, cupric chloride, ferric chloride, cuprammonium complex solution, or the like is used.

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. For example, Patent Literature 1 describes a photosensitive resin composition whose resolution is enhanced by using a specific thermoplastic resin, a monomer, and a photopolymerization initiator. Patent Literature 2 describes a method of forming a resist pattern including a step of heating both an exposed photosensitive resin composition layer and a substrate under pressure using a pressure heating mechanism. Patent Document 3 describes a method for forming a resist pattern, including the steps of exposing, heat-treating, and developing a laminate in which (a) a photosensitive layer and (b) a resin layer are formed on a substrate. ing. Patent Literature 4 describes a method of forming a resist pattern, which includes a step of leaving the laminate in a reduced-pressure atmosphere or a low-oxygen concentration atmosphere at least between exposure and heat treatment. Patent Document 5 describes various additives optionally included in the photosensitive resin layer of DF. US Pat. No. 6,300,009 describes a protective layer that is preferably applied to DF.

JP 2010-249884 A JP 2014-191318 A JP 2016-224161 A JP 2016-224162 A JP 2013-156369 A JP-A-59-202457

After the exposure step, in some cases, the photosensitive resin layer is subjected to a heating step (post-exposure heating: PEB), followed by development. 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 performed, the improvement in adhesion is insufficient with conventional photosensitive resin compositions. Moreover, when a long time has passed after exposure, even if the post-exposure heating process is performed, good adhesion may not be obtained.

The present invention has been proposed in view of such conventional circumstances, and an object of the present invention is to provide a photosensitive resin composition that can remarkably improve adhesion when heated after exposure and then developed. One of the purposes is to provide In particular, in a preferred embodiment, one object is to provide a photosensitive resin composition that exhibits good adhesion even when a long time elapses from exposure to heating.

As a result of extensive studies to solve the above problems, the inventors of the present application have found an alkali-soluble polymer having an inorganic value (I value) within a specific range; The inventors have found that the above problems can be solved by a photosensitive resin composition containing an alkali-soluble polymer (A-1) having a molecule; or a structural unit having a specific structure, and have completed the present invention. Examples of embodiments of the present invention are listed in the following embodiment examples [1] to [29].
[1]
After exposure, a photosensitive resin composition for obtaining a resin cured product by heating and then developing, wherein the photosensitive resin composition has the following, based on the total solid mass of the photosensitive resin composition: Ingredients of:
(A) 10% to 90% by mass of an alkali-soluble polymer;
(B) 5% to 70% by mass of a compound having an ethylenically unsaturated double bond;
(C) 0.01% to 20% by mass of a photopolymerization initiator,
A photosensitive resin composition, wherein the alkali-soluble polymer (A) has an inorganic value (I value) of 720 or less.
[2]
The photosensitive resin composition according to item 1, wherein the alkali-soluble polymer (A) has an I value of 635 or less.
[3]
3. The photosensitive resin composition according to item 2, wherein the alkali-soluble polymer (A) has an I value of 600 or less.
[4]
4. The photosensitive resin composition according to any one of items 1 to 3, wherein the alkali-soluble polymer (A) has an I value of 300 or more.
[5]
5. The photosensitive resin composition according to item 4, wherein the alkali-soluble polymer (A) has an I value of 400 or more.
[6]
6. The photosensitive resin composition according to item 5, wherein the alkali-soluble polymer (A) has an I value of 450 or more.
[7]
7. The photosensitive resin composition according to item 6, wherein the alkali-soluble polymer (A) has an I value of 500 or more.
[8]
8. The photosensitive resin composition according to item 7, wherein the alkali-soluble polymer (A) has an I value of 550 or more.
[9]
After exposure, a photosensitive resin composition for obtaining a resin cured product by heating and then developing, wherein the photosensitive resin composition has the following, based on the total solid mass of the photosensitive resin composition: Ingredients of:
(A) 10% to 90% by mass of an alkali-soluble polymer;
(B) 5% to 70% by mass of a compound having an ethylenically unsaturated double bond;
(C) 0.01% to 20% by mass of a photopolymerization initiator,
The photosensitive resin composition, wherein the alkali-soluble polymer (A) has a solubility parameter (sp value) of 21.45 MPa ^1/2 or less.
[10]
10. The photosensitive resin composition according to item 9, wherein the alkali-soluble polymer (A) has a solubility parameter (sp value) of 21.40 MPa< ^1/2 > or less.
[11]
11. The photosensitive resin composition according to item 10, wherein the alkali-soluble polymer (A) has a solubility parameter (sp value) of 21.20 MPa< ^1/2 > or less.
[12]
The photosensitive resin composition according to any one of items 9 to 11, wherein the alkali-soluble polymer (A) has a solubility parameter (sp value) of 19.00 MPa ^1/2 or more.
[13]
13. The photosensitive resin composition according to item 12, wherein the alkali-soluble polymer (A) has a solubility parameter (sp value) of 19.50 MPa ^1/2 or more.
[14]
14. The photosensitive resin composition according to item 13, wherein the alkali-soluble polymer (A) has a solubility parameter (sp value) of 20.00 MPa ^1/2 or more.
[15]
15. The photosensitive resin composition according to item 14, wherein the alkali-soluble polymer (A) has a solubility parameter (sp value) of 20.50 MPa ^1/2 or more.
[16]
After exposure, a photosensitive resin composition for obtaining a resin cured product by heating and then developing, wherein the photosensitive resin composition has the following, based on the total solid mass of the photosensitive resin composition: Ingredients of:
(A) 10% to 90% by mass of an alkali-soluble polymer;
(B) 5% to 70% by mass of a compound having an ethylenically unsaturated double bond;
(C) 0.01% to 20% by mass of a photopolymerization initiator,
The photosensitive resin composition contains, as the alkali-soluble polymer (A), an alkali-soluble polymer (A-1) containing 52% by mass or more of structural units derived from styrene and/or a styrene derivative as a monomer component. , a photosensitive resin composition containing 3% by mass or more based on the total solid mass in the photosensitive resin composition.
[17]
17. The photosensitive resin composition according to item 16, wherein the photosensitive resin composition contains 10% by mass or more of the alkali-soluble polymer (A-1) with respect to the total solid mass in the photosensitive resin composition. .
[18]
18. The photosensitive resin composition according to item 16 or 17, wherein the alkali-soluble polymer (A-1) contains 55% by mass or more of structural units derived from styrene and/or a styrene derivative as a monomer component.
[19]
19. The photosensitive resin composition according to item 18, wherein the alkali-soluble polymer (A-1) contains 58% by mass or more of structural units derived from styrene and/or a styrene derivative as a monomer component.
[20]
20. The photosensitive resin composition according to any one of Items 16 to 19, wherein the alkali-soluble polymer (A-1) contains 27% by mass or more of structural units derived from (meth)acrylic acid as a monomer component. thing.
[21]
20. The photosensitive resin composition according to any one of items 16 to 19, wherein the alkali-soluble polymer (A-1) further contains a structural unit derived from benzyl (meth)acrylate as a monomer component.
[22]
The following steps:
A step of exposing the layer of the photosensitive resin composition according to any one of items 1 to 21;
A method of forming a resist pattern, comprising: a heating step of heating the exposed layer of the photosensitive resin composition; and a developing step of developing the heated layer of the photosensitive resin composition.
[23]
23. The method of forming a resist pattern according to item 22, wherein the heating temperature in the heating step is in the range of 30.degree. C. to 150.degree.
[24]
24. The method of forming a resist pattern according to item 22 or 23, wherein the heating step is performed within 15 minutes after the exposure is stopped.
[25]
25. The method of forming a resist pattern according to any one of items 22 to 24, wherein the exposure step is performed by an exposure method that directly draws a drawing pattern or an exposure method that projects an image of a photomask through a lens.
[26]
26. A method of forming a resist pattern according to item 25, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern.
[27]
27. A method of forming a resist pattern according to item 26, 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.
[28]
28. The method of forming a resist pattern according to item 27, 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.
[29]
A circuit comprising forming a circuit board by producing a resist pattern on a substrate by the method according to any one of items 22 to 28, and etching or plating the substrate having the resist pattern. Substrate manufacturing method.

According to the present invention, it is possible to remarkably improve the adhesion of a resist pattern when it is developed after being subjected to post-exposure baking (PEB). In a preferred embodiment, it is possible to provide a photosensitive resin composition that exhibits good adhesion even after a long time has passed from exposure to heating. It should be noted that the above description should not be considered as disclosing all embodiments of the invention or all advantages associated with the invention. Further embodiments of the invention and advantages thereof will become apparent with reference to the following description.

Embodiments of the present invention will be described in detail below for the purpose of illustrating, but the present invention is not limited to these embodiments. In the specification of the present application, the upper limit and lower limit of each numerical range can be arbitrarily combined.

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment is a photosensitive resin composition for obtaining a resin cured product by heating after exposure and development. The photosensitive resin composition comprises (A) 10% by mass to 90% by mass of an alkali-soluble polymer and (B) 5% by mass to 70% by mass, based on the total solid content of the photosensitive resin composition. It contains a compound having an ethylenically unsaturated double bond and (C) 0.01% by mass to 20% by mass of a photopolymerization initiator.

<(A) alkali-soluble polymer>
In this embodiment, the photosensitive resin composition may have an inorganic value (I value) of the alkali-soluble polymer (A) of 720 or less. Here, the "I value" is also called an "inorganic value" and indicates the degree of physical properties mainly due to electrical affinity. The “O value” is also called “Organic Value” and mainly indicates the degree of physical properties according to van der Waalska. The I/O value is a parameter representing a measure of the lipophilicity/hydrophilicity of a compound or substituent and is determined based on the I and O values specific to that compound or substituent. The higher the I/O value, the higher the inorganicity. For details of the I/O value, refer to Yoshio Koda, "Organic Conceptual Diagram", Sankyo Publishing, 1984, and the like.

In this embodiment, in the photosensitive resin composition, the solubility parameter (sp value) of the alkali-soluble polymer (A) may be 21.45 MPa ^1/2 or less. The solubility parameter (sp value) is the square root of the cohesive energy density of a substance. ”, Journal of Adhesion Society of Japan, 1993, vol. 29, No. 5, pp. 8-15, etc. In the specification of the present application, the SP value means a value calculated by the Okitsu method.

In the present embodiment, the photosensitive resin composition includes, as the alkali-soluble polymer (A), an alkali-soluble polymer (A- 1) may be contained in an amount of 3% by mass or more based on the total solid mass in the photosensitive resin composition.

The photosensitive resin composition of the present embodiment has one or more characteristics of the inorganic value (I value), the solubility parameter (sp value), or the alkali-soluble polymer (A-1). Therefore, the adhesiveness can be remarkably improved when developing after heating after exposure. In the photosensitive resin composition of the present embodiment, for example, the alkali-soluble polymer (A) has an inorganic value (I value) of 720 or less and a solubility parameter (sp value) of 21.45 MPa ^1/2 or less. The inorganic value (I value) of the alkali-soluble polymer (A) is 720 or less, and the alkali-soluble polymer (A-1) is contained in an amount of 3% by mass or more based on the total solid mass. The solubility parameter (sp value) of the alkali-soluble polymer (A) is 21.45 MPa ^1/2 or less, and the alkali-soluble polymer (A-1) is 3% by mass based on the total solid mass. Alternatively, the alkali-soluble polymer (A) has an inorganic value (I value) of 720 or less, a solubility parameter (sp value) of 21.45 MPa ^1/2 or less, and has high alkali solubility The molecule (A-1) may be contained in an amount of 3% by mass or more based on the total solid mass.

In general, a dry film resist obtained from a photosensitive resin composition tends to be difficult to improve adhesion unless it is heated immediately after exposure. On the other hand, the dry film resist obtained from the photosensitive resin composition of the present embodiment can exhibit good adhesion even after a long time from exposure to heating, and a fine resist pattern can be obtained. be able to.

The reason why the adhesion is improved when the film is developed after being heated after exposure is not limited to theory, but the inventors presume as follows. When the inorganic value (I value) of the alkali-soluble polymer is 720 or less, the alkali-soluble polymer has a low electrical affinity, suppresses permeability during development, and increases swelling/dissolution resistance. As a result, even a fine resist pattern can be maintained without being damaged by development. In addition, if the elapsed time from exposure to heating is long, radicals generated during exposure collide with oxygen in the alkali-soluble polymer and are deactivated, reducing the effect of PEB. However, alkali-soluble polymers with low electrical affinity are less likely to contain water molecules because water is less likely to ionize, which hinders the movement of oxygen. Conceivable. When the solubility parameter (sp value) of the alkali-soluble polymer is 21.45 MPa ^1/2 or less, the alkali-soluble polymer has high hydrophobicity and high resistance to swelling and dissolution during development. Even a pattern is considered to be retained without being damaged by development. In addition, highly hydrophobic, alkali-soluble polymers have low hygroscopicity and hinder the movement of oxygen via water molecules. Conceivable. The photosensitive resin composition contains 3% by mass or more of the alkali-soluble polymer (A-1) relative to the total solid mass in the photosensitive resin composition, so that the mobility of the resin is greatly improved by heating after exposure. However, the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly compatible. As a result, adhesion can be significantly improved. Further, since the adhesion is remarkably improved, good adhesion can be obtained even after a long time has passed after the exposure.

The upper limit of the inorganic value (I value) of the alkali-soluble polymer is preferably 635 or less, or 600 or less, and the lower limit is preferably 300 or more, 350 or more, 400 or more, 450 or more, 500 or more, or 550 or more. When the inorganic value (I value) is 350 or more, there is an advantage that residue of the alkali-soluble polymer is less likely to remain between fine wirings. Alkali-soluble polymers can be used singly or in combination of two or more. When two or more types are mixed and used, the inorganic value (I value) of the alkali-soluble polymer mixture is preferably within the specific range in the present embodiment. The inorganic value (I value) of a mixture can be determined as the sum of the values obtained by multiplying the I value of each component by the weight fraction, assuming that there is additivity.

The upper limit of the solubility parameter (sp value) of the alkali-soluble polymer is preferably 21.40 MPa ^1/2 or less, or 21.20 MPa ^1/2 or less, and the lower limit is preferably 19.00 MPa ^1/2 or more. , 19.50 MPa ^1/2 or more, 20.00 MPa ^1/2 or more, or 20.50 MPa ^1/2 or more. When the solubility parameter (sp value) is 19.00 MPa ^1/2 or more, there is an advantage that residue of the alkali-soluble polymer is less likely to remain between fine wirings. Alkali-soluble polymers can be used singly or in combination of two or more. When two or more types are mixed and used, the solubility parameter (sp value) of the alkali-soluble polymer mixture is preferably within the specific range in the present embodiment. The solubility parameter (sp value) of a mixture can be determined as the sum of the values obtained by multiplying the sp value of each component by the weight fraction, assuming that there is additivity.

In the present embodiment, the alkali-soluble polymer refers to a polymer that is easily soluble in an alkaline substance to the extent that the resulting photosensitive resin layer has developability and peelability with respect to an alkaline aqueous solution. More specifically, the amount of carboxyl groups contained in the alkali-soluble polymer is preferably 100 g to 600 g, or 250 g to 450 g in acid equivalent. The acid equivalent is the mass (unit: gram) of a polymer having one equivalent of carboxyl groups in its molecule. The carboxyl group in the alkali-soluble polymer gives the photosensitive resin layer developability and releasability with respect to an alkaline aqueous solution. When the acid equivalent is 100 or more, development resistance, resolution and adhesion are improved. More preferably, the acid equivalent is 250 g or more. When the acid equivalent is 600 g or less, developability and releasability are improved. More preferably, the acid equivalent is 450 g or less. In the specification of the present application, the acid equivalent is a value measured by a potentiometric titration method using a potentiometric titrator and titrating with a 0.1 mol/L NaOH aqueous solution.

The weight average molecular weight (Mw) of the alkali-soluble polymer is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, resolution and developability are improved. The weight average molecular weight is more preferably 100,000 or less, 70,000 or less, 60,000 or less, or 50,000 or less. When the weight-average molecular weight is 5,000 or more, it is easier to control the properties of development aggregates and the properties of unexposed films such as edge-fuse properties and cut-chip properties in the photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more, or 20,000 or more. Edge fuseability refers to the degree of ease with which the photosensitive resin layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll. The cut chip property refers to the degree of easiness of chip flying when an 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.

The dispersity defined as the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alkali-soluble polymer is preferably 1.0 to 6.0, preferably 1.0 It is more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, even more preferably from 1.0 to 3.0. Both the weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble polymer are polystyrene equivalent values measured by gel permeation chromatography (GPC).

In order to provide higher adhesion when developing after heating after exposure, particularly better adhesion when a long time has passed after exposure, the alkali-soluble polymer is a single compound having an aromatic hydrocarbon group. It preferably contains a structural unit derived from the mer component. Examples of aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The lower limit of the amount of the monomer component having an aromatic hydrocarbon group in the alkali-soluble polymer is preferably 20% by mass or more and 40% by mass, based on the total mass of all monomer components in the alkali-soluble polymer. % by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more. Although the upper limit of the amount of the monomer component having an aromatic hydrocarbon group is not limited, it may be, for example, 95% by mass or less, or 80% by mass or less. When the photosensitive resin composition contains multiple kinds of alkali-soluble polymers, the amount of the monomer component having an aromatic hydrocarbon group is obtained as a weight average value.

Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and styrene derivatives. Higher resolution can be provided when the alkali-soluble polymer contains structural units derived from a monomer having an aralkyl group, styrene, or a styrene derivative. Preferred examples of such an alkali-soluble polymer include a copolymer containing methacrylic acid, benzyl methacrylate and styrene, and a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene.

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; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinyl benzyl alcohol and the like. A preferred comonomer having a benzyl group is benzyl (meth)acrylate.

The alkali-soluble polymer is preferably a polymer of a first monomer having a polymerizable unsaturated group and a carboxyl group in the molecule. More preferably, it is a copolymer with a non-acidic second monomer having a group. When the alkali-soluble polymer contains a monomer component having an aromatic hydrocarbon group, the alkali-soluble polymer contains at least one of a monomer having an aromatic hydrocarbon group and a first monomer. and/or a copolymer with at least one second monomer.

The first monomer is a monomer having a polymerizable unsaturated group and a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. . The first monomer is preferably (meth)acrylic acid. 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" , "acrylate" or "methacrylate".

The amount of the first monomer in the alkali-soluble polymer is preferably 10% by mass to 50% by mass based on the total mass of all monomer components constituting the alkali-soluble polymer. When the amount of the first monomer is 10% by mass or more, it is possible to provide better developability and to control the edge fuse property more easily. The amount of the first monomer is more preferably 15% by mass or more, or 20% by mass or more. When the amount of the first monomer is 50% by mass or less, it is possible to provide a higher resolution of the resist pattern, a better edge shape, and a higher chemical resistance. The amount of the first monomer is more preferably 35% by mass or less, 32% by mass or less, or 30% by mass or less.

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, and 2-ethylhexyl (meth)acrylate; acetic acid; ester compounds of vinyl alcohol such as vinyl; and (meth)acrylonitrile. The second monomer is preferably at least one selected from the group consisting of methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate.

The amount of the second monomer in the alkali-soluble polymer is preferably 10% by mass to 50% by mass based on the total mass of all monomer components constituting the alkali-soluble polymer. When the amount of the second monomer is 10% by mass or more, it is possible to provide better developability and to control the edge fuse property more easily. The amount of the second monomer is more preferably 15% by mass or more, or 20% by mass or more. When the amount of the second monomer is 50% by mass or less, it is possible to provide a higher resolution of the resist pattern, a better slant shape, and a higher chemical resistance. The amount of the second monomer is more preferably 35% by mass or less, 32% by mass or less, or 30% by mass or less.

The alkali-soluble polymer can consist of only one kind of alkali-soluble polymer, or can be a mixture of two or more kinds of alkali-soluble polymer. When it is a mixture of two or more alkali-soluble polymers, the alkali-soluble polymer contains two or more alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group, or an aromatic hydrocarbon It is preferable to include one or more alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group and one or more alkali-soluble polymers containing no monomer component having an aromatic hydrocarbon group. In the latter case, the amount of the alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more, 70% by mass or more, 80% by mass or more, based on the total mass of the alkali-soluble polymer. % by mass or more, 90% by mass or more, or 95% by mass or more.

The alkali-soluble polymer is more preferably an alkali-soluble polymer (A-1) containing structural units of styrene and/or styrene derivatives as monomer components. Examples of styrene derivatives include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer and styrene trimer.

The amount of the alkali-soluble polymer (A-1) contained in the photosensitive resin composition is preferably 3% by mass or more, 5% by mass or more, based on the total solid content in the photosensitive resin composition. 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more.

The total amount of styrene and/or styrene derivatives, which are constituent units of the alkali-soluble polymer (A-1), is preferably 52% by mass or more and 55% by mass, based on the total mass of the alkali-soluble polymer (A-1). % or more, 58 mass % or more, or 60 mass % or more. By containing 52% by mass or more of structural units derived from styrene and/or a styrene derivative, and developing after heating after exposure, even in a system having a high styrene skeleton content, the mobility of the resin is enhanced by heating. The hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly compatible. 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.

When the content of the styrene skeleton is small, it is easier to obtain the desired reactivity and adhesion without excessively reducing the mobility of the resin (resin cured product to be obtained). In addition, since the radicals in the system are deactivated when a long period of time elapses after exposure, the effect of improving adhesion by post-exposure heating decreases with the lapse of time. From these points of view, the total amount of styrene and/or styrene derivatives, which are constituent units of the alkali-soluble polymer (A-1), is preferably 90 mass based on the total mass of the alkali-soluble polymer (A-1). % or less, 80 mass % or less, 75 mass % or less, or 70 mass % or less.

In order to provide higher adhesion when developing after heating after exposure, particularly better adhesion when a long time has passed after exposure, the alkali-soluble polymer (A-1) is a monomer. It is preferable to further include a structural unit derived from (meth)acrylic acid as a component. The amount of structural units derived from (meth)acrylic acid is preferably 25% by mass or more, 26% by mass or more, 27% by mass or more, and 28% by mass, based on the total mass of the alkali-soluble polymer (A-1). % or more, or 29% by mass or more. From the same point of view, the amount of structural units derived from (meth)acrylic acid is preferably 35% by mass or less, 32% by mass or less, or 30% by mass, based on the total mass of the alkali-soluble polymer (A-1). % by mass or less.

In order to provide higher adhesion when developing after heating after exposure, particularly better adhesion when a long time has passed after exposure, the alkali-soluble polymer (A-1) is a monomer. It is preferable to further include a structural unit derived from benzyl (meth)acrylate as a component. The amount of structural units derived from benzyl (meth)acrylate is preferably 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass, based on the total mass of the alkali-soluble polymer (A-1). % by mass or more. From a similar point of view, the amount of structural units derived from benzyl (meth)acrylic acid, based on the total mass of the alkali-soluble polymer (A-1), is preferably 35% by mass or less, 32% by mass or less, or It is 30% by mass or less.

The weight average value Tg ^total of the glass transition temperature Tg of the alkali-soluble polymer (A) is preferably 30°C or higher and 150°C or lower. Since the Tg ^total of the alkali-soluble polymer is 150° C. or less, it provides higher adhesion when developing after heating after exposure, particularly better adhesion when a long time has passed after exposure. be able to. The Tg ^total of the alkali-soluble polymer is more preferably 135° C. or lower, 130° C. or lower, 125° C. or lower, 120° C. or lower, or 110° C. or lower. When the Tg ^total of the alkali-soluble polymer is 30°C or higher, higher edge fuse resistance can be provided. The Tg ^total of the alkali-soluble polymer is more preferably 40°C or higher, 50°C or higher, or 60°C or higher.

The amount of the alkali-soluble polymer (A) contained in the photosensitive resin composition is preferably 10% by mass to 90% by mass, 30% by mass to 70% by mass, based on the total solid content of the photosensitive resin composition. % by mass, or 40% to 60% by mass. When the amount of the alkali-soluble polymer in the photosensitive resin composition is 90% by mass or less, it is easier to control the development time. When the amount of the alkali-soluble polymer in the photosensitive resin composition is 10% by mass or more, higher edge fuse resistance can be provided.

Synthesis of the alkali-soluble polymer (A) is carried out by diluting one or more types of monomers constituting the alkali-soluble polymer with a solvent, adding an appropriate amount of a radical polymerization initiator, and heating and stirring to polymerize. It can be carried out. Solvents such as acetone, methyl ethyl ketone, and isopropanol may be used as solutions for polymerization. Radical polymerization initiators include benzoyl peroxide, azoisobutyronitrile, and the like. Instead of diluting all of the monomers with the solution at once, the synthesis may be carried out while a portion of the mixture of monomers is added dropwise to the reaction solution. After completion of the reaction, a solvent may be further added to adjust the desired concentration. Synthesis methods include bulk polymerization, suspension polymerization, and emulsion polymerization in addition to solution polymerization.

<(B) a compound having an ethylenically unsaturated double bond>
The compound (B) having an ethylenically unsaturated double bond has a (meth)acryloyl group in the molecule in order to provide better curability of the resin composition and higher compatibility with alkali-soluble polymers. It preferably contains a compound having The number of (meth)acryloyl groups may be 1 or more per molecule of compound (B). From the viewpoint of providing better releasability and flexibility of the cured film, the compound having one (meth)acryloyl group includes, for example, a compound obtained by adding (meth)acrylic acid to one end of a polyalkylene oxide; compounds obtained by adding (meth)acrylic acid to one end of a polyalkylene oxide and alkyl-etherifying or allyl-etherifying the other end; and phthalic acid compounds.

Examples of compounds having one (meth)acryloyl group include phenoxyhexaethylene glycol mono(meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polyethylene glycol to a phenyl group; 4-Normal nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polypropylene glycol and polyethylene glycol added with an average of 7 mol of ethylene oxide to nonylphenol; average 1 mol 4-normal nonylphenoxypentaethylene glycol, which is a (meth)acrylate of a compound obtained by adding polypropylene glycol to which propylene oxide is added and polyethylene glycol to which average 5 mol of ethylene oxide is added to nonylphenol, monopropylene glycol (meth) acrylate; and 4-normal nonylphenoxyoctaethylene glycol (meth)acrylate (e.g., M-114, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol to which an average of 8 mol of ethylene oxide is added to nonylphenol. ) and the like. From the viewpoint of providing higher sensitivity, resolution, and adhesion, the compound having one (meth)acryloyl group also includes γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate. Also mentioned.

Examples of compounds having two (meth)acryloyl groups include compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain, and alkylene oxide chains in which an ethylene oxide chain and a propylene oxide chain are randomly or block-bonded. Examples thereof include compounds having (meth)acryloyl groups at both ends.

Examples of compounds having two (meth)acryloyl groups include tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, and heptaethylene glycol di(meth)acrylate. , octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, and 12 moles of polyethylene glycols having (meth)acryloyl groups at both ends of the ethylene oxide chain. and polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, and polyalkylene oxide di(meth)acrylate containing an ethylene oxide group and a propylene oxide group in the molecule. (Meth)acrylate compounds and the like. As the polyalkylene oxide di(meth)acrylate compound containing an ethylene oxide group and a propylene oxide group in the molecule, 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. dimethacrylate of a glycol obtained by adding an average of 18 mol of propylene oxide to both ends of a polypropylene glycol having an average of 15 mol of ethylene oxide further added to each end thereof; More specific examples include FA-023M, FA-024M, FA-027M (product name, manufactured by Hitachi Chemical Co., Ltd.). These are preferred because they can provide higher flexibility, resolution and adhesion.

｛式中、Ｒ_１及びＲ_２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、ｎ_１及びｎ_３は各々独立に１～３９の整数であり、かつｎ_１＋ｎ_３は２～４０の整数であり、ｎ_２及びｎ_４は各々独立に０～２９の整数であり、かつｎ_２＋ｎ_４は０～３０の整数であり、－（Ａ－Ｏ）－及び－（Ｂ－Ｏ）－の繰り返し単位の配列は、ランダムであってもブロックであってもよい。そして、ブロックの場合、－（Ａ－Ｏ）－と－（Ｂ－Ｏ）－とのいずれがビスフェニル基側でもよい。｝で表される化合物が好ましい。As an example of a compound having two (meth)acryloyl groups in the molecule, from the viewpoint of providing higher resolution and adhesion, bisphenol A is modified with alkylene oxide to have (meth)acryloyl groups at both ends. compound. Specifically, the following general formula (I):

{wherein R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ and n ₃ each independently an integer of 1 to 39, n ₁ +n ₃ is an integer of 2 to 40, n ₂ and n ₄ are each independently an integer of 0 to 29, and n ₂ +n ₄ is an integer of 0 to 30 and the arrangement of repeating units of -(AO)- and -(B-O)- 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. } is preferred.

From the viewpoint of providing higher resolution and adhesion, dimethacrylate of polyethylene glycol obtained by adding an average of 5 moles of ethylene oxide to both ends of bisphenol A, and an average Dimethacrylate of polyethylene glycol to which 2 mol each of ethylene oxide is added and dimethacrylate of polyethylene glycol to which 1 mol each of ethylene oxide on average is added to both ends of bisphenol A are preferable. The aromatic ring in the general formula (I) may have heteroatoms and/or substituents.

Examples of heteroatoms include halogen atoms. Examples of 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, phenacyl groups, amino groups, and alkylamino groups having 1 to 10 carbon atoms. , a dialkylamino group having 2 to 20 carbon atoms, a nitro group, a cyano group, a carbonyl group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an aryl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group , a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, and 2 carbon atoms to 10 alkylcarbonyl groups, alkenyl groups having 2 to 10 carbon atoms, N-alkylcarbamoyl groups having 2 to 10 carbon atoms, groups containing a heterocyclic ring, and aryl groups substituted with these substituents. These substituents may form a condensed ring. A hydrogen atom in these substituents may be substituted with a heteroatom such as a halogen atom. 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, A compound obtained by (meth)acrylate-forming an alcohol obtained by adding an alkyleneoxy group such as a butyleneoxy group can be mentioned. In this case, examples of compounds that can serve as the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings. Compounds having 3 or more (meth)acryloyl groups include tri(meth)acrylates such as ethoxylated glycerin tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri(meth)acrylate, methylolpropane tri(meth)acrylate, etc.; tetra(meth)acrylates, such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.; penta(meth)acrylate, Examples include dipentaerythritol penta(meth)acrylate and the like; and hexa(meth)acrylates such as dipentaerythritol hexa(meth)acrylate and the like. A compound having 3 or more (meth)acryloyl groups is preferable from the viewpoint of resolution, adhesion, and resist shape, and more preferably has 3 or more methacrylic groups.

As trimethylolpropane tri(meth)acrylate, from the viewpoint of suppressing high flexibility and adhesion and bleeding out, for example, trimethacrylate obtained by adding an average of 21 mol of ethylene oxide to trimethylolpropane, and trimethylolpropane Trimethacrylate with an average addition of 30 moles of ethylene oxide is preferred.

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

The (meth)acrylate compounds can be used individually or in combination. The photosensitive resin composition may also contain other compounds as the compound (B) 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 and the like.

The amount of the compound (B) having an ethylenically unsaturated double bond contained in the photosensitive resin composition is preferably 5% by mass to 70% by mass based on the total solid mass in the photosensitive resin composition. %. It is preferable from the viewpoint of sensitivity, resolution and adhesion that the amount of compound (B) is 5% by mass or more. The amount of compound (B) is more preferably 20% by mass or more, or 30% by mass or more. When the amount of the compound (B) is 70% by mass or less, it is preferable from the viewpoint of suppressing the peeling delay of the edge fuse and the hardened resist. The amount of compound (B) is more preferably 50% by mass or less.

｛式（ＩＩ）中、Ａは炭素数４以上の２価の炭化水素基である。｝で表される構造を有する化合物（Ｂ１）であってもよい。化合物（Ｂ）が化合物（Ｂ１）を含む場合、化合物（Ｂ１）のみから成ってもよく、又は、化合物（Ｂ１）とともに、エチレン性不飽和二重結合を有し、かつ上記一般式（ＩＩ）で表される構造を有さない化合物（Ｂ２）を更に含んでいてもよい。In this embodiment, the compound (B) is a compound having an ethylenically unsaturated double bond and represented by the following general formula (II):

{In formula (II), A is a divalent hydrocarbon group having 4 or more carbon atoms. } may be a compound (B1) having a structure represented by When the compound (B) contains the compound (B1), it may consist of the compound (B1) alone, or, together with the compound (B1), has an ethylenically unsaturated double bond and has the general formula (II) It may further contain a compound (B2) that does not have a structure represented by

[Compound (B1)]
The number of ethylenically unsaturated double bonds contained in the compound (B1) may be 1 or more, and from the viewpoint of improving the residual film property during development and the physical properties of the cured product, preferably 2 or more, The number is preferably 2 or more and 6 or less, more preferably 2 or more and 4 or less, and still more preferably 2. The ethylenically unsaturated double bond contained in the compound (B1) is a group selected from an acryloyl group and a methacryloyl group (hereinafter , also referred to as “(meth)acryloyl group”).

｛式中、（Ａ－Ｏ）部分は上記（ＩＩ）に対応し、Ａは炭素数４以上の２価の炭化水素基、好ましくは炭素数４～８の２価の炭化水素基であり、Ｂ^１及びＢ^２は、それぞれ独立に、エチレン基又はプロピレン基であり、（Ｂ^１－Ｏ）、（Ａ－Ｏ）、及び（Ｂ^２－Ｏ）の配列はランダムでもブロックでもよく、ｎ１は０～５０の整数であり、ｎ２は２～１００の整数であり、ｎ３は０～５０の整数であり、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又はメチル基である。｝で表される化合物が挙げられる。As the compound (B1), for example, the following general formula (III):

{Wherein, the (AO) portion corresponds to (II) above, A is a divalent hydrocarbon group having 4 or more carbon atoms, preferably a divalent hydrocarbon group having 4 to 8 carbon atoms, B ¹ and B ² are each independently an ethylene group or a propylene group, the arrangement of (B ¹ -O), (AO), and (B ² -O) may be random or block, and n1 is is an integer of 0 to 50, n2 is an integer of 2 to 100, n3 is an integer of 0 to 50, and R ¹ and R ² are each independently a hydrogen atom or a methyl group. } is exemplified.

A in formula (III) is a divalent hydrocarbon group having 4 or more carbon atoms, preferably a divalent hydrocarbon group having 4 to 8 carbon atoms. This divalent hydrocarbon group may be linear, branched, or contain an alicyclic ring. A is preferably a linear or branched alkylene group. Specific examples of A include tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, butane-2,3-diyl group, butane-1,2-diyl group, and pentane-2,3-diyl group. , pentane-1,4-diyl group, 2,2-dimethyl-1,3-propylene group, hexane-1,5-diyl group and the like. A is preferably a divalent hydrocarbon group having 4 carbon atoms, more preferably an alkylene group having 4 carbon atoms, and particularly preferably a tetramethylene group. n2 is an integer of 2-100, preferably an integer of 3-75, more preferably an integer of 4-50.

B ¹ and B ² in formula (III) may each independently be selected from a 1,2-ethylene group, a 1,2-propylene group, a 1,3-propylene group, and the like. n1 and n3 are each independently an integer of 0-50, preferably an integer of 0-30, an integer of 0-20, or an integer of 0-10. n1+n3 is preferably an integer of 0-10. The arrangement of (B ¹ -O), (AO), and (B ² -O) can be random or block. R ¹ and R ² are each independently a hydrogen atom or a methyl group.

Compounds (B1) include compounds in which n1 and n3 are both 0 in formula (III), and compounds in formula (III) in which both n1 and n3 are 1 to 50 (preferably 1 to 30, 1 to 20 , or 1 to 10). Compounds in which n1 and n2 are both 0 in formula (III) include, for example, di(meth)acrylate of polytetramethylene glycol to which 2 to 100 mol of tetramethylene oxide is added. As a compound in which n1 and n2 are both 1 to 50 in formula (III), for example, 2 to 100 mol of tetramethylene oxide is added to polytetramethylene glycol, and ethylene oxide or propylene oxide is further added at each end of 1 Examples include di(meth)acrylates of polyalkylene glycols to which up to 50 moles are added.

Compound (B1) may consist of only one compound, or one or more of 1, B ¹ , B ² , R ¹ , R ² , n1, n2, and n3 in formula (III) may be It may be a mixture of two or more different compounds.

Compound (B2) is a compound that has an ethylenically unsaturated double bond and does not have the structure represented by formula (II). The number of ethylenically unsaturated double bonds contained in the compound (B2) may be 1 or more, and from the viewpoint of improving the residual film property during development and the physical properties of the cured product, preferably 2 or more, Preferably, it is 2 or more and 10 or less, 2 or more and 8 or less, or 2 or more and 6 or less. The ethylenically unsaturated double bond contained in the compound (B2) is preferably a (meth)acryloyl group from the viewpoint of compatibility with alkali-soluble polymers and curability of the photosensitive resin composition.

Among the compound (B2), the compound having two (meth)acryloyl groups includes, for example, a compound having (meth)acryloyl groups at both ends of an alkylene oxide chain, and a compound having both alkylene oxide chains of bisphenol A modified with alkylene oxide. Examples thereof include compounds having a (meth)acryloyl group added to the terminal.

Among the compounds (B2), the alkylene oxide chain in the compound having (meth)acryloyl groups at both ends of the alkylene oxide chain is a group in which two or more alkylene oxides of one or more selected from ethylene oxide and propylene oxide are linked. be. When the compound (B2) contains both ethylene oxide and propylene oxide, they may be linked randomly or in blocks, or a mixture of random linking sites and block linking sites.

Examples of such compound (B2) include tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, and octaethylene. Glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, compound having (meth)acryloyl groups at both ends of 12 mol of ethylene oxide chain, polypropylene glycol di(meth) Acrylate, polybutylene glycol di(meth)acrylate, polypropylene glycol with an average of 12 mol of propylene oxide further added with an average of 3 mol of ethylene oxide at both ends of the glycol dimethacrylate, with an average of 18 mol Dimethacrylate of glycol obtained by further adding an average of 15 mol of ethylene oxide to both ends of polypropylene glycol to which propylene oxide is added, and the like. More specific examples include FA-023M, FA-024M and FA-027M (manufactured by Hitachi Chemical Co., Ltd.). These are preferable from the viewpoint of flexibility, resolution, adhesion and the like.

｛式（Ｉ）中、Ｒ_１及びＲ_２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、それぞれ独立に、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、それぞれ独立に、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く、そして、ブロックの場合、－（Ａ－Ｏ）－ブロックと－（Ｂ－Ｏ）－ブロックとのいずれがビスフェニル基側でもよい。｝で表される化合物であってよい。Among the compounds (B2), the compound obtained by adding (meth)acryloyl groups to both ends of the alkylene oxide chain of alkylene oxide-modified bisphenol A specifically includes, for example, the following general formula (I):

{In formula (I), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n1 and n3 are each independently an integer of 1 to 39, 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; The arrangement of repeating units of -(AO)- and -(B-O)- may be random or block, and in the case of block, -(AO)-block and- Either the (B—O)—block may be on the bisphenyl group side. } may be a compound represented by.

Examples of such compound (B2) include, for example, dimethacrylate of polyethylene glycol obtained by adding an average of 5 mol each of ethylene oxide to both ends of bisphenol A; dimethacrylate of polyethylene glycol to which ethylene oxide is added; It is preferable from the viewpoint of adhesion and the like.

Among the compounds (B2), a compound having 3 or more (meth)acryloyl groups has, for example, 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 is added thereto. Alternatively, a compound obtained by converting an alcohol obtained by adding a propyleneoxy group to a (meth)acrylate can be mentioned. In this case, examples of compounds that can serve as the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings. These tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates, hexa(meth)acrylates and the like can be used as the compound (B2) having 3 or more (meth)acryloyl groups.

Among the compounds (B2), tri(meth)acrylates include, for example, ethoxylated glycerin tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ) acrylates and the like. Among trimethylolpropane tri(meth)acrylates, for example, trimethacrylate obtained by adding an average of 21 mol of ethylene oxide to trimethylolpropane, trimethacrylate obtained by adding an average of 30 mol of ethylene oxide to trimethylolpropane, etc. have flexibility and adhesion. It is preferable from the viewpoint of properties, bleed-out suppression, and the like.

Among compounds (B2), tetra(meth)acrylate includes, for example, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate and the like. Among these, pentaerythritol tetra(meth)acrylate is preferred. The pentaerythritol tetra(meth)acrylate is preferably a tetra(meth)acrylate in which a total of 1 mol or more and 40 mol or less of alkylene oxide is added to four terminals of pentaerythritol.

Examples of the penta(meth)acrylate in the compound (B2) include dipentaerythritol penta(meth)acrylate.

Among the compounds (B2), the hexa(meth)acrylate includes, for example, hexa(meth)acrylate in which a total of 1 mol or more and 40 mol or less of ethylene oxide is added to the six terminals of dipentaerythritol, dipentaerythritol. Hexa(meth)acrylate having a total of 1 to 20 mol of ε-caprolactone added to six ends is preferred.

Compound (B2) may consist of only one compound, or may be a mixture of two or more compounds.

When compound (B) contains compound (B1) and compound (B2), the amount of compound (B1) is preferably 5% by mass or more, 7% by mass or more, based on the total mass of compound (B). , 8% by mass or more, 9% by mass or more, or 10% by mass or more. The amount of compound (B1) is preferably 50% by mass or less, 30% by mass or less, or 20% by mass or less based on the total mass of compound (B).

｛式（ＩＩ）中、Ａは炭素数４以上の２価の炭化水素基である。｝で表される構造を有する化合物（Ｂ１）を含む、
感光性樹脂組成物。
［態様２］
上記化合物（Ｂ１）が、エチレン性不飽和二重結合を２個以上有する化合物である、態様１に記載の感光性樹脂組成物。
［態様３］
上記化合物（Ｂ１）が、下記一般式（ＩＩＩ）：

｛式（ＩＩＩ）中、Ａは炭素数４～８の２価の炭化水素基であり、Ｂ^１及びＢ^２は、それぞれ独立に、エチレン基又はプロピレン基であり、（Ｂ^１－Ｏ）、（Ａ－Ｏ）、及び（Ｂ^２－Ｏ）の配列はランダムでもブロックでもよく、ｎ１は０～５０の整数であり、ｎ２は２～１００の整数であり、ｎ３は０～５０の整数であり、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又はメチル基である。｝で表される化合物である、態様１又は２に記載の感光性樹脂組成物。
［態様４］
上記一般式（ＩＩＩ）中のｎ１及びｎ３が、それぞれ独立に、０～３０の整数である、態様３に記載の感光性樹脂組成物。
［態様５］
上記一般式（ＩＩＩ）中、ｎ１＋ｎ３が０～１０の整数である、態様３又は４に記載の感光性樹脂組成物。
［態様６］
上記一般式（ＩＩＩ）中のＡが、炭素数４の２価の炭化水素基である、態様１～５のいずれか一項に記載の感光性樹脂組成物。
［態様７］
上記エチレン性不飽和二重結合を有する化合物（Ｂ）が、エチレン性不飽和二重結合を有し、かつ上記一般式（ＩＩ）で表される構造を有さない化合物（Ｂ２）を更に含む、態様１～６のいずれか一項に記載の感光性樹脂組成物。
［態様８］
光増感剤を更に含む、態様１～７のいずれか一項に記載の感光性樹脂組成物。
［態様９］
上記光増感剤がアントラセン化合物を含む、態様８に記載の感光性樹脂組成物。
［態様１０］
上記光増感剤がピラゾリン化合物を含む、態様８又は９に記載の感光性樹脂組成物。
［態様１１］
上記光重合開始剤（Ｃ）がイミダゾール化合物を含む、態様１～１０のいずれか一項に記載の感光性樹脂組成物。
［態様１２］
支持層と、
上記支持層上の態様１～１１のいずれか一項に記載の感光性樹脂組成物の層と
を有する、感光性樹脂積層体。
［態様１３］
以下の工程：
態様１～１１のいずれか一項に記載の感光性樹脂組成物の層を露光する工程；
露光工程後の感光性樹脂組成物の層を加熱する加熱工程；及び
加熱工程後の感光性樹脂組成物の層を現像する現像工程；
を含む、レジストパターンの形成方法。
［態様１４］
上記加熱工程における加熱温度が３０℃以上１５０℃以下の範囲である、態様１３に記載のレジストパターンの形成方法。
［態様１５］
上記露光工程を、描画パターンの直接描画による露光方法、又はフォトマスクの像を、レンズを通して投影させる露光方法により行う、態様１３又は１４に記載のレジストパターンの形成方法。
［態様１６］
上記露光工程を、描画パターンの直接描画による露光方法により行う、態様１３又は１４に記載のレジストパターンの形成方法。
［態様１７］
上記露光工程を、中心波長３９０ｎｍ未満の第１のレーザー光と、中心波長３９０ｎｍ以上の第２のレーザー光と、により露光する方法により行う、態様１６に記載のレジストパターンの形成方法。
［態様１８］
上記第１のレーザー光の中心波長が３５０ｎｍ以上３８０ｎｍ以下であり、上記第２のレーザー光の中心波長が４００ｎｍ以上４１０ｎｍ以下である、態様１７に記載のレジストパターンの形成方法。Particularly preferred embodiments in the case where compound (B) contains compound (B1) are listed in [Aspect 1] to [Aspect 18] below.
[Aspect 1]
A photosensitive resin composition for obtaining a resist pattern by performing exposure, heating, and development in this order,
The photosensitive resin composition contains the following components, based on the total solid content of the photosensitive resin composition:
(A) 10% by mass or more and 90% by mass or less of an alkali-soluble polymer;
(B) 5% by mass or more and 70% by mass or less of a compound having an ethylenically unsaturated double bond;
(C) 0.01% by mass or more and 20% by mass or less of a photopolymerization initiator, and
The compound (B) having an ethylenically unsaturated double bond has the following general formula (II):

{In formula (II), A is a divalent hydrocarbon group having 4 or more carbon atoms. } including a compound (B1) having a structure represented by
A photosensitive resin composition.
[Aspect 2]
The photosensitive resin composition according to aspect 1, wherein the compound (B1) is a compound having two or more ethylenically unsaturated double bonds.
[Aspect 3]
The compound (B1) has the following general formula (III):

{In formula (III), A is a divalent hydrocarbon group having 4 to 8 carbon atoms, B ¹ and B ² are each independently an ethylene group or a propylene group, (B ¹ -O), The arrangement of (AO) and (B ² -O) may be random or block, n1 is an integer from 0 to 50, n2 is an integer from 2 to 100, n3 is an integer from 0 to 50. and R ¹ and R ² are each independently a hydrogen atom or a methyl group. } The photosensitive resin composition according to aspect 1 or 2, which is a compound represented by:
[Aspect 4]
The photosensitive resin composition according to aspect 3, wherein n1 and n3 in the general formula (III) are each independently an integer of 0 to 30.
[Aspect 5]
The photosensitive resin composition according to aspect 3 or 4, wherein n1+n3 is an integer of 0 to 10 in general formula (III).
[Aspect 6]
The photosensitive resin composition according to any one of aspects 1 to 5, wherein A in the general formula (III) is a divalent hydrocarbon group having 4 carbon atoms.
[Aspect 7]
The compound (B) having an ethylenically unsaturated double bond further includes a compound (B2) having an ethylenically unsaturated double bond and not having the structure represented by the general formula (II). , The photosensitive resin composition according to any one of aspects 1 to 6.
[Aspect 8]
The photosensitive resin composition according to any one of aspects 1 to 7, further comprising a photosensitizer.
[Aspect 9]
The photosensitive resin composition according to aspect 8, wherein the photosensitizer comprises an anthracene compound.
[Aspect 10]
The photosensitive resin composition according to aspect 8 or 9, wherein the photosensitizer comprises a pyrazoline compound.
[Aspect 11]
The photosensitive resin composition according to any one of aspects 1 to 10, wherein the photopolymerization initiator (C) comprises an imidazole compound.
[Aspect 12]
a support layer;
A photosensitive resin laminate having a layer of the photosensitive resin composition according to any one of aspects 1 to 11 on the support layer.
[Aspect 13]
The following steps:
exposing the layer of the photosensitive resin composition according to any one of aspects 1 to 11;
A heating step of heating the layer of the photosensitive resin composition after the exposure step; and a developing step of developing the layer of the photosensitive resin composition after the heating step;
A method of forming a resist pattern, comprising:
[Aspect 14]
The method for forming a resist pattern according to aspect 13, wherein the heating temperature in the heating step is in the range of 30°C or higher and 150°C or lower.
[Aspect 15]
15. The method of forming a resist pattern according to aspect 13 or 14, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern or an exposure method by projecting an image of a photomask through a lens.
[Aspect 16]
15. The method of forming a resist pattern according to aspect 13 or 14, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern.
[Aspect 17]
17. The method of forming a resist pattern according to aspect 16, wherein the exposure step is performed by 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.
[Aspect 18]
18. The method of forming a resist pattern according to aspect 17, 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.

<(C) Photoinitiator>
The photopolymerization initiator (C) is a compound that polymerizes a monomer with light, and may be a photopolymerization initiator generally known in this technical field.

The amount of the photopolymerization initiator in the photosensitive resin composition is preferably 0.01 to 20% by mass, 0.05% to 10% by mass, based on the total solid content of the photosensitive resin composition, 0.1% to 7% by mass, or 0.1% to 6% by mass. When the total amount of the photopolymerization initiator is 0.01% by mass or more, sufficient sensitivity can be obtained, and when it is 20% by mass or less, the light is sufficiently transmitted to the bottom of the resist, resulting in a good high resolution. You can get sex.

Examples of photopolymerization initiators include quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin or benzoin ether compounds, dialkylketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, and acridine compounds. , hexaarylbiimidazole, pyrazoline compounds, anthracene compounds, coumarin compounds, N-arylamino acids or their ester compounds, and halogen compounds.

Examples of aromatic ketone compounds include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. can be done. Among these, 4,4'-bis(diethylamino)benzophenone is preferable from the viewpoint of adhesion. From the viewpoint of transmittance, the content of the aromatic ketone compound in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass based on the total solid mass of the photosensitive resin composition. , or 0.02% by mass to 0.3% by mass.

Examples of acridine compounds include 9-phenylacridine, bisacridinylheptane, 9-(p-methylphenyl)acridine, and 9-(m-methylphenyl)acridine. point is preferable. As an anthracene compound, an alkoxy group having 1 to 40 carbon atoms which may have a substituent and/or an aryl group having 6 to 40 carbon atoms which may have a substituent at the 9-position and/or 10-position. For example, 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, and 9,10-diethoxyanthracene are preferred in terms of sensitivity, resolution and adhesion. As the coumarin compound, for example, 7-diethylamino-4-methylcoumarin is preferable in terms of sensitivity, resolution and adhesion. As the N-arylamino acid or its ester compound, for example, N-phenylglycine is preferable in terms of sensitivity, resolution and adhesion. As the halogen compound, for example, tribromomethylphenylsulfone is preferable. Other photopolymerization initiators include 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.

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 )-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 and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole. 2-(o-Chlorophenyl)-4,5-diphenylimidazole dimer is preferable as the hexaarylbiimidazole from the viewpoints of high sensitivity, resolution and adhesion. The amount of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass to 7% by mass and 0.1% by mass from the viewpoint of improving the peeling property and/or sensitivity of the photosensitive resin layer. % to 6% by weight, or 1% to 5% by weight.

A photoinitiator can be used individually by 1 type or in combination of 2 or more types.

<Photosensitizer>
The photosensitive resin composition may further contain a photosensitizer from the viewpoint of improving high transmittance, release properties of the photosensitive resin layer, and/or sensitivity. Photosensitizers include pyrazoline compounds and anthracene compounds. The content of the photosensitizer in the photosensitive resin composition is preferably 0.01% by mass to 10% by mass or less, 0.05% by mass to 5% by weight, 0.1% to 3% by weight, 0.1% to 1% by weight, or 0.1% to 0.7% by weight. When the amount of the photosensitizer is 0.01% by mass or more, the release property and sensitivity of the photosensitive resin layer can be further improved. When the amount of the photosensitizer is 10% by mass or less, the light transmittance of the photosensitive resin layer is maintained at a high level, which is preferable from the viewpoint of exposure efficiency.

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 and the like. be done. As the pyrazoline compound, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferable.

Examples of anthracene compounds include sialkoxyanthracene compounds such as 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, and 9,10-diethoxyanthracene. is preferred.

<Phenol derivative>
From the viewpoint of resolution and adhesion, the photosensitive resin composition preferably further contains a phenol derivative. 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 (for example, 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), and biphenol.

The amount of the phenol derivative in the photosensitive resin composition is preferably 0.001% by mass to 10% by mass based on the total solid mass of the photosensitive resin composition. From the viewpoint of resolution and adhesion, the lower limit of the amount of the phenol derivative is more preferably 0.005% by mass or more, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass. That's it. The lower limit of the amount of the phenol derivative is more preferably 5% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, from the viewpoint of little decrease in sensitivity and improvement of resolution. Or it is 0.3% by mass or less.

<Additive>
The photosensitive resin composition may optionally contain additives such as colorants, stabilizers, adhesion aids, and plasticizers. For example, additives listed in JP-A-2013-156369 may be used.

(coloring agent)
In the present embodiment, the photosensitive resin composition may optionally further contain at least one selected from the group consisting of coloring agents such as dyes and coloring substances.

Examples of coloring substances include fuchsine, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, and malachite green (e.g., Eizen (registered trademark) MALACHITE GREEN, manufactured by Hodogaya Chemical Co., Ltd.). , Basic Blue 20, and Diamond Green (for example, Eisen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). The amount of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass based on the total solid mass of the photosensitive resin composition. When the amount of the coloring substance is 0.001% by mass or more, the handleability of the photosensitive resin composition is improved. When the amount of the coloring substance is 1% by mass or less, the storage stability of the photosensitive resin composition is easily maintained.

The photosensitive resin composition is preferable from the standpoint of visibility because the photosensitive resin composition contains a dye so that the exposed portion develops color. When an inspection machine or the like reads an alignment marker for exposure, it is advantageous to increase the contrast between the exposed portion and the unexposed portion for easier recognition. From these points of view, preferred dyes 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]. Leuco crystal violet is more preferable as the leuco dye from the viewpoint of good contrast. The amount of the dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass based on the total solid weight of the photosensitive resin composition. When the amount of dye is 0.1% by mass or more, the contrast between the exposed and unexposed areas becomes better. The amount of dye is more preferably 0.2% by mass or more, or 0.4% by mass or more. When the amount of the dye is 10% by mass or less, the storage stability of the photosensitive resin composition is easily maintained. The amount of dye is more preferably 5% by mass or less, or 2% by mass or less.

From the viewpoint of optimizing adhesion and contrast, the photosensitive resin composition preferably contains a combination of a leuco dye and the halogen compound described in the section "(C) Photopolymerization initiator" above. When the leuco dye is used in combination with the halogen compound, the amount of the halogen compound in the photosensitive resin composition is 0.01% by mass to 3% by mass based on the total solid mass of the photosensitive resin composition. Storage stability of the hue in the layer is easily maintained.

(stabilizer)
The photosensitive resin composition may further contain a stabilizer in order to improve thermal stability and storage stability. The stabilizer may be, for example, at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazole compounds, and carboxybenzotriazole compounds.

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.

Benzotriazole compounds include, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole and the like.

Carboxybenzotriazole compounds 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.

The total amount of the stabilizer in the photosensitive resin composition is preferably 0.01% by mass to 3% by mass, or 0.05% by mass to 1% by mass, based on the total solid content of the photosensitive resin composition. %. When the total amount of the stabilizer is 0.01% by mass or more, high storage stability can be imparted to the photosensitive resin composition. When the total amount of the stabilizer is 3% by mass or less, it is preferable from the viewpoint of maintaining the sensitivity and suppressing decolorization of the dye. 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 layer and the photosensitive resin composition layer at a wavelength of 630 nm is preferably 80% or less, 78% or less, 75% or less, 72% or less, 70% or less, 68% or less, 65%. 62% or less, 60% or less, 58% or less, 55% or less, 52% or less, or 50% or less. This transmittance is the transmittance of the laminate of the support layer and the photosensitive resin composition layer, and does not include the protective layer.

(Adhesion aid)
The photosensitive resin composition may further contain a bisphenol A epoxy compound. The epoxy compound of bisphenol A includes, for example, a compound obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminal.

(Plasticizer)
The photosensitive resin composition may further contain a plasticizer. Examples of plasticizers include phthalate compounds (e.g., diethylflate, etc.), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl triethyl citrate, -n-propyl, tri-n-butyl acetylcitrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether. More specifically, ADEKA NOL SDX-1569, ADEKA NOL SDX-1570, ADEKA NOL SDX-1571, and ADEKA NOL SDX-479 (manufactured by Asahi Denka Co., Ltd.); Newpole BP-23P, Newpole BP-3P, Newpole BP -5P, Nieupole BPE-20T, Nieupole BPE-60, Nieupole BPE-100, and Nieupole BPE-180 (manufactured by Sanyo Kasei Co., Ltd.); Uniol DB-400, Uniol DAB-800, Uniol DA-350F , Uniol DA-400, and Uniol DA-700 (manufactured by NOF Corporation); and compounds having a bisphenol skeleton such as BA-P4U glycol and BA-P8 glycol (manufactured by Nippon Emulsifier Co., Ltd.).

The amount of the plasticizer in the photosensitive resin composition is preferably 1% to 50% by weight, or 1% to 30% by weight, based on the total solid weight of the photosensitive resin composition. It is preferable that the amount of the plasticizer is 1% by mass or more from the viewpoint of suppressing the development time delay and imparting flexibility to the cured film. A plasticizer content of 50% by mass or less is preferable from the viewpoint of suppressing insufficient curing and cold flow.

<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 ketone compounds and alcohol compounds. Ketone compounds include methyl ethyl ketone (MEK) and acetone. Alcohol compounds include methanol, ethanol, and isopropanol. The amount of the solvent added to the photosensitive resin composition should be such that the viscosity at 25° C. of the photosensitive resin composition preparation applied onto the support layer is 500 mPa·s to 4,000 mPa·s. is preferred.

If the amount of water in the photosensitive resin composition is high, the local plasticization of the photosensitive resin composition is rapidly promoted, and edge fuses may occur. It is preferable that the water content in the resin composition is small. The amount of water in the photosensitive resin composition is 0.00, based on the weight of the photosensitive resin composition after the prepared solution of the photosensitive resin composition is applied to the support layer and dried (water content after drying). The amount is preferably 7% by mass or less. The moisture content after drying in the photosensitive resin composition is more preferably 0.65% by mass or less, 0.6% by mass or less, 0.55% by mass or less, 0.5% by mass or less, and 0.45% by mass. 0.4% by mass or less, 0.35% by mass or less, 0.3% by mass or less, 0.25% by mass or less, or 0.2% by mass or less.

[Photosensitive resin laminate]
In the present embodiment, the photosensitive resin laminate of the present invention comprises a support layer and a layer of the photosensitive resin composition of the present embodiment (hereinafter also referred to as "photosensitive resin layer") on the support layer. have. A protective layer may be further provided on the photosensitive resin layer.

<Support layer>
The support layer is preferably a transparent support film that transmits light emitted from the exposure light source. Examples of the support film include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, A polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, and the like are included. As the support layer, a stretched support film may be used as necessary.

From the viewpoint of suppressing light scattering during exposure, the support layer preferably has a haze of 5% or less, 2% or less, 1.5% or less, or 1.0% or less. From the same point of view, the surface roughness Ra of the surface of the support layer in contact with the photosensitive layer is preferably 30 nm or less, 20 nm or less, or 10 nm or less. The thickness of the support layer is preferably 10 μm to 30 μm in order to maintain the strength of the photosensitive resin laminate, although the thinner the support layer, the better the image formability and economic efficiency. If desired, the support layer may contain fine particles such as a lubricant. The size of the microparticles is preferably less than 5 μm.

The support layer may have a single layer structure, or may have a multilayer 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. Examples of the multilayer structure include a two-layer support layer having a resin layer on one side of a substrate and a three-layer support layer having resin layers on both sides of the substrate. As an embodiment of the support layer having a three-layer structure, for example, the support film exemplified above is used as the base material, one surface A thereof has a resin layer containing fine particles, and the other surface B has
(1) It has a resin layer containing approximately the same amount of fine particles as the resin layer on the surface A side;
(2) having a resin layer containing a smaller amount of fine particles than the resin layer on the face A side;
(3) having a resin layer containing finer particles than those contained in the resin layer on the surface A side; and (4) having a resin layer containing no fine particles. In the case of the structures (2), (3), and (4) above, it is preferable to have a photosensitive resin layer on the surface B side. In this case, it is preferable from the viewpoint of the slipperiness of the film that there is a resin layer containing fine particles on the surface A side opposite to the photosensitive resin layer. The size of the fine particles contained in the resin layer is preferably less than 1.5 μm.

<Photosensitive resin layer>
A photosensitive resin laminate has a photosensitive resin layer on a support layer. The photosensitive resin layer is a layer formed from the photosensitive resin composition of this embodiment. 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, 3 μm to 100 μm, 5 μm to 60 μm, or 10 μm to 30 μm. When the thickness of the photosensitive resin layer is 1 μm or more, the film strength becomes higher. When the thickness of the photosensitive resin layer is 300 µm or less, the resolution becomes higher.

<Protective layer>
The photosensitive resin laminate has a photosensitive resin layer on the support layer, and may further have a protective layer on the photosensitive resin layer. 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. As a protective layer, for example, a protective film such as a polyethylene film or a polypropylene film can be used. A film having excellent releasability described 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 a protective film, 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.

[Method for producing photosensitive resin laminate]
An example of a method for producing a photosensitive resin laminate using the photosensitive resin composition of the present embodiment will be described. A photosensitive resin laminate can be produced by sequentially laminating a support layer, a photosensitive resin layer, and, if necessary, a protective layer. For example, first, the photosensitive resin composition of the present embodiment is mixed with a solvent for dissolving it, to prepare a mixed solution of a uniform photosensitive resin composition. A prepared solution of a photosensitive resin composition is coated on the support layer using a bar coater or roll coater, and then dried to remove the solvent, thereby forming a photosensitive resin composition comprising the photosensitive resin composition on the support layer. Layers can be stacked. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

[Manufacturing method of resist pattern]
An example of a method of manufacturing a resist pattern using the photosensitive resin laminate of this embodiment will be described. The method for manufacturing a resist pattern according to this embodiment comprises the following steps:
Step of exposing the layer (photosensitive resin layer) of the photosensitive resin composition of the present embodiment;
A heating step of heating the exposed photosensitive resin layer; and a developing step of developing the heated photosensitive resin layer.

The photosensitive resin layer exposed in the exposure step is typically laminated on the substrate. The method of forming a resist pattern of the present embodiment may include a lamination step of laminating a photosensitive resin layer on the substrate prior to the exposure step.

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.

<Lamination process>
In the lamination process, a laminator is used to form a photosensitive resin layer on the substrate. 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).

The photosensitive resin layer may be laminated on only 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. The adhesion of the obtained resist pattern to the substrate may be improved by performing the heat-press bonding at the time of lamination two or more times. 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 for compression bonding.

<Exposure process>
In the exposure step, the photosensitive resin layer is exposed. As the exposure method, 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, which is the desired wiring pattern; and a photomask. Examples include an exposure method in which an image is projected through a lens.

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

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.

<Heating process>
In the heating step, the exposed photosensitive resin is heated (post-exposure heating). The heating temperature is preferably 30°C to 150°C, more preferably 60°C to 120°C. By performing this heating step, resolution and adhesion are improved. As a heating method, hot air, infrared rays, 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. A hot roll is preferable as the heating method because the treatment can be performed in a short time, and two or more hot rolls are more preferable.

The elapsed time from exposure to heating, more strictly, the elapsed time from the time the exposure is stopped to the time the temperature is started is preferably 15 minutes or less, or 10 minutes or less. The elapsed time from the time the exposure was stopped to the time the temperature was started is 10 seconds or more, 20 seconds or more, 30 seconds or more, 1 minute or more, 2 minutes or more, 3 minutes or more, 4 minutes or more, or 5 minutes or more. may be

<Development process>
In the developing step, the photosensitive resin layer is developed. For example, after exposure, a resist pattern can be formed on a substrate by peeling off the support layer on the photosensitive resin layer and then removing the unexposed portion by development using an alkaline aqueous developer.

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.

[Method for manufacturing circuit board]
A circuit board can be manufactured using a substrate having a resist pattern formed by the above method. The manufacturing method of the circuit board of the present embodiment includes a circuit forming step of forming the circuit board by etching or plating the substrate having the resist pattern of the present embodiment.

<Circuit formation process>
In the circuit forming step, a circuit is formed by etching or plating a substrate having a resist pattern. Specifically, the substrate surface exposed by development (for example, the copper surface of a copper-clad laminate) is etched or plated to produce a conductor pattern.

<Peeling process>
The circuit board manufacturing method of the present embodiment may typically further include a stripping step of stripping the resist pattern from the substrate after the circuit forming step. The resist pattern is stripped from the substrate using a suitable stripper. Examples of stripping solutions include alkaline aqueous solutions and amine-based stripping solutions. However, a resist pattern formed from the photosensitive resin composition of the present invention through post-exposure heating exhibits good releasability with respect to an amine-based stripping solution, and excessive miniaturization of exfoliated pieces is suppressed. Therefore, when an amine-based stripping solution is used as the stripping solution, the advantageous effects of the present invention are exhibited more satisfactorily.

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.

Examples of ethanolamine include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, aminoethoxyethanol and the like. mentioned. Examples of propanolamine include 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol and the like. Examples of alkylamines include monomethylamine, dimethylamine, trimethylamine, ethyleneamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, and tetraethylenepentamine. Cyclic amines include, for example, choline, morpholine, and the like. 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.

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 this embodiment can be used for printed wiring boards, flexible substrates, lead frame substrates, touch panel substrates, COF substrates, semiconductor package substrates, transparent electrodes for liquid crystals, wiring for TFTs for liquid crystals, electrodes for PDPs, and the like. It is a photosensitive resin laminate suitable for manufacturing a conductor pattern.

EXAMPLES Hereinafter, embodiments of the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

[Examples 1 to 8 and Comparative Examples 1 to 4]
<Preparation of photosensitive resin laminate>
As shown in Tables 1 to 3 below, each component (however, the amount of each component indicates the amount (parts by mass) as a solid content) is sufficiently stirred and mixed to form a photosensitive resin composition. A mixture was obtained. In Tables 2 and 3, the I value of the binder indicates the I value as a mixture of alkali-soluble polymers indicated by symbols A-1 to A-3. 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.

<Substrate 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.

<laminate>
While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, roll the photosensitive resin laminate onto a copper-clad laminate preheated to 50°C using a hot roll laminator (AL-700, manufactured by Asahi Kasei Co., Ltd.). Lamination was performed at a 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 (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 using the Stouffer 41-stage step tablet as a mask, and the exposure was carried out with an exposure amount such that the maximum number of remaining film stages was 18 stages when exposed and developed.

<Post-exposure heating>
One minute 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 1.5 m/min. Also, a separately prepared evaluation substrate was used and heated in the same manner after 7 minutes had elapsed after the exposure. Note that if the elapsed time after exposure is increased, the effect of heating is reduced, so heating is normally performed about 1 minute after exposure. Therefore, the heating after 7 minutes of exposure in this embodiment is a very severe condition.

<developing>
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 development time.

<Image property 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 an index of adhesion. Adhesion was evaluated based on the following criteria.
A: The minimum adhesion line width of the independent pattern is less than 9 μm B: The minimum adhesion line width of the independent pattern is 9 μm or more and less than 10 μm C: The minimum adhesion line width of the independent pattern is 10 μm or more and less than 11 μm D: The minimum adhesion line width of the independent pattern is 11 μm or more

The materials used in Examples 1-8 and Comparative Examples 1-4 are shown in Table 1 below, and the results are shown in Tables 2 and 3 below.

[Examples 9 to 16 and Comparative Examples 5 to 8]
<Preparation of photosensitive resin laminate>
As shown in Tables 4 to 6 below, each component (however, the amount of each component indicates the amount (parts by mass) as a solid content) is sufficiently stirred and mixed to form a photosensitive resin composition. A mixture was obtained. In Tables 5 and 6, the sp value (MPa ^1/2 ) of the binder indicates the sp value as a mixture of alkali-soluble polymers indicated by symbols A-1 to A-3. 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.

<Substrate 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.

<laminate>
While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, roll the photosensitive resin laminate onto a copper-clad laminate preheated to 50°C using a hot roll laminator (AL-700, manufactured by Asahi Kasei Co., Ltd.). Lamination was performed at a 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 (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 using the Stouffer 41-stage step tablet as a mask, and the exposure was carried out with an exposure amount such that the maximum number of remaining film stages was 18 stages when exposed and developed.

<Post-exposure heating>
One minute 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 1.5 m/min. Also, a separately prepared evaluation substrate was used and heated in the same manner after 7 minutes had elapsed after the exposure. Note that if the elapsed time after exposure is increased, the effect of heating is reduced, so heating is normally performed about 1 minute after exposure. Therefore, the heating after 7 minutes of exposure in this embodiment is a very severe condition.

<developing>
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 development time.

<Image property 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 an index of adhesion. Adhesion was evaluated based on the following criteria.
A: The minimum adhesion line width of the independent pattern is less than 9 μm B: The minimum adhesion line width of the independent pattern is 9 μm or more and less than 10 μm C: The minimum adhesion line width of the independent pattern is 10 μm or more and less than 11 μm D: The minimum adhesion line width of the independent pattern is 11 μm or more

The materials used in Examples 9-16 and Comparative Examples 5-8 are shown in Table 4 below, and the results are shown in Tables 5 and 6 below.

[Examples 17 to 24 and Comparative Example 9]
<Measurement of weight average molecular weight or number average molecular weight of polymer>
The weight average molecular weight (Mw) or number average molecular weight (Mn) of the polymer is determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: manufactured by Showa Denko Co., Ltd. Shodex (registered trademark) (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) was calculated as polystyrene conversion. Also, the dispersity of the polymer was calculated as the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn).

<Preparation of photosensitive resin laminate>
As shown in Tables 7 and 8 below, each component (however, the amount of each component indicates the amount (mass part) as a solid content. "A-1 content" is component A shown in Table 7 -1 shows the content (% by mass) relative to the solid content in the photosensitive resin composition) and the solvent were sufficiently stirred and mixed to obtain a photosensitive resin composition preparation liquid. 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.

<Substrate 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.

<laminate>
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 (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 using the Stouffer 41-stage step tablet as a mask, and the exposure was carried out with an exposure amount such that the maximum number of remaining film stages was 18 stages when exposed and developed.

<Post-exposure 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.

<developing>
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 development time.

<Image property 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.

The materials used in Examples 17 to 23 and Comparative Example 9 are shown in Table 7 below, and the results are shown in Table 8 below.

From the results in Tables 7 and 8, it was confirmed that the examples within the scope of the constituent elements of the present invention were superior to the comparative examples, which were outside the scope of the present invention.

The post-exposure heating conditions in this example are very strict because the heating is after 7 minutes of exposure. For example, when the compositions of Example 17 and Comparative Example 9 were developed without heating after exposure, the adhesion was 10.6 μm for both. That is, in the composition of Comparative Example 9, no effect was observed by heating after 7 minutes of exposure, but in Example 23, the adhesion was able to be improved even under extremely severe conditions. Moreover, under the condition of heating one minute after the exposure, the adhesion of 9.0 μm was obtained for both the compositions of Example 23 and Comparative Example 9.

From the above results, even if the adhesion is good under general heating conditions after exposure, the adhesion is improved under the severe conditions of heating 7 minutes after exposure in this example. is not. 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.

[Examples 24-38 and Comparative Examples 10-11]
<Measurement of weight average molecular weight of polymer>
The weight average molecular weight (Mw) of the polymer was obtained as a polystyrene equivalent value by gel permeation chromatography (GPC) under the following conditions.
Measuring device: Gel permeation chromatography (GPC) manufactured by JASCO Corporation
Pump: manufactured by JASCO Corporation, Gulliver PU-1580 type Column: manufactured by Showa Denko Co., Ltd., Shodex (registered trademark) KF-807, KF-806M, KF-806M, and KF-802.5 in series Mobile phase solvent: Tetrahydrofuran Standard sample: Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.

<Preparation of photosensitive resin laminate>
The photosensitive resin composition prepared in each example and comparative example was uniformly coated on the surface of a polyethylene terephthalate film (FB-40, 16 μm thick, manufactured by Toray Industries, Inc.) as a support layer using a bar coater. It was applied and dried in a dryer at 95° C. for 3 minutes to form a photosensitive resin layer. The dry thickness of the photosensitive resin layer was 25 μm. Next, a polyethylene film (GF-818, 19 μm thick, manufactured by Tamapoly Co., Ltd.) is laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film is not laminated, and the photosensitive resin is laminated. got a body

<Substrate surface preparation>
A 0.4 mm thick copper clad laminate laminated with a 35 μm thick rolled copper foil was used as a substrate. This copper-clad laminate was jet-scrubbed using an abrasive (manufactured by Ujiden Chemical Industry Co., Ltd., #400) at a spray pressure of 0.2 MPa, and then surface-cleaned with a 10% by mass H ₂ SO ₄ aqueous solution. to smooth the substrate surface.

<laminate>
Using a hot roll laminator (AL-700, manufactured by Asahi Kasei Co., Ltd.), a photosensitive resin laminate is laminated on a copper clad laminate preheated to 50 ° C. while peeling off the polyethylene film (protective layer). , to obtain a substrate for evaluation. At this time, the roll temperature was 105° C., the air pressure was 0.35 MPa, and the lamination speed was 1.5 m/min.

<exposure>
Direct drawing exposure machine (Nuvogo Fine 10, manufactured by Orbotech Co., Ltd., light source: 375 nm (30%) + 405 nm (70%)) was used on the evaluation substrate 2 hours after lamination, using a Stouffer 41-step step tablet. exposed. The exposure was carried out with the exposure using the above-mentioned Stouffer 41 step tablet as a mask, and the exposure with the amount of exposure such that the maximum number of remaining film steps was 19 steps when development was carried out.

<Post-exposure heating>
One minute after the exposure, the substrate for evaluation was heated by a hot roll laminator (AL-700, manufactured by Asahi Kasei Corp.), and the photosensitive resin layer in the exposed area was made into a cured film. The roll temperature was 105° C., the air pressure was 0.30 MPa, and the lamination speed was 1.5 m/min.

<developing>
After peeling off the polyethylene terephthalate film (support layer) from the substrate for evaluation after exposure and heating, using an alkali developing machine (manufactured by Fuji Kiko, dry film developing machine), a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. and Development was carried out by spraying pure water sequentially at each predetermined time. The development spray time was twice the shortest development time, and the washing spray time after development was three times the shortest development time. Here, the shortest development time means the shortest time required for completely dissolving the unexposed portion of the photosensitive resin layer.

<Adhesion evaluation>
In a line-and-space test pattern in which the space width is a fixed value of 200 μm and the line width is varied, the minimum line width that is normally formed was measured with an optical microscope. This measurement was performed for 8 sets of test patterns, and the average value was used as an index of adhesion.

<Peeling time evaluation>
Two hours after lamination, the substrate for evaluation was exposed with a solid pattern of 5 cm long and 3 cm wide. One minute after the exposure, the substrate for evaluation was heated with a hot roll laminator (AL-700, manufactured by Asahi Kasei Corp.). Next, development was carried out at twice the minimum development time, and the washing spray time after development was set at three times the shortest development time to obtain an evaluation sample. As the stripping solution, a mixed aqueous solution of R-100S (12 vol %) and R-101 (4 vol %) manufactured by Ryoko Kagaku Co., Ltd. was adjusted to 50° C. and used. An evaluation sample was immersed in a stripping solution, and the time required for the cured film to be stripped from the substrate was recorded.
A (good): peeling time of 45 seconds or less B (acceptable): peeling time of more than 45 seconds and 50 seconds or less C (poor): peeling time of more than 50 seconds

<Peeled piece size evaluation>
In the peeling time evaluation, the evaluation sample was immersed in the peeling liquid, the size of the cured film peeled from the substrate was observed, and the evaluation was made according to the following criteria.
AA (extremely good): Peel piece size is 1 cm square or more A (Good): Peel piece size is 7 mm square or more and less than 1 cm square B (Fair): Peel piece size is 3 mm square or more and less than 7 mm square C (Poor): Peel piece Less than 3mm square

(A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and optional additives (D) a photosensitizer, a colorant, and a stabilizer As an agent, the type and amount (mass parts in terms of solid content) of the components shown in Table 1 and ethanol as a solvent are mixed and thoroughly stirred to obtain a photosensitive resin having a solid content concentration of 55% by mass. A composition formulation was prepared.

The materials used in Examples 24-38 and Comparative Examples 10-11 are shown in Table 9 below, and the results are shown in Tables 10-12 below.

From the results of Tables 10 to 12, in the examples using the photosensitive resin composition of the present invention, the adhesion, the peeling time by the amine-based stripping solution, and the peeled piece were better than the comparative examples outside the scope of the present invention. It has been confirmed that at least one, preferably both, of size is excellent.

Claims (15)

The following steps:
exposing the layer of the photosensitive resin composition;
A method for forming a resist pattern for manufacturing a circuit board , comprising a heating step of heating the exposed photosensitive resin composition layer; and a developing step of developing the heated photosensitive resin composition layer,
The elapsed time from the time when the exposure is stopped to the time when the heating is started is 4 minutes or more,
The photosensitive resin composition contains the following components, based on the total solid content of the photosensitive resin composition:
(A) 10% to 90% by mass of an alkali-soluble polymer;
(B) 5% to 70% by weight of a compound having an ethylenically unsaturated double bond, and (C) 0.01% to 20% by weight of a photopolymerization initiator,
A method for forming a resist pattern, wherein the inorganic value (I value) of the alkali-soluble polymer (A) is 720 or less. 2. The method of forming a resist pattern according to claim 1, wherein the alkali-soluble polymer (A) has an I value of 635 or less. 3. The method of forming a resist pattern according to claim 2, wherein the alkali-soluble polymer (A) has an I value of 600 or less. 4. The method of forming a resist pattern according to claim 1, wherein the alkali-soluble polymer (A) has an I value of 300 or more. 5. The method of forming a resist pattern according to claim 4, wherein the alkali-soluble polymer (A) has an I value of 400 or more. 6. The method of forming a resist pattern according to claim 5, wherein the alkali-soluble polymer (A) has an I value of 450 or more. 7. The method of forming a resist pattern according to claim 6, wherein the alkali-soluble polymer (A) has an I value of 500 or more. 8. The method of forming a resist pattern according to claim 7, wherein the alkali-soluble polymer (A) has an I value of 550 or more. 9. The method of forming a resist pattern according to claim 1 , wherein the heating temperature in said heating step is in the range of 30.degree. C. to 150.degree. The method of forming a resist pattern according to any one of claims 1 to 9 , wherein the heating step is performed within 15 minutes after the exposure is stopped. 11. The method of forming a resist pattern according to any one of claims 1 to 10 , wherein the exposure step is performed by an exposure method that directly draws a drawing pattern or an exposure method that projects an image of a photomask through a lens. 12. The method of forming a resist pattern according to claim 11 , wherein said exposure step is performed by an exposure method by direct drawing of a drawing pattern. 13. The method of forming a resist pattern according to claim 12 , wherein said 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. 14. The method of forming a resist pattern according to claim 13 , 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. A resist pattern is produced on a substrate by the method according to any one of claims 1 to 14 , the substrate having the resist pattern is etched or plated, and the resist pattern is peeled off from the substrate. A method of manufacturing a circuit board, comprising forming a circuit board by means of a method.