TW202005995A - Photosensitive resin composition and resist pattern formation method - Google Patents

Abstract

Provided is a photosensitive resin composition which is exposed to light and then heated and developed into a resin cured product. This photosensitive resin composition contains, on the basis of the total mass of solids thereof: (A) 10-90% by mass of an alkali-soluble polymer; (B) 5-70% by mass of a compound having an ethylenically unsaturated double bond; and (C) 0.01-20% by mass of a photoinitiator. The alkali-soluble polymer (A) has an inorganic value (I value) of 720 or less or a solubility parameter (sp value) of 21.45 MPa1/2 or less. Alternatively, the photosensitive resin composition contains an alkali-soluble polymer (A1) in an amount of 3% by mass or more on the basis of the total mass of solids of the photosensitive resin composition, the alkali-soluble polymer (A1) containing 52% by mass or more of constituent units derived from styrene and/or a styrene derivative as a monomer component.

Description

Photosensitive resin composition and method for forming resist pattern

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

In electronic devices such as personal computers and mobile phones, printed wiring boards and the like are used for mounting parts, semiconductors, and the like. As a resist for the production of printed wiring boards, etc., a photosensitive resin laminate having a support layer, a photosensitive resin layer laminated on the support layer, and a protective layer laminated on the photosensitive resin layer as necessary is used in the past 2. The so-called dry film photoresist (hereinafter sometimes referred to as "DF"). As the photosensitive resin layer, an alkaline developing type that uses a weakly alkaline aqueous solution as a developing solution is generally used at present.

Examples of the method for producing a printed wiring board using DF include the following methods. When the DF has a protective layer, the protective layer is first peeled off. Thereafter, DF is laminated on a substrate such as a copper-clad laminate or a flexible substrate such as a substrate for permanent circuit production using a bonding machine or the like. The laminated DF is exposed via a wiring pattern masking film or the like. If necessary, peel off the support layer, use a developing solution to dissolve or disperse the photosensitive resin layer of the uncured part (for example, the unexposed part in the negative type), and form a cured resist pattern on the substrate (hereinafter, sometimes (Referred to as "resist pattern").

There are roughly two methods for forming a circuit after forming a resist pattern. The first method is an etching method, which includes the following operations: etching away the substrate surface not covered by the resist pattern (for example, the copper surface of the copper-clad laminate); using a stronger alkali than the developer in the resist pattern portion Solution. The second method is a plating method, which includes the following operations: performing plating treatment of copper, solder, nickel, tin, etc. on the substrate surface; removing the resist pattern portion in the same manner as the first method, and then etching to expose The substrate surface (for example, the copper surface of the copper clad laminate). As a solution during etching, copper chloride, ferric chloride, or a cuprammonium complex solution is used.

In recent years, with the miniaturization and weight reduction of electronic devices, the miniaturization and high density of printed wiring boards have been carried out, and a high-performance DF with high resolution and high adhesion has been sought in the manufacturing steps described above. For example, Patent Literature 1 describes a photosensitive resin composition that improves resolution by using a specific thermoplastic resin, monomer, and photopolymerizable initiator. Patent Document 2 describes a method for forming a resist pattern, which includes a step of using a pressurized heating mechanism together with the exposed photosensitive resin composition layer and a substrate, and heating under pressurization. Patent Document 3 describes a method for forming a resist pattern, which includes the steps of exposing a laminate having (a) a photosensitive layer and (b) a resin layer formed on a substrate, performing heat treatment, and developing. Patent Document 4 describes a method for forming a resist pattern, which includes a step of placing the layered body under a reduced pressure atmosphere or a low oxygen concentration atmosphere at least during exposure to heat treatment. Patent Document 5 describes various additives arbitrarily included in the photosensitive resin layer of DF. Patent Document 6 describes a protective layer that is preferably applied to DF. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-249884 [Patent Document 2] Japanese Patent Laid-Open No. 2014-191318 [Patent Document 3] Japanese Patent Laid-Open No. 2016-224161 [Patent Document 4] Japanese Patent Laid-Open No. 2016-224162 [Patent Document 5] Japanese Patent Laid-Open No. 2013-156369 [Patent Document 6] Japanese Patent Laid-Open No. 59-202457

[Problems to be solved by the invention]

After the exposure step, the photosensitive resin layer may be subjected to a heating step (heating after exposure: PEB), and then developed. By performing this heating step, high resolution or high adhesion can be further improved. However, even if the post-exposure heating step is performed, the improvement of adhesion in the previous photosensitive resin composition is insufficient. In addition, if a long time passes after exposure, even if a post-exposure heating step is performed, good adhesion may not be obtained.

The present invention has been proposed in view of such previous actual circumstances, and an object of the present invention is to provide a photosensitive resin composition that can significantly improve the adhesiveness when developing after heating after exposure. An object of the present invention is, in particular, to provide a photosensitive resin composition that, in a preferred embodiment, exhibits good adhesion even when exposed to heating for a long period of time. [Technical means to solve the problem]

In order to solve the above problems, the inventors of the present invention have repeatedly conducted diligent research, and found that by including an alkali-soluble polymer having a specific range of inorganic value (I value); an alkali soluble having a specific range of solubility parameter (sp value) The photosensitive resin composition of a polymer; or an alkali-soluble polymer (A-1) having a structural unit with a specific structure can solve the above-mentioned problems and complete the present invention. Examples of embodiments of the present invention are listed in the following examples of embodiments [1] to [29]. [1] A photosensitive resin composition for heating after exposure, followed by development to obtain a resin cured product, and the photosensitive resin composition is based on the total solid content of the photosensitive resin composition As a basis, the following components are included: (A) 10% by mass to 90% by mass of alkali-soluble polymer, (B) 5% by mass to 70% by mass of a compound having an ethylenically unsaturated double bond, and (C) 0.01 Mass% to 20% by mass of the photopolymerization initiator; the inorganic value (I value) of the alkali soluble polymer (A) is 720 or less. [2] The photosensitive resin composition according to item 1, wherein the I value of the alkali-soluble polymer (A) is 635 or less. [3] The photosensitive resin composition according to item 2, wherein the alkali-soluble polymer (A) has an I value of 600 or less. [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] The photosensitive resin composition according to item 4, wherein the alkali-soluble polymer (A) has an I value of 400 or more. [6] The photosensitive resin composition according to item 5, wherein the alkali-soluble polymer (A) has an I value of 450 or more. [7] The photosensitive resin composition according to item 6, wherein the I value of the alkali-soluble polymer (A) is 500 or more. [8] The photosensitive resin composition according to item 7, wherein the alkali-soluble polymer (A) has an I value of 550 or more. [9] A photosensitive resin composition for heating after exposure, followed by development to obtain a cured resin, and the photosensitive resin composition is based on the total solid content of the photosensitive resin composition As a basis, the following components are included: (A) 10% by mass to 90% by mass of alkali-soluble polymer, (B) 5% by mass to 70% by mass of a compound having an ethylenically unsaturated double bond, and (C) 0.01 Mass% to 20% by mass of photopolymerization initiator; The solubility parameter (sp value) of the above (A) alkali-soluble polymer is 21.45 MPa ^1/2 or less. [10] The photosensitive resin composition according to item 9, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 21.40 MPa ^1/2 or less. [11] The photosensitive resin composition according to item 10, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 21.20 MPa ^1/2 or less. [12] The photosensitive resin composition according to any one of items 9 to 11, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 19.00 MPa ^1/2 or more. [13] The photosensitive resin composition according to item 12, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 19.50 MPa ^1/2 or more. [14] The photosensitive resin composition according to item 13, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 20.00 MPa ^1/2 or more. [15] The photosensitive resin composition according to item 14, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 20.50 MPa ^1/2 or more. [16] A photosensitive resin composition for heating after exposure, followed by development to obtain a resin cured product, and the photosensitive resin composition is based on the total solid content of the photosensitive resin composition As a basis, the following components are included: (A) 10% by mass to 90% by mass of alkali-soluble polymer, (B) 5% by mass to 70% by mass of a compound having an ethylenically unsaturated double bond, and (C) 0.01 Mass% to 20% by mass of photopolymerization initiator; the above-mentioned photosensitive resin composition contains 3% by mass or more of alkali-soluble polymer (A-1) based on the mass of the total solid content in the above-mentioned photosensitive resin composition ) As the alkali-soluble polymer (A), the alkali-soluble polymer (A-1) contains 52% by mass or more of structural units derived from styrene and/or styrene derivatives as a monomer component. [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 relative to the mass of the total solid content in the photosensitive resin composition ( A-1). [18] The photosensitive resin composition according to item 16 or 17, wherein the alkali-soluble polymer (A-1) contains 55 mass% or more of structural units derived from styrene and/or styrene derivatives as a single unit Body composition. [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 styrene derivatives as monomer components . [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 single Body composition. [21] 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] A method for forming a resist pattern, including the following steps: a step of exposing the layer of the photosensitive resin composition as described in any one of items 1 to 21; A heating step of heating the layer of the resin composition; and a developing step of developing the heated layer of the photosensitive resin composition. [23] The method for forming a resist pattern according to item 22, wherein the heating temperature in the above heating step is in the range of 30°C to 150°C. [24] The method for forming a resist pattern as described in item 22 or 23, wherein the above heating step is performed within 15 minutes after stopping the exposure. [25] The method for forming a resist pattern as described in any one of items 22 to 24, which is an exposure method using direct drawing by drawing patterns or an exposure method of projecting an image of a photomask through a lens Instead, the above exposure step is performed. [26] The method for forming a resist pattern as described in item 25 is to perform the above exposure step using an exposure method by direct drawing of a drawing pattern. [27] The method for forming a resist pattern as described in item 26 is performed by exposing the first laser light with a center wavelength of less than 390 nm and the second laser light with a center wavelength of 390 nm or more The above exposure steps. [28] The method for forming a resist pattern as described in 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 method of manufacturing a circuit board, comprising: manufacturing a resist pattern on a substrate by the method as described in any one of items 22 to 28, and etching or etching the above substrate having the above resist pattern Plating, thereby forming a circuit substrate. [Effect of invention]

According to the present invention, the adhesion of the resist pattern during development after heating after exposure (PEB) can be significantly improved. In a preferred embodiment, it is possible to provide a photosensitive resin composition that exhibits good adhesion even when exposed to heat for a long period of time. Furthermore, the above description should not be regarded as revealing all the embodiments of the present invention and all the advantages related to the present invention. Further embodiments and advantages of the present invention will be understood by referring to the following description.

The following is a detailed description for the purpose of illustrating the embodiment of the present invention, but the present invention is not limited to this embodiment. In the specification of this case, the upper and lower limits of each numerical range can be arbitrarily combined.

[Photosensitive resin composition] The photosensitive resin composition of this embodiment is a photosensitive resin composition obtained by heating after exposure and then developing to obtain a cured resin. The photosensitive resin composition contains (A) 10% by mass to 90% by mass of alkali soluble polymer and (B) 5% by mass to 70% by mass based on the mass of the total solid content of the photosensitive resin composition. Ethylene unsaturated double bond compound, and (C) 0.01% by mass to 20% by mass photopolymerization initiator.

＜(A)Alkali soluble polymer＞ In this embodiment, the inorganic value (I value) of the alkali-soluble polymer (A) of the photosensitive resin composition may be 720 or less. Here, the "I value" is also referred to as "inorganic value", which mainly indicates the degree of physical properties brought by electrical affinity. "O value" is also called "Organic Value", which mainly means the degree of physical properties brought by Van der Waals force. The I/O value is a standard parameter indicating the lipophilicity/hydrophilicity of a compound or substituent, and is determined based on the inherent I and O values of the compound or substituent. The larger the I/O value, the higher the inorganicity. Regarding the I/O value, please refer to the book by Shinda Koda, "Organic Concept Map", published by Sankyo, 1984, etc.

In this embodiment, the solubility parameter (sp value) of the alkali-soluble polymer (A) of the photosensitive resin composition may be 21.45 MPa ^1/2 or less. The solubility parameter (sp value) is the square root of the cohesive energy density of the substance. For the detailed content or calculation method, please refer to Otsujin Junzhi, "The Role of the Solubility Parameter (SP) in the Theory of Solubility (Report 1)", Japan then academic journal, 1993, vol.29, No.5, pp.8-15 and so on. In the specification of this case, the SP value means the value calculated by the Chongjin method.

In the present embodiment, the photosensitive resin composition may contain 3% by mass or more of the alkali-soluble polymer (A-1) as the alkali-soluble polymer (A) relative to the mass of the total solid content in the photosensitive resin composition The alkali-soluble polymer (A-1) contains 52% by mass or more of structural units derived from styrene and/or styrene derivatives as monomer components.

The photosensitive resin composition of this embodiment can be significantly improved by having any one or more of the above-mentioned inorganic value (I value), the above-mentioned solubility parameter (sp value), or the above-mentioned alkali-soluble polymer (A-1) Adhesion when developing after exposure and heating. The photosensitive resin composition of this 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; alkali-soluble polymer (A) The inorganic value (I value) is 720 or less, and contains 3% by mass or more of the alkali-soluble polymer (A-1) relative to the total solid content; the solubility parameter of the alkali-soluble polymer (A) (sp value) is 21.45 MPa ^1/2 or less, and contains 3% by mass or more of alkali soluble polymer (A-1) relative to the total solid content; or the inorganic value of alkali soluble polymer (A) ( I value) is 720 or less, the solubility parameter (sp value) is 21.45 MPa ^1/2 or less, and contains 3% by mass or more of the alkali-soluble polymer (A-1) with respect to the total solid content.

In general, the dry film resist obtained from the photosensitive resin composition tends to have difficulty in improving the adhesiveness without heating immediately after exposure. In contrast, the dry film resist obtained from the photosensitive resin composition of the present embodiment can exhibit good adhesion even after a long period of time after exposure to heating, and a fine resist pattern can be obtained.

The reason for the improvement in adhesion during development after heating after exposure is not limited to theory, but the inventors and others presumed the following. If the inorganic value (I value) of the alkali-soluble polymer is 720 or less, the electrical affinity of the alkali-soluble polymer is low, the permeability during development is suppressed, and the swelling and dissolution resistance become high. It is considered that the result is that even a fine resist pattern can be maintained without being damaged by development. In addition, if the elapsed time from exposure to heating becomes longer, the radicals generated during exposure collide with the oxygen in the alkali-soluble polymer to be inactivated, so the effect of reducing PEB is reduced. However, it is considered that the alkali-soluble polymer having a low electrical affinity is difficult to contain because of water, so it does not easily contain water molecules and hinders the transfer of oxygen. Therefore, even if the elapsed time becomes longer, the effect of PEB is maintained. It is considered that if the solubility parameter (sp value) of the alkali-soluble polymer is 21.45 MPa ^1/2 or less, the hydrophobicity of the alkali-soluble polymer is high, and the swelling and dissolution resistance at the time of development become high, and as a result, even fine particles The resist pattern is also maintained without being damaged by development. In addition, it is considered that the alkali-soluble polymer with high hydrophobicity has low hygroscopicity and hinders the transfer of oxygen through water molecules. Therefore, even if the elapsed time from exposure to heating becomes longer, the effect of PEB is maintained. The photosensitive resin composition contains 3% by mass or more of alkali-soluble polymer (A-1) relative to the total solid content of the photosensitive resin composition, and the fluidity of the resin can be greatly improved by heating after exposure , Highly achieve the hydrophobicity of styrene skeleton and the reactivity of carbon-carbon double bond at the same time. As a result, the adhesion can be significantly improved. Furthermore, by significantly improving the adhesion, good adhesion can be obtained even after a long time after 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. With an inorganic value (I value) of 350 or more, there is an advantage that residues of alkali-soluble polymers are less likely to remain in fine wiring. One type of alkali-soluble polymer may be used alone, or two or more types may be used in combination. When two or more kinds are mixed and used, the inorganic value (I value) of the alkali-soluble polymer mixture is preferably within a specific range in the embodiment. The inorganic value (I value) of the mixture can be assumed to be additive, and is obtained as the sum of the values obtained by multiplying the I value of each component by the weight fraction.

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 and 19.50 MPa ^1/2 Above, 20.00 MPa ^1/2 or above or 20.50 MPa ^1/2 or above. With a solubility parameter (sp value) of 19.00 MPa ^1/2 or more, there is an advantage that the residue of the alkali-soluble polymer does not easily remain in the fine wiring room. One type of alkali-soluble polymer may be used alone, or two or more types may be used in combination. When two or more kinds are mixed and used, the solubility parameter (sp value) of the alkali-soluble polymer mixture is preferably within a specific range in the embodiment. The solubility parameter (sp value) of the mixture can be assumed to be additive, and is obtained as the sum of the values obtained by multiplying the sp value of each component by the weight fraction.

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 obtained photosensitive resin layer has developability and peelability to an alkaline aqueous solution. More specifically, the amount of carboxyl groups contained in the alkali-soluble polymer is calculated as an acid equivalent, and is preferably 100 g to 600 g or 250 g to 450 g. The acid equivalent is the mass (unit: gram) of a polymer having 1 equivalent of carboxyl groups in its molecule. The carboxyl group in the alkali-soluble polymer imparts developability and peelability to the alkaline aqueous solution to the photosensitive resin layer. If the acid equivalent is 100 or more, development resistance, resolution, and adhesion are improved. The acid equivalent is more preferably 250 g or more. If the acid equivalent is 600 g or less, developability and peelability are improved. The acid equivalent is more preferably 450 g or less. In the specification of this case, the acid equivalent value is the value measured by the potentiometric titration method using a potentiometric titration device in a 0.1 mol/L NaOH aqueous solution.

The weight average molecular weight (Mw) of the alkali-soluble polymer is preferably from 5,000 to 500,000. If the weight average molecular weight is 500,000 or less, the 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. If the weight average molecular weight is 5,000 or more, it is easier to control the properties of the developing aggregate and the properties of the unexposed film such as edge meltability and wafer dicing properties in the photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more or 20,000 or more. Edge meltability refers to the degree of ease of overflow of the photosensitive resin layer from the end surface of the roller when the photosensitive resin laminate is wound up in a roll shape. Wafer dicing refers to the degree of ease of wafer jumping when the unexposed film is cut by a dicing machine. If the wafer is attached to the upper surface of the photosensitive resin laminate or the like, it will be transferred to the mask in the subsequent exposure step or the like, which will cause a defective product.

The dispersion degree defined as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw/Mn) of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and further preferably 1.0 ~4.0, and further preferably 1.0~3.0. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the alkali-soluble polymer are the values converted from polystyrene measured by gel permeation chromatography (GPC).

In order to provide a higher adhesiveness when developing after heating after exposure, especially when a long time has passed after exposure, the alkali-soluble polymer preferably contains a monomer derived from an aromatic hydrocarbon group The structural unit of the composition. Examples of the aromatic hydrocarbon group 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 based on the total mass of all monomer components of the alkali-soluble polymer as a reference, preferably 20% by mass or more, 40% by mass or more, 50 More than mass%, more than 55 mass% or more than 60 mass%. The upper limit of the amount of the monomer component having an aromatic hydrocarbon group is not limited, and may be, for example, 95% by mass or less or 80% by mass or less. When the photosensitive resin composition contains a plurality of alkali-soluble polymers, the amount of the monomer component having an aromatic hydrocarbon group is obtained as the weight average value.

Examples of the monomer having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and styrene derivatives. When the alkali-soluble polymer contains a structural unit derived from a monomer having an aralkyl group, styrene or a styrene derivative, higher resolution can be provided. As such an alkali-soluble polymer, for example, a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, and a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene are preferable. Things.

Examples of the aralkyl group include substituted or unsubstituted phenylalkyl (except for benzyl), substituted or unsubstituted benzyl, etc., preferably substituted or unsubstituted benzyl base. Examples of the comonomer having a phenylalkyl group include phenylethyl (meth)acrylate. Examples of the comonomer having a benzyl group include (meth)acrylate having a benzyl group, for example, benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomer having a benzyl group Examples include vinyl benzyl chloride and vinyl benzyl alcohol. As the comonomer having a benzyl group, benzyl (meth)acrylate is preferred.

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

A monomer with a polymerizable unsaturated group and a carboxyl group in the molecule of the first single system. 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. Acid half ester etc. The first monomer is preferably (meth)acrylic acid. In the specification of this case, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acrylic acid ester" means Refers to "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. If the amount of the first monomer is 10% by mass or more, better developability can be provided, and edge meltability can be more easily controlled. The amount of the first monomer is more preferably 15% by mass or more or 20% by mass or more. If the amount of the first monomer is 50% by mass or less, it can provide higher resolution of the resist pattern, better bottom shape, and 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 system 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, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, third butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid ring (Meth)acrylate compounds such as hexyl ester and 2-ethylhexyl (meth)acrylate; vinyl alcohol ester compounds such as vinyl acetate; 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. If the amount of the second monomer is 10% by mass or more, better developability can be provided, and edge meltability can be more easily controlled. The amount of the second monomer is more preferably 15% by mass or more or 20% by mass or more. If the amount of the second monomer is 50% by mass or less, it can provide higher resolution of the resist pattern, better bottom shape, and 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 may be composed of only one kind of alkali-soluble polymer, or may be a mixture of two or more kinds of alkali-soluble polymers. In the case of a mixture of two or more types of alkali-soluble polymers, the alkali-soluble polymer preferably contains two or more types of alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group, or contains one or more types of An alkali-soluble polymer having a monomer component having an aromatic hydrocarbon group, and one or more types of alkali-soluble polymers not containing a monomer component having an aromatic hydrocarbon group. In the latter case, the amount of the alkali-soluble polymer containing the monomer component having an aromatic hydrocarbon group relative to the total mass of the alkali-soluble polymer is preferably 50% by mass or more, 70% by mass or more, and 80% 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 methyl styrene, vinyl toluene, third butoxy styrene, acetoxy styrene, 4-vinyl benzoic acid, styrene dimer, and styrene tri. Polymer etc.

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, 10 based on the mass of the total solid content in the photosensitive resin composition % 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 as the structural unit of the alkali-soluble polymer (A-1) is preferably 52% by mass or more based on the total mass of the alkali-soluble polymer (A-1), 55 mass% or more, 58 mass% or more, or 60 mass% or more. By including 52% by mass or more of structural units derived from styrene and/or styrene derivatives, and heating after exposure, and then developing, even for a system with a large content of styrene skeleton, by heating It can greatly improve the fluidity of the resin, and at the same time realize the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond at the same time. As a result, the adhesion can be significantly improved. Moreover, by significantly improving the adhesion, good adhesion can also be obtained when the elapsed time after exposure becomes longer.

If the content of the styrene skeleton is small, the fluidity of the resin (the obtained resin cured product) will not be excessively reduced, and it is easier to obtain the required reactivity and adhesion. In addition, if a long time passes after exposure, the free radicals in the system are deactivated, so as time passes, the effect of improving the adhesion caused by heating after exposure decreases. From these viewpoints, the total amount of styrene and/or styrene derivatives as the structural unit of the alkali-soluble polymer (A-1) is based on the total mass of the alkali-soluble polymer (A-1), It is preferably 90% by mass or less, 80% by mass or less, 75% by mass or less, or 70% by mass or less.

In order to provide higher adhesiveness when heating is performed after exposure and then developing, especially better adhesion after a long period of time after exposure, the alkali-soluble polymer (A-1) preferably further contains The structural unit of (meth)acrylic acid is used as a monomer component. The amount of the structural unit derived from (meth)acrylic acid is based on the total mass of the alkali-soluble polymer (A-1), and is preferably 25% by mass or more, 26% by mass or more, 27% by mass or more, and 28% by mass or more Or more than 29% by mass. From the same viewpoint, 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). %the following.

In order to provide higher adhesiveness when heating is performed after exposure and then developing, especially better adhesion after a long period of time after exposure, the alkali-soluble polymer (A-1) preferably further contains The structural unit of benzyl (meth)acrylate serves as a monomer component. The amount of the structural unit derived from benzyl (meth)acrylate is based on the total mass of the alkali-soluble polymer (A-1), and is preferably 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass %the above. From the same viewpoint, the amount of the structural unit derived from benzyl (meth)acrylate is based on the total mass of the alkali-soluble polymer (A-1), preferably 35 mass% or less, 32 mass% or less or 30% by mass or less.

The weight average Tg ^total of the glass transition temperature Tg of the alkali-soluble polymer (A) is preferably 30°C or more and 150°C or less. When the Tg ^total of the alkali-soluble polymer is 150° C. or lower, it can provide higher adhesiveness when developing after heating after exposure, especially better adhesion after a long time after exposure. 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. If the Tg ^total of the alkali-soluble polymer is above 30°C, it can provide higher resistance to edge melting. 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 based on the mass of the total solid content of the photosensitive resin composition, and is preferably 10% by mass to 90% by mass, 30% by mass to 70% by mass % Or 40% by mass to 60% by mass. If 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. If the amount of the alkali-soluble polymer in the photosensitive resin composition is 10% by mass or more, higher edge melting resistance can be provided.

The synthesis of the alkali-soluble polymer (A) can be carried out by diluting one or more monomers constituting the alkali-soluble polymer with a solvent, adding an appropriate amount of a radical polymerization initiator, and heating and stirring, thereby carrying out polymerization. Examples of the solution used in the polymerization include solvents such as acetone, methyl ethyl ketone, and isopropyl alcohol. Examples of the radical polymerization initiator include benzoyl peroxide and azoisobutyronitrile. It is also possible to synthesize a part of the monomer mixture while dropping it into the reaction solution, instead of diluting all the monomers with a solution at one time. After the reaction, the solvent can be further added to adjust to the desired concentration. As the synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization can also be mentioned.

＜(B) Compounds with ethylenically unsaturated double bonds＞ The compound (B) having an ethylenically unsaturated double bond preferably includes a compound having a (meth)acryloyl group in the molecule to provide better curability of the resin composition and higher with alkali-soluble polymer Of compatibility. The number of (meth)acryloyl groups may be as long as the compound (B) is one or more per molecule. From the viewpoint of providing better peelability and flexibility of the cured film, examples of the compound having one (meth)acryloyl group include addition of (methyl) to one end of polyalkylene oxide A compound made of acrylic acid; a compound made by adding (meth)acrylic acid to one end of the polyalkylene oxide and alkylating or allyl etherifying the other end; and a phthalic acid compound.

Examples of the compound having one (meth)acryloyl group include phenoxyhexaethylene glycol mono(meth)acrylate (meth)acrylate which is a compound obtained by adding polyethylene glycol to p-phenyl group. Base) acrylate; as a compound of p-nonylphenol addition with polypropylene glycol with an average of 2 moles of propylene oxide and polyethylene glycol with an average of 7 moles of ethylene oxide (Meth)acrylate of 4-n-nonylphenoxy heptaethylene glycol dipropylene glycol (meth)acrylate; polypropylene glycol with an average of 1 mole of propylene oxide as an addition addition to p-nonylphenol, And (meth)acrylic acid ester of (meth)acrylic acid ester of compound added with an average of 5 moles of ethylene oxide and polyethylene glycol (meth)acrylic acid ester (meth)acrylate ; And 4-n-nonylphenoxyoctaethylene glycol (methyl) as an acrylate of a compound formed by addition of p-nonylphenol to polyethylene glycol having an average of 8 moles of ethylene oxide Acrylic ester (for example, M-114 manufactured by East Asia Synthetic Co., Ltd.), etc. In addition, from the viewpoint of providing higher sensitivity, resolution, and adhesion, as the compound having one (meth)acryloyl group, phthalic acid γ-chloro-β-hydroxypropyl can also be cited -β'- methacrylic acid ethyl ester.

As the compound having two (meth)acryloyl groups, for example, a compound having (meth)acryloyl groups at both ends of the alkylene oxide chain; and neither the ethylene oxide chain nor the propylene oxide chain Compounds having (meth)acryloyl groups at both ends of the alkylene oxide chain formed by combining regular or block.

Examples of the compound having two (meth)acryloyl groups include tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, and hexaethylene glycol di(meth)acrylate. ) Acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate Polyethylene glycol (meth)acrylates such as esters and compounds having (meth)acryloyl groups at both ends of the ethylene oxide chain of 12 moles; and polypropylene glycol di(meth)acrylates, poly Butylene glycol di(meth)acrylate, and polyalkylene oxide di(meth)acrylate compounds containing ethylene oxide and propylene oxide in the molecule. Examples of the polyalkylene oxide di(meth)acrylate compound containing ethylene oxide and propylene oxide in the molecule include, for example, both ends of polypropylene glycol added with an average of 12 moles of propylene oxide Separately, add dimethacrylates of glycols with an average of 3 moles of ethylene oxide; add an average of 15 moles to the two ends of polypropylene glycol to which an average of 18 moles of propylene oxide is added. Dimethacrylate of diol made from ethylene oxide in the ear. More specifically, FA-023M, FA-024M, FA-027M (product name, manufactured by Hitachi Chemical Industries) and the like can be mentioned. These are preferable because they can provide higher flexibility, resolution, and adhesion.

{式中，R₁ 及R₂ 分別獨立地表示氫原子或甲基，A為C₂ H₄ ，B為C₃ H₆ ，n₁ 及n₃ 分別獨立地為1~39之整數，且n₁ +n₃ 為2~40之整數，n₂ 及n₄ 分別獨立地為0~29之整數，且n₂ +n₄ 為0~30之整數，-(A-O)-及-(B-O)-之重複單元之排列可為無規，亦可為嵌段。而且，於嵌段之情形時，-(A-O)-及-(B-O)-中之任一者可為聯苯側}所表示之化合物。As an example of a compound having two (meth)acryloyl groups in the molecule, from the viewpoint of providing higher resolution and adhesion, it can be exemplified by modifying bisphenol A with alkylene oxide. A compound having (meth)acryloyl groups at both ends. Specifically, the following general formula (I) is preferred: [Chem. 1]

{In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ and n ₃ are each independently an integer from 1 to 39, and n ₁ +n ₃ is an integer from 2 to 40, n ₂ and n ₄ are independently integers from 0 to 29, and n ₂ +n ₄ are integers from 0 to 30, -(AO)- and -(BO)- The arrangement of the repeating units may be random or block. Furthermore, in the case of a block, any of -(AO)- and -(BO)- may be a compound represented by biphenyl side}.

From the viewpoint of providing higher resolution and adhesion, it is preferable to add diethylene acrylic acid of polyethylene glycol formed by adding an average of 5 moles of ethylene oxide to both ends of bisphenol A, respectively. Ester; dimethacrylate of polyethylene glycol formed by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A; adding an average of 1 mole to both ends of bisphenol A Dimethacrylate of polyethylene glycol made from ethylene oxide. The aromatic ring in the general formula (I) may have a hetero atom and/or a substituent.

Examples of heteroatoms include halogen atoms. Examples of the 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, benzoylmethyl groups, amine groups, and 1 to 10 carbon atoms. Alkylamine group, C2-C20 dialkylamine group, nitro group, cyano group, carbonyl group, mercapto group, C1-C10 alkyl mercapto group, aryl group, hydroxyl group, C1-C20 hydroxyl group Alkyl group, carboxyl group, carboxyl alkyl group with 1-10 carbon atoms, acetyl group with 1-10 carbon atoms, alkoxy group with 1-20 carbon atoms, alkoxy group with 1-20 carbon atoms Carbonyl group, alkyl carbonyl group having 2 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, N-alkylamine carboxamide group having 2 to 10 carbon atoms or a group containing a heterocyclic ring, and substitution to these substituent groups The aryl and so on. Such substituents may form condensed rings. The hydrogen atoms in these substituents may be replaced with hetero atoms such as halogen atoms. In the case where the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

Examples of the compound having 3 or more (meth)acryloyl acetyl groups in the molecule include the addition of an oxyalkylene group to the group that has 3 or more moles of an alkylene oxide group in the molecule. , Alcohols such as propoxy, butoxy, etc. are obtained by (meth)acrylate esterification as the central skeleton. In this case, examples of the compound that can become the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate ring. Examples of the compound having three or more (meth)acryloyl groups include tri(meth)acrylates, such as ethoxylated glycerin tri(meth)acrylate, and ethoxylated isocyanuric tris(methyl). ) Acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc.; tetra(meth)acrylate, such as di-trimethylolpropane tetra(meth)acrylate , Pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.; penta(meth)acrylate, such as dipentaerythritol penta(meth)acrylate, etc.; and hexa(meth)acrylate, For example, dipentaerythritol hexa(meth)acrylate and the like. From the viewpoint of resolution, adhesion, and bottom shape of the resist, a compound having three or more (meth)acryloyl groups is preferable, and more preferably has three or more methacryloyl groups.

As trimethylolpropane tri(meth)acrylate, from the viewpoint of high flexibility and adhesion, and suppression of bleeding, for example, it is preferable to add an average ring of 21 moles to trimethylolpropane Trimethacrylate made from ethylene oxide; and trimethacrylate made by adding an average of 30 moles of ethylene oxide to trimethylolpropane.

As tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate is preferred. The pentaerythritol tetra(meth)acrylate may be, for example, tetra(meth)acrylate obtained by adding a total of 1 to 40 moles of alkylene oxide to the four ends of pentaerythritol. As the hexa(meth)acrylate, for example, it is preferable to add hexa(meth)acrylate formed by adding a total of 1 to 40 moles of ethylene oxide to the 6 ends of dipentaerythritol; 6 to dipentaerythritol Hexa (meth) acrylate made by adding ε-caprolactone at a total of 1-20 moles at the end.

The (meth)acrylate compounds can be used independently or in combination. The photosensitive resin composition may contain other compounds as the compound (B) having an ethylenically unsaturated bond. Examples of other compounds include (meth)acrylates having a urethane bond, compounds obtained by reacting α,β-unsaturated carboxylic acids with polyols, and α,β-unsaturated carboxylic acids. A compound obtained by reacting with a glycidyl group-containing compound, 1,6-hexanediol di(meth)acrylate, etc.

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 mass of the total solid content in the photosensitive resin composition. If the amount of the compound (B) is 5% by mass or more, it is preferable from the viewpoint of sensitivity, resolution, and adhesion. The amount of the compound (B) is more preferably 20% by mass or more or 30% by mass or more. If the amount of the compound (B) is 70% by mass or less, it is preferable from the viewpoint of suppressing edge melting and the delay of peeling of the hardened resist. The amount of the compound (B) is more preferably 50% by mass or less.

{式(II)中，A為碳數4以上之二價烴基}所表示之結構之化合物(B1)。於化合物(B)包含化合物(B1)之情形時，可僅由化合物(B1)所構成，或者亦可與化合物(B1)一起，進而包含具有乙烯性不飽和雙鍵且不具有上述通式(II)所表示之結構之化合物(B2)。In this embodiment, the compound (B) may be a compound having an ethylenically unsaturated double bond, or may have the following general formula (II):

{In formula (II), A is a compound (B1) represented by the structure of a divalent hydrocarbon group having 4 or more carbon atoms}. When the compound (B) contains the compound (B1), it may be composed of the compound (B1) alone, or it may be combined with the compound (B1), and further include an ethylenically unsaturated double bond and not have the above general formula ( II) The compound represented by the structure (B2).

[Compound (B1)] The number of ethylenically unsaturated double bonds included in the compound (B1) may be at least one. From the viewpoint of improving the residual film property during development and the physical properties of the cured product, it is preferably at least two, and more It is preferably 2 or more and 6 or less, more preferably 2 or more and 4 or less, and still more preferably 2 pieces. From the viewpoint of compatibility with the alkali-soluble polymer and the curability of the photosensitive resin composition, the ethylenically unsaturated double bond contained in the compound (B1) is preferably selected from acryl and methacrylic The base in the acyl group (hereinafter, also referred to as "(meth)acryl acyl group").

{式中，(A-O)部分係與上述(II)對應，A為碳數4以上之二價烴基，較佳為碳數4~8之二價烴基，B¹ 及B² 分別獨立地為伸乙基或伸丙基，(B¹ -O)、(A-O)及(B² -O)之排列可為無規，亦可為嵌段，n1為0~50之整數，n2為2~100之整數，n3為0~50之整數，R¹ 及R² 分別獨立地為氫原子或甲基}所表示之化合物。Examples of the compound (B1) include the following general formula (III):

{In the formula, the (AO) part 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, and B ¹ and B ² are each independently Ethyl or propyl, the arrangement of (B ¹ -O), (AO) and (B ² -O) can be random or block, n1 is an integer of 0~50, n2 is 2~100 Integer, n3 is an integer from 0 to 50, and R ¹ and R ² are each independently a compound represented by a hydrogen atom or a methyl group}.

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. The divalent hydrocarbon group may be linear, branched, or may contain an alicyclic ring. A is preferably a linear or branched alkylene group. Specific examples of A include, for example, tetramethylene, pentamethylene, hexamethylene, octamethylene, butane-2,3-diyl, butane-1,2-diyl, Pentane-2,3-diyl, pentane-1,4-diyl, 2,2-dimethyl-1,3-propylene, hexane-1,5-diyl, etc. As A, a C4 divalent hydrocarbon group is preferred, a C4 alkylene group is more preferred, and tetramethylene is particularly preferred. n2 is an integer from 2 to 100, preferably an integer from 3 to 75, and more preferably an integer from 4 to 50.

B ¹ and B ² in formula (III) may be independently selected from 1,2-ethylidene, 1,2-propylene, 1,3-propylene, 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 from 0 to 10. The arrangement of (B ¹ -O), (AO) and (B ² -O) may be random or block. R ¹ and R ² are each independently a hydrogen atom or a methyl group.

As the compound (B1), it is preferably selected from a compound in which both of n1 and n3 in formula (III) are 0, and both of n1 and n3 in formula (III) are 1 to 50 (preferably In the compound of 1~30, 1~20 or 1~10). Examples of compounds in which n1 and n2 in formula (III) are 0 are, for example, di(meth)acrylates of polytetramethylene glycol obtained by adding 2 to 100 moles of tetrahydrofuran. . As the compound of formula (III) where both of n1 and n2 are 1 to 50, for example, polytetramethylene glycol formed by adding 2 to 100 moles of tetrahydrofuran is further added at both ends. Di(meth)acrylate of polyalkylene glycol made from 1 to 50 moles of ethylene oxide or propylene oxide.

The compound (B1) may be composed of only one kind of compound, or it may be one of 1, B ¹ , B ² , R ¹ , R ² , n1, n2, and n3 different in formula (III) 2 A mixture of more than one compound.

The compound (B2) is a compound having an ethylenically unsaturated double bond and having no structure represented by formula (II). The number of ethylenically unsaturated double bonds included in the compound (B2) may be at least one, and from the viewpoint of improving the residual film property at the time of development and the physical properties of the cured product, it is preferably at least two, and more It is preferably 2 or more and 10 or less, 2 or more and 8 or less, or 2 or more and 6 or less. From the viewpoints of compatibility with alkali-soluble polymers and curability of the photosensitive resin composition, the ethylenically unsaturated double bond contained in the compound (B2) is preferably (meth)acryloyl.

As the compound having two (meth)acryloyl groups in the compound (B2), for example, a compound having (meth)acryloyl groups at both ends of the alkylene oxide chain, modified with alkylene oxide A compound formed by adding (meth)acryloyl groups to both ends of the alkylene oxide chain of bisphenol A.

In the compound (B2), the alkylene oxide chain in the compound having (meth)acryloyl groups at both ends of the alkylene oxide chain is one or more types selected from the group consisting of ethylene oxide and propylene oxide. Based on the above alkylene oxide. When the compound (B2) contains both ethylene oxide and propylene oxide, these may be connected randomly or in blocks, or a random connection site and a block connection site may be mixed.

Examples of such a compound (B2) 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, at 12 moles Compounds with (meth)acryloyl groups at both ends of the ethylene oxide chain, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, with an average addition of 12 moles The two ends of polypropylene glycol made of propylene oxide are added with an average of 3 moles of ethylene oxide, and the dimethacrylate of glycol is added with an average of 18 moles of propylene oxide. Polypropylene glycol was added to both ends of ethylene glycol with an average of 15 moles of ethylene oxide, such as dimethacrylate. More specifically, FA-023M, FA-024M, FA-027M (manufactured by Hitachi Chemical Industries) and the like can be mentioned. These systems are preferable from the viewpoints of flexibility, resolution, and adhesion.

{式(I)中，R₁ 及R₂ 分別獨立地表示氫原子或甲基，A為C₂ H₄ ，B為C₃ H₆ ，n1及n3分別獨立地為1~39之整數，且n1+n3為2~40之整數，n2及n4分別獨立地為0~29之整數，且n2+n4為0~30之整數，-(A-O)-及-(B-O)-之重複單元之排列可為無規，亦可為嵌段，而且，於嵌段之情形時，-(A-O)-嵌段及-(B-O)-嵌段中之任一者可為聯苯側}所表示之化合物。As a compound in which the (meth)acryloyl group is added to both ends of the alkylene oxide chain of the alkylene oxide-modified bisphenol A in the compound (B2), specifically, for example, the following compounds can be used: Formula (I): [Chemical 4]

{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 from 1 to 39, and n1+n3 are integers from 2 to 40, n2 and n4 are independently integers from 0 to 29, and n2+n4 are integers from 0 to 30, and the arrangement of -(AO)- and -(BO)- repeating units It may be random or block, and in the case of block, any one of -(AO)-block and -(BO)-block may be a compound represented by biphenyl side} .

As such a compound (B2), for example, in terms of resolution and adhesion, polyethylene glycol obtained by adding an average of 5 moles of ethylene oxide to both ends of bisphenol A is preferred Dimethacrylate; polyethylene glycol dimethacrylate formed by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A; and adding separately to both ends of bisphenol A Dimethacrylate of polyethylene glycol made of ethylene oxide with an average of 1 mole.

The compound having more than three (meth)acryloyl groups in the compound (B2) can be exemplified by the following compounds, which have an alkylene oxide-addition group of 3 moles or more in the molecule, The alcohol obtained by addition of ethoxylated or propoxylated is obtained by using (meth)acrylate as the central skeleton. In this case, examples of the compound that can become the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate ring. These tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates, hexa(meth)acrylates, etc., can be used as having more than three (meth)acryl acetyl groups Compound (B2).

Examples of the tri(meth)acrylate in the compound (B2) include ethoxylated glycerin tri(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. ) Acrylate, trimethylolpropane tri(meth)acrylate, etc. Among trimethylolpropane tri(meth)acrylates, for example, trimethylolpropane is added to an average of 21 moles of ethylene oxide, and trimethacrylate is added to trimethylolpropane. Trimethacrylate made of 30 moles of ethylene oxide is preferred from the viewpoints of flexibility, adhesion, and suppression of bleeding.

Examples of the tetra(meth)acrylate in the compound (B2) include di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol tetra(methyl). Acrylic esters, etc. Among these, pentaerythritol tetra(meth)acrylate is preferred. The pentaerythritol tetra(meth)acrylate is preferably a tetra(meth)acrylate obtained by adding a total of 1 mole or more and 40 mole or less of alkylene oxide to the four ends of pentaerythritol.

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

As the hexa(meth)acrylate in the compound (B2), for example, hexa(methyl) formed by adding a total of 1 mole or more and 40 mole or less of ethylene oxide to the 6 terminals of dipentaerythritol is preferable. Acrylic acid ester; hexa(meth)acrylic acid ester obtained by adding ε-caprolactone at a total of 1 mol to 20 mol at the 6 ends of dipentaerythritol.

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

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

{式(II)中，A為碳數4以上之二價烴基}所表示之結構之化合物(B1)。 [態樣2] 如態樣1所記載之感光性樹脂組合物，其中上述化合物(B1)係具有2個以上之乙烯性不飽和雙鍵之化合物。 [態樣3] 如態樣1或2所記載之感光性樹脂組合物，其中上述化合物(B1)係下述通式(III)： [化6]

{式(III)中，A為碳數4~8之二價烴基，B¹ 及B² 分別獨立地為伸乙基或伸丙基，(B¹ -O)、(A-O)及(B² -O)之排列可為無規，亦可為嵌段，n1為0~50之整數，n2為2~100之整數，n3為0~50之整數，R¹ 及R² 分別獨立地為氫原子或甲基}所表示之化合物。 [態樣4] 如態樣3所記載之感光性樹脂組合物，其中上述通式(III)中之n1及n3分別獨立地為0~30之整數。 [態樣5] 如態樣3或4所記載之感光性樹脂組合物，其中於上述通式(III)中，n1+n3為0~10之整數。 [態樣6] 如態樣1至5中任一項所記載之感光性樹脂組合物，其中上述通式(III)中之A為碳數4之二價烴基。 [態樣7] 如態樣1至6中任一項所記載之感光性樹脂組合物，其中上述具有乙烯性不飽和雙鍵之化合物(B)進而包含具有乙烯性不飽和雙鍵且不具有上述通式(II)所表示之結構之化合物(B2)。 [態樣8] 如態樣1至7中任一項所記載之感光性樹脂組合物，其進而包含光增感劑。 [態樣9] 如態樣8所記載之感光性樹脂組合物，其中上述光增感劑包含蒽化合物。 [態樣10] 如態樣8或9所記載之感光性樹脂組合物，其中上述光增感劑包含吡唑啉化合物。 [態樣11] 如態樣1至10中任一項所記載之感光性樹脂組合物，其中上述光聚合起始劑(C)包含咪唑化合物。 [態樣12] 一種感光性樹脂積層體，其具有支持層、及 上述支持層上之如態樣1至11中任一項所記載之感光性樹脂組合物之層。 [態樣13] 一種抗蝕劑圖案之形成方法，其包括以下之步驟： 對如態樣1至11中任一項所記載之感光性樹脂組合物之層進行曝光之步驟； 對曝光步驟後之感光性樹脂組合物之層進行加熱之加熱步驟；及 對加熱步驟後之感光性樹脂組合物之層進行顯影之顯影步驟。 [態樣14] 如態樣13所記載之抗蝕劑圖案之形成方法，其中上述加熱步驟中之加熱溫度為30℃以上150℃以下之範圍。 [態樣15] 如態樣13或14所記載之抗蝕劑圖案之形成方法，其中藉由利用繪圖圖案之直接繪圖之曝光方法、或通過透鏡使光罩之圖像投影之曝光方法而進行上述曝光步驟。 [態樣16] 如態樣13或14所記載之抗蝕劑圖案之形成方法，其中藉由利用繪圖圖案之直接繪圖之曝光方法而進行上述曝光步驟。 [態樣17] 如態樣16所記載之抗蝕劑圖案之形成方法，其中藉由以中心波長未達390 nm之第1雷射光及中心波長為390 nm以上之第2雷射光進行曝光之方法而進行上述曝光步驟。 [態樣18] 如態樣17所記載之抗蝕劑圖案之形成方法，其中上述第1雷射光之中心波長為350 nm以上380 nm以下，上述第2雷射光之中心波長為400 nm以上410 nm以下。Preferred embodiments when the compound (B) contains the compound (B1) are listed in the following [Aspect 1] to [Aspect 18]. [Aspect 1] A photosensitive resin composition for sequentially exposing, heating, and developing to obtain a resist pattern, and the photosensitive resin composition is a total solid of the photosensitive resin composition The quality of the components is based on the following components: (A) 10% by mass or more and 90% by mass or less of alkali-soluble polymer, (B) 5% by mass or more and 70% by mass or less of a compound having an ethylenically unsaturated double bond, and (C) 0.01% by mass or more and 20% by mass or less of a photopolymerization initiator; and the above-mentioned compound (B) having an ethylenically unsaturated double bond contains the following general formula (II):

{In formula (II), A is a compound (B1) represented by the structure of a divalent hydrocarbon group having 4 or more carbon atoms}. [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 photosensitive resin composition according to aspect 1 or 2, wherein the compound (B1) is 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 independently ethyl or propyl, (B ¹ -O), (AO) and (B ² -O) can 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, R ¹ and R ² are independently hydrogen Compound represented by atom or methyl}. [Aspect 4] The photosensitive resin composition according to aspect 3, wherein n1 and n3 in the above 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 in the above general formula (III), n1+n3 is an integer of 0-10. [Aspect 6] The photosensitive resin composition according to any one of aspects 1 to 5, wherein A in the above general formula (III) is a divalent hydrocarbon group having a carbon number of 4. [Aspect 7] The photosensitive resin composition according to any one of aspects 1 to 6, wherein the compound (B) having an ethylenically unsaturated double bond further includes an ethylenically unsaturated double bond and does not have The compound (B2) of the structure represented by the general formula (II). [Aspect 8] The photosensitive resin composition as described in any one of Aspects 1 to 7, which further contains a photosensitizer. [Aspect 9] The photosensitive resin composition according to aspect 8, wherein the light sensitizer contains an anthracene compound. [Aspect 10] The photosensitive resin composition according to aspect 8 or 9, wherein the light sensitizer includes a pyrazoline compound. [Aspect 11] The photosensitive resin composition according to any one of aspects 1 to 10, wherein the photopolymerization initiator (C) contains an imidazole compound. [Aspect 12] A photosensitive resin laminate having a support layer and a layer of the photosensitive resin composition according to any one of aspects 1 to 11 on the support layer. [Aspect 13] A method for forming a resist pattern, comprising the following steps: a step of exposing the layer of the photosensitive resin composition as described in any one of aspects 1 to 11; after the exposure step The heating step of heating the layer of the photosensitive resin composition; and the developing step of developing the layer of the photosensitive resin composition after the heating step. [Aspect 14] The method for forming a resist pattern as described in Aspect 13, wherein the heating temperature in the heating step is within a range of 30°C or more and 150°C or less. [Aspect 15] The method of forming a resist pattern as described in Aspect 13 or 14, which is performed by an exposure method using direct drawing of a drawing pattern or an exposure method of projecting an image of a photomask through a lens The above exposure steps. [Aspect 16] The method for forming a resist pattern as described in Aspect 13 or 14, wherein the exposure step is performed by an exposure method using direct drawing of a drawing pattern. [Aspect 17] The method for forming a resist pattern as described in Aspect 16, wherein the first laser light with a center wavelength of less than 390 nm and the second laser light with a center wavelength of 390 nm or more are used for exposure Method to perform the above exposure step. [Aspect 18] The method for forming a resist pattern as described in 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 410 Below nm.

＜(C) Photopolymerization initiator＞ The photopolymerization initiator (C) is a compound that polymerizes the monomer by light, and may be a photopolymerization initiator generally known in the art.

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

化合物、二烷基胺基苯甲酸酯化合物、肟酯化合物、吖啶化合物、六芳基聯咪唑、吡唑啉化合物、蒽化合物、香豆素化合物、N-芳基胺基酸或其酯化合物、及鹵素化合物等。Examples of the photopolymerization initiator include quinone compounds, aromatic ketone compounds, acetophenone compounds, acetylphosphine oxide compounds, benzoin or benzoin ether compounds, dialkyl ketal compounds, and 9-oxosulfur compounds.

Compounds, dialkylaminobenzoate compounds, oxime ester compounds, acridine compounds, hexaarylbiimidazole, pyrazoline compounds, anthracene compounds, coumarin compounds, N-arylamino acids or their esters Compounds, halogen compounds, etc.

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

As the acridine compound, in terms of sensitivity, resolution, and adhesion, for example, 9-phenylacridine, bisacridylheptane, 9-(p-methylphenyl)acridine, and 9 -(M-methylphenyl) acridine. The anthracene compound is preferably an anthracene derivative having 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. In terms of sensitivity, resolution, and adhesion, for example, 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, and 9,10-diethoxyanthracene are preferred. The coumarin compound is preferably 7-diethylamino-4-methylcoumarin in terms of sensitivity, resolution, and adhesion. The N-arylamino acid or its ester compound is preferably N-phenylglycine in terms of sensitivity, resolution, and adhesion, for example. As the halogen compound, for example, tribromomethylphenyl sulfone is preferred. In addition, as the photopolymerization initiator, 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-methyl-1-(4- (Methylthiophenyl)-2-morpholinylpropane-1-one, 2,4,6-trimethylbenzyl diphenylphosphine oxide, triphenylphosphine oxide.

Examples of hexaarylbiimidazole include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tri-(o-chlorophenyl)-4-(3, 4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)- Diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxy Phenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2, 2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis- (2,4-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluoro Phenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4 ',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5 '-Tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetra-( 3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxy Phenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-bi Imidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2 '-Bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis -(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole and 2,2'-bis-(2 , 3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, etc. From the viewpoint of high sensitivity, resolution, and adhesion, the hexaarylbiimidazole is preferably 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer. From the viewpoint of improving the peeling characteristics and/or sensitivity of the photosensitive resin layer, the amount of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass to 7% by mass, 0.1% by mass to 6% by mass % Or 1% by mass to 5% by mass.

One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

<Photosensitizer> From the viewpoints of higher transmittance and improvement of the peeling characteristics and/or sensitivity of the photosensitive resin layer, the photosensitive resin composition may further include a photosensitizer. Examples of the photosensitizer include pyrazoline compounds and anthracene compounds. The content of the photosensitizer in the photosensitive resin composition is based on the mass of the total solid content of the photosensitive resin composition, and is preferably 0.01% by mass to 10% by mass or less, 0.05% by mass to 5% by mass, and 0.1% by mass % To 3% by mass, 0.1% to 1% by mass, or 0.1% to 0.7% by mass. If the amount of the photosensitizer is 0.01% by mass or more, the peeling characteristics and sensitivity of the photosensitive resin layer can be further improved. If 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-third butyl-styryl)-5-(4-third butyl-phenyl)-pyrazoline and 1- (4-(Benzoxazol-2-yl)phenyl)-3-(4-third butyl-styryl)-5-(4-third butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-third butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4 -Third octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1- Phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyrene Group)-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)-pyrazole Porphyrin, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-( 2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline and 1-phenyl-3-(2,4-dimethoxystyrene Group)-5-(2,4-dimethoxyphenyl)-pyrazoline and the like. As the pyrazoline compound, 1-phenyl-3-(4-biphenyl)-5-(4-third butyl-phenyl)-pyrazoline is more preferable.

As the anthracene compound, in terms of sensitivity, resolution, and adhesion, for example, 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, and 9,10-diethoxyanthracene are preferred Such dialkoxyanthracene compounds.

<Phenol derivatives> 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-pentyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 2,2'- Methylbis(4-methyl-6-tert-butylphenol), bis(2-hydroxy-3-tert-butyl-5-ethylphenyl)methane, triethylene glycol-bis[3-( 3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxy Phenyl) propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylidene bis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-phenylpropionamide), 3,5-di-tert-butyl-4- Hydroxybenzylphosphonic acid-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tri-( 3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'- Butylene bis(3-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, styrenated Phenol (for example, manufactured by Kawaguchi Chemical Industry Co., Ltd., Antage SP), tribenzylphenol (for example, manufactured by Kawaguchi Chemical Industry Co., Ltd., TBP, phenol having 1 to 3 benzyl groups), biphenol, and the like.

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

<Additives> The photosensitive resin composition may contain additives such as colorants, stabilizers, adhesion aids, and plasticizers as needed. For example, the additives listed in Japanese Patent Laid-Open No. 2013-156369 can be used.

(Colorant) In this embodiment, the photosensitive resin composition may further contain a coloring agent, if necessary, for example, at least one selected from the group consisting of dyes and coloring substances.

Examples of the coloring substance include magenta, phthalocyanine green, auramine, p-magenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, and malachite green (e.g., manufactured by Hodogaya Chemical Co., Ltd., Aizen (registered trademark) MALACHITE GREEN), basic blue 20 and diamond green (for example, made by Hodogaya Chemical Co., Ltd., Aizen (registered trademark) DIAMOND GREEN GH). The amount of the coloring substance in the photosensitive resin composition is based on the mass of the total solid content of the photosensitive resin composition, and is preferably 0.001% by mass to 1% by mass. If the amount of the coloring substance is 0.001% by mass or more, the workability of the photosensitive resin composition is improved. If the amount of the coloring substance is 1% by mass or less, it is easy to maintain the storage stability of the photosensitive resin composition.

The photosensitive resin composition contains a dye and the exposed portion develops color, so it is preferable in terms of visibility. When the alignment mark for exposure is read by an inspection machine or the like, it is easy to identify the greater contrast between the exposed portion and the unexposed portion, which is advantageous. From these viewpoints, preferred dyes include leuco dyes and fluorane dyes. Examples of the leuco dye include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leuco malachite green], etc. . From the viewpoint of good contrast, the leuco dye is more preferably leuco crystal violet. The amount of the dye in the photosensitive resin composition is based on the mass of the total solid content of the photosensitive resin composition, and is preferably 0.1% by mass to 10% by mass. If the amount of the dye is 0.1% by mass or more, the contrast between the exposed part and the unexposed part is better. The amount of the dye is more preferably 0.2% by mass or more or 0.4% by mass or more. If the amount of the dye is 10% by mass or less, it is easy to maintain the storage stability of the photosensitive resin composition. 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 includes a combination of a leuco dye and the halogen compound described in the above-mentioned "(C) Photopolymerization Initiator" column. When a leuco dye and a halogen compound are used together, it is easy if the amount of the halogen compound in the photosensitive resin composition is 0.01% by mass to 3% by mass based on the mass of the total solid content of the photosensitive resin composition Maintain the storage stability of the hue in the photosensitive layer.

(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 a radical polymerization inhibitor, a benzotriazole compound, and a carboxybenzotriazole compound.

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

Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis(N-2-ethylhexyl)amino Methyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl ) Amino methylene-1,2,3-benzotriazole and so on.

Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N-(N,N-di -2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N,N -Di-2-ethylhexyl)aminoethylethylcarboxybenzotriazole and the like.

The total amount of stabilizer in the photosensitive resin composition is based on the mass of the total solid content of the photosensitive resin composition, and is preferably 0.01% by mass to 3% by mass or 0.05% by mass to 1% by mass. If the total amount of the stabilizer is 0.01% by mass or more, a higher storage stability can be imparted to the photosensitive resin composition. If the total amount of the stabilizer is 3% by mass or less, it is preferable from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye. The decolorization of the dye can be measured at a transmittance of 630 nm. A higher transmittance at a wavelength of 630 nm indicates that the dye has 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% or less , 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.

(Then the additives) The photosensitive resin composition may further contain an epoxy compound of bisphenol A. Examples of epoxy compounds of bisphenol A include compounds 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 (such as diethyl phthalate), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, and triethyl citrate Ester, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether and polypropylene glycol alkyl Ether and so on. More specifically, Adekanol SDX-1569, Adekanol SDX-1570, Adekanol SDX-1571 and Adekanol SDX-479 (manufactured by Asahi Denka Co., Ltd.); Newpol BP-23P, Newpol BP-3P, Newpol BP-5P , Newpol BPE-20T, Newpol BPE-60, Newpol BPE-100 and Newpol BPE-180 (manufactured by Sanyo Chemical Co., Ltd.); Uniol DB-400, Uniol DAB-800, Uniol DA-350F, Uniol DA-400 and Uniol DA-700 (manufactured by Nippon Oil and Fats Co., Ltd.); and compounds with a bisphenol skeleton such as BA-P4U glycol and BA-P8 glycol (manufactured by Japan Emulsifier Co., Ltd.).

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

<Solvent> The photosensitive resin composition can be dissolved in a solvent, and is used in the production of a photosensitive resin laminate in the form of a photosensitive resin composition blending liquid. Examples of the solvent include ketone compounds and alcohol compounds. Examples of the ketone compound include methyl ethyl ketone (MEK) and acetone. Examples of alcohol compounds include methanol, ethanol, and isopropanol. The amount of the solvent added to the photosensitive resin composition is preferably an amount such that the viscosity of the photosensitive resin composition mixing solution applied on the support layer at 25°C becomes 500 mPa·s to 4,000 mPa·s.

If the amount of water in the photosensitive resin composition is large, the local plasticization of the photosensitive resin composition is rapidly promoted, and edge melting may occur. Therefore, from the viewpoint of suppressing edge melting, a photosensitive resin is preferred The amount of water in the composition is less. The moisture content in the photosensitive resin composition is preferably based on the mass of the photosensitive resin composition after applying the formulation liquid of the photosensitive resin composition to the support layer and drying it (moisture content after drying) 0.7 mass% or less. The moisture content after drying in the photosensitive resin composition is more preferably 0.65 mass% or less, 0.6 mass% or less, 0.55 mass% or less, 0.5 mass% or less, 0.45 mass% or less, 0.4 mass% or less, 0.35 mass% or less, 0.3 Mass% or less, 0.25 mass% or less, or 0.2 mass% or less.

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

<Support layer> As the support layer, a transparent support film that transmits light emitted from the exposure light source is preferred. Examples of the support film include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymerization film, and polymer film. Methyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. As a support layer, an extended support film can also be used as needed.

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 viewpoint, 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 thinner the thickness of the support layer is, the more advantageous it is to improve image formation and economy. However, in order to maintain the strength of the photosensitive resin laminate, it is preferably 10 μm to 30 μm. The support layer may also contain microparticles such as lubricants as needed. The size of the fine particles is preferably less than 5 μm.

The support layer may have a single-layer structure or a multi-layer structure formed by laminating resin layers formed by plural kinds of compositions. In the case of a multilayer structure, an antistatic layer may also be provided. As an example of the multilayer structure, for example, a support layer composed of two layers having a resin layer on one side of the substrate, and a support layer composed of three layers each having a resin layer on both sides of the substrate, and the like. Examples of the three-layer support layer include the support film exemplified above as a substrate, a resin layer containing fine particles on one side A, and B on the other side. (1) Having a resin layer containing fine particles in substantially the same amount as the resin layer on the surface A side; (2) A resin layer having particles smaller than the amount of the resin layer on the side A; (3) A resin layer having finer particles than those contained in the resin layer on the surface A side; and (4) A resin layer that does not contain fine particles. In the case of the structures of (2), (3), and (4) above, it is preferable to have a photosensitive resin layer on the surface B side. In this case, if a resin layer containing fine particles is provided on the surface A side opposite to the photosensitive resin layer, it is preferable from the viewpoint of film slippage and the like. The size of the fine particles contained in the resin layer is preferably less than 1.5 μm.

<Photosensitive resin layer> The photosensitive resin lamination system has a photosensitive resin layer on the 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, and is preferably 1 μm to 300 μm, 3 μm to 100 μm, 5 μm to 60 μm, or 10 μm to 30 μm. If the thickness of the photosensitive resin layer is 1 μm or more, the film strength is higher. If the thickness of the photosensitive resin layer is 300 μm or less, the resolution is higher.

<Protective layer> The photosensitive resin laminate may have 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 with the photosensitive resin layer is sufficiently smaller than that of the support layer and can be easily peeled off. As the protective layer, for example, a protective film such as polyethylene film or polypropylene film can be used. A film excellent in peelability described in Japanese Patent Laid-Open No. 59-202457 can also be used. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

There may be a gel called fisheye on the surface of the polyethylene film. In the case of using a polyethylene film with a fisheye as a protective film, the fisheye may be transferred to the photosensitive resin layer. If the fish eyes are transferred to the photosensitive resin layer, air may be trapped during lamination and become voids, resulting in a defect of the resist pattern. From the viewpoint of preventing fish eyes, the material of the protective layer is preferably extended polypropylene. As a specific example, Alphan E-200A manufactured by Oji Paper Co., Ltd. may be mentioned.

[Manufacturing method of photosensitive resin laminate] An example of a method of manufacturing a photosensitive resin laminate using the photosensitive resin composition of this embodiment will be described. The photosensitive resin laminate can be manufactured by sequentially laminating a support layer, a photosensitive resin layer, and a protective layer as needed. For example, first, the photosensitive resin composition of this embodiment is mixed with the solvent in which it is dissolved to prepare a uniform mixing solution of the photosensitive resin composition. Using a bar coater or roll coater, apply the mixed solution of the photosensitive resin composition on the support layer, followed by drying to remove the solvent, thereby allowing the photosensitive resin composition to be laminated on the support layer Photosensitive resin layer. Then, if necessary, a protective layer is laminated on the photosensitive resin layer, whereby a photosensitive resin laminate can be manufactured.

[Method for manufacturing 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 of this embodiment includes the following steps: The step of exposing the layer (photosensitive resin layer) of the photosensitive resin composition of this embodiment; A heating step of heating the exposed photosensitive resin layer; and The heated photosensitive resin layer is subjected to a development step of development.

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

Examples of the resist pattern include printed wiring boards, semiconductor elements, printing plates, liquid crystal display panels, touch panels, flexible substrates, lead frame substrates, COF (chip on film) substrates, and semiconductors. Patterns for substrates for packaging, transparent electrodes for liquid crystal, wiring for TFT (thin-film transistor) for liquid crystal, electrodes for PDP (Plasma Display Panel), etc.

<Lamination step> In the laminating step, a laminating machine is used to form a photosensitive resin layer on the substrate. Specifically, when the photosensitive resin laminate has a protective layer, after the protective layer is peeled off, the photosensitive resin layer is heated and pressure-bonded to the substrate surface by a laminator to be laminated. Examples of the material of the substrate 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 necessary. The heating temperature during lamination is generally 40℃~160℃. By performing heat and pressure bonding at the time of lamination at least twice, the adhesion of the obtained resist pattern to the substrate can be improved. In the case of heating and pressure bonding, a two-stage laminating machine equipped with a double-roller may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the roller several times for pressure bonding.

<Exposure step> In the exposure step, the photosensitive resin layer is exposed. Examples of the exposure method include: an exposure method in which a mask film having a desired wiring pattern is in close contact with a supporting layer using an active light source; an exposure method by direct drawing as a drawing pattern of a desired wiring pattern ; And the exposure method by projecting the image of the reticle through the lens, etc.

As the exposure method, an exposure method by direct drawing of a drawing pattern or an exposure method of projecting an image of a photomask through a lens is preferable, and an exposure method by direct drawing of a drawing pattern is more preferable. The advantages of the photosensitive resin composition of this embodiment are more obvious in the exposure method by direct drawing of the drawing pattern or the exposure method of projecting the image of the reticle through the lens, and the direct drawing by the drawing pattern This is particularly evident in the exposure method.

In the case where the exposure step is an exposure method by direct drawing, it is preferable that the laser light has a center wavelength of less than 390 nm or the laser light having a center wavelength of 390 nm or more. More preferably, the laser light has a center wavelength of 350 nm or more and 380 nm or less, or a center wavelength of 400 nm or more and 410 nm or less. Preferably, it is performed by a method of exposing with the first laser light having a center wavelength of less than 390 nm and the second laser light having a center wavelength of 390 nm or more. Furthermore, it is more preferable that the center wavelength of the first laser light is 350 nm or more and 380 nm or less, and the center wavelength of the second laser light is 400 nm or more and 410 nm or less.

<heating step> In the heating step, the exposed photosensitive resin is heated (heating after exposure). The heating temperature is preferably 30°C to 150°C, and more preferably 60°C to 120°C. By performing this heating step, the resolution and adhesion are improved. As a heating method, hot air, infrared rays, far infrared rays, a constant temperature bath, a heating plate, a hot air dryer, an infrared dryer, a heating roller, or the like can be used. If the heating method is a heating roller, it can be processed in a short time, so it is preferable, and more preferably a heating roller of two or more pairs.

The elapsed time from exposure to heating, and more precisely, the elapsed time from the time when the exposure is stopped to the time when the temperature is started is preferably within 15 minutes or within 10 minutes. The elapsed time from the time when the exposure is stopped to the time when the temperature is started can also be 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.

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

As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, and is preferably a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2% by mass to about 2% by mass and about 20° C. to about 40° C.

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

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

<Peeling step> The method of manufacturing a circuit board of this embodiment may also include a stripping step of stripping the resist pattern from the substrate after the circuit forming step. Using an appropriate stripping solution, the resist pattern is stripped from the substrate. Examples of the stripping liquid include alkaline aqueous solutions and amine-based stripping liquids. However, the resist pattern formed by heating the photosensitive resin composition of the present invention after exposure shows good peelability to the amine-based peeling liquid, and suppresses excessive miniaturization of the peeling sheet. Therefore, if the amine-based peeling liquid is used as the peeling liquid, the advantageous effects of the present invention can be more effectively exerted.

The amine contained in the amine-based stripping solution may be an inorganic amine or an organic amine. Examples of inorganic amines include ammonia, hydroxylamine, and hydrazine. Examples of organic amines include ethanolamine, propanolamine, alkylamines, cyclic amines, and quaternary ammonium salts.

Examples of ethanolamines include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, and aminoethoxy. Alcohol, etc. Examples of propanolamines include 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, etc. . Examples of alkylamines include monomethylamine, dimethylamine, trimethylamine, ethylideneamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and hexamethylene. Base tetraamine, tetraethylidene pentaamine, etc. Examples of the cyclic amines include choline and oxoline. Examples of the quaternary ammonium salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, N,N,N-triethyl-N-(2-hydroxyethyl) Ammonium hydroxide, N,N-diethyl-N,N-bis(2-hydroxyethyl)ammonium hydroxide, etc.

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 the amine in the aqueous solution can be appropriately set according to the purpose, composition of the photosensitive resin layer, development conditions, and the like.

The amine stripper used in the present invention may further contain additives commonly used in strippers, such as surfactants, defoamers, pH adjusters, preservatives, re-adhesion inhibitors, and the like.

The peeling step is performed at a temperature of, for example, 0°C or more and 100°C or less, preferably room temperature (23°C) or more and 50°C or less, for example, for 1 second or more and 1 hour or less, preferably 10 seconds or more and 10 minutes or less.

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

The photosensitive resin laminate system of this embodiment is suitable for printed wiring boards, flexible substrates, lead frame substrates, touch panel substrates, COF substrates, semiconductor package substrates, liquid crystal transparent electrodes, liquid crystal TFT wiring, and PDP electrodes The photosensitive resin laminated body manufactured by the conductor pattern etc. [Example]

Hereinafter, the embodiments of the present invention will be specifically described by 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] <Manufacture of photosensitive resin laminate> As shown in Tables 1 to 3 disclosed below, each component (wherein the amount of each component represents the blending amount (parts by mass) based on the solid content) is sufficiently stirred and mixed to obtain a photosensitive resin composition blending liquid . In Tables 2 and 3, the I value of the adhesive represents the I value of the mixture of alkali-soluble polymers indicated by symbols A-1 to A-3. Using a polyethylene terephthalate film (manufactured by Toray Co., Ltd., FB-40) with a thickness of 16 μm as a supporting film, and using a bar coater, apply the blending liquid uniformly on the surface of the film. It was dried in a dryer at 95°C for 3 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer is 25 μm. Then, a polyethylene film (made by Tamapoly Co., Ltd., GF-818) with a thickness of 19 μm was laminated on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film was not laminated. Thus, a photosensitive resin laminate is obtained.

<Overall surface of substrate> As a graphical evaluation substrate, a grinding agent (Uji Electrochemical Industry Co., Ltd., #400) was used to apply a spray pressure of 0.2 MPa to the deposited layer. The thickness of the rolled copper foil was 35 μm and the thickness was 0.4 mm. After sandblasting the board, the substrate surface was washed with 10% by mass H ₂ SO ₄ aqueous solution.

<Lamination> While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, on the other hand, the photosensitive resin laminate was laminated on the pre-cursor at a roller temperature of 105°C using a heated roller bonding machine (manufactured by Asahi Kasei Co., Ltd., AL-700). Copper-clad laminates heated to 50°C. The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m/min.

<Exposure> For the evaluation substrate that passed 2 hours after lamination, the direct drawing exposure machine (manufactured by Orbotech Co., Ltd., Nuvogo 1000, light source: 375 nm (30%) + 405 nm (70%)), and Stuart 41 Exposure using a step-wise exposure meter. The exposure was carried out at the exposure amount using the above-mentioned Stuffer 41-stage stepped exposure meter as a mask, and the maximum number of remaining film stages during development was 18 exposures.

<Heating after exposure> Using a heat roller bonding machine (manufactured by Asahi Kasei Co., Ltd., AL-700), the substrate for evaluation that passed 1 minute after exposure was heated. The roller temperature was set at 105°C, the air pressure was set at 0.30 MPa, and the lamination speed was set at 1.5 m/min. In addition, a separately prepared evaluation substrate was used, and after 7 minutes had passed after exposure, heating was performed in the same manner. Furthermore, if the elapsed time after exposure is extended, the effect of heating is reduced, so heating is usually performed about 1 minute after exposure. Therefore, the heating after 7 minutes of exposure in this embodiment is very strict.

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

<Image evaluation> The minimum line width of the pattern normally formed with the mask pattern L/S=X μm/200 μm is measured by an optical microscope. This measurement was performed on 8 wires, and the average value of the 8 wire widths was obtained as an indicator of adhesion. The adhesion was evaluated based on the following criteria. A: The minimum dense wiring width of independent patterns is less than 9 μm B: The minimum dense wire width of independent patterns is more than 9 μm and less than 10 μm C: The minimum dense wiring width of independent patterns is more than 10 μm and less than 11 μm D: The minimum dense wiring width of independent patterns is more than 11 μm

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

[Table 1]

[Table 2]

[table 3]

[Examples 9 to 16 and Comparative Examples 5 to 8] <Preparation of photosensitive resin laminate> As shown in Tables 4 to 6 disclosed below, each component (wherein the amount of each component is expressed as a solid component) The blending amount (parts by mass)) is sufficiently stirred and mixed to obtain a photosensitive resin composition blending liquid. In Tables 5 and 6, the sp value of the binder (MPa ^1/2 ) represents the sp value of the mixture of alkali-soluble polymers indicated by symbols A-1 to A-3. Using a polyethylene terephthalate film (manufactured by Toray Co., Ltd., FB-40) with a thickness of 16 μm as a supporting film, and using a bar coater, apply the blending liquid uniformly on the surface of the film. Dry in a dryer at 95°C for 3 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer is 25 μm. Then, a polyethylene film (made by Tamapoly Co., Ltd., GF-818) with a thickness of 19 μm was laminated on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film was not laminated. Thus, a photosensitive resin laminate is obtained.

<Whole surface of substrate> As a substrate for evaluation of the imageability, the thickness of 0.4 mm copper clad with 35 μm rolled copper foil was deposited on the laminate with a grinding agent (Uji Electrochemical Industry Co., Ltd., #400) at a spray pressure of 0.2 MPa. After the laminate board was sandblasted and brushed, the substrate surface was washed with a 10% by mass H ₂ SO ₄ aqueous solution.

<Lamination> While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, on the other hand, the photosensitive resin laminate was laminated on the pre-cursor at a roller temperature of 105°C using a heated roller bonding machine (manufactured by Asahi Kasei Co., Ltd., AL-700). Copper-clad laminates heated to 50°C. The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m/min.

<Exposure> For the evaluation substrate that passed 2 hours after lamination, a direct drawing exposure machine (Orbotech Co., Ltd., Nuvogo 1000, light source: 375 nm (30%) + 405 nm (70%)) was used, and the Stuffer 41 stage was used Exposure meter. The exposure was carried out at the exposure amount using the above-mentioned Stuffer 41-stage stepped exposure meter as a mask, and the maximum number of remaining film segments during the development was 18.

<Heating after exposure> Using a heat roller bonding machine (manufactured by Asahi Kasei Co., Ltd., AL-700), the substrate for evaluation that passed 1 minute after exposure was heated. The roller temperature was set at 105°C, the air pressure was set at 0.30 MPa, and the lamination speed was set at 1.5 m/min. In addition, a separately prepared evaluation substrate was used, and after 7 minutes had passed after exposure, heating was performed in the same manner. Furthermore, if the elapsed time after exposure is extended, the effect of heating is reduced, so heating is usually performed about 1 minute after exposure. Therefore, the heating after 7 minutes of exposure in this embodiment is very strict.

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

<Image evaluation> Determine the minimum line width of the pattern that normally forms the mask pattern L/S=X μm/200 μm using an optical microscope. This measurement was performed on 8 wires, and the average value of the 8 wire widths was determined as an index of adhesion. The adhesion was evaluated based on the following criteria. A: The minimum dense wiring width of independent patterns is less than 9 μm B: The minimum dense wire width of independent patterns is more than 9 μm and less than 10 μm C: The minimum dense wiring width of independent patterns is more than 10 μm and less than 11 μm D: The minimum dense wiring width of independent patterns is more than 11 μm

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

[Table 4]

[table 5]

[Table 6]

[Examples 17 to 24 and Comparative Example 9] <Measurement of weight average molecular weight or number average molecular weight of polymers> The weight-average molecular weight (Mw) or number-average molecular weight (Mn) of the polymer is a gel permeation chromatograph (GPC) manufactured by JASCO Corporation (using a pump: Gulliver, PU-1580, column: Showa Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Denko Co., Ltd. in series, fluidized layer solvent: tetrahydrofuran, polystyrene standard sample (manufactured by Showa Denko Co., Ltd.) The calibration curve obtained by Shodex STANDARD SM-105) is obtained in the form of polystyrene conversion. In addition, as the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn), the degree of dispersion of the polymer was calculated.

<Manufacture of photosensitive resin laminate> As shown in Tables 7 and 8 disclosed below, each component (wherein the amount of each component represents the blended amount (parts by mass) based on the solid content. "A-1 content" indicates the component A- shown in Table 7 1 The content (mass %) of the solid content in the photosensitive resin composition and the solvent are sufficiently stirred and mixed to obtain a photosensitive resin composition blending liquid. Using a polyethylene terephthalate film (manufactured by Toray Co., Ltd., FB-40) with a thickness of 16 μm as a supporting film, and using a bar coater, apply the blending liquid uniformly on the surface of the film. Dry in a dryer at 95°C for 3 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer is 25 μm. Then, a polyethylene film (made by Tamapoly Co., Ltd., GF-818) with a thickness of 19 μm was laminated on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film was not laminated. Thus, a photosensitive resin laminate is obtained.

<Whole surface of substrate> As a substrate for evaluation of the imageability, the thickness of 0.4 mm copper clad with 35 μm rolled copper foil was deposited on the laminate with a grinding agent (Uji Electrochemical Industry Co., Ltd., #400) at a spray pressure of 0.2 MPa. After the laminate board was sandblasted and brushed, the substrate surface was washed with a 10% by mass H ₂ SO ₄ aqueous solution.

<Lamination> While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, on the other hand, the photosensitive resin laminate was laminated on the pre-cursor at a roller temperature of 105°C using a heated roller bonding machine (manufactured by Asahi Kasei Co., Ltd., AL-700). Copper-clad laminates heated to 50°C. The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m/min.

<Exposure> For the evaluation substrate that passed 2 hours after lamination, a direct drawing exposure machine (Orbotech Co., Ltd., Nuvogo 1000, light source: 375 nm (30%) + 405 nm (70%)) was used, and the Stuffer 41 stage was used Exposure meter. The exposure was carried out at the exposure amount using the above-mentioned Stuffer 41-stage stepped exposure meter as a mask, and the maximum number of remaining film segments during the development was 18.

<Heating after exposure> Using a heat roller bonding machine (manufactured by Asahi Kasei Co., Ltd., AL-700), the evaluation substrate after 7 minutes of exposure was heated. The roller temperature was set at 105°C, the air pressure was set at 0.30 MPa, and the lamination speed was set at 1 m/min. Furthermore, if the elapsed time after exposure is extended, the heating effect disappears, so heating is usually performed about 1 minute after exposure. Therefore, the heating after 7 minutes of exposure in this embodiment is very strict.

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

<Image evaluation> Determine the minimum line width of the pattern that normally forms the mask pattern L/S=X μm/200 μm using an optical microscope. This measurement was performed on 8 wires, and the average value of the 8 wire widths was determined as the value of adhesion.

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.

[Table 7]

[Table 8]

From the results of Tables 7 and 8, it was confirmed that the examples falling within the scope of the constitutional requirements of the present invention are superior to the comparative examples outside the scope of the present invention in terms of the imageability evaluation results.

The heating conditions after the exposure in this embodiment are the heating after 7 minutes of exposure, so they are very strict conditions. For example, when the composition of Example 17 and Comparative Example 9 was developed without heating after exposure, the adhesiveness was 10.6 μm. That is, in the composition of Comparative Example 9, heating after 7 minutes of exposure did not show an effect, but in Example 23, even under very strict conditions, adhesion can be improved. In addition, under the condition of heating for 1 minute after exposure, adhesion of 9.0 μm was obtained in the compositions of Example 23 and Comparative Example 9.

According to the above results, even in the case where the adhesion is good under the general heating conditions after exposure, the adhesion is not good under the strict conditions of heating 7 minutes after exposure in this embodiment. However, with the photosensitive resin composition of the present invention having a specific composition, the adhesiveness can also be improved under the strict post-exposure heating conditions for the first time. In this way, when manufacturing a circuit board, even if the elapsed time after exposure becomes longer, good adhesion can be obtained, so that a high-definition circuit pattern can be stably formed.

[Examples 24 to 38 and Comparative Examples 10 to 11] <Measurement of weight average molecular weight of polymer> The weight-average molecular weight (Mw) of the polymer is determined as a polystyrene conversion value using a gel permeation chromatography (GPC) under the following conditions. Measuring device: manufactured by Nippon Spectroscopy Co., Ltd., gel permeation chromatography (GPC) Pump: manufactured by Japan Spectro Co., Ltd., Gulliver PU-1580 Pipe 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: Showa Denko Co., Ltd., Shodex STANDARD SM-105

<Manufacture of photosensitive resin laminate> Using a bar coater, the photosensitive resin composition preparation liquid prepared in each of Examples and Comparative Examples was uniformly applied to a polyethylene terephthalate film (manufactured by Toray Co., Ltd.) as a support layer , FB-40, thickness 16 μm), dried in a dryer at 95 ℃ for 3 minutes to form a photosensitive resin layer. The dry thickness of the photosensitive resin layer is 25 μm. Then, on the surface of the side of the photosensitive resin layer where the polyethylene terephthalate film is not laminated, a polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818, thickness 19 μm) is applied as a protective layer, A photosensitive resin laminate is obtained.

<The entire surface of the substrate> As the substrate, a copper clad laminate with a thickness of 0.4 mm and a rolled copper foil with a thickness of 35 μm is laminated. Using a grinding agent (manufactured by Uji Electrochemical Industry Co., Ltd., #400), after sandblasting the copper-clad laminate with a spray pressure of 0.2 MPa, the surface was washed with a 10% by mass H ₂ SO ₄ aqueous solution. The entire surface of the substrate is made.

<Lamination> Using a heat roller bonding machine (manufactured by Asahi Kasei Co., Ltd., AL-700), the photosensitive resin laminate was peeled off the polyethylene film (protective layer) and laminated on a copper-clad laminate preheated to 50°C to obtain Evaluation substrate. At this time, the roller temperature was set to 105°C, the air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m/min.

<Exposure> For the evaluation substrate that passed 2 hours after lamination, a direct drawing exposure machine (manufactured by Orbotech Co., Ltd., Nuvogo Fine 10, light source: 375 nm (30%) + 405 nm (70%)) was used, and Stuart 41 Exposure using a step-wise exposure meter. The exposure was carried out under exposure with the above-mentioned Stuffer 41-stage stepped exposure meter as a mask, and the maximum number of remaining film segments during exposure and exposure was 19.

<Heating after exposure> Using a heating roller bonding machine (manufactured by Asahi Kasei Co., Ltd., AL-700), the evaluation substrate after one minute of exposure was heated to form a cured film of the photosensitive resin layer of the exposed portion. The roller temperature was set to 105°C, the air pressure was set to 0.30 MPa, and the lamination speed was set to 1.5 m/min.

<Development> After peeling the polyethylene terephthalate film (support layer) from the evaluation substrate after exposure and heating, an alkaline developing machine (manufactured by Fujikiko, developing machine for dry film) was used for each specific time Spray 1 mass% Na ₂ CO ₃ aqueous solution and pure water at 30°C in sequence to develop. The development spray time is set to a time twice the shortest development time, and the water spray spray time after development is set to a time three times the shortest development time. Here, the shortest development time means the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve.

<Evaluation of adhesion> In the test pattern of lines and gaps where the gap width is a certain value of 200 μm and the line width varies, an optical microscope is used to determine the minimum line width that is normally formed. This measurement was performed on 8 sets of test patterns, and the average value was used as an index of adhesion.

<Evaluation of peeling time> The evaluation substrate that passed 2 hours after lamination was exposed in a solid pattern with a length of 5 cm and a width of 3 cm. Using a heat roller bonding machine (manufactured by Asahi Kasei Co., Ltd., AL-700), the substrate for evaluation that passed 1 minute after exposure was heated. Then, development was carried out at twice the minimum development time, and the time of water spray after development was set at 3 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 Chemical Co., Ltd. was used at a temperature of 50°C. The evaluation sample was immersed in the peeling liquid, and the time until the cured film was peeled off from the substrate was recorded, and this time was taken as the peeling time, and the evaluation was performed by the following criteria. A (good): The peeling time is 45 seconds or less B (preferred): The peeling time exceeds 45 seconds and is less than 50 seconds C (bad): The peeling time exceeds 50 seconds

<Evaluation of size of release sheet> In the above peeling time evaluation, the evaluation sample was immersed in the peeling liquid, the size of the cured film peeled off from the substrate was observed, and the evaluation was performed according to the following criteria. AA (extremely good): The size of the peeling sheet is 1 cm square or more A (good): The size of the peeling sheet is more than 7 mm square and less than 1 cm square B (better): The size of the peeling sheet is 3 mm square or more and less than 7 mm square C (bad): The size of the peeling piece is less than 3 mm square

As (A) alkali-soluble polymer, (B) compound with ethylenic unsaturated double bond, and (C) photopolymerization initiator, and (D) photosensitizer, colorant and stabilizer as optional additives , Mix the components of the types and amounts (mass parts converted from solid content) described in Table 1, and ethanol as a solvent, and stir them sufficiently to prepare a photosensitive resin combination with a solid content concentration of 55% by mass物调调液。 Material blending liquid.

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

[Table 9]

[Table 10]

[Table 11]

[Table 12]

From the results of Tables 10 to 12, it was confirmed that in the examples using the photosensitive resin composition of the present invention, the adhesion and the peeling time using the amine-based peeling liquid were compared with the comparative examples outside the scope of the present invention. At least one of the dimensions of the release sheet and preferably both are excellent.

Claims (29)

A photosensitive resin composition for heating a resin after exposure and then developing to obtain a cured resin, and the photosensitive resin composition is based on the total solid content of the photosensitive resin composition as a reference, Contains the following ingredients: (A) 10% by mass to 90% by mass of alkali-soluble polymer, (B) 5 mass% to 70 mass% of a compound having an ethylenically unsaturated double bond, and (C) 0.01 to 20% by mass of photopolymerization initiator; The inorganic value (I value) of the alkali-soluble polymer (A) is 720 or less. The photosensitive resin composition according to claim 1, wherein the alkali-soluble polymer (A) has an I value of 635 or less. The photosensitive resin composition according to claim 2, wherein the I value of the alkali-soluble polymer (A) is 600 or less. The photosensitive resin composition according to any one of claims 1 to 3, wherein the alkali-soluble polymer (A) has an I value of 300 or more. The photosensitive resin composition according to claim 4, wherein the I value of the alkali-soluble polymer (A) is 400 or more. The photosensitive resin composition according to claim 5, wherein the alkali-soluble polymer (A) has an I value of 450 or more. The photosensitive resin composition according to claim 6, wherein the alkali-soluble polymer (A) has an I value of 500 or more. The photosensitive resin composition according to claim 7, wherein the alkali-soluble polymer (A) has an I value of 550 or more. A photosensitive resin composition for heating a resin after exposure and then developing to obtain a cured resin, and the photosensitive resin composition is based on the total solid content of the photosensitive resin composition as a reference, Contains the following components: (A) 10% by mass to 90% by mass of alkali-soluble polymer, (B) 5% by mass to 70% by mass of a compound having an ethylenically unsaturated double bond, and (C) 0.01% by mass~ 20% by mass of photopolymerization initiator; the solubility parameter (sp value) of the above (A) alkali-soluble polymer is 21.45 MPa ^1/2 or less. The photosensitive resin composition according to claim 9, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 21.40 MPa ^1/2 or less. The photosensitive resin composition according to claim 10, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 21.20 MPa ^1/2 or less. The photosensitive resin composition according to any one of claims 9 to 11, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 19.00 MPa ^1/2 or more. The photosensitive resin composition according to claim 12, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 19.50 MPa ^1/2 or more. The photosensitive resin composition according to claim 13, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 20.00 MPa ^1/2 or more. The photosensitive resin composition according to claim 14, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 20.50 MPa ^1/2 or more. A photosensitive resin composition for heating a resin after exposure and then developing to obtain a cured resin, and the photosensitive resin composition is based on the total solid content of the photosensitive resin composition as a reference, Contains the following ingredients: (A) 10% by mass to 90% by mass of alkali-soluble polymer, (B) 5 mass% to 70 mass% of a compound having an ethylenically unsaturated double bond, and (C) 0.01 to 20% by mass of photopolymerization initiator; The said photosensitive resin composition contains 3 mass% or more of alkali soluble polymers (A-1) as the said alkali soluble polymer (A) based on the mass of the total solid content in the said photosensitive resin composition as the said The soluble polymer (A-1) contains 52% by mass or more of structural units derived from styrene and/or styrene derivatives as monomer components. The photosensitive resin composition according to claim 16, wherein the photosensitive resin composition contains 10% by mass or more of the alkali-soluble polymer (A-1) relative to the mass of the total solid content in the photosensitive resin composition . The photosensitive resin composition according to claim 16 or 17, wherein the alkali-soluble polymer (A-1) contains 55 mass% or more of structural units derived from styrene and/or styrene derivatives as monomer components. The photosensitive resin composition according to claim 18, wherein the alkali-soluble polymer (A-1) contains 58% by mass or more of structural units derived from styrene and/or styrene derivatives as monomer components. The photosensitive resin composition according to any one of claims 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. The photosensitive resin composition according to any one of claims 16 to 19, wherein the alkali-soluble polymer (A-1) further contains a structural unit derived from benzyl (meth)acrylate as a monomer component. A method for forming a resist pattern includes the following steps: The step of exposing the layer of the photosensitive resin composition according to any one of claims 1 to 21; A heating step of heating the exposed layer of the above-mentioned photosensitive resin composition; and The layer of the above-mentioned photosensitive resin composition heated is subjected to a development step of development. The method for forming a resist pattern according to claim 22, wherein the heating temperature in the above heating step is in the range of 30°C to 150°C. The method for forming a resist pattern according to claim 22 or 23, wherein the above heating step is performed within 15 minutes after the exposure is stopped. The method for forming a resist pattern according to any one of claims 22 to 24, wherein the exposure step is performed by an exposure method using direct drawing of a drawing pattern or an exposure method of projecting an image of a photomask through a lens . The method for forming a resist pattern according to claim 25, wherein the above exposure step is performed by an exposure method using direct drawing of a drawing pattern. The method for forming a resist pattern according to claim 26, wherein the above exposure step is performed by a method of exposing with the first laser light having a center wavelength of less than 390 nm and the second laser light having a center wavelength of 390 nm or more. The method for forming a resist pattern according to claim 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. A method for manufacturing a circuit board, comprising: manufacturing a resist pattern on the substrate by the method as in any one of claims 22 to 28, and etching or plating the above substrate with the above resist pattern, by This forms a circuit substrate.