Photosensitive resin composition and photosensitive element

Abstract

The photosensitive resin composition comprises an alkali-soluble polymer, a compound having an ethylenically unsaturated double bond, a photopolymerization initiator, and the following general formula (1): {wherein, R 1 and R 2 Each independently selected from the group consisting of organic groups having 1 to 20 carbon atoms, excluding an azo group.} is a compound represented by

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a lamination method, a method for producing a conductive pattern, and the like. Background Art

[0002] In the past, printed circuit boards were usually manufactured by photolithography. In the photolithography method, first, a photosensitive resin layer stacked on a substrate such as a copper-clad laminate or a flexible substrate is subjected to pattern exposure. The exposed portion of the photosensitive resin layer is polymerized and cured (in the case of a negative type) or is soluble in a developer (in the case of a positive type). Next, the unexposed portion (in the case of a negative type) or the exposed portion (in the case of a positive type) is removed using a developer to form a resist pattern on the substrate. Furthermore, etching or plating is performed to form a conductor pattern, and then the cured resist pattern (hereinafter also referred to as a "resist pattern") is peeled off and removed from the substrate. By going through these steps, a conductor pattern is formed on the substrate.

[0003] Conductor patterning processes based on etching or plating are generally divided into two types. The first method is to etch away the substrate surface not covered by the resist pattern (e.g., the copper surface of a copper-clad laminate), and then remove the resist pattern portion with an alkaline aqueous solution that is more alkaline than the developer. The second method is to plate the substrate surface with copper, solder, nickel, or tin, and then similarly remove the resist pattern portion and etch the exposed substrate surface (plating method). In either case, etching uses copper chloride, ferric chloride, copper ammonia complex solutions, etc.

[0004] Typically, a photosensitive resin layer is formed in photolithography by applying a solution of a photosensitive resin composition to a substrate and drying it, or by laminating a photosensitive resin layer of a dry film resist (a photosensitive resin laminate in which a photosensitive resin layer formed from a photosensitive resin composition is laminated on a support) onto the substrate. Furthermore, substrates having various external shapes (e.g., flat, concave-convex, non-flat, grooved, or pre-formed lines / spaces) are also used in photolithography.

[0005] In recent years, in order to cope with the increasing fineness and density of printed circuit boards, DLP (Digital Light Processing) exposure methods have been studied as laser direct writing (DI) methods, which can form finer patterns than before, and photosensitive resin compositions for DLP have also been studied (Patent Document 1).

[0006] In addition, the use of nitrogen-containing compounds such as pyridine compounds or cyanides (Patent Document 2) and base generators synthesized starting from 2-(2-hydroxyphenyl)-1H-benzimidazole (Patent Document 3) for improving photosensitivity in the composition of photosensitive resin compositions has been studied.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: International Publication No. 2009 / 133817

[0010] Patent Document 2: Japanese Patent Application Laid-Open No. 2005-309384

[0011] Patent Document 3: Japanese Patent Application Publication No. 2015-075551 Summary of the Invention

[0012] Problems to be solved by the invention

[0013] In the above-described photolithography method, for forming a laminated body composed of a substrate and a dry film resist, when laminating the dry film resist on the substrate, there are known methods such as a method of laminating in the absence of a liquid (so-called "dry lamination"), a method of using a liquid between the substrate and the dry film resist to fill the gap between the substrate and the dry film resist with the liquid (so-called "wet lamination"), and a method of laminating under a gas pressure lower than atmospheric pressure (so-called "vacuum lamination").

[0014] Among them, the followability and adhesion of the resist to the substrate during vacuum lamination are required. In particular, achieving both the followability of the resist to height differences when laminating the resist on the substrate and the adhesion to the copper (Cu) substrate when the substrate is a Cu substrate is an important issue.

[0015] However, the photosensitive resin compositions and resist materials obtained therefrom described in Patent Documents 1 to 3 do not focus on the behavior during vacuum lamination.

[0016] Therefore, an object of the present invention is to provide a photosensitive resin composition capable of achieving both conformability to a substrate and adhesion, and a photosensitive element, a lamination method, and a method for producing a conductive pattern using the same.

[0017] Solutions for solving problems

[0018] The present inventors have discovered that the above-mentioned problems can be solved by the following technical means. [1]

[0020] A photosensitive resin composition comprising:

[0021] (A) Alkali-soluble polymer;

[0022] (B) a compound having an ethylenically unsaturated double bond;

[0023] (C) a photopolymerization initiator; and

[0024] (D) A compound represented by the following general formula (1).

[0025]

[0026] {where R 1 and R 2 Each independently selected from the group consisting of monovalent organic groups having 1 to 20 carbon atoms, excluding an azo group. [2]

[0028] The photosensitive resin composition according to item [1], wherein the compound (D) is solid at 25°C. [3]

[0030] The photosensitive resin composition according to item [1] or [2], wherein the molecular weight of the compound (D) is 100 g / mol or more and 250 g / mol or less. [4]

[0032] The photosensitive resin composition according to any one of items [1] to [3], wherein the compound (D) is contained in an amount of 0.0001% by mass to 0.0150% by mass based on the total amount of solid content of the photosensitive resin composition. [5]

[0034] The photosensitive resin composition according to any one of items [1] to [4], wherein the compound (D) is contained in an amount of 0.0001% by mass to 0.0100% by mass based on the total amount of solid content of the photosensitive resin composition. [6]

[0036] The photosensitive resin composition according to any one of items [1] to [5], wherein the compound (D) is contained in an amount of 0.0001% by mass to 0.0050% by mass based on the total amount of solid content of the photosensitive resin composition. [7]

[0038] The photosensitive resin composition according to any one of items [1] to [6], wherein the compound (D) is a compound represented by the following general formula (2A).

[0039]

[0040] {where R 1 is a monovalent organic group having 1 to 20 carbon atoms and excluding an azo group, and R 3 It is a monovalent organic group having 1 to 19 carbon atoms and excluding an azo group. [8]

[0042] A photosensitive element comprising a support and a layer formed on the support and composed of the photosensitive resin composition according to any one of items [1] to [7]. [9]

[0044] The photosensitive element according to Item [8], which is a dry film resist.

[10]

[0046] A method of laminating the photosensitive element according to item [8] or [9] on a substrate under a pressure lower than atmospheric pressure.

[11]

[0048] A method for manufacturing a conductor pattern, comprising:

[0049] A step of laminating the photosensitive element according to item [8] or [9] on a substrate at a pressure lower than atmospheric pressure.

[0050] Effects of the Invention

[0051] According to the present invention, it is possible to achieve both conformability and adhesion to the substrate during lamination of the resist material and the substrate, and to provide a photosensitive element and a conductor pattern that achieve both conformability and adhesion. Furthermore, according to the present invention, it is possible to achieve both conformability to height differences and adhesion to the Cu substrate, particularly during vacuum lamination. DETAILED DESCRIPTION

[0052] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit and scope of the present invention.

[0053] <Photosensitive resin composition>

[0054] One embodiment of the present invention is a photosensitive resin composition. The photosensitive resin composition can be used in photolithography or in the production of photosensitive elements such as dry film resists.

[0055] In one embodiment of the present invention, the photosensitive resin composition contains (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated double bond; (C) a photopolymerization initiator; and (D) a compound represented by the following general formula (1).

[0056]

[0057] {where R 1 and R 2 Each independently selected from the group consisting of monovalent organic groups having 1 to 20 carbon atoms, excluding an azo group.

[0058] If necessary, the photosensitive resin composition may further contain various additives such as a color-changing agent, a dye, a plasticizer, an antioxidant, an organic halogen compound, a nonionic surfactant, a crosslinking agent, and a stabilizer.

[0059] In addition to forming resist materials, such as dry film resists, photosensitive resin compositions can also be used for lamination with substrates, exposure using a photomask or exposure using a direct drawing device without a photomask (direct imaging exposure), and formation of conductive patterns by development. The components of the photosensitive resin composition are described below.

[0060] (A) Alkali-soluble polymer

[0061] From the perspective of alkali solubility, the alkali-soluble polymer (A) preferably contains a carboxyl group, and from the perspective of developability and releasability, preferably contains a hydroxyl group. Typically, the alkali-soluble polymer (A) is a thermoplastic copolymer containing a carboxyl group-containing monomer as a copolymerization component, having a carboxyl group content of 100 to 600 in acid equivalent and a weight-average molecular weight of 5,000 to 500,000.

[0062] In order to make the photosensitive resin composition developable and releasable to a developer and a stripping solution formed by an alkaline aqueous solution, a carboxyl group in the (A) alkali-soluble polymer is necessary. The acid equivalent is preferably 100 to 600, and more preferably 250 to 450. From the viewpoint of ensuring compatibility with the solvent or other components in the photosensitive resin composition, especially the (b) addition polymerizable monomer described later, it is preferably 100 or more. In addition, from the viewpoint of maintaining developability and strippability, it is preferably 600 or less. Here, the acid equivalent refers to the mass (gram) of the thermoplastic copolymer having 1 equivalent of carboxyl groups. It should be noted that the acid equivalent is determined by potentiometric titration using a titrator (e.g., Hiranuma automatic titrator (COM-555)) with a 0.1 mol / L NaOH aqueous solution.

[0063] The weight-average molecular weight of the thermoplastic copolymer is preferably 5,000 to 500,000. To maintain uniform thickness of the dry film resist and achieve developer resistance, a weight-average molecular weight of 5,000 or higher is preferred. To maintain developability, a weight-average molecular weight of 500,000 or lower is preferred. More preferably, the weight-average molecular weight is 20,000 to 100,000. The conditions for measuring the weight-average molecular weight are described in detail in the following examples.

[0064] The thermoplastic copolymer is preferably obtained by copolymerizing a copolymerization component consisting of one or more first monomers described below and one or more second monomers described below.

[0065] The first monomer is a monomer containing a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half esters. Among these, (meth)acrylic acid is particularly preferred. Here, (meth)acrylic acid refers to acrylic acid or methacrylic acid. The same applies hereinafter.

[0066] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, esters of vinyl alcohol such as vinyl acetate, (meth)acrylonitrile, styrene, and polymerizable styrene derivatives. Among these, methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, and benzyl (meth)acrylate are particularly preferred.

[0067] The amount of the alkali-soluble polymer (A) contained in the photosensitive resin composition according to the present embodiment (this amount is relative to the total solid content of the photosensitive resin composition. Hereinafter, the same applies to the content of each component except for cases where it is particularly limited) is preferably 35% by mass or more from the viewpoint of developability, more preferably 40% to 70% by mass from the viewpoint of balancing alkali developability and viscosity, and further preferably 40% to 60% by mass, 41% to 58% by mass, 42% to 57% by mass, or 43% to 56% by mass.

[0068] (B) Compounds having ethylenically unsaturated double bonds

[0069] (B) The compound having an ethylenically unsaturated double bond can be polymerizable by having an ethylenically unsaturated double bond in its structure. From the viewpoint of addition polymerizability, the ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.

[0070] (B) The compound having an ethylenically unsaturated double bond may include at least one selected from the group consisting of the following (b1) to (b8).

[0071] (b1) Ethylene glycol di(meth)acrylate compound represented by the following general formula (I)

[0072]

[0073] {wherein, R1 and R2 each independently represent a hydrogen atom or a methyl group, and m1 is a number satisfying 2 to 40.};

[0074] (b2) Alkylene oxide-modified bisphenol A di(meth)acrylate compound represented by the following general formula (II)

[0075]

[0076] {wherein, R3 and R4 each independently represent a hydrogen atom or a methyl group, A is C2H4, B is C3H6, n1, n2, n3, and n4 are integers satisfying the relationship n1+n2+n3+n4=2 to 50, and the arrangement of the repeating units of -(AO)- and -(BO)- may be random or block. In the case of a block arrangement, either -(AO)- or -(BO)- may be on the bisphenol group side.};

[0077] (b3) a tri(meth)acrylate compound represented by the following general formula (III)

[0078]

[0079] {wherein, R5 to R7 each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, m2, m3, and m4 each independently represent an integer of 0 to 40, m2+m3+m4 is 1 to 40, and when m2+m3+m4 is 2 or more, multiple Xs may be the same or different};

[0080] (b4) a polyurethane di(meth)acrylate compound represented by the following general formula (IV)

[0081]

[0082] {wherein, R8 and R9 each independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, and s and t each independently represent an integer of 0 to 40, and s+t≥1};

[0083] (b5) Hexa(meth)acrylate compound represented by the following general formula (V)

[0084]

[0085] {wherein, R each independently represents a hydrogen atom or a methyl group, and n is an integer from 0 to 30, and the total value of all n is 1 or greater.};

[0086] (b6) Phthalate compound represented by the following general formula (VI)

[0087]

[0088] {wherein, A represents C2H4, R 61 represents a hydrogen atom or a methyl group, R 62represents a hydrogen atom, a methyl group or a halogenated methyl group, R 63 represents an alkyl group having 1 to 6 carbon atoms, a halogen atom or a hydroxyl group, a is an integer of 1 to 4, k is an integer of 0 to 4, and k is an integer of 2 or more, multiple R 63 can be the same or different};

[0089] (b7) Epoxy (meth)acrylate compound represented by the following formula (VII)

[0090]

[0091] {wherein, R3 and R4 each independently represent a hydrogen atom or a methyl group.}; and

[0092] (b8) Addition polymerizable monomers other than the above-mentioned (b1) to (b7).

[0093] Among the above-described (b1) to (b8), it is preferred that the composition contains at least one compound selected from the group consisting of the component (b2), the component (b3), and the component (b5), from the viewpoint of the resolution and releasability of the resist pattern.

[0094] From the viewpoint of adjusting the peeling time of the resist pattern and the size of the peelable sheet, the compound (B) having an ethylenically unsaturated double bond preferably includes an ethylene glycol di(meth)acrylate compound (b1) represented by the general formula (I).

[0095] In general formula (I), m1 is preferably 2 or greater from the viewpoint of peeling time and peeling sheet size, preferably 20 or greater from the viewpoint of short-circuit suppression after the etching process, and preferably 40 or less from the viewpoint of resolution, plating resistance, and etching resistance. In photolithography including vacuum lamination, from the viewpoint of resist pattern developability or resolution, m1 is preferably 2 to 29, 4 to 20, or 6 to 15.

[0096] Specific examples of the ethylene glycol di(meth)acrylate compound represented by the general formula (I) include tetraethylene glycol di(meth)acrylate with m1=4, nonaethylene glycol di(meth)acrylate with m1=9 (for example, in the case of dimethacrylate, the product name "SR610" available from Arkema Co., Ltd.), polyethylene glycol di(meth)acrylate with m1=14, polyethylene glycol di(meth)acrylate with m1=23, polyethylene glycol di(meth)acrylate with m1=30, or polyethylene glycol di(meth)acrylate with m1=40.

[0097] From the perspective of suppressing short circuits after the etching process, the compound (B) having an ethylenically unsaturated double bond preferably includes (b2) an alkylene oxide-modified bisphenol A di(meth)acrylate compound represented by general formula (II). B in general formula (II) can be -CH2CH2CH2- or -CH(CH3)CH2-.

[0098] The hydrogen atoms on the aromatic ring in the general formula (II) may be substituted with heteroatoms and / or substituents. Examples of heteroatoms include halogen atoms. Examples of substituents include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 18 carbon atoms, phenacyl groups, amino groups, alkylamino groups having 1 to 10 carbon atoms, dialkylamino groups having 2 to 20 carbon atoms, nitro groups, cyano groups, carbonyl groups, mercapto groups, alkylmercapto groups having 1 to 10 carbon atoms, aryl groups, hydroxyl groups, hydroxyalkyl groups having 1 to 20 carbon atoms, carboxyl groups, carboxyalkyl groups having 1 to 10 carbon atoms in an alkyl group, acyl groups having 1 to 10 carbon atoms in an alkyl group, alkoxy groups having 1 to 20 carbon atoms, alkoxycarbonyl groups having 1 to 20 carbon atoms, alkylcarbonyl groups having 2 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, N-alkylcarbamoyl groups having 2 to 10 carbon atoms, heterocyclic ring-containing groups, and aryl groups substituted with these substituents. These substituents may form a condensed ring or the hydrogen atoms in these substituents may be substituted with heteroatoms such as halogen atoms. When the aromatic ring in the general formula (II) has multiple substituents, the multiple substituents may be the same or different.

[0099] R3 and R4 in general formula (II) can each independently be a hydrogen atom or a methyl group, but from the perspective of ensuring contrast immediately after exposure of the photosensitive resin layer formed from the photosensitive resin composition, it is preferred that one or both of R3 and R4 are hydrogen atoms, and it is more preferred that both R3 and R4 are hydrogen atoms.

[0100] From the perspective of achieving a balance between suppressing etching short-circuiting defects and achieving high resolution, the alkylene oxide-modified bisphenol A di(meth)acrylate compound represented by general formula (II) (b2) preferably has 10 or more alkylene oxides added thereto. More specifically, in general formula (II), n1, n2, n3, and n4 preferably satisfy the relationship n1+n2+n3+n4=4-50, more preferably n1+n2+n3+n4=6-40, further preferably n1+n2+n3+n4=8-30, and even more preferably n1+n2+n3+n4=10-20.

[0101] In the general formula (II), for n1+n3, from the viewpoint of photosensitivity, developability or resolution in photolithography including vacuum lamination, when the component (b2) forms the (B1) monomer, it is preferably 3 to 30 or 5 to 20, and when the component (b2) forms the (B2) monomer, it is preferably 3 to 30, and more preferably 5 to 20.

[0102] Preferred specific examples of the alkylene oxide-modified bisphenol A type di(meth)acrylate compound represented by the general formula (II) (b2) include polyethylene glycol di(meth)acrylate having an average of 1 mol of ethylene oxide added to each of the two ends of bisphenol A, polyethylene glycol di(meth)acrylate having an average of 2 mol of ethylene oxide added to each of the two ends of bisphenol A (for example, in the case of dimethacrylate, the product name "BLEMMER" available from NOF Corporation) PDBE-200", etc.), di(meth)acrylate of polyethylene glycol with an average of 2 mol of ethylene oxide added to each of the two ends of bisphenol A, di(meth)acrylate of polyethylene glycol with an average of 5 mol of ethylene oxide added to each of the two ends of bisphenol A (for example, in the case of diacrylate, the product name "A-BPE-10" available from Shin-Nakamura Chemical Co., Ltd.; in the case of dimethacrylate, the product name "FA-321" available from Hitachi Chemical Co., Ltd., the product name "BP-321" available from Shin-Nakamura Chemical Co., Ltd. E-500", etc.), di(meth)acrylate of polyethylene glycol with an average of 7 mols of ethylene oxide added to both ends of bisphenol A, di(meth)acrylate of polyalkylene glycol with an average of 6 mols of ethylene oxide and an average of 2 mols of propylene oxide added to both ends of bisphenol A, di(meth)acrylate of polyalkylene glycol with an average of 15 mols of ethylene oxide added to both ends of bisphenol A, di(meth)acrylate of polyalkylene glycol with an average of 15 mols of ethylene oxide and an average of 2 mols of propylene oxide added to both ends of bisphenol A, etc.

[0103] From the perspective of resolution, the compound (B) having an ethylenically unsaturated double bond preferably includes a tri(meth)acrylate compound represented by general formula (III) (b3). X in general formula (III) is an alkylene group having 2 to 6 carbon atoms, such as -CH2CH2-, -CH2CH2CH2-, or -CH(CH3)CH2-. When component (b3) is used as the monomer having an EO unit as described above, at least one of X in general formula (III) has 2 carbon atoms.

[0104] Preferred specific examples of the tri(meth)acrylate compound represented by the general formula (III) (b3) include ethylene oxide (EO)-modified trimethylolpropane tri(meth)acrylate (average EO addition mole number: 2 to 40, 3 to 35, 3 to 20 or 30 to 35), propylene oxide (PO)-modified trimethylolpropane tri(meth)acrylate (average PO addition mole number: 10 to 40), and the like.

[0105] EO-modified trimethylolpropane tri(meth)acrylate having an average EO addition mole number of 3, for example, in the case of triacrylate, may be obtained under the product name "A-TMPT-3EO" available from Shin-Nakamura Chemical Industry Co., Ltd. EO-modified trimethylolpropane tri(meth)acrylate having an average EO addition mole number of 9, for example, in the case of triacrylate, may be obtained under the product name "Miramer M3160" available from Miwon Specialty Chemical Co., Ltd.

[0106] From the viewpoint of resolution, the compound (B) having an ethylenically unsaturated double bond preferably includes a urethane di(meth)acrylate compound (b4) represented by the general formula (IV).

[0107] In the general formula (IV), Z represents a divalent organic group, for example, an alkylene group having 1 to 10 carbon atoms, an alkylene oxide group having 2 to 10 carbon atoms, a divalent alicyclic group having 3 to 10 carbon atoms which may have a substituent, etc. In the general formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, for example, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, etc.

[0108] From the perspective of hole blocking, it is preferred that the -(YO)s- and -(YO)t- portions in general formula (IV) are each independently replaced by -(C2H4O)-(C3H6O)9-. From the perspective of suppressing short circuits after the etching process, it is preferred that s+t=20 to 40 in general formula (IV).

[0109] As preferred specific examples of the polyurethane di(meth)acrylate compound represented by the general formula (IV) (b4), there can be cited addition reaction products of a (meth)acrylic monomer having a hydroxyl group at the β position with a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate and 1,6-hexamethylene diisocyanate, tris((meth)acryloyloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified polyurethane di(meth)acrylate and EO, PO-modified polyurethane di(meth)acrylate. Among them, the urethane compound of hexamethylene diisocyanate and polypropylene glycol mono(meth)acrylate is preferred. It should be noted that EO represents ethylene oxide, and the EO-modified compound has a block structure of ethylene oxide groups. In addition, PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups.

[0110] Examples of EO-modified polyurethane di(meth)acrylates include "UA-11" manufactured by Shin-Nakamura Chemical Co., Ltd. Examples of EO, PO-modified polyurethane di(meth)acrylates include "UA-13" manufactured by Shin-Nakamura Chemical Co., Ltd. These may be used alone or in combination of two or more.

[0111] From the viewpoint of resolution, the compound (B) having an ethylenically unsaturated double bond preferably includes the hexa(meth)acrylate compound (b5) represented by the general formula (V).

[0112] In order to further improve the resolution, in the general formula (V), the average value of all n is preferably 6 or more, or each n is preferably 1 or more. The total value of n in the general formula (V) is preferably 180 or less, and more preferably 30 to 180, 30 to 36, 1 to 29, or 6 to 29, from the viewpoint of photosensitivity, developability, or resolution in photolithography including vacuum lamination.

[0113] Preferred specific examples of the hexa(meth)acrylate compound represented by the general formula (V) (b5) include dipentaerythritol hexa(meth)acrylate, hexa(meth)acrylate obtained by adding a total of 1 to 36 mol of ethylene oxide to the six ends of dipentaerythritol, and hexa(meth)acrylate obtained by adding a total of 1 to 10 mol of ε-caprolactone to the six ends of dipentaerythritol.

[0114] From the perspective of resolution, the compound (B) having an ethylenically unsaturated double bond may include a phthalate compound (b6) represented by the general formula (VI). Examples of the phthalate compound represented by the general formula (VI) include γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate. Among them, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate is preferred. These substances may be used alone or in combination of two or more.

[0115] From the perspective of photosensitivity, developability, and resolution in photolithography including vacuum lamination, the compound (B) having an ethylenically unsaturated double bond preferably includes an epoxy (meth)acrylate compound represented by general formula (VII) (b7). More preferably, component (b7) and trimethylolpropane tri(meth)acrylate, described later as component (b8), are used together. While not wishing to be bound by theory, it is believed that the hydroxyl groups present at sites other than the polymerizable terminals in general formula (VII) of component (b7) contribute to the releasability of the resist pattern.

[0116] The mixing ratio of the component (b7) and the later-described component (b8) trimethylolpropane tri(meth)acrylate is preferably (mass of the component (b7)) / mass of the trimethylolpropane tri(meth)acrylate) = 50 to 80 / 50 to 20, more preferably 55 to 75 / 45 to 25, and even more preferably 60 / 40.

[0117] (B) The compound having an ethylenically unsaturated double bond may contain an addition polymerizable monomer other than the components (b1) to (b7) as the component (b8).

[0118] Component (b8) includes di(meth)acrylates other than components (b1), (b2), and (b7), such as polyalkylene glycol di(meth)acrylates such as polypropylene glycol-polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polybutylene glycol di(meth)acrylate. More specifically, component (b8) includes polyalkylene glycol di(meth)acrylates obtained by adding an average of 3 moles of ethylene oxide to polypropylene glycol to which an average of 12 moles of propylene oxide has been added, and to both ends of the polypropylene glycol.

[0119] In addition, the following substances can be cited as the component (b8):

[0120] Mono(meth)acrylates, such as 4-nonylphenyl-heptaethylene glycol-dipropylene glycol (meth)acrylate (for example, in the case of acrylates, the product name "DISPANOL LS-100A" available from NOF Corporation);

[0121] tri(meth)acrylates other than component (b3), such as trimethylolpropane tri(meth)acrylate (for example, in the case of triacrylates, the product name "A-TMPT" available from Shin-Nakamura Chemical Industry Co., Ltd.), ethoxylated glycerol tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and the like;

[0122] Tetra(meth)acrylates, such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, pentaerythritol (poly)alkoxy tetra(meth)acrylate, etc.;

[0123] Penta(meth)acrylates, such as dipentaerythritol penta(meth)acrylate;

[0124] Compounds obtained by reacting α,β-unsaturated carboxylic acids with polyols; and

[0125] Compounds obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound.

[0126] From the viewpoint of resolution and short-circuit failure suppression after etching, the total amount of all (B) compounds having an ethylenically unsaturated double bond in the photosensitive resin composition is preferably 1% by mass to 49% by mass, more preferably 1% by mass to 44% by mass, 2% by mass to 47% by mass, or 2% by mass to 42% by mass, further preferably 4% by mass to 39% by mass, and particularly preferably 15% by mass to 38% by mass, 20% by mass to 35% by mass, or 30% by mass to 34% by mass.

[0127] (C) Photopolymerization initiator

[0128] The photopolymerization initiator (C) can be any photopolymerization initiator commonly used in the field of photosensitive resins. The amount of the photopolymerization initiator (C) in the photosensitive resin composition is 0.1% to 20% by mass. From the perspective of sensitivity, this amount is 0.1% by mass or more, and from the perspective of resolution, it is 20% by mass or less. The content is preferably 0.1% to 15% by mass, and more preferably 0.9% to 10% by mass. The photopolymerization initiator (C) can be used alone or in combination of two or more.

[0129] In one embodiment of the present invention, the photopolymerization initiator (C) is preferably at least one selected from the group consisting of acridine derivatives, anthracene derivatives, and pyrazoline derivatives. By using at least one selected from the group consisting of acridine derivatives, anthracene derivatives, and pyrazoline derivatives, it is possible to achieve high sensitivity of the photosensitive composition to ultraviolet light, and there is a tendency for the followability and adhesion in the vacuum lamination process to be improved. From this viewpoint, among the photopolymerization initiators (C), acridine derivatives are more preferred. The photopolymerization initiator (C) may include any combination of acridine derivatives, anthracene derivatives, and pyrazoline derivatives, or these derivatives and other photopolymerization initiators may be used simultaneously.

[0130] Examples of acridine derivatives include 9-phenylacridine, 1,6-bis(9-acridyl)hexane, 1,7-bis(9-acridyl)heptane, 1,8-bis(9-acridyl)octane, 1,9-bis(9-acridyl)nonane, 1,10-bis(9-acridyl)decane, 1,11-bis(9-acridyl)undecane, and 1,12-bis(9-acridyl)dodecane. Among them, 9-phenylacridine is preferred.

[0131] From the viewpoint of improving sensitivity and / or resolution and good tracking and adhesion, it is preferred to use the above-mentioned acridine derivative and N-aryl amino acid simultaneously. Examples of N-aryl amino acids include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine, among which N-phenylglycine is preferred.

[0132] In this specification, the term "anthracene derivative" includes both anthracene and compounds derived therefrom. Examples of anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, and 1-chloroanthraquinone.

[0133] Examples of pyrazoline derivatives include 1-phenyl-3-(4-tert-butylphenylphenyl)pyrazoline, 1-(4-(benzoxazol-2-yl)phenyl)-3-(4-tert-butylphenylphenyl)pyrazoline, 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butylphenyl)pyrazoline, and 1-phenyl-3-(4-biphenylyl)-5-(4-tert-octylphenyl)pyrazoline.

[0134] As the (C) photopolymerization initiator that can be used in this embodiment, the above-mentioned derivatives and hexaarylbisimidazole derivatives (hereinafter also referred to as dimers of triarylimidazole derivatives or triarylimidazole dimers) can also be used together. Examples of the triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (hereinafter also referred to as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-bisimidazole), 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylimidazole dimer, 2,4-bis(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)diphenylimidazole dimer, 2,4,5-tris(o-chlorophenyl)diphenylimidazole dimer, 2-(o-chlorophenyl)-bis-4,5- (3,4-dimethoxyphenyl) imidazole dimer, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl) imidazole dimer, 2,2'-bis(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl) imidazole dimer, 2,2'-bis(2,4-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl) imidazole dimer, 2,2'-bis(2,5-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl) imidazole dimer, 2,2'-bis(2,6-difluorophenyl)- 2,2'-bis(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)imidazole dimer, 2,2'-bis(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)imidazole dimer, 2,2'-bis(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)imidazole dimer, 2,2'-bis(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)imidazole dimer The photopolymerization initiator includes 2,2'-bis(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)imidazole dimer, 2,2'-bis(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)imidazole dimer, 2,2'-bis(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)imidazole dimer, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)imidazole dimer. In particular, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is a photopolymerization initiator that has a high effect on resolution and cured film strength and can be preferably used.

[0135] Examples of compounds that can be used as the photopolymerization initiator (C) other than the above include quinones such as 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone; aromatic ketones such as benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], and 4,4'-bis(diethylamino)benzophenone; benzoin ethers such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin; combinations of thioxanthones such as benzyldimethylketal, benzyldiethylketal, and 2,4-diethylthioxanthone with alkylaminobenzoic acid; and oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoin oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime.

[0136] It should be noted that, as the combination of the above-mentioned thioxanthones and alkylaminobenzoic acid, for example, the combination of ethylthioxanthone and ethyl dimethylaminobenzoate, the combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, and the combination of isopropylthioxanthone and ethyl dimethylaminobenzoate can be listed. In addition, the combination of hexaarylbisimidazole derivatives and aromatic ketones is preferred.

[0137] (D) Compound represented by general formula (1)

[0138] The photosensitive resin composition according to one embodiment of the present invention contains a compound represented by the following general formula (1) as the compound (D).

[0139]

[0140] {where R 1 and R 2 Each independently selected from the group consisting of monovalent organic groups having 1 to 20 carbon atoms, excluding an azo group.

[0141] The compound represented by the general formula (1) does not contain an azo group (RN=N-R') but contains a cyano group (-CN). The dipole moment of the C≡N bond in the cyano group of the compound represented by the general formula (1) is large and easily interacts with copper (Cu). Therefore, by simultaneously containing components (A) to (C) and the compound represented by the general formula (1), the photosensitive resin composition can interact with the Cu surface of a copper (Cu) substrate, etc., thereby improving adhesion, and there is a tendency to take into account both the followability and adhesion to the substrate when laminating with the substrate. This tendency is significant when the substrate has a height difference or the substrate contains copper (Cu).

[0142] During lamination of the laminate of the support and photosensitive resin composition onto the substrate, good conformability prevents gaps from forming between the resist material and the substrate, resulting in an advantage in that defects are less likely to occur during the wiring formation step after lamination. Furthermore, better adhesion during lamination also has the advantage of enabling the formation of finer resist patterns.

[0143] The compound represented by general formula (1) is preferably solid at 25°C. It is believed that a compound that is solid at 25°C softens due to heating during lamination with a substrate, exhibiting flexibility, thereby improving its ability to follow the substrate. It should be noted that when the compound represented by general formula (1) is liquid or waxy at 25°C, it is believed that it has no temperature responsiveness during lamination with a substrate.

[0144] As a means for making the compound represented by the general formula (1) solid at 25°C, it is preferred to control the molecular weight of the compound represented by the general formula (1) within an appropriate range, more preferably to control the molecular weight within the range of 100 g / mol to 250 g / mol, and further preferably to control the molecular weight within the range of 111 g / mol to 240 g / mol.

[0145] From the perspective of being solid at 25°C as described above, and from the perspective of the conformability of the photosensitive resin composition or photosensitive element to the substrate, the molecular weight of the compound represented by general formula (1) is preferably 100 g / mol or more and 250 g / mol or less. When the molecular weight is 100 g / mol or more, the compound represented by general formula (1) becomes solid at 25°C, and temperature responsiveness is easily achieved when laminating with the substrate. On the other hand, when the molecular weight is 250 g / mol or less, the softening point of the compound represented by general formula (1) and the photosensitive resin composition containing the same is lowered, thereby easily exhibiting flexibility.

[0146] Furthermore, by including a compound having a molecular weight in the range of 100 g / mol to 250 g / mol, the compound, which is solid at 25°C, softens upon heating during lamination, exhibiting flexibility, thereby tending to improve conformability to the substrate. From this perspective, the molecular weight of the compound represented by general formula (1) is more preferably in the range of 111 g / mol to 240 g / mol.

[0147] Next, the specific structure of the compound represented by the general formula (1) will be described.

[0148] In the general formula (1), R 1 and R 2 Both of them do not contain an azo group (RN = N-R'). Azo groups have the property of decomposing to generate free radicals by heating or light irradiation. Therefore, in the general formula (1), R 1 and R 2At least one of the above-mentioned compounds does not contain an azo group, and an unintended polymerization reaction of the photosensitive resin composition of the present invention during storage or use can be suppressed.

[0149] In the general formula (1), R 1 and R 2 Each independently selected from the group consisting of monovalent organic groups having 1 to 20 carbon atoms and excluding an azo group. 1 and R 2 The number of carbon atoms is preferably 1 to 19 from the viewpoint of adhesion to the substrate and followability during lamination, more preferably 1 to 16, 1 to 14, 1 to 12, 1 to 10, 1 to 9, 1 to 8 or 1 to 7 in the case of a chain group, and more preferably 3 to 19, 3 to 18, 3 to 15, 3 to 12, 3 to 9, 3 to 8, 3 to 7, 6 to 18 or 6 to 12 in the case of a cyclic group.

[0150] The monovalent organic group having 1 to 20 carbon atoms may have a substituent, a heteroatom, or a halogen atom as desired. Examples of the monovalent organic group having 1 to 20 carbon atoms include the following:

[0151] For example, straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl;

[0152] Unsaturated aliphatic hydrocarbon groups such as vinyl, allyl, propenyl, 3-butenyl, 2-butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, pentynyl and hexynyl;

[0153] For example, groups containing heteroatoms such as alkoxy and epoxy groups;

[0154] For example, halogen-containing groups such as mono-, di- or tri-fluoromethyl, mono-, di- or tri-chloromethyl;

[0155] Cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;

[0156] For example, aromatic groups such as phenyl, aryl, benzyl, phenoxy, benzoyl, naphthyl, anthracenyl, phenanthrenyl, and their halides:

[0157] ·With amide bond and C 1～19 A branched hydrocarbon group, for example, a group represented by the following formula,

[0158]

[0159] {where R=C 1～9 alkyl};

[0160] ·Has cyano and C 1～19 Examples of the branched hydrocarbon group include groups represented by the following formula.

[0161]

[0162] {where R=C 1～9 or C 1～8 alkyl}

[0163] In the general formula (1), R 1 and R 2 In the same situation, as R 1 and R 2 Preferred combinations include the same aromatic groups, such as the same benzyl groups, the same phenyl groups, etc.

[0164] In the general formula (1), R 1 and R 2 In different cases, R 1 With R 2 The preferred combination may be as follows:

[0165] Combinations of straight-chain alkyl groups with different carbon numbers;

[0166] A combination of straight-chain and branched-chain alkyl groups;

[0167] Combinations of straight-chain alkyl groups and aromatic groups;

[0168] Combination of branched alkyl groups and aromatic groups;

[0169] ·Straight chain alkyl with amide bond and C 1～19 a combination of branched hydrocarbon groups;

[0170] ·Straight chain alkyl with cyano and C 1～19 A combination of branched hydrocarbon groups.

[0171] As compound (D), preferably, R in general formula (1) 1 and / or R 2 The compound having an amide bond is more preferably a compound represented by the following general formula (2) or (2A).

[0172]

[0173] {where R 1 and R 2 Each independently selected from the group consisting of monovalent organic groups having 1 to 20 carbon atoms, excluding an azo group.

[0174]

[0175] {where R1 is a monovalent organic group having 1 to 20 carbon atoms and excluding an azo group, and R 3 It is a monovalent organic group having 1 to 19 carbon atoms and excluding an azo group.

[0176] The compound represented by the general formula (2) or (2A) can increase the force of interaction with the Cu surface of a Cu substrate or the like by having a cyano group and an amide bond, and tends to have excellent adhesion to the substrate.

[0177] The group R in the general formula (2) 1 and R 2 and the group R in the general formula (2A) 1 can be respectively combined with the group R defined in the general formula (1) 1 and R 2 In addition, the group R in the general formula (2A) 3 The group R defined in the general formula (1) 2 The same as long as the carbon number is 1 to 19.

[0178] The photosensitive resin composition according to one embodiment of the present invention preferably contains the compound (D) described above in an amount of 0.0001% by mass to 0.0150% by mass, more preferably 0.0001% by mass to 0.0100% by mass, and even more preferably 0.0001% by mass to 0.0050% by mass, relative to the total solid content of the photosensitive resin composition. When the content of compound (D) is adjusted to within the range of 0.0001 to 0.0150% by mass, when a photosensitive element formed from the photosensitive resin composition is laminated with a copper (Cu) substrate having a step, there is a tendency to achieve both step conformability and Cu adhesion.

[0179] Other ingredients

[0180] The photosensitive resin composition may further contain various additives in addition to the above-described components (A) to (D), such as a color-changing agent, a dye, a plasticizer, an antioxidant, an organic halogen compound, a nonionic surfactant, a crosslinking agent, and a stabilizer.

[0181] Color-changing agent

[0182] Examples of the color-changing agent include leuco dyes and fluoran dyes. Examples of the leuco dye include leuco crystal violet and leuco malachite green. The content of the color-changing agent in the photosensitive resin composition is preferably 0.01% by mass or more to achieve good colorability (i.e., color development) and preferably 5% by mass or less to achieve hue stability and good image characteristics.

[0183] dye

[0184] Examples of the dye include Basic Green 1 [CAS: 633-03-4] (e.g., Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Malachite Green Oxalate [2437-29-8] (e.g., Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Brilliant Green [633-03-4], Magenta [632-99-5], Methyl Violet [603-47-4], Methyl Violet 2B [8004-87-3], Crystal Violet [548-62-9], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue BOH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2], etc. Among them, Basic Green 1, Malachite Green Oxalate, and Basic Blue 7 are preferred.

[0185] The amount of the dye in the photosensitive resin composition is preferably in the range of 0.001% to 0.3% by mass, more preferably in the range of 0.01% to 0.12% by mass. From the perspective of achieving good colorability and visibility, the amount of the dye is preferably 0.001% by mass or more, and from the perspective of maintaining sensitivity, it is preferably 0.3% by mass or less.

[0186] plasticizers

[0187] Examples of plasticizers include glycol esters such as polyethylene glycol, polypropylene glycol (e.g., Mw≈2000), polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, and polyoxyethylene polyoxypropylene monoethyl ether; phthalate esters such as diethyl phthalate; sulfonamides such as o-toluenesulfonic acid amide and p-toluenesulfonic acid amide; tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, and acetyl tri-n-butyl citrate. Among these, sulfonamides are preferred.

[0188] The amount of plasticizer in the photosensitive resin composition is preferably 0.1% to 50% by mass, more preferably 1% to 20% by mass, and even more preferably 3% to 10% by mass. From the perspectives of ensuring viscosity stability, suppressing delays in development time, and imparting flexibility or releasability to the cured film, the amount of plasticizer is preferably 0.1% by mass or more, and from the perspective of suppressing insufficient curing and cold flow, it is preferably 50% by mass or less.

[0189] antioxidants

[0190] Examples of antioxidants include triphenyl phosphite (e.g., manufactured by ADEKA Corporation, trade name: TPP), tris(2,4-di-tert-butylphenyl)phosphite (e.g., manufactured by ADEKA Corporation, trade name: 2112), tris(mononylphenyl)phosphite (e.g., manufactured by ADEKA Corporation, trade name: 1178), and bis(mononylphenyl)dinonylphenylphosphite (e.g., manufactured by ADEKA Corporation, trade name: 329K). The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01 to 0.8% by mass, more preferably in the range of 0.01 to 0.3% by mass. When the content is 0.01% by mass or greater, the photosensitive resin composition exhibits excellent hue stability, and the photosensitive resin composition exhibits good sensitivity during exposure. Furthermore, when the content is 0.8% by mass or less, color development is suppressed, resulting in excellent hue stability and good adhesion.

[0191] Organohalogen compounds

[0192] Examples of the organic halogen compound include amyl bromide, isopentyl bromide, isobutylene bromide, vinyl bromide, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethylphenyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and chlorinated triazine compounds. Among these, tribromomethylphenyl sulfone is particularly preferably used. The amount of the organic halogen compound in the photosensitive resin composition is preferably 0.001% to 3% by mass, more preferably 0.005% to 2.5% by mass, or 0.01% to 1.0% by mass.

[0193] Nonionic surfactants

[0194] As the nonionic surfactant, sorbitan / fatty acid compounds, such as polyoxyethylene sorbitan trioleate (e.g., "Newcol 3-85" available from Nippon Emulsifier Co., Ltd.), are preferred from the viewpoints of low toxicity, emulsification, rust prevention, and antistatic properties. The amount of the nonionic surfactant in the photosensitive resin composition is preferably 0.001% to 3% by mass, more preferably 0.01% to 2.5% by mass, and even more preferably 0.5% to 2.0% by mass, or 1% to 2% by mass.

[0195] crosslinking agent

[0196] As the crosslinking agent, from the viewpoint of water resistance or heat resistance, a dithiol compound having a triazine skeleton, such as 2-(dibutylamino)-1,3,5-triazine-4,6-dithiol (e.g., the product name "BSH" available from Kawaguchi Chemical Industry Co., Ltd.) is preferred. The amount of the crosslinking agent in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.005% by mass to 2.5% by mass, 0.01% by mass to 1.0% by mass, or 0.02% by mass to 0.1% by mass.

[0197] stabilizer

[0198] From the viewpoint of improving the thermal stability and / or storage stability of the photosensitive resin composition, the stabilizer is preferably one or more compounds selected from the group consisting of radical polymerization inhibitors, thiazoles, thiadiazoles, benzotriazoles, carboxybenzotriazoles, and cresols.

[0199] Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), aluminum nitrosophenylhydroxylamine (for example, amine addition molar number: 3), and diphenylnitrosoamine.

[0200] Examples of the thiazoles include 2-mercaptobenzothiazole, 6-amino-2-mercaptobenzothiazole, 2-mercapto-5-methoxybenzothiazole, and 5-chloro-2-mercaptobenzothiazole.

[0201] Examples of the thiadiazoles include 2-amino-5-mercapto-1,3,4-thiadiazole.

[0202] Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole, and 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,3-benzotriazole.

[0203] Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole, and a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole.

[0204] Examples of the cresols include 4,4′-butylenebis(6-tert-butyl-m-cresol), specifically, “ANTAGE W-300” available from Kawaguchi Chemical Industry Co., Ltd., and the like.

[0205] The total amount of stabilizers in the photosensitive resin composition is preferably 0.001% by mass to 4.0% by mass, more preferably 0.01% by mass to 2.0% by mass, and even more preferably 0.05% by mass to 1.9% by mass. From the perspective of imparting good storage stability to the photosensitive resin composition, the total amount is preferably 0.001% by mass or more, and from the perspective of maintaining good sensitivity, it is preferably 4.0% by mass or less.

[0206] <Photosensitive resin composition preparation liquid>

[0207] The photosensitive resin composition of the present invention can be used as a prepared photosensitive resin composition solution by adding a solvent thereto. Preferred solvents include ketones such as methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. The solvent is preferably added to the photosensitive resin composition so that the viscosity of the prepared photosensitive resin composition solution is 500 to 4000 mPa·s at 25°C.

[0208] <Photosensitive element (photosensitive resin laminate)>

[0209] Another embodiment of the present invention provides a photosensitive resin laminate (hereinafter also referred to as a photosensitive element) comprising a support and a photosensitive resin layer formed from the photosensitive resin composition of the present invention and laminated on the support. In the photosensitive element, in addition to the photosensitive resin layer and the support supporting the photosensitive resin layer, a protective layer may be provided on the surface of the photosensitive resin layer opposite to the support-formed side, as needed. From the perspective of use in photolithography, the photosensitive element preferably comprises a resist material in the form of a dry film (hereinafter also referred to as a dry film resist).

[0210] The support is preferably a transparent support that transmits light emitted by the exposure light source. Examples of such supports include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. If desired, stretched products of these films may also serve as the support. The haze of the film used as the support is preferably 5 or less. A thinner film is more advantageous in terms of image formation and economic efficiency, but from the perspective of maintaining strength, a thickness of 10 μm to 30 μm is preferred.

[0211] Another important characteristic of the protective layer used in a photosensitive element is that the adhesion between the protective layer and the photosensitive resin layer is weaker than the adhesion between the support and the photosensitive resin layer, allowing for easy peeling. For example, polyethylene films and polypropylene films are preferred as protective layers. Furthermore, films with excellent peelability, such as those described in Japanese Patent Application Laid-Open No. 59-202457, can be used as protective layers. The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

[0212] The thickness of the photosensitive resin layer in the photosensitive element is preferably 3 μm to 100 μm, more preferably 5 μm to 60 μm. A thinner photosensitive resin layer improves resolution, while a thicker photosensitive resin layer improves film strength. Therefore, the thickness can be appropriately selected depending on the application.

[0213] Conventionally known methods can be used to fabricate a photosensitive element by sequentially laminating a support, a photosensitive resin layer, and, if desired, a protective layer. For example, a photosensitive resin composition for forming a photosensitive resin layer can be prepared as a prepared liquid of the photosensitive resin composition described above. This liquid is then coated onto a support using a bar coater or a roll coater and dried. The photosensitive resin layer formed from the photosensitive resin composition is then laminated onto the support. Subsequently, a protective layer can be laminated onto the photosensitive resin layer as desired to fabricate a photosensitive element.

[0214] <Lamination>

[0215] Another embodiment of the present invention is a method of laminating the above-mentioned photosensitive element of the present invention on a substrate.

[0216] From the perspective of suppressing the formation of bubbles (voids) or wrinkles in the laminate of the photosensitive element and substrate, lamination of the photosensitive element and substrate is preferably performed by vacuum lamination. Specifically, it is preferably performed at a pressure lower than atmospheric pressure. Vacuum lamination can be performed using, for example, a perforated plate laminator or a hydraulic press laminator.

[0217] When the photosensitive element is a dry film resist, lamination of the dry film resist and the substrate can be performed by dry lamination in the absence of a liquid, wet lamination in which a liquid is placed between the substrate and the dry film resist to fill the gap between the substrate and the dry film resist with the liquid, or vacuum lamination performed at a pressure lower than atmospheric pressure. From the perspective of conformability and adhesion between the dry film resist and the substrate, vacuum lamination is preferred. Vacuum lamination can be performed, for example, at a vacuum degree of 1 to 1000 Pa, preferably 50 to 500 Pa.

[0218] <Resist Pattern Formation Method>

[0219] A resist pattern forming method can be provided that, after lamination as described above, sequentially performs an exposure step of exposing the photosensitive resin layer of a photosensitive element; and a development step of developing the exposed photosensitive resin layer with a developer to form a resist pattern. An example of a specific method for forming a resist pattern using the dry lamination and / or vacuum lamination described above is as follows.

[0220] After dry lamination / vacuum lamination, in the exposure process, an exposure machine is used to expose the photosensitive resin composition in the photosensitive resin layer to active light. The exposed portion of the photosensitive resin layer is polymerized and cured (when the photosensitive resin composition is a negative type) or is soluble in a developer (when the photosensitive resin composition is a positive type). Exposure can be performed after the support is peeled off as needed. When exposure is performed through a photomask, the exposure amount can be determined according to the illuminance of the light source and the exposure time, or it can be measured using a light meter. In the exposure process, a maskless exposure method can be used. In maskless exposure, exposure is performed on the substrate by a direct drawing device without using a photomask. As a light source, a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350nm to 410nm can be used. The drawing pattern is controlled by a computer, and the exposure amount at this time is determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0221] Next, in the development process, a developing device is used to remove the unexposed portion (when the photosensitive resin composition is a negative type) or the exposed portion (when the photosensitive resin composition is a positive type) in the photosensitive resin layer after exposure using a developer. After exposure, if there is a support on the photosensitive resin layer, it is removed. Next, a developer composed of an alkaline aqueous solution is used to develop and remove the unexposed portion or the exposed portion to obtain a resist image. As the alkaline aqueous solution, an aqueous solution such as Na2CO3 or K2CO3 is preferred. These alkaline aqueous solutions can be selected according to the characteristics of the photosensitive resin layer, but are generally Na2CO3 aqueous solutions with a concentration of 0.2% to 2% by mass. Surfactants, defoaming agents, a small amount of organic solvents for promoting development, etc. can also be mixed into the alkaline aqueous solution. It should be noted that the temperature of the developer in the development process is preferably kept constant in the range of 20°C to 40°C.

[0222] The resist pattern can be obtained through the above steps. However, a further heating step at 100°C to 300°C may be performed depending on the situation. This heating step can further improve the chemical resistance of the pattern. Heating can be performed using a heating furnace using hot air, infrared rays, or far-infrared rays.

[0223] <Method for Manufacturing Conductive Pattern>

[0224] Another embodiment of the present invention is a method for producing a conductive pattern comprising laminating the aforementioned photosensitive element and substrate. To prevent the formation of voids or wrinkles in the laminated product, lamination of the photosensitive element and substrate is preferably performed at a pressure lower than atmospheric pressure. An example of a conductive pattern production method using the dry lamination and / or vacuum lamination described above is as follows.

[0225] A method for producing a conductive pattern according to one embodiment of the present invention can be implemented by using a metal plate or a metal-coated insulating plate as a substrate, forming a resist pattern using the aforementioned resist pattern forming method, and then performing a conductive pattern forming step. For example, after dry lamination or vacuum lamination, an exposure step of exposing the photosensitive resin layer to light can be performed; a development step of developing the exposed photosensitive resin layer with a developer to form a resist pattern; and a conductive pattern forming step of etching or plating the substrate having the resist pattern formed thereon can be performed in sequence.

[0226] In the conductor pattern forming step, a conductor pattern is formed on the substrate surface (eg, copper surface) exposed by development using a known etching method or plating method on the substrate on which the resist pattern has been formed as described above.

[0227] Furthermore, the present invention is suitably applicable to the following uses, for example.

[0228] <Manufacturing of printed circuit boards>

[0229] It should be noted that, according to the present invention, after manufacturing a conductor pattern by the method described above, a stripping process is further performed in which the resist pattern is stripped from the substrate using an aqueous solution having an alkalinity stronger than that of the developer, thereby obtaining a printed circuit board having a desired wiring pattern. In the manufacture of printed circuit boards, a copper-clad laminate or a flexible substrate is preferably used as the substrate. There are no particular restrictions on the aqueous alkaline solution for stripping (hereinafter also referred to as "stripping solution"), and an aqueous solution of NaOH or KOH with a concentration of 2% by mass to 5% by mass is generally used. A small amount of a water-soluble solvent may be added to the stripping solution. The temperature of the stripping solution in the stripping process is preferably in the range of 40°C to 70°C.

[0230] Lead Frame Manufacturing

[0231] A lead frame can be manufactured by using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate, forming a resist pattern using the aforementioned resist pattern forming method, and then performing the following steps. First, the substrate exposed by development is etched to form a conductor pattern. Then, a stripping step is performed to remove the resist pattern using the same method as the aforementioned printed circuit board manufacturing method, yielding the desired lead frame.

[0232] <Manufacturing of a substrate having a concavo-convex pattern>

[0233] The resist pattern formed by the resist pattern forming method of the present invention can be used as a protective mask member when a substrate is processed by a sandblasting method. As the substrate at this time, glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramics, sapphire, metal materials, etc. can be listed. The resist pattern is formed on these substrates using the same method as the aforementioned resist pattern forming method. Then, through a sandblasting process in which an abrasive is blown from above the formed resist pattern to cut to the target depth, and a stripping process in which the resist pattern portion remaining on the substrate is removed from the substrate using an alkaline stripping solution, a base material with a fine concave-convex pattern on the substrate can be manufactured. As the abrasive used in the sandblasting process, known abrasives can be used, for example, particles with a particle size of 2μm to 100μm, such as SiC, SiO2, Al2O3, CaCO3, ZrO, glass, and stainless steel, can be used.

[0234] Semiconductor Package Manufacturing

[0235] A wafer with a large-scale integrated circuit (LSI) formed thereon is used as a substrate. After forming a resist pattern thereon using the aforementioned resist pattern forming method, a semiconductor package can be manufactured through the following steps. First, the opening exposed by development is plated with a columnar coating of copper, solder, or the like to form a conductor pattern. Next, a stripping step is performed to remove the resist pattern using the same method as the aforementioned printed circuit board manufacturing method. Furthermore, a step is performed to remove the thin metal layer excluding the columnar plating by etching, thereby obtaining the desired semiconductor package.

[0236] Example

[0237] The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples.

[0238] The methods for preparing the evaluation samples of Examples 1 to 15 and Comparative Examples 1 and 2, and the evaluation methods and evaluation results of the obtained samples are as follows.

[0239] <Method for preparing evaluation samples>

[0240] Evaluation samples were prepared as follows.

[0241] <Production of Photosensitive Elements>

[0242] The components shown in Table 1 below (wherein the numbers for each component represent the amount (parts by mass) of each component as a solid component) were thoroughly stirred and mixed with methyl ethyl ketone measured to a solid content concentration of 55% to obtain a photosensitive resin composition liquid. The components shown in Table 1 are detailed in Tables 2 and 3. A 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Ltd., 16FB40) was used as a support film. The prepared liquid was evenly applied to the surface of the film using a bar coater and dried in a dryer at 95°C for 2 minutes and 30 seconds to form a photosensitive resin layer. The dried thickness of the photosensitive resin layer was 25 μm.

[0243] Next, a 19 μm thick polyethylene film (TAMAPOLY CO., LTD., GF-18) was bonded as a protective layer to the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated, thereby obtaining a photosensitive element.

[0244] In addition, content of the compound (D) in Table 1 means the concentration based on the total solid content in the photosensitive resin composition.

[0245] <Substrate leveling>

[0246] As an evaluation substrate for image properties, a 0.4 mm thick copper-clad laminate laminated with 35 μm rolled copper foil was spray-scraped using a grinding agent (manufactured by Uji Denka Kogyo Co., Ltd., #400) at a spray pressure of 0.2 MPa, and the substrate surface was then cleaned with a 10% by mass H2SO4 aqueous solution.

[0247] <Lamination>

[0248] While peeling the polyethylene film (protective layer) from the photosensitive element, the photosensitive element was laminated onto a copper-clad laminate preheated to 50°C using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) at a roll temperature of 105°C. The air pressure was set to 0.35 MPa and the lamination speed was set to 1.5 m / min.

[0249] <Exposure>

[0250] Two hours after lamination, the evaluation substrates were exposed using a direct writing exposure machine (INPREX IP-8 8000, manufactured by ADTEC Engineering Co., Ltd.) using a Stouffer 41-step step meter. Exposure was performed at an exposure dose such that the maximum residual film level during exposure and development reached 14 steps using the Stouffer 41-step step meter as a mask.

[0251] <Development>

[0252] The polyethylene terephthalate film (support film) was peeled from the photosensitive element and developed using an alkali developer (manufactured by Fuji Kiko Co., Ltd., a dry film developer) by spraying a 1% by mass aqueous solution of NaCO at 30°C for a predetermined time. The development spray time was set to twice the minimum development time, and the post-development water rinse spray time was set to twice the minimum development time. The minimum development time was the minimum time required to completely dissolve the unexposed portion of the photosensitive resin layer.

[0253] <Evaluation>

[0254] Next, the evaluation method of the samples will be described.

[0255] <Quantitative determination method of compound (D)>

[0256] The content of compound (D) in the photosensitive resin composition was determined by an internal standard method using a gas chromatograph (hereinafter abbreviated as GC) manufactured by Shimadzu Corporation. The detector was a flame ionization detector (hereinafter abbreviated as FID), and n-dodecane was used as the internal standard.

[0257] <Followability>

[0258] The copper-clad laminate was laminated, exposed, developed, etched and peeled using a commercially available dry film resist (DFR) to produce a pit substrate with a circular depression of 310 μm in diameter and about 10 μm in depth. For the photosensitive element obtained above, a roller-type hot vacuum laminator (MCK Co., Ltd., MVR-250) was used at a roller temperature of 80°C, a cylinder pressure of 0.4 MPa, a vacuum degree of 100 Pa and a speed of 1 m / min. The surface of the photosensitive element (thickness = 25 μm) with the protective film peeled off was laminated to the pit substrate. At this time, the average value of the diameter of 10 points of the air that was not completely followed by the photosensitive element and remained inside the pit was calculated and evaluated according to the following criteria. If the evaluation is "acceptable" or above, it is considered qualified.

[0259] (Evaluation Criteria)

[0260] Excellent: 100μm or less

[0261] Good: more than 100μm and less than 150μm

[0262] Acceptable: More than 150μm and less than 200μm

[0263] Not allowed: more than 200μm

[0264] <Adhesion>

[0265] In the exposure step, exposure was performed using drawing data with a line pattern having a ratio of x μm to 200 μm between the width of the exposed and unexposed areas. Development was performed according to the above-mentioned development conditions, and the minimum line width required to properly form a cured resist line was measured using an optical microscope. This measurement was performed on four lines, and the average of these four line widths was calculated as the adhesion value. Adhesion was evaluated according to the following criteria. A rating of "Acceptable" or higher was considered acceptable.

[0266] (Evaluation Criteria)

[0267] Excellent: 7μm or less

[0268] Good: more than 7μm and less than 9μm

[0269] Acceptable: More than 9μm and less than 11μm

[0270] Not allowed: more than 12μm

[0271] <Evaluation Results>

[0272] The evaluation results of Examples 1 to 15 and Comparative Examples 1 and 2 are shown in Tables 1 to 3.

[0273] [Table 1-1]

[0274]

[0275] [Table 1-2]

[0276]

[0277] [Table 2]

[0278]

[0279] [Table 3]

[0280]

Claims

1. A photosensitive resin composition comprising: (A) Alkali-soluble polymer; (B) a compound having an ethylenically unsaturated double bond; (C) a photopolymerization initiator; and (D) a compound represented by the following general formula (1), In the general formula (1), R 1 and R 2 are each independently selected from the group consisting of monovalent organic groups having 1 to 20 carbon atoms, excluding an azo group, in, The compound (D) is contained in an amount of 0.0001% by mass or more and 0.0150% by mass or less based on the total amount of solid content of the photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein The compound (D) is solid at 25°C.

3. The photosensitive resin composition according to claim 1 or 2, wherein The molecular weight of the compound (D) is 100 g / mol or more and 250 g / mol or less.

4. The photosensitive resin composition according to claim 1 or 2, wherein The molecular weight of the compound (D) is 111 g / mol or more and 240 g / mol or less.

5. The photosensitive resin composition according to claim 1 or 2, wherein The compound (D) is contained in an amount of 0.0001% by mass or more and 0.0100% by mass or less relative to the total amount of solid content of the photosensitive resin composition.

6. The photosensitive resin composition according to claim 1 or 2, wherein The compound (D) is contained in an amount of 0.0001% by mass or more and 0.0050% by mass or less relative to the total amount of solid content of the photosensitive resin composition.

7. The photosensitive resin composition according to claim 1 or 2, wherein The compound (D) is a compound represented by the following general formula (2): In the general formula (2), R 1 and R 2 Each is independently selected from the group consisting of monovalent organic groups having 1 to 20 carbon atoms, excluding an azo group.

8. The photosensitive resin composition according to claim 1 or 2, wherein The compound (D) is a compound represented by the following general formula (2A), In the general formula (2A), R 1 is a monovalent organic group having 1 to 20 carbon atoms and excluding an azo group, and R 3 It is a monovalent organic group having 1 to 19 carbon atoms and excluding an azo group. 9 . A photosensitive element comprising a support and a layer formed on the support and composed of the photosensitive resin composition according to claim 1 . 10 . The photosensitive element according to claim 9 , which is a dry film resist.

11. A method of laminating the photosensitive element according to claim 9 or 10 on a substrate at a pressure lower than atmospheric pressure.

12. The method according to claim 11, wherein Lamination is performed under a vacuum degree of 1 to 1000 Pa.

13. The method according to claim 11 or 12, wherein: Lamination is performed under a vacuum degree of 50 to 500 Pa.

14. A method for manufacturing a conductor pattern, comprising: A step of laminating the photosensitive element according to claim 9 or 10 on a substrate at a pressure lower than atmospheric pressure.

15. The manufacturing method according to claim 14, wherein: Lamination is performed under a vacuum degree of 1 to 1000 Pa.

16. The manufacturing method according to claim 14 or 15, wherein: Lamination is performed under a vacuum degree of 50 to 500 Pa.

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