TWI592748B - Photosensitive resin composition and photosensitive resin laminated body - Google Patents

Description

Photosensitive resin composition and photosensitive resin laminate

The present invention relates to a photosensitive resin composition and the like.

In an electronic device such as a computer or a mobile phone, a printed wiring board or the like is used for mounting components, semiconductors, and the like. As a resist for manufacturing a printed wiring board or the like, a so-called dry film resist (hereinafter sometimes referred to as DF) is used, and the dry film resist is formed by laminating a photosensitive resin layer on a support film, and further, the photosensitivity A photosensitive resin laminate in which a protective film is laminated as needed on the resin layer. As the photosensitive resin layer, an alkali-developing type using a weakly alkaline aqueous solution as a developing solution is generally used. When a printed wiring board or the like is produced using DF, for example, the following steps are performed. In the case where the DF has a protective film, the protective film is first peeled off. Then, DF is laminated on a substrate for producing a permanent circuit such as a copper foil laminate or a flexible substrate using a laminator or the like, and exposure is performed via a wiring pattern mask film or the like. Next, the support film is peeled off as needed, and the photosensitive resin layer of the uncured portion (for example, the unexposed portion in the negative type) is dissolved or dispersed by the developer to form a hardened resist pattern on the substrate (hereinafter sometimes only It is called a resist pattern).

The process of forming a circuit after forming a resist pattern can be roughly divided into two methods. The first method is a method of removing a portion of a resist pattern by using an alkaline aqueous solution stronger than a developing solution by etching a substrate surface not covered by a resist pattern (for example, a copper surface of a copper foil laminated board) (etching method) ). In the second method, after the plating treatment of copper, solder, nickel, tin, or the like on the surface of the substrate, the resist pattern portion is removed in the same manner as the first method, and the exposed substrate surface (for example, a copper foil layer is removed). The copper surface of the board) etching method (plating method). When etching A copper chloride, a ferric chloride, a copper ammonia complex solution or the like is used. In recent years, with the miniaturization and weight reduction of electronic equipment, the miniaturization and high density of printed wiring boards have progressed, and high-performance DFs having high resolution and the like are required in the above-described manufacturing steps. Patent Document 1 discloses a photosensitive resin composition which is improved in resolution by a specific thermoplastic resin, a monomer, and a photopolymerizable initiator.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-249884

However, in the case of an exposure method using a direct drawing or the like of a drawing pattern which has been used in recent years, the position of the focus has a large influence on the resolution. For example, if the position of the focus at the time of exposure is moved from the substrate surface due to warpage and deformation of the substrate, poor setting of the exposure device, or the like, the resolution is greatly deteriorated. As a result, there is a problem that a short circuit occurs when a circuit is formed by an etching method, and a problem such as a defect, a disconnection, or a plating failure occurs when a circuit is formed by a plating method. From this point of view, there is still room for improvement in the technique disclosed in the above Patent Document 1.

Therefore, an object of the present invention is to provide a photosensitive resin laminate which exhibits high resolution when the focus is exposed during exposure, and a photosensitive resin composition for forming the photosensitive resin laminate, and provides a use. A method of forming a resist pattern of the photosensitive resin laminate and a method of forming a conductor pattern.

The present inventors conducted intensive studies and repeated experiments in order to solve the above problems. As a result, it has been found that the subject can be solved by the following technical methods.

That is, the present invention is as follows.

[1] A photosensitive resin composition containing (A) an alkali-soluble polymer, (B) A resist obtained by forming a photosensitive resin layer containing the photosensitive resin composition on a surface of a substrate and exposing and developing the compound having an ethylenically unsaturated double bond and (C) a photopolymerization initiator In the pattern, the pattern resolution a when the focus position is focused on the surface of the substrate and the exposure is performed, and the focus position is focused on a position shifted by 300 μm from the surface of the substrate in the thickness direction of the substrate toward the inside of the substrate. The difference in pattern resolution b at the time of exposure was less than 15 μm.

[2] The photosensitive resin composition according to [1], wherein the (A) alkali-soluble polymer is contained in an amount of 10% by mass to 90% by mass based on the total solid content of the photosensitive resin composition; The above (B) compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; and the above (C) photopolymerization initiator: 0.01% by mass to 20% by mass.

[3] The photosensitive resin composition according to [2], further comprising (D) a phenol derivative: 0.001% by mass to 10% by mass based on the total solid content of the photosensitive resin composition.

[4] The photosensitive resin composition according to [3], which comprises a compound represented by the following formula (I) as (D) a phenol derivative:

Wherein R ¹ represents a linear alkyl group which may be substituted, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group which mediates a divalent linking group, a branched alkyl group which mediates a divalent linking group, and an intermediate divalent group The aryl group of the cyclohexyl group or the intermediate divalent linking group of the linking group, the plurality of R ^{1 's} may be the same or different from each other, m represents an integer of 0 to 4, n represents an integer of 1 or more, and when n is 1, A is a The valence organic group, when n is 2 or more, A represents a divalent or higher organic group, a single bond or a linking group containing a conjugated bond}.

[5] The photosensitive resin composition as described in [3] or [4] which contains the compound represented by the following formula (II) as (D) phenol derivative:

Wherein R ² represents a linear alkyl group which may be substituted, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group which mediates a divalent linking group, a branched alkyl group which mediates a divalent linking group, and an intermediate divalent group An aryl group of a cyclohexyl group or an intermediate divalent linking group, and each of R ³ , R ⁴ and R ⁵ independently represents hydrogen or a substituted linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, or an intermediate a linear alkyl group of a valent linking group, a branched alkyl group of an intermediate divalent linking group, a cyclohexyl group of an intermediate divalent linking group or an aryl group of an intermediate divalent linking group}.

[6] The photosensitive resin composition according to [3] or [4], which contains a compound represented by the following formula (III) as (D) a phenol derivative: [Chemical 3]

Wherein R ⁶ and R ⁷ each independently represent a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group having an intermediate divalent linking group, and a branched alkyl group intervening a divalent linking group; a plurality of R ⁶ and R ⁷ may be the same or different from each other, and p and q each independently represent an integer of 0 to 4, and B represents a single group. A bond or a linker containing a conjugate bond}.

[7] A photosensitive resin composition containing (A) an alkali-soluble polymer: 10% by mass to 90% by mass based on the total solid content of the photosensitive resin composition; (B) having an ethyl group Compound of unsaturated double bond: 5% by mass to 70% by mass; (C) photopolymerization initiator: 0.01% by mass to 20% by mass; and (D) phenol derivative: 0.001% by mass to 10% by mass, and (D) a phenol derivative containing at least one selected from the group consisting of a compound represented by the following formula (II) and a compound represented by the following formula (III):

Wherein R ² represents a linear alkyl group which may be substituted, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group which mediates a divalent linking group, a branched alkyl group which mediates a divalent linking group, and an intermediate divalent group An aryl group of a cyclohexyl group or an intermediate divalent linking group, and each of R ³ , R ⁴ and R ⁵ independently represents hydrogen or a substituted linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, or an intermediate a linear alkyl group of a valent linking group, a branched alkyl group of an intermediate divalent linking group, a cyclohexyl group of an intermediate divalent linking group or an aryl group of an intermediate divalent linking group},

Wherein R ⁶ and R ⁷ each independently represent a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group having an intermediate divalent linking group, and a branched alkyl group intervening a divalent linking group; a plurality of R ⁶ and R ⁷ may be the same or different from each other, and p and q each independently represent an integer of 0 to 4, and B represents a single group. A bond or a linker containing a conjugate bond}.

[8] The photosensitive resin composition according to [6] or [7] wherein, in the above formula (III), B is a single bond.

[9] The photosensitive resin composition according to any one of [6] to [8] wherein p = q = 0 in the above formula (III).

[10] The photosensitive resin composition according to any one of [3] to [9] wherein a compound having a reaction rate constant with peroxyradical of 20 Lmol ^-1 ‧ sec ^-1 or more is contained as (D) a phenol derivative.

[11] The photosensitive resin composition as described in any one of [1] to [10] wherein (A) a base The monomer component of the soluble polymer has an aromatic hydrocarbon group.

[12] The photosensitive resin composition according to any one of [1] to [11] which contains an acridine as (C) photopolymerization initiator.

[13] A photosensitive resin laminate in which a photosensitive resin layer containing the photosensitive resin composition according to any one of [1] to [12] is laminated on a support layer.

[14] A method of forming a resist pattern, comprising the step of laminating a photosensitive resin laminated layer layer as described in [13] on a substrate; and exposing the photosensitive resin layer of the photosensitive resin laminated body An exposure step; and a development step of developing and removing the unexposed portion of the photosensitive resin layer.

[15] The method for forming a resist pattern according to [14], wherein the exposing step is performed by an exposure method of directly drawing a pattern or by an exposure method of projecting an image of the mask through a lens.

[16] The method for forming a resist pattern according to [15], wherein the exposure step is performed by an exposure method using direct drawing of a drawing pattern.

[17] The photosensitive resin composition according to any one of [1] to [12], which is used in a method of forming a resist pattern by performing an exposure step by an exposure method directly drawing a drawing pattern .

According to the present invention, it is possible to provide a photosensitive resin laminate which exhibits high resolution even when the focus is moved during exposure, and a photosensitive resin composition for forming the photosensitive resin laminate, and the use of the photosensitive resin A method of forming a resist pattern of a laminate and a method of forming a conductor pattern. As a result, even if the position of the focus at the time of exposure is shifted from the substrate surface due to warpage and deformation of the substrate, poor setting of the exposure device, or the like, the short-circuit problem can be reduced when the circuit is formed by the etching method, and plating can be performed by plating. When the circuit is formed by the method, the defects such as defects, disconnection, and poor plating are reduced.

Hereinafter, an exemplary embodiment (hereinafter simply referred to as "embodiment") for carrying out the present invention will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

[Photosensitive Resin Composition]

In the embodiment, the photosensitive resin composition is characterized in that a photosensitive resin layer containing the photosensitive resin composition is formed on the surface of the substrate and exposed and developed in a resist pattern, and the focus position is focused. The pattern resolution a at the time of the exposure on the surface of the substrate, and the focus position are focused on a position shifted by 300 μm from the surface of the substrate in the thickness direction of the substrate toward the inside of the substrate, and the pattern resolution b at the time of exposure is performed. The difference is less than 15 μm. Thereby, even if the position of the focus at the time of exposure is moved from the substrate surface due to warping and deformation of the substrate, poor setting of the exposure device, etc., the short circuit problem can be reduced when the circuit is formed by the etching method, by plating When the circuit is formed by the method, the defects such as defects, disconnection, and poor plating are reduced. The difference between the pattern resolution a and the pattern resolution b is preferably 12 μm or less, and more preferably 10 μm or less. On the other hand, the difference between the pattern resolution a and the pattern resolution b is preferably 0 μm or more, more preferably 5 μm or more, and still more preferably 7 μm or more from the viewpoints of ease of production and a decrease in sensitivity. In addition, the various measured values in the present specification are measured by the method disclosed in the [Examples] of the present invention or by the same method as the above, unless otherwise specified.

With the miniaturization and thinning of electronic devices in recent years, there has been an increasing demand for higher density of wiring, application of flexible printed wiring boards, and multilayering. Further, with the development of the multilayer, the undulation of the surface is gradually increased, and there is a concern that the resolution of the focus shifts during exposure or the deterioration of the line width reproducibility is caused. As a result, short-circuit defects or defects, disconnection, plating The problem of poorly applied and the inability to form the desired copper wire is becoming increasingly important. In the large substrate, poor adsorption due to exposure or film thickness non-uniformity in the plane The same problem may occur. Therefore, it has been found that by focusing on the focus of the substrate on the surface of the substrate and performing the exposure, the degree of resolution a, and focusing the focus position on the substrate from the surface of the substrate in the thickness direction of the substrate by 300 μm (as It is effective to solve the above problem by designing a photosensitive resin composition with respect to the difference between the pattern resolutions b at the time of exposure, such as the amount of fluctuation in the focus position such as the amount of fluctuation of the surface, which is set to a very large shift amount. . In other words, it has been found that the specific photosensitive resin composition which is used in a specific range in which the difference between the pattern resolution a and the pattern resolution b is selected is effective in the following aspects: even in the case where the wiring is increased in density and multilayered in recent years. It also reduces the problem of poor short circuit or defect, wire breakage, poor plating, and the inability to form the desired copper wire.

In addition, the method of setting the difference between the pattern resolution a and the pattern resolution b within the above-described specific range is not particularly limited, and for example, the composition of the photosensitive resin composition is as described below in detail. Make various adjustments.

In the embodiment, the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator. The photosensitive resin composition preferably contains (A) an alkali-soluble polymer: 10% by mass to 90% by mass based on the total solid content of the photosensitive resin composition; (B) having an ethylenically unsaturated double The compound of the bond: 5% by mass to 70% by mass; and (C) the photopolymerization initiator: 0.01% by mass to 20% by mass. Hereinafter, each component will be described in order.

<(A) alkali soluble polymer>

In the present invention, the (A) alkali-soluble polymer contains a polymer which is easily soluble in an alkaline substance. More specifically, the amount of the carboxyl group contained in the (A) alkali-soluble polymer is from 100 to 600, preferably from 250 to 450, in terms of acid equivalent. The acid equivalent refers to the mass (unit: gram) of a polymer having 1 equivalent of a carboxyl group in its molecule. In order to impart developability and releasability to an aqueous alkaline solution to the photosensitive resin layer, (A) a carboxyl group in the alkali-soluble polymer is required. From the viewpoint of improving development resistance, resolution, and adhesion, it is preferred to use an acid equivalent. Set to 100 or more. More preferably, the acid equivalent is set to 250 or more. On the other hand, from the viewpoint of improving developability and peelability, it is preferred to set the acid equivalent to 600 or less. More preferably, the acid equivalent is set to 450 or less. In the present invention, the acid equivalent is a value measured by a potentiometric titration method using a potentiometric titration apparatus to titrate with a 0.1 mol/L NaOH aqueous solution.

The weight average molecular weight of the (A) alkali-soluble polymer is preferably from 5,000 to 500,000. From the viewpoint of improving the resolution and developability, it is preferred to set the weight average molecular weight to 500,000 or less. More preferably, the weight average molecular weight is set to 300,000 or less, and more preferably 200,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed coacervate and the properties of the unexposed film such as the edge fusion property and the dicing property when the photosensitive resin laminate is formed, it is preferred to set the weight average molecular weight. It is 5,000 or more. More preferably, the weight average molecular weight is set to 10,000 or more, and further preferably set to 20,000 or more. When the edge fusion property is wound into a roll shape as a photosensitive resin laminate, the ease of overflow of the photosensitive resin layer (that is, the layer containing the photosensitive resin composition) from the end surface of the roll. The term "cutting fragmentation" refers to the ease with which the chips are splashed when the unexposed film is cut by the cutter. When the chips adhere to the upper surface of the photosensitive resin laminate or the like, they are transferred to the mask in the subsequent exposure step or the like, which is a cause of defective products.

(A) The alkali-soluble polymer is preferably a copolymer obtained by at least one or more of the following first monomers and at least one or more of the following second monomers.

A carboxylic acid or anhydride having a polymerizable unsaturated group in the first single system molecule. The first monomer may be classified into a first monomer having an aromatic hydrocarbon group and a first monomer having no aromatic hydrocarbon group. Examples of the first monomer having an aromatic hydrocarbon group include cinnamic acid and the like. Examples of the first monomer having no aromatic hydrocarbon group include (meth)acrylic acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like. . In particular, from the viewpoint of easiness of production and developability, (meth)acrylic acid is preferred. In the present invention The term "(meth)acrylic" means acrylic acid and/or methacrylic acid. The same is true below.

The second single system is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. The second monomer may be classified into a second monomer having an aromatic hydrocarbon group and a second monomer having no aromatic hydrocarbon group. Examples of the second monomer having an aromatic hydrocarbon group include benzyl (meth)acrylate, styrene, and a styrene derivative. Examples of the second monomer having no aromatic hydrocarbon group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate Ester, 2-ethylhexyl (meth)acrylate, ester of vinyl alcohol, such as vinyl acetate, (meth)acrylonitrile, and the like. Among them, preferred are methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate. From the viewpoint of improving the resolution and adhesion of the resist pattern, styrene and benzyl (meth)acrylate are preferred. Further, from the viewpoint of reducing the difference in resolution between when the focus position at the time of exposure is focused on the substrate surface and when the focus position at the time of exposure is shifted from the substrate surface, styrene and (meth)acrylic acid are preferable. Benzyl ester.

(A) The alkali-soluble polymer is preferably one containing a monomer component having an aromatic hydrocarbon group. The content ratio of the monomer component having an aromatic hydrocarbon group in the (A) alkali-soluble polymer is preferably 10% by mass or more, and more preferably 20% by mass or more based on the total mass of all the monomer components. Further, it is preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 80% by mass or less.

In a preferred embodiment, the (A) alkali-soluble polymer may contain a polymer having a structure derived from (meth)acrylic acid, an alkyl (meth)acrylate, and styrene, and/or having a source derived from (a) A polymer having a structure of acrylic acid, benzyl (meth) acrylate, and alkyl (meth) acrylate.

Regarding the copolymerization ratio of the first monomer and the second monomer, with the mass of all the polymerization components Preferably, the first monomer is 10% by mass to 60% by mass and the second monomer is 40% by mass to 90% by mass, more preferably the first monomer is 15% by mass to 35% by mass and second. The monomer is from 65 mass% to 85% by mass.

(A) The alkali-soluble polymer may be used alone or in combination of two or more. When two or more types are used in combination, it is preferred to use two kinds of alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group, and an alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group, It is used in combination with an alkali-soluble polymer which does not contain a monomer component having an aromatic hydrocarbon group. In the case of the latter, the use ratio of the alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group to all of the (A) alkali-soluble polymer is preferably 50% by mass or more, and more preferably 70% by mass or more. Further, it is preferably 80% by mass or more, and more preferably 90% by mass or more.

(A) the synthesis of the alkali-soluble polymer is preferably carried out by diluting a mixture of the first monomer and the second monomer in a solvent such as acetone, methyl ethyl ketone or isopropanol. An appropriate amount of a radical polymerization initiator such as benzamidine peroxide or azoisobutyronitrile is added and heated and stirred. There is also a case where a part of the mixture is added dropwise to the reaction liquid for synthesis. Further, after the completion of the reaction, a solvent is further added to adjust the concentration to a desired concentration. As the synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization or emulsion polymerization can also be used.

The ratio of the (A) alkali-soluble polymer to the total solid content of the photosensitive resin composition is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, still more preferably 40% by mass to 60% by mass. In view of controlling the development time, the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition is preferably 90% by mass or less. On the other hand, from the viewpoint of improving the edge-fusing resistance, the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition is preferably 10% by mass or more.

<(B) Compound having an ethylenically unsaturated double bond>

From the viewpoint of curability and compatibility with the (A) alkali-soluble polymer, it is preferred that (B) a compound having an ethylenically unsaturated double bond contains a compound having a (meth) acrylonitrile group in the molecule. . (B) The number of (meth) acrylonitrile groups in the compound may be one or more.

Examples of the (B) compound having one (meth) acrylonitrile group include a compound obtained by adding a (meth)acrylic acid to a single terminal of a polyalkylene oxide; or a single terminal of a polyalkylene oxide. A compound obtained by forming (meth)acrylic acid and alkylating or allyl etherifying the other end.

Examples of such a compound include phenoxy hexaethylene glycol mono(meth) acrylate which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to a phenyl group; Nonylphenoxy heptaethylene glycol dipropylene glycol (meth) acrylate, which is an addition of 2 moles of propylene oxide to polypropylene glycol, and an average of 7 moles of ethylene oxide. Polyethylene glycol, (meth) acrylate of a compound added to nonylphenol; 4-n-decylphenoxypentaethylene glycol monopropylene glycol (meth) acrylate, which has an average of addition 1 molar propylene oxide polypropylene glycol, and polyethylene glycol with an average of 5 moles of ethylene oxide, (meth) acrylate added to the nonylphenol compound; Nonylphenoxy octaethylene glycol (meth) acrylate (for example, M-114 manufactured by Toagosei Co., Ltd.), which is a polyethylene glycol added with an average of 8 moles of ethylene oxide. An acrylate or the like which is a compound on the nonylphenol.

Examples of the compound having two (meth)acryl fluorenyl groups in the molecule include a compound having a (meth)acryl fluorenyl group at both ends of the alkylene oxide chain; or an ethylene oxide chain and an epoxy group. A compound having a (meth) acrylonitrile group at both ends of an alkylene oxide chain in which a propane chain is bonded in a random or block form.

Examples of such a compound include tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, and heptaethylene glycol. (meth) acrylate, octaethylene glycol di(meth) acrylate, octaethylene glycol di(methyl) propyl Poly(ethylene glycol) (meth) acrylate such as a compound having a (meth) acrylonitrile group at both ends of a 12-mole ethylene oxide chain Other examples include polypropylene glycol di(meth)acrylate and polybutylene glycol di(meth)acrylate. Examples of the polyalkylene oxide di(meth)acrylate compound containing an oxirane group and an oxypropylene group in the compound include, for example, two kinds of polypropylene glycol having an average of 12 moles of propylene oxide added thereto. The ends are further added with a dimethacrylate of a diol having an average of 3 moles of ethylene oxide, and an addition of an average of 15 at the two ends of the polypropylene glycol having an average of 18 moles of propylene oxide. a diol of a molar ethylene oxide such as dimethacrylate.

As another example of the compound having two (meth) acryloyl fluorenyl groups in the molecule, from the viewpoint of analyticity and adhesion, it is preferred to modify the bisphenol A at both ends by alkylene oxide modification. A compound having a (meth) acrylonitrile group. The alkylene oxide modification includes ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, and hexylene oxide modification. A compound having a (meth) acrylonitrile group at both terminals by modifying bisphenol A with ethylene oxide is preferred. As such a compound, for example, 2,2-bis(4-((meth)propenyloxydiethoxy)phenyl)propane (for example, NK ester BPE manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) can be cited. 200), 2,2-bis(4-((meth)propenyloxytriethoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxytetraethoxy) Phenyl)propane, 2,2-bis(4-((meth)propenyloxypentaethoxy)phenyl)propane (eg NK ester BPE-500, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) , 2,2-bis(4-((meth)propenyloxyhexaethoxy)phenyl)propane, 2,2-bis(4-((methyl)acryloxy)heptaethoxy) Phenyl)propane, 2,2-bis(4-((meth)propenyloxy octaethoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy) Ethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxydecaethoxy)phenyl)propane, 2,2-bis(4-((meth)propene)醯oxyundecyloxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxydodecyloxy)phenyl)propane, 2,2-bis(4- ((Meth)propenyloxytridecylethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxytetradecyloxy)phenyl)propane, 2, 2-double (4 -((meth)acrylonitrile 2,2-bis(4-(4-(ethoxy))phenyl)propane, 2,2-bis(4-((meth)propenyloxyhexadecyloxy)phenyl)propane (Meth) propylene decyloxypolyethoxy)phenyl)propane or the like. Further, for example, a bis(meth) acrylate having an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide of a polyalkylene glycol is added to both ends of bisphenol A, or The two ends of bisphenol A are respectively added with an average of 2 moles of propylene oxide and an average of 15 moles of ethylene oxide of a polyalkylene glycol bis(meth) acrylate, etc. Alkane-modified and propylene oxide-modified compounds are also preferred. From the viewpoint of further improving analyticity, adhesion, and flexibility, ethylene oxide in a compound having a (meth) acrylonitrile group at both terminals by modifying bisphenol A with an alkylene oxide The number of ears is preferably 10 m or more and 30 m or less.

For example, a compound having more than two (meth) acryloyl fluorenyl groups in one molecule can be obtained by using, as a central skeleton, an alkylene group having an alkyl group having 3 mol or more in a molecule. An alkoxy group such as an ethoxy group, a propoxy group, or a butoxy group is added to obtain an alcohol, and the alcohol is made into a (meth) acrylate. In this case, examples of the compound which can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and an isocyanurate ring.

Examples of such a compound include ethylene oxide (EO) 3 molar modified triacrylate of trimethylolpropane, EO 6 molar modified triacrylate of trimethylolpropane, and trishydroxyl EO 9 molar modified triacrylate of propane, EO 12 molar modified triacrylate of trimethylolpropane, and the like. Examples of such a compound include EO 3 molar modified triacrylate of glycerin (for example, A-GLY-3E manufactured by Shin-Nakamura Chemical Co., Ltd.), and EO 9 molar modified triacrylate of glycerin ( For example, A-GLY-9E manufactured by Xinzhongcun Chemical Industry Co., Ltd., EO 6 molar and propylene oxide (PO) 6 molar modified triacrylate (A-GLY-0606PE), EO 9 of glycerin Moer PO 9 Moer Modified Triacrylate (A-GLY-0909PE), 4 EO modified tetraacrylate of pentaerythritol (such as SR-494 manufactured by Sartomer Co., Ltd.), 35 EO modified 4 of pentaerythritol Acrylate (for example, NK ester ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd.).

In addition to the above compounds, the compounds listed below and the like can be suitably used. For example, 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 2-bis(p-hydroxyphenyl)propane di(methyl) Acrylate, 2,2-bis[(4-(methyl)propenyloxypolypropoxy)phenyl]propane, 2,2-bis[(4-(methyl)propene oxime) Butoxy)phenyl]propane, tris(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyoxypropyltrimethylolpropane tri(meth)acrylate, dipentaerythritol Penta(meth)acrylate, trimethylolpropane triglycidyl ether tri(meth)acrylate, β-hydroxypropyl-β'-(propylene decyloxy)propyl phthalate, hydrazine Phenoxypolypropylene glycol (meth) acrylate, nonyl phenoxy polybutylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like. Further, a urethane compound as described below can also be mentioned. For example, hexamethylene diisocyanate, toluene diisocyanate or a diisocyanate compound (for example, 2,2,4-trimethylhexamethylene diisocyanate), and a hydroxyl group and (meth) propylene in one molecule are mentioned. A sulfhydryl compound such as hydroxypropyl acrylate or propylene glycol monomethacrylate urethane compound. Specifically, there is a reaction product of hexamethylene diisocyanate and oligomeric polypropylene glycol monomethacrylate (for example, Blemmer PP1000 manufactured by Nippon Oil & Fats Co., Ltd.). Further, examples thereof include di- or tri(meth)acrylates of isomeric cyanurate modified by polypropylene glycol or polycaprolactone. Further, for example, an amine group obtained by reacting a terminal of a urethane compound obtained as a polyaddition of a diisocyanate with a polyhydric alcohol with a compound having an ethylenically unsaturated double bond and a hydroxyl group may be mentioned. Formate oligomers, etc.

(B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid content of the photosensitive resin composition is preferably from 5% by mass to 70% by mass. From the viewpoints of sensitivity, resolution, and adhesion, the ratio is preferably set to 5% by mass or more. More preferably, the ratio is set to 20% by mass or more, and more preferably 30% by mass or more. On the other hand, from the viewpoint of suppressing the edge fusion and the peeling delay of the hardened resist, it is preferred The ratio is set to 70% by mass or less. More preferably, the ratio is set to 50% by mass or less.

<(C) Photopolymerization initiator>

Examples of the (C) photopolymerization initiator include a hexaarylbiimidazole compound, an N-aryl-α-amino acid compound, an anthraquinone, an aromatic ketone, an acetophenone, and a fluorenylphosphine oxide. Class, benzoin or benzoin ethers, dialkyl ketals, 9-oxosulfur And dialkylamino benzoate, oxime ester, acridine, pyrazoline derivative, ester compound of N-arylamino acid, halogen compound, and the like.

As the hexaarylbiimidazole compound, for example, 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-( 3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl )-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-di Methoxyphenyl)-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- Difluorophenyl)-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'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-four -(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-A Oxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetra-(3 -Methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxybenzene Bis-diimidazole, 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, 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole and the like.

As the N-aryl-α-amino acid compound, for example, N-phenylglycine, N- Methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like. In particular, the sensitizing effect of N-phenylglycine is better and better.

Examples of the hydrazines include 2-ethyl hydrazine, octaethyl hydrazine, 1,2-benzopyrene, 2,3-benzopyrene, 2-phenyl fluorene, and 2,3-. Diphenylanthracene, 1-chloroindole, 2-chloroindole, 2-methylindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylhydrazine, 3-chloro-2-methylindole, and the like.

Examples of the aromatic ketones include benzophenone, mischidone [4,4'-bis(dimethylamino)benzophenone], and 4,4'-bis(diethylamino). Benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, and the like.

Examples of the acetophenones include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane. 1-ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl (2-hydroxy- 2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2- Orolinyl-acetone-1 and the like. As a commercial item of acetophenone, Irgacure 907, Irgacure 369 and Irgacure 379 by Ciba Specialty Chemicals company are mentioned, for example.

Examples of the fluorenylphosphine oxides include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phosphine oxide, and bis ( 2,6-Dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Examples of the commercially available fluorenylphosphine oxides include Lucirin TPO manufactured by BASF Corporation and Irgacure 819 manufactured by Ciba Specialty Chemicals.

Examples of the benzoin or benzoin ethers include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.

Examples of the dialkyl ketal include benzoin dimethyl ketal and benzoin diethyl ketal.

9-oxosulfur For the class, for example, 2,4-diethyl-9-oxosulfur 2,4-diisopropyl-9-oxosulfur 2-chloro-9-oxosulfur Wait.

Examples of the dialkylamino benzoate include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl p-dimethylaminobenzoate, and 4-(dimethylamino). ) 2-ethylhexyl benzoate and the like.

Examples of the oxime esters include 1-phenyl-1,2-propanedione-2-O-benzimidoxime, 1-phenyl-1,2-propanedione-2-(O- Ethoxycarbonyl) hydrazine and the like. As a commercial item of an oxime ester, CGI-325, Irgacure OXE01, and Irgacure OXE02 by Ciba Specialty Chemicals company are mentioned, for example.

Examples of the acridines include 1,7-bis(9,9'-acridinyl)heptane, 9-phenyl acridine, 9-methyl acridine, 9-ethyl acridine, and 9- Chloroethyl acridine, 9-methoxyacridine, 9-ethoxy acridine, 9-(4-methylphenyl)acridine, 9-(4-ethylphenyl)acridine, 9- (4-n-propylphenyl) acridine, 9-(4-n-butylphenyl)acridine, 9-(4-t-butylphenyl)acridine, 9-(4-methoxybenzene Acridine, 9-(4-ethoxyphenyl)acridine, 9-(4-ethylphenylphenyl)acridine, 9-(4-dimethylaminophenyl)acridine, 9- (4-chlorophenyl) acridine, 9-(4-bromophenyl)acridine, 9-(3-methylphenyl)acridine, 9-(3-tert-butylphenyl)acridine, 9-(3-Ethylphenyl) acridine, 9-(3-dimethylaminophenyl) acridine, 9-(3-diethylaminophenyl) acridine, 9-(3-chloro Phenyl) acridine, 9-(3-bromophenyl)acridine, 9-(2-pyridyl)acridine, 9-(3-pyridyl)acridine, 9-(4-pyridyl)acridine Wait. Among these, in terms of sensitivity, resolution, availability, and the like, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred.

Examples of the pyrazoline derivative include 1-(4-t-butyl-phenyl)-3-styryl-5-phenyl-pyrazoline and 1-phenyl-3-(4- Tert-butyl-styryl-5-(4-tert-butyl-phenyl)-pyrazoline, 1,5-bis-(4-tert-butyl-phenyl)-3-(4 -T-butyl-styryl)-pyrazoline, 1-(4-t-octyl-phenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3 -(4-t-butyl-styryl)-5-(4-ethoxy-phenyl)-pyrazoline, 1-phenyl-3-(4-th-octyl-styryl) -5-(4-t-octyl-phenyl)-pyrazoline, 1,5-bis-(4-t-octyl-phenyl)-3-(4-trioctyl-styryl )-pyrazoline, 1-(4-dodecyl-phenyl)-3-styrene 5-phenyl-pyrazoline, 1-phenyl-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1 -(4-dodecyl-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4 -Third octyl-phenyl)-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-(4-third Butyl-phenyl)-3-(4-t-octyl-styryl)-5-(4-th-octyl-phenyl)-pyrazoline, 1-(4-dodecyl- Phenyl)-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-(4-t-butyl-phenyl) -3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-dodecyl-phenyl)-3- (4-tert-octyl-styryl)-5-(4-th-octyl-phenyl)-pyrazoline, 1-(4-t-octyl-phenyl)-3-(4- Dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(2,4-dibutyl-phenyl)-3-(4-12 Alkyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline and the like.

Further, as the pyrazoline derivative, 1-phenyl-3-(3,5-di-t-butyl-styryl)-5-(3,5-di-t-butyl-benzene) -Pyrazoline, 1-phenyl-3-(2,6-di-t-butyl-styryl)-5-(2,6-di-t-butyl-phenyl)-pyridyl Oxazoline, 1-phenyl-3-(2,5-di-t-butyl-styryl)-5-(2,5-di-t-butyl-phenyl)-pyrazoline, 1 -phenyl-3-(2,6-di-n-butyl-styryl)-5-(2,6-di-n-butyl-phenyl)-pyrazoline, 1-(3,4- Di-t-butyl-phenyl)-3-styryl-5-phenyl-pyrazoline, 1-(3,5-di-t-butyl-phenyl)-3-styryl- 5-phenyl-pyrazoline, 1-(4-t-butyl-phenyl)-3-(3,5-di-t-butyl-phenyl)-5-phenyl-pyrazoline, 1-(3,5-di-t-butyl-phenyl)-3-(3,5-di-t-butyl-styryl)-5-(3,5-di-t-butyl -phenyl)-pyrazoline, 1-(4-(5-tert-butyl-benzo) Zin-2-yl)phenyl)-3-styryl-5-phenyl-pyrazoline, 1-(4-(benzoxyl) Zin-2-yl)phenyl)-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-(4-(4) - tert-butyl-benzo Zin-2-yl)phenyl)-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-(4-(5) - third octyl-benzo Zin-2-yl)phenyl)-3-styryl-5-phenyl-pyrazoline, 1-(4-(benzoxyl) Zin-2-yl)phenyl)-3-(4-t-octyl-styryl)-5-(4-th-octyl-phenyl)-pyrazoline, 1-(4-(5) - third octyl-benzo Zin-2-yl)phenyl)-3-(4-t-octyl-styryl)-5-(4-th-octyl-phenyl)-pyrazoline, 1-(4-(5) -dodecyl-benzo Zin-2-yl)phenyl)-3-styryl-5-phenyl-pyrazoline, 1-(4-(benzoxyl) Zin-2-yl)phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-(5 -dodecyl-benzo Zin-2-yl)phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-(5 - third octyl-benzo Zyridin-2-yl)phenyl)-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline and the like.

Further, as the pyrazoline derivative, 1-(4-(5-tert-butyl-benzo) Zin-2-yl)phenyl)-3-(4-t-octyl-styryl)-5-(4-th-octyl-phenyl)-pyrazoline, 1-(4-(5) -dodecyl-benzo Zin-2-yl)phenyl)-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-(4-(5) - tert-butyl-benzo Zin-2-yl)phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-(5 -dodecyl-benzo Zin-2-yl)phenyl)-3-(4-t-octyl-styryl)-5-(4-th-octyl-phenyl)-pyrazoline, 1-(4-(5) - third octyl-benzo Zin-2-yl)phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-(4) ,6-dibutyl-benzo Zin-2-yl)phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-(benzene and Zin-2-yl)phenyl)-3-(3,5-di-t-butylstyryl)-5-(3,5-di-t-butyl-phenyl)-pyrazoline, 1-(4-(benzo) Zin-2-yl)phenyl)-3-(2,6-di-t-butyl-styryl)-5-(2,6-di-t-butyl-phenyl)-pyrazoline , 1-(4-(benzoxyl) Zin-2-yl)phenyl)-3-(2,5-di-tert-butyl-styryl)-5-(2,5-di-tert-butyl-phenyl)-pyrazoline , 1-(4-(benzoxyl) Zin-2-yl)phenyl)-3-(2,6-di-n-butyl-styryl)-5-(2,6-di-n-butyl-phenyl)-pyrazoline, 1 -(4-(4,6-di-t-butyl-benzo-benzo) Zin-2-yl)phenyl)-3-styryl-5-phenyl-pyrazoline, 1-(4-(5,7-di-t-butyl-benzo) Zin-2-yl)phenyl)-3-styryl-5-phenyl-pyrazoline, 1-(4-(5-tert-butyl-benzo) Zin-2-yl)phenyl)-3-(3,5-di-t-butyl-styryl)-5-phenyl-pyrazoline, 1-(4-(4,6-di-) Third butyl-benzo Zin-2-yl)phenyl)-3-(3,5-di-t-butyl-styryl)-5-(3,5-di-t-butyl-phenyl)-pyrazoline , 1-phenyl-3-(4-t-butyl-styryl)-5-(4-amino-phenyl)-pyrazoline, 1-phenyl-3-(4-third -styryl)-5-(4-N-ethyl-phenyl)-pyrazoline and 1-phenyl-3-(4-t-butyl-styryl)-5-(4- N,N-Diethyl-phenyl)-pyrazoline and the like.

Further, as the pyrazoline derivative, 1-phenyl-3-(4-biphenyl)-5-(4-n-butyl-phenyl)-pyrazoline, 1-phenyl-3- (4-biphenyl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-isobutyl- Phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-n-pentyl-phenyl)-pyrazoline, 1-phenyl-3-(4- Biphenyl)-5-(4-isopentyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-neopentyl-phenyl)- Pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-hexyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5 -(4-heptyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-n-octyl-phenyl)-pyrazoline, 1-benzene 3-(4-biphenyl)-5-(4-t-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4- Mercapto-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-indolyl-phenyl)-pyrazoline, 1-phenyl-3-( 4-biphenyl)-5-(4-undecyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-dodecyl- Phenyl)-pyrazoline and the like.

Among the above-mentioned pyrazoline derivatives, from the viewpoint of the adhesion and the rectangularity of the resist pattern, it is preferred to use a substrate selected from 1-phenyl-3-(4-t-butyl-styrene). 5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-t-butyl-phenyl)- At least one of a group consisting of pyrazoline and 1-phenyl-3-(4-biphenyl)-5-(4-thanooctyl-phenyl)-pyrazoline.

Examples of the ester compound of the N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, and n-propyl N-phenylglycine. Isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, and third butyl ester of N-phenylglycine And amyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, amyl ester of N-phenylglycine, octyl ester of N-phenylglycine, and the like.

Examples of the halogen compound include bromopentane, bromoisopentane, bromoisobutylene, dibromoethane, diphenylbromomethane, benzyl bromide, dibromomethane, tribromomethylphenylhydrazine, and carbon tetrabromide. Tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)B Alkane, chlorination A compound, a diallyl hydrazine compound or the like is particularly preferably tribromomethylphenyl hydrazine.

The (C) photopolymerization initiators listed above may be used singly or in combination of two or more. Among these (C) photopolymerization initiators, from the viewpoints of sensitivity and resolution of the photosensitive resin composition, etc., it is preferred to use a compound selected from a hexaarylbiimidazole compound and an N-aryl-α-amine. At least one selected from the group consisting of a basic acid compound, an anthracene, an acridine, and a pyrazoline derivative, more preferably a compound selected from the group consisting of a hexaarylbiimidazole compound, an N-aryl-α-amino acid compound, and At least one of the group consisting of acridines. From the viewpoints of sensitivity, resolution, and the like of the photosensitive resin composition, the viewpoint of deterioration of resolution at the time of focus shift during exposure or the narrowing of a gap portion between adjacent resist lines at the time of focus shift during exposure is suppressed. From the viewpoint of chemistry, it is further preferred to use an acridine.

The ratio of the (C) photopolymerization initiator to the total solid content of the photosensitive resin composition is preferably from 0.01% by mass to 20% by mass. From the viewpoint of obtaining a good sensitivity, the ratio is preferably set to 0.01% by mass or more. The ratio is more preferably set to 0.1% by mass or more, and further preferably set to 0.5% by mass or more. On the other hand, from the viewpoint of obtaining high resolution and suppressing cohesiveness in the developer, it is preferred to set the ratio to 20% by mass or less. The ratio is more preferably set to 10% by mass or less.

When the hexaarylbiimidazole compound is used as the (C) photopolymerization initiator, the content of the hexaarylbiimidazole compound is preferably 0.1% by mass based on the total solid content of the photosensitive resin composition. ~15% by mass. From the viewpoint of obtaining good sensitivity, it is preferred to set the blending amount to 0.1% by mass or more. The blending amount is more preferably 1% by mass or more, and particularly preferably 3% by mass or more. On the other hand, from the viewpoint of obtaining high resolution and suppressing cohesiveness in the developer, it is preferred to set the blending amount to 15% by mass or less. The blending amount is more preferably set to 10% by mass or less, and particularly preferably set to 6% by mass or less.

Further, in the case where an N-aryl-α-amino acid compound is used as the (C) photopolymerization initiator, the N-aryl-α- is relative to the total solid component mass of the photosensitive resin composition. The content of the amino acid compound is preferably from 0.001% by mass to 5% by mass. From the viewpoint of obtaining a good sensitivity, it is preferred to set the blending amount to 0.001% by mass or more. The blending amount is more preferably 0.01% by mass or more, and particularly preferably 0.1% by mass or more. On the other hand, from the viewpoint of obtaining high resolution and improving hue stability, it is preferred to set the blending amount to 5% by mass or less. The blending amount is more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

Further, when acridine is used as the (C) photopolymerization initiator, the content of the acridine is preferably 0.01% by mass to 5% by mass based on the total solid content of the photosensitive resin composition. From the viewpoint of obtaining good sensitivity, it is preferred to set the blending amount to 0.01% by mass or more. The blending amount is more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. On the other hand, from the viewpoint of obtaining a rectangular resist shape and improving hue stability, the blending amount is preferably set to 5% by mass or less. The blending amount is more preferably set to 3% by mass or less, and particularly preferably set to 2% by mass or less. Further, from the viewpoint of reducing the difference between the resolution when the position of the focus at the time of exposure is focused on the substrate surface and the position of the focus at the time of exposure from the substrate surface, the amount of the setting is also set to the above range. Preferably.

<(D) phenol derivative>

In the embodiment, the photosensitive resin composition preferably further contains (D) a phenol derivative. Among them, the photosensitive resin composition preferably contains a compound represented by the following formula (I) as (D) a phenol derivative: [Chem. 6]

Wherein R ¹ represents a linear alkyl group which may be substituted, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group which mediates a divalent linking group, a branched alkyl group which mediates a divalent linking group, and an intermediate divalent group The aryl group of the cyclohexyl group or the intermediate divalent linking group of the linking group, the plurality of R ^{1 's} may be the same or different from each other, m represents an integer of 0 to 4, n represents an integer of 1 or more, and when n is 1, A is a The valence organic group, when n is 2 or more, A represents a divalent or higher organic group, a single bond or a linking group containing a conjugated bond}. The compound represented by the formula (I) is excellent in terms of suppressing the sensitivity of the photosensitive resin composition and maintaining a good resolution without being affected by the focus position. From the same viewpoint, n is preferably an integer of 2 or more.

The compound represented by the formula (I) preferably contains a compound selected from the group consisting of the following formula (II):

Wherein R ² represents a linear alkyl group which may be substituted, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group which mediates a divalent linking group, a branched alkyl group which mediates a divalent linking group, and an intermediate divalent group An aryl group of a cyclohexyl group or an intermediate divalent linking group, and each of R ³ , R ⁴ and R ⁵ independently represents hydrogen or a substituted linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, or an intermediate a linear alkyl group of a valent linking group, a branched alkyl group of an intermediate divalent linking group, a cyclohexyl group of an intermediate divalent linking group or an aryl group of an intermediate divalent linking group, and a compound represented by the following formula (III) :

Wherein R ⁶ and R ⁷ each independently represent a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group having an intermediate divalent linking group, and a branched alkyl group intervening a divalent linking group; a plurality of R ⁶ and R ⁷ may be the same or different from each other, and p and q each independently represent an integer of 0 to 4, and B represents a single group. At least one of the group consisting of a bond or a linking group containing a conjugated bond is more preferably a compound represented by the formula (III). Further, the compound represented by the formula (II) is excluded from the compound represented by the formula (III).

The viewpoint of improving the resolution of the photosensitive resin composition, the viewpoint of suppressing the deterioration of the resolution at the time of focus shift during exposure, and the gap between the resist line and the resist line when the focus shift during exposure is suppressed. The compound represented by the formula (II) and the compound represented by the formula (III) are particularly excellent from the viewpoint of the narrowness of the partial reduction and the decrease in the suppression sensitivity.

From the viewpoint of improving the resolution of the photosensitive resin composition, the viewpoint of suppressing the deterioration of the resolution at the time of focus shift during exposure, and the prevention of the resist during the focus shift during exposure, respectively, the compound represented by the formula (II) From the viewpoint of narrowing the gap portion between the agent line and the resist line and suppressing the decrease in sensitivity, it is preferable that at least R ² , R ³ , R ⁴ and R ⁵ in the formula (II) One has an aromatic ring. From the same viewpoint, the compound represented by the formula (II) is preferably a phenol core having two or more cores.

From the same viewpoint, the hydroxyl group concentration of the compound represented by the formula (II) is preferably from 0.10 mol/100 g to 0.75 mol/100 g. Further, from the same viewpoint, it is preferred that in the above formula (II), at least one of R ² is a linear or branched alkyl group, a benzyl group, a 1- or 2-phenylethyl group, or a phenylthio group which may be substituted with a hydroxyl group or an alkyl group. Further, preferred examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, and a t-butyl group.

From the same viewpoint, the molecular weight of the compound represented by the formula (II) is preferably from about 130 to about 1,000, more preferably from about 130 to about 600, still more preferably from about 130 to about 400, and most preferably about 180 ~ about 400. From the same viewpoint, the compound represented by the formula (II) preferably has a specific gravity of from about 1.02 to about 1.12, or a melting point of about 155 ° C or higher (for example, about 208 ° C or higher), or is poorly soluble with respect to water. Further, it is easily soluble with respect to an organic solvent such as methanol, acetone or toluene, or is a solid (for example, powder, crystal, etc.) or a liquid at the time of use.

Examples of the compound represented by the formula (II) include 4,4′-thiobis(6-t-butyl-m-cresol) and 4,4′-butylenebis(3-methyl-). 6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, styrenated phenol (eg Kawaguchi Chemical Industry Co., Ltd.) Antage SP) manufactured, tribenzyl phenol (for example, TBP manufactured by Kawaguchi Chemical Industry Co., Ltd., phenol having 1 to 3 benzyl groups), and the like.

In the compound represented by the formula (III), B represents a single bond or a linking group containing a conjugated bond. The linking group containing a conjugated bond is preferably a conjugated linking group formed of C, N, O, S or the like, more preferably an alkenyl group, an alkynyl group, an extended aryl group or a divalent aromatic group. a ring, an azo, and an imine, and a combination of one or more of these and N.

For the compound represented by the formula (III), the resolution of the photosensitive resin composition is improved. From the viewpoint of the nature, the viewpoint of suppressing the deterioration of the resolution at the time of focus shift during exposure, the viewpoint of suppressing the narrowing of the gap portion between the resist line and the resist line at the time of focus shift during exposure, and the suppression sensitivity From the viewpoint of the decrease, it is preferred that B in the formula (III) is a single bond.

From the same viewpoint, the compound represented by the formula (III) is preferably p = q = 0 in the formula (III), and particularly preferably biphenol.

In the embodiment, the (D) phenol derivative may further contain a compound other than the compound represented by the formula (II) and the formula (III). Examples of the compound other than the compound represented by each of the formula (II) and the formula (III) include 2,6-di-tert-butyl-4-methylphenol and 2,5-di-third. Pentohydroquinone, 2,5-di-t-butyl hydroquinone, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), double (2- Hydroxy-3-t-butyl-5-ethylphenyl)methane, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetraki [3-(3,5-di-) Tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-di-extension ethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propane Acid ester], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di- Third butyl-4-hydroxy-phenylpropanamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2 , 4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, etc. .

The reaction rate constant of the (D) phenol derivative and the peroxy radical in the embodiment is preferably 20 L ‧ mol ^-1 ‧ sec ^-1 or more (more preferably 30 L ‧ mol ^-1 ‧ sec ^-1 or more, and further Preferably, it is a compound of 40 L ‧ mol ^-1 ‧ sec ^-1 or more, and is preferably 500 L ‧ mol ^-1 ‧ sec ^-1 or less (more preferably 300 L ‧ mol ^-1 ‧ sec ^-1 or less, further preferably 200 L ‧ mol ^-1 ‧ sec ^-1 or less of the compound.

Here, whether the selection of the (D) phenol derivative as described above affects the value of the difference between the pattern resolution a and the pattern resolution b, and whether or not the wiring is increased in density and multilayered in recent years. Reduce the problem of poor short circuit or defect, wire breakage, poor plating The selection of the photosensitive resin composition which does not cause the problem of the desired copper wire affects, and the detailed mechanism is not clear, but can be considered as follows.

Regarding the antioxidant action of the phenol derivative, it is considered that there is an optimum point in terms of the reactivity with the radical species and the stability of the phenoxy radical generated after the reaction with the radical species. For example, the larger the substituent which is ortho to the OH group of phenol, the more stable the phenoxy radical becomes. On the other hand, if the steric hindrance of the ortho substituent is too large, the reactivity with the radical species becomes low. Moreover, the optimum value of the degree of steric hindrance varies depending on the characteristics of the oxidized chemical species (easy to be oxidized).

Here, since the photosensitive resin composition in the embodiment is photoradical polymerizable, the (D) phenol derivative is required to have high reactivity with a radical species in order to capture peroxy radicals which may cause deterioration in resolution.

In view of the above various factors, the (D) phenol derivative is preferably a compound represented by the formula (I), and more preferably a compound represented by the formula (II) and a formula ( III) at least one of the group consisting of the compounds represented. With respect to the compound represented by the formula (II), it is considered that since the steric hindrance of the ortho substituent is adjusted to be optimum, both the reactivity with the peroxy radical and the stability of the phenoxy radical are excellent. Further, in the compound represented by the formula (III), it is considered that if the steric hindrance of the ortho substituent is small, the reactivity with the peroxy radical is high, and the biphenol type phenoxy free gene phenoxy is free. The resonance structure of the base is many and stable.

The compound disclosed as a specific example of the compound represented by the formula (II) or the formula (III) and satisfying the range of the above reaction rate constant, for example, 1,1,3-tris(2-methyl-) 4-hydroxy-5-t-butylphenyl)butane is 45.4 L ‧ mol ^-1 ‧ sec ^-1 , 4,4'-butylene bis(3-methyl-6-tert-butylphenol) 48.6L‧mol ^-1 ‧sec ^-1 .

The γ value (gamma value) obtained from the residual film ratio of the photosensitive resin composition is preferably 0.5 or more, more preferably 1.0 or more, still more preferably 2.0 or more, and particularly preferably 5.0 or more. The γ value (gamma value) obtained from the reaction rate of the C=C double bond is preferably 0.18 or more, more preferably 0.19 or more. It is preferably 0.20 or more, and particularly preferably 0.25 or more.

The ratio of the (D) phenol derivative to the total solid content of the photosensitive resin composition is preferably 0.001% by mass to 10% by mass. From the viewpoint of improving the resolution of the photosensitive resin composition, the viewpoint of suppressing the deterioration of the resolution at the time of focus shift during exposure, and the gap between the resist line and the resist line when the focus shift during exposure is suppressed. The ratio is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, and most preferably 0.5% by mass. the above. On the other hand, the ratio is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably in terms of a decrease in sensitivity and an improvement in resolution. 2% by mass or less, preferably 1.5% by mass or less.

<additive> (dye and coloring matter)

In the embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of a dye (for example, a leuco dye, a fluorescein dye, etc.) and a coloring matter, as desired.

Examples of the coloring matter include magenta, phthalocyanine green, golden amine base, p-magenta, crystal violet, methyl orange, Nero blue 2B, Victoria blue, and malachite green (for example, manufactured by Hodogaya Chemical Co., Ltd.). Aizen (registered trademark) MALACHITE GREEN), alkaline blue 20, diamond green (for example, Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). The content of the coloring matter in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass when the total solid content of the photosensitive resin composition is 100% by mass. From the viewpoint of improving the rationality of the photosensitive resin composition, the content is preferably set to 0.001% by mass or more. On the other hand, from the viewpoint of maintaining the storage stability of the photosensitive resin composition, the content is preferably set to 1% by mass or less.

The photosensitive resin composition develops an exposed portion by containing a dye, so In the case of the visibility, when the inspection machine or the like reads the alignment mark for exposure, it is advantageous to easily recognize the contrast between the exposed portion and the unexposed portion. From this point of view, preferred dyes include leuco dyes and fluorin dyes.

Examples of the leuco dye include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [hidden malachite green], and the like. In particular, from the viewpoint of a good contrast, it is preferable to use a leuco crystal violet as a leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably from 0.1% by mass to 10% by mass based on the total solid content of the photosensitive resin composition. From the viewpoint of making the contrast between the exposed portion and the unexposed portion good, the content is preferably made 0.1% by mass or more. The content is more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more. On the other hand, from the viewpoint of maintaining storage stability, it is preferred to set the content to 10% by mass or less. The content is more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

Moreover, from the viewpoint of optimizing the adhesion and the contrast, it is preferred to use the above-mentioned halogen compound in combination with the leuco dye and (C) photopolymerization initiator in the photosensitive resin composition. When the leuco dye is used in combination with the halogen compound, the photosensitive solid content of the photosensitive resin composition is set to 100% by mass, and the photosensitive material is maintained at a mass stability of the photosensitive layer. The content of the halogen compound in the resin composition is preferably from 0.01% by mass to 3% by mass.

(other additives)

In order to improve thermal stability and storage stability, the photosensitive resin composition may further contain at least one compound selected from the group consisting of a radical polymerization inhibitor, a benzotriazole, and a carboxybenzotriazole.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, and 2,6-di- Tributyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylene double (4-B Base-6-tert-butylphenol), nitrosophenylhydroxylamine aluminum salt, diphenylnitrosamine, and the like. In order not to impair the sensitivity of the photosensitive resin composition, a nitrosophenylhydroxylamine aluminum salt is preferred.

Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis(N-2-ethylhexyl)aminone. Methyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-toluenetriazole, bis(N-2-hydroxyethyl) Aminomethylene-1,2,3-benzotriazole and the like.

Examples of the carboxybenzotriazoles 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)aminomethylenecarboxybenzotriazole and the like.

The total content of the radical polymerization inhibitor, the benzotriazole, and the carboxybenzotriazole is preferably 0.01% by mass when the total solid content of the photosensitive resin composition is 100% by mass. 3 mass%, more preferably 0.05 mass% to 1 mass%. From the viewpoint of imparting storage stability to the photosensitive resin composition, it is preferred to set the content to 0.01% by mass or more. On the other hand, from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye, it is preferred to set the content to 3% by mass or less.

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

In the embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalic acid esters (for example, diethyl phthalate), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, and triethyl citrate. , Ethyltriethyl citrate, tri-n-propyl ethyl citrate, tri-n-butyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl Ether, etc. Also, list: ADEKANOL SDX-1569, ADEKANOL SDX-1570, ADEKANOL SDX-1571, ADEKANOL SDX-479 (above is manufactured by Asahi Kasei Co., Ltd.), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, Newpol BPE-20T, Newpol BPE-60, Newpol BPE-100, Newpol BPE-180 (above is manufactured by Sanyo Chemical Co., Ltd.), Uniol DB-400, Uniol DAB-800, Uniol DA-350F, Uniol DA-400, Uniol DA-700 (above manufactured by Japan Oils and Fats Co., Ltd.), BA a compound having a bisphenol skeleton such as P4U glycol or BA-P8 glycol (manufactured by Nippon Emulsifier Co., Ltd.).

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

[solvent]

The photosensitive resin composition can be used in the production of a photosensitive resin laminate in the form of a photosensitive resin composition solution in a solvent. Examples of the solvent include ketones, alcohols, and the like. The above ketones are represented by methyl ethyl ketone (MEK). The above alcohols are represented by methanol, ethanol and isopropanol. In the production of the photosensitive resin laminate, the solvent is preferably added to the photosensitive material at a viscosity of 25 mPa·s to 4,000 mPa·s at 25° C. of the photosensitive resin composition preparation liquid applied to the support layer. In the resin composition.

[Photosensitive Resin Laminate]

In the embodiment, a photosensitive resin laminate in which a photosensitive resin containing the photosensitive resin composition as described above is laminated on a support layer (for example, a support film or the like) is provided. The photosensitive resin laminate may have a protective layer on the surface opposite to the support layer side of the photosensitive resin layer, as needed.

As the support layer, a transparent support film which can penetrate light emitted from the exposure light source is preferable. Examples of such a support film include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, and a vinylidene chloride. An olefin copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, or the like. These films may also be used as extensions as needed. The support film preferably has a haze of 5 or less. The thinner the thickness of the film, the more advantageous the image formation property and the economical efficiency are. However, in order to maintain the strength of the photosensitive resin laminate, 10 μm to 30 μm can be preferably used.

The important property of the protective layer used in the photosensitive resin laminate is that the adhesion to the photosensitive resin layer is sufficiently smaller than that of the support layer, and can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. Further, a film excellent in peeling properties as shown in Japanese Laid-Open Patent Publication No. SHO 59-202457 can also be used. The film thickness of the protective layer is preferably from 10 μm to 100 μm, more preferably from 10 μm to 50 μm.

On the surface of a polyethylene film, there is sometimes a gel called a fisheye. In the case where a polyethylene film having a fisheye is used as the protective layer, the fisheye is sometimes transferred onto the photosensitive resin layer. When the fisheye is transferred onto the photosensitive resin layer, air may be trapped during lamination to form a void, resulting in a defect in the resist pattern. From the viewpoint of preventing fish eyes, as a material of the protective layer, extended polypropylene is preferred. As a specific example, ALPHAN E-200A manufactured by Oji Paper Co., Ltd. can be cited.

The thickness of the photosensitive resin layer in the photosensitive resin laminate is different depending on the application, and is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. The thinner the thickness of the photosensitive resin layer, the higher the resolution, and the thicker the film strength is.

Next, a method of producing a photosensitive resin laminate will be described.

A known method can be employed as a method of producing a photosensitive resin laminate by sequentially laminating a support layer, a photosensitive resin layer, and an optional protective layer. For example, a photosensitive resin composition used in a photosensitive resin layer is mixed with a solvent dissolved therein to form a uniform solution, which is first applied onto a support layer by a bar coater or a roll coater, and then dried. By removing the solvent, a photosensitive resin layer containing the photosensitive resin composition can be laminated on the support layer. Then, a protective layer is laminated on the photosensitive resin layer as needed, thereby making it possible Photosensitive resin laminate.

<Method of Forming Resist Pattern>

Next, an example of a method of producing a resist pattern using the photosensitive resin laminate of the present embodiment will be described. The method may include the steps of laminating a photosensitive resin layer on a substrate, exposing the photosensitive resin layer of the photosensitive resin laminate, and developing the unexposed portion of the photosensitive resin layer. The development step of removal. Examples of the resist pattern include a printed wiring board, a semiconductor element, a printing plate, a liquid crystal display panel, a flexible substrate, a lead frame substrate, a COF (Chip On Film) substrate, and a semiconductor package substrate. A transparent electrode for liquid crystal, a TFT for liquid crystal (Thin Film Transistor), a PDP (Plasma Display Panel) electrode, or the like. As an example, a method of manufacturing a printed wiring board will be described below.

The printed wiring board is manufactured through the following steps.

(1) Lamination step

In the present step, the photosensitive resin laminate is adhered to a substrate such as a copper foil laminate or a flexible substrate by using a hot roll laminator while peeling off the protective layer of the photosensitive resin laminate (in the case of a protective layer). .

(2) Exposure step

In this step, the photosensitive resin layer is exposed by the following exposure method: an exposure method in which a mask film having a desired wiring pattern is adhered to the support layer and an active light source is used, and the desired wiring pattern is utilized. An exposure method for directly drawing a pattern or an exposure method for projecting an image of a reticle through a lens. The advantage of the photosensitive resin composition of the embodiment is more remarkable in an exposure method using a direct drawing of a drawing pattern or an exposure method in which an image of a mask is projected through a lens, in an exposure method using a direct drawing of a drawing pattern. Especially remarkable.

(3) Development step

In this step, after the exposure, the support layer on the photosensitive resin layer is peeled off, and then the unexposed portion is developed and removed using a developing solution of an alkaline aqueous solution, whereby a resist pattern is 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 depending on the characteristics of the photosensitive resin layer, and is preferably a Na ₂ CO ₃ aqueous solution having a concentration of from about 0.2% by mass to about 2% by mass and from about 20 ° C to about 40 ° C.

A resist pattern can be obtained through each of the above steps (1) to (3). After the steps, depending on the case, a heating step of about 100 ° C to about 300 ° C may be further carried out. By performing this heating step, the chemical resistance can be further improved. When heating, a heating furnace of hot air, infrared rays or far infrared rays can be used.

(4) etching step or plating step

A conductor pattern is produced by etching or plating a surface of a substrate exposed by development (for example, a copper surface of a copper foil laminate).

(5) Stripping step

Thereafter, the resist pattern is peeled off from the substrate by an aqueous solution having a more alkaline solution than the developer. The alkaline aqueous solution for peeling is not particularly limited, and is preferably an aqueous solution of NaOH or KOH having a concentration of about 2% by mass to about 5% by mass and a temperature of about 40 to about 70 °C. A small amount of a water-soluble solvent may also be added to the stripping solution.

The photosensitive resin layering system of the present embodiment is suitable for producing a printed wiring board, a flexible substrate, a lead frame substrate, a COF substrate, a semiconductor package substrate, a liquid crystal transparent electrode, a liquid crystal TFT wiring, and a PDP electrode. A patterned photosensitive resin laminate.

Incidentally, the above various parameters are measured by the measurement method of the following examples or by the same method as the above, unless otherwise specified.

[Examples]

Next, the present embodiment will be further specifically described by way of examples and comparative examples. Of course However, the present embodiment is not limited to the following examples as long as the gist of the present invention is not removed. The physical properties in the examples were determined by the following methods.

<sensitivity evaluation>

First, a 0.4 mm-thick copper foil laminate having a laminated copper foil of 35 μm laminated was spray-brushed using a polishing material (manufactured by Carlit, Japan, Saku random R (registered trademark #220)) at a spray pressure of 0.2 MPa.

Next, the polyethylene film (protective layer) of the photosensitive resin laminate was peeled off, and the laminate was preheated to 60 ° C on a copper foil laminate, and was manufactured by Asahi Kasei Co., Ltd., AL- 700) The photosensitive resin laminate was laminated at a roll temperature of 105 °C. The air pressure was set to 0.35 MPa, and the laminating speed was set to 1.5 m/min.

Then, by a direct delineation exposure apparatus (manufactured by Orbotech Co., Ltd., Paragon-Ultra 100), a 21-stage stage exposure meter manufactured by Stauffer was used as a mask, and exposure was performed at various exposure amounts. At this time, the position of the focus at the time of exposure is focused on the surface of the substrate.

Further, after the polyethylene terephthalate film (support layer) was peeled off, an alkali developing machine (manufactured by Fuji Machine Co., Ltd., a dry film developing machine) was used to spray a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C for a specific period of time. The unexposed portion of the photosensitive resin layer was dissolved and removed by twice the minimum development time. At this time, the minimum time required to completely dissolve the photosensitive resin layer of the unexposed portion was taken as the minimum development time.

A hardened resist pattern is obtained by the above operation. The amount of exposure of the residual film limit level after development was determined to be 7 steps.

<resolution evaluation (usual)>

First, a 0.4 mm-thick copper foil laminate having a laminated copper foil of 35 μm laminated was spray-brushed using a polishing material (manufactured by Carlit, Japan, Saku random R (registered trademark #220)) at a spray pressure of 0.2 MPa.

Then, the polyethylene film (protective layer) of the photosensitive resin laminate was peeled off from the copper foil laminate which was preheated to 60 ° C by a hot roll laminator (Asahi Kasei Co., Ltd.) Manufacture, AL-700) A photosensitive resin laminate was laminated at a roll temperature of 105 °C. The air pressure was set to 0.35 MPa, and the laminating speed was set to 1.5 m/min.

Then, the pattern in which the unexposed portion was a line (gap) was exposed by a direct drawing exposure apparatus (manufactured by Orbotech Co., Ltd., Paragon-Ultra 100). At this time, the exposure was performed by exposing the above-mentioned Stauffer 21-stage staged exposure meter as a mask to an exposure amount in which the highest residual film level was 7 steps. At this time, the position of the focus at the time of exposure is focused on the surface of the substrate. Further, after the polyethylene terephthalate film (support layer) was peeled off, development was carried out at a development time twice as long as the minimum development time. At this time, the value of the minimum line width of the line and the gap in which the unexposed portion is normally formed is taken as the pattern resolution a.

In the present invention, the minimum time required to completely dissolve the photosensitive resin layer of the unexposed portion is taken as the minimum development time. Further, in the hardened resist pattern, no resist remains on the surface of the unexposed portion of the substrate, and the surface of the substrate appears, and there is no protrusion of the resist component and the linearity of the line as the hardened resist is drawn. The minimum line width which was also good and the hardened resists were not closely bonded to each other and were normally formed was evaluated. As a value of the resolution, a drawing pattern obtained by using 30 μm or less in units of 2 μm and 30 μm or more in units of 5 μm is used for exposure.

<resolution evaluation (focus shift)>

The position of the focus at the time of exposure was shifted from the substrate surface to the inside of the substrate by 300 μm in the thickness direction of the substrate. Except for this, the operation is performed in the same manner as the above-described resolution evaluation (usually). At this time, the value of the minimum line width of the line (gap) in which the unexposed portion is normally formed is taken as the pattern resolution b.

<difference in resolution>

The difference in resolution when the position of the focus at the time of exposure is focused on the surface of the substrate and the position of the focus at the time of exposure is shifted by 300 μm from the substrate surface is determined by the above-mentioned <resolution evaluation (focus shift) pattern The value of the resolution b is obtained by subtracting the value of the pattern resolution a of the <resolution evaluation (normal)>.

<difference in gap width>

First, a 0.4 mm-thick copper foil laminate having a laminated copper foil of 35 μm laminated was spray-brushed using a polishing material (manufactured by Carlit, Japan, Saku random R (registered trademark #220)) at a spray pressure of 0.2 MPa.

Next, the polyethylene film (protective layer) of the photosensitive resin laminate was peeled off, and the laminate was preheated to 60 ° C on a copper foil laminate, and was manufactured by Asahi Kasei Co., Ltd., AL- 700) The photosensitive resin laminate was laminated at a roll temperature of 105 °C. The air pressure was set to 0.35 MPa, and the laminating speed was set to 1.5 m/min.

Next, the pattern of each of the exposed portion and the unexposed portion was formed to have a ratio of 2:1 by a direct drawing exposure apparatus (manufactured by Orbotech Co., Ltd., Paragon-Ultra 100). At this time, the exposure was performed by exposing the above-mentioned Stauffer 21-stage staged exposure meter as a mask to an exposure amount in which the highest residual film level was 7 steps. Further, after the polyethylene terephthalate film (support layer) was peeled off, development was carried out at a development time twice as long as the minimum development time. The width of the line (gap) of the unexposed portion in the obtained pattern was 40 μm wide, and the gap width was measured by a microscope. For the sample of each laminated body, the case where the position of the focus at the time of exposure is focused on the surface of the substrate, and the case where the position of the focus at the time of exposure is shifted from the substrate surface to the inside of the substrate by 300 μm in the thickness direction of the substrate Pattern formation.

The difference in the gap width when the position of the focus at the time of exposure is focused on the surface of the substrate and the position of the focus at the time of exposure is shifted from the substrate surface by 300 μm is achieved by focusing the position of the focus at the time of exposure on the surface of the substrate. The gap width was obtained by subtracting the gap width when the position of the focus at the time of exposure was shifted from the substrate surface to the inside of the substrate by 300 μm.

<weight average molecular weight>

Gel permeation chromatography (GPC) manufactured by Japan Spectroscopic Co., Ltd. [Pump: Gulliver, PU-1580, column: Shodex (registered trademark) manufactured by Showa Denko (share) (KF-807, KF- 806M, KF-806M, KF-802.5) 4 in series, moving layer solvent: tetrahydrofuran, The weight average molecular weight was determined as a polystyrene-converted value using a calibration curve obtained from a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.).

<Reaction rate constant with peroxy radicals>

According to the method described in J. Macromol. Sci. Chem., A11 (10), p1975 (1977).

<γ value (gamma value) obtained from the residual film rate>

First, a 0.4 mm-thick copper foil laminate having a laminated copper foil of 35 μm laminated was spray-brushed using a polishing material (manufactured by Carlit, Japan, Saku random R (registered trademark #220)) at a spray pressure of 0.2 MPa.

Next, the polyethylene film (protective layer) of the photosensitive resin laminate was peeled off, and the laminate was preheated to 60 ° C on a copper foil laminate, and was manufactured by Asahi Kasei Co., Ltd., AL- 700) The photosensitive resin laminate was laminated at a roll temperature of 105 °C. The air pressure was set to 0.35 MPa, and the laminating speed was set to 1.5 m/min.

Next, a direct-drawing type exposure apparatus (manufactured by Orbotech Co., Ltd., Paragon-Ultra 100) was used as a mask by a 41-stage stage exposure meter manufactured by Stauffer, and exposure was performed at various exposure amounts. At this time, the position of the focus at the time of exposure is focused on the surface of the substrate.

Further, after the polyethylene terephthalate film (support layer) was peeled off, an aqueous solution of 1% by mass Na ₂ CO _{3 at} 30 ° C was sprayed for a predetermined time using an alkaline developing machine (manufactured by Fuji Machine Co., Ltd., a dry film developing machine). The unexposed portion of the photosensitive resin layer was dissolved and removed by twice the minimum development time.

The film thickness of the hardened resist pattern obtained by the above operation was measured by a surface roughness measuring machine (manufactured by Tokyo Seiko Co., Ltd., SURFCOM 575A), and the residual film ratio was determined from the film thickness. Further, the substantial exposure amount was calculated from the exposure amount and the transmittance of the 41-stage stage exposure meter manufactured by Stauffer. The γ value was obtained from the residual film ratio and the substantial exposure amount. In addition, the calculation method of the gamma value can be obtained by the method described in "The photosensitive resin is learned from the beginning, P.60, Ikeda Akiko, Mizuno, and the industrial investigation meeting".

<γ value (gamma value) obtained from the reaction rate of the C=C double bond>

From the side of the polyethylene terephthalate film (support layer) of the photosensitive resin laminate, a 41-stage stage exposure meter was prepared by Stauffer by a direct drawing exposure apparatus (Orragon Co., Paragon-Ultra 100). As a mask, exposure is performed at various exposure amounts. At this time, the position of the focus at the time of exposure is focused on the bottom of the resist.

The reaction rate of the C=C double bond of the hardened resist pattern obtained by the above operation was determined by FT-IR (manufactured by Thermo SCIENTIFIC, NICOLET 380). Further, the C=C double bond system measures the peak height of 810 cm ^-1 . Further, the substantial exposure amount was calculated from the exposure amount and the transmittance of the 41-stage stage exposure meter manufactured by Stauffer. The γ value was obtained from the reaction rate of the C=C double bond and the substantial exposure amount. Furthermore, the calculation method of the γ value is the same as described above.

<Hue phase stability of photosensitive resin composition blending liquid>

The transmittance of the photosensitive resin laminate at 600 nm and 630 nm was measured by using an ultraviolet-visible (UV-Vis) measuring device (manufactured by Hitachi Hitachi High-Tech Co., Ltd., U-3010 spectrophotometer) as follows:

(i) The polyethylene film of the photosensitive resin laminate was peeled off and the transmittance at 600 nm and 630 nm was measured.

(ii) A photosensitive resin laminate was prepared by using a photosensitive resin composition preparation liquid which was stored at 40 ° C for 3 days, and the polyethylene film of the photosensitive resin laminate was peeled off, and the transmittances at 600 nm and 630 nm were measured.

The change in hue is obtained by calculation of the transmittance of (ii) penetration rate - (i).

[Examples 1 to 11 and Comparative Examples 1 to 15]

The photosensitive resin composition and the solvent (methyl ethyl ketone and ethanol) which have the composition shown in Tables 1 and 2 (the number of each component shows the compounding amount (mass part) as a solid content component) are fully stirred, The mixture was mixed to obtain a photosensitive resin composition-containing solution (a solution in which the photosensitive resin composition was 55% by mass). A 16 μm thick polyethylene terephthalate film (manufactured by Teijin DuPont Film Co., Ltd., GR-16) was prepared as a support layer, and a bar coater was used on the surface of the film. The photosensitive resin composition conditioning liquid was uniformly applied, and dried in a dryer at 95 ° C for 4 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 35 μm.

Then, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-18) which adhered to a protective layer on the surface of the uncovered polyethylene terephthalate film of the photosensitive resin layer was obtained to obtain a photosensitive resin. Laminated body. Various evaluations were performed on the obtained photosensitive resin laminate. The results are also shown in Table 1. Further, the result of the difference in the gap width was -5.9 μm in Example 1, -5.2 μm in Example 3, -5.6 μm in Example 4, and -6.0 μm in Example 5, in comparison. In Example 1, it was -7.5 μm, and in Comparative Example 2, it was -9.5 μm. Further, the result of the γ value (gamma value) obtained from the residual film ratio was 1.3 in Example 4 and 0.6 in Example 5. The γ value (gamma value) obtained from the reaction rate of the C=C double bond was 0.192 in Example 3 and 0.177 in Comparative Example 1.

The circuit pattern of L/S = 60/60 μm by etching was repeated eight times, and lamination was attempted, and the undulation of the outermost surface was about 30 μm. In the circuit pattern on the outermost surface at this time, in the case of the composition of Comparative Example 1, a short circuit of the copper wire was observed, and in the case of the composition of Example 3, no short circuit was observed, and it was presumed that the defect was reduced.

[Embodiment 12]

H-1 (1 part by mass) of Example 1 shown in Table 1 was changed to 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane (with The reaction rate constant of the peroxide radical = 45.4 L ‧ mol ^-1 ‧ sec ^-1 ) (1 part by mass) was set to be the same as in Example 1. As a result, the sensitivity (required exposure amount) was 21 mJ/cm ² , the resolution (usually) was 18 μm, the resolution (focus shift) was 30 μm, and the difference in resolution was 12 μm.

[Comparative Example 16]

The same procedure as in Example 1 was carried out except that H-1 (1 part by mass) of Example 1 shown in Table 1 was changed to H-4 (1 part by mass). As a result, the sensitivity (required exposure amount) was 80 mJ/cm ² and the resolution (usually) was 45 μm.

As a result of the hue stability of the photosensitive resin composition blending solution, in Example 1. 1% at 600nm, 5% at 630nm, 0% at 600nm in Example 3, 5% at 630nm, 2% at 600nm in Example 12, 7% at 630nm, and 600nm in Comparative Example 1 It is 0%, 5% at 630 nm, -21% at 600 nm in Comparative Example 2, 3% at 630 nm, 5% at 600 nm in Comparative Example 8, 11% at 630 nm, and 600% at 630 nm in Comparative Example 9. 11%, 27% at 630 nm, -41% at 600 nm in Comparative Example 16, and -8% at 630 nm. With respect to Comparative Examples 13, 14, and 15, the discoloration was extremely large at the time point of the usual (i) transmittance, and therefore, the transmittance of (ii) - the transmittance of (i) of Comparative Example 1 was calculated. The comparison was found to be 12% at 600 nm in Comparative Example 13 and 30% at 630 nm, 16% at 600 nm in Comparative Example 14, 37% at 630 nm, 16% at 600 nm in Comparative Example 15, and 37 at 630 nm. %.

The following can be read from the results of Tables 1 and 2.

According to the comparison between the examples and the comparative examples, when the photosensitive resin composition of the present embodiment is used, high resolution can be exhibited, and in particular, high resolution can be exhibited even when the focus is shifted during exposure. Furthermore, high sensitivity can be maintained. When the photosensitive resin composition is used, when it is applied to a multilayer wiring, the short-circuit problem can be suppressed when a circuit is formed by an etching method.

[Industrial availability]

The photosensitive resin laminate of the present embodiment can exhibit high sensitivity and high resolution, and can exhibit high resolution even when the focus is shifted during exposure. Therefore, even if the substrate is warped and deformed, the exposure device is set. When the position of the focus at the time of exposure is shifted from the surface of the substrate due to defects or the like, the short circuit problem can be prevented when the circuit is formed by the etching method, and defects such as defects, disconnection, plating failure, and the like can be prevented when the circuit is formed by the plating method. . Therefore, the photosensitive resin laminate can be preferably used for manufacturing a printed wiring board, a flexible substrate, and a lead frame base. A conductor pattern such as a plate, a COF (Chip On Film) substrate, a semiconductor package substrate, a liquid crystal transparent electrode, a liquid crystal TFT wiring, or a PDP (Plasma Display Panel) electrode.

Claims (14)

A photosensitive resin composition containing (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a phenol derivative, The photosensitive resin composition contains the above-mentioned (A) alkali-soluble polymer: 10% by mass to 90% by mass based on the total solid content of the photosensitive resin composition, and the (B) has an ethylenically unsaturated double bond. The compound: 5 mass% to 70 mass%, the above (C) photopolymerization initiator: 0.01% by mass to 20% by mass, and the above (D) phenol derivative: 0.001% by mass to 10% by mass; and the above (C) The photopolymerization initiator contains an acridine, and the (D) phenol derivative contains a compound having a reaction rate constant with a peroxy radical of 20 Lmol ^-1 ‧ sec ^-1 or more. The photosensitive resin composition of claim 1, wherein a resist pattern obtained by forming a photosensitive resin layer containing the photosensitive resin composition on the surface of the substrate and performing exposure and development is focused on the focus position The pattern resolution a at the time of the exposure of the substrate surface, and the difference in the pattern resolution b when the focus position is focused on the substrate from the substrate in the thickness direction of the substrate by 300 μm and the exposure is performed. Up to 15μm. The photosensitive resin composition of claim 1, which comprises a compound represented by the following formula (I) as (D) a phenol derivative: Wherein R ¹ represents a linear alkyl group which may be substituted, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group which mediates a divalent linking group, a branched alkyl group which mediates a divalent linking group, and an intermediate divalent group The aryl group of the cyclohexyl group or the intermediate divalent linking group of the linking group, the plurality of R ^{1 's} may be the same or different from each other, m represents an integer of 0 to 4, n represents an integer of 1 or more, and when n is 1, A is a The valence organic group, when n is 2 or more, A represents a divalent or higher organic group, a single bond or a linking group containing a conjugated bond}. The photosensitive resin composition of claim 3, wherein n in the above formula (I) is 2 or more. The photosensitive resin composition of claim 1, which comprises a compound represented by the following formula (II) as (D) a phenol derivative: Wherein R ² represents a linear alkyl group which may be substituted, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group which mediates a divalent linking group, a branched alkyl group which mediates a divalent linking group, and an intermediate divalent group An aryl group of a cyclohexyl group or an intermediate divalent linking group, and each of R ³ , R ⁴ and R ⁵ independently represents hydrogen or a substituted linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, or an intermediate a linear alkyl group of a valent linking group, a branched alkyl group of an intermediate divalent linking group, a cyclohexyl group of an intermediate divalent linking group or an aryl group of an intermediate divalent linking group}. The photosensitive resin composition of claim 1, which comprises a compound represented by the following formula (III) as (D) a phenol derivative: Wherein R ⁶ and R ⁷ each independently represent a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group having an intermediate divalent linking group, and a branched alkyl group intervening a divalent linking group; a plurality of R ⁶ and R ⁷ may be the same or different from each other, and p and q each independently represent an integer of 0 to 4, and B represents a single group. A bond or a linker containing a conjugate bond}. The photosensitive resin composition of claim 6, wherein in the above formula (III), B is a single bond. The photosensitive resin composition of claim 6, wherein in the above formula (III), p = q = 0. The photosensitive resin composition according to any one of claims 1 to 8, wherein the monomer component of the (A) alkali-soluble polymer has an aromatic hydrocarbon group. A photosensitive resin laminate which is obtained by laminating a photosensitive resin layer containing the photosensitive resin composition according to any one of claims 1 to 9 on a support layer. A method for forming a resist pattern, comprising: a step of laminating a photosensitive resin laminated layer on a substrate according to claim 10; an exposing step of exposing the photosensitive resin layer of the photosensitive resin laminate; and The developing step of developing and removing the unexposed portion of the photosensitive resin layer. The method of forming a resist pattern according to claim 11, wherein the exposing step is performed by an exposure method using a direct drawing of a drawing pattern or an exposure method of projecting an image of the mask through a lens. The method of forming a resist pattern of claim 12, wherein the exposing step is performed by an exposure method using direct drawing of a drawing pattern. The photosensitive resin composition according to any one of claims 1 to 8, which is used in a method of forming a resist pattern by performing an exposure step by an exposure method directly drawing a drawing pattern.