TWI752606B - Photosensitive resin composition and photosensitive element - Google Patents

Abstract

{式中，R¹ 及R² 分別獨立地選自由碳數1～20之有機基所組成之群，但不包含偶氮基}The photosensitive resin composition of the present invention contains an alkali-soluble polymer, a compound having an ethylenically unsaturated double bond, a photopolymerization initiator, and a compound represented by the following general formula (1).

{In the formula, R ¹ and R ² are independently selected from the group consisting of organic groups having 1 to 20 carbon atoms, but azo groups are not included}

Description

Photosensitive resin composition and photosensitive element

The present invention relates to a photosensitive resin composition, a photosensitive element using the photosensitive resin composition, a lamination method, a method for producing a conductor pattern, and the like.

Previously, printed wiring boards were generally fabricated by photolithography. In the photolithography method, pattern exposure is first performed on the photosensitive resin layer laminated on a substrate such as a copper foil laminate and a flexible substrate. The exposed part of the photosensitive resin layer is polymerized and cured (in the case of negative type) or solubilized with respect to a developer (in the case of positive type). Then, the unexposed part (in the case of negative type) or the exposed part (in the case of positive type) is removed by the developing solution, and a photoresist pattern is formed on the substrate. Furthermore, after performing etching or a plating process to form a conductive pattern, the cured photoresist pattern (hereinafter also referred to as a "photoresist pattern") is peeled and removed from the substrate. After these steps, a conductor pattern is formed on the substrate.

There are roughly two types of processes for forming conductor patterns by etching or plating. The first method is as follows: after etching and removing the surface of the substrate not covered by the photoresist pattern (such as the copper surface of a copper foil laminate, etc.), the photoresist pattern portion is removed by an aqueous solution with stronger alkalinity than the developer. The second method is the following method (plating method): after the substrate surface is plated with copper, solder, nickel, or tin, the photoresist pattern portion is similarly removed, and the exposed substrate surface is etched. Regardless of which of the two methods is used, copper chloride, ferric chloride, cuprammonium complex solution, etc. are used for etching.

Usually, when photolithography is used to form the photosensitive resin layer, a method of applying a solution of the photosensitive resin composition to a substrate and drying it, or applying a dry film photoresist (which will contain a photosensitive resin composition) Any of the methods of layering the photosensitive resin layer on the substrate (photosensitive resin layered product obtained by layering the photosensitive resin layer on the support). In addition, the photolithography method also uses substrates with various shapes (eg, flat, uneven, non-planar, grooves, pre-formed lines/spaces, etc.).

In recent years, in order to adapt to the refinement and high density of printed wiring boards, the DLP (Digital Light Processing) exposure method, which can form a finer pattern than before, has been studied as a direct laser writing (DI) method. Furthermore, the photosensitive resin composition used for DLP has also been studied (Patent Document 1).

In addition, regarding the composition of the photosensitive resin composition, a pyridine compound or cyanide (Patent Document 2) for improving the photosensitivity, a compound synthesized from 2-(2-hydroxyphenyl)-1H-benzimidazole as a starting material The use of nitrogen-containing compounds such as alkali generators (Patent Document 3) has also been studied. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2009/133817 [Patent Document 2] Japanese Patent Laid-Open No. 2005-309384 [Patent Document 3] Japanese Patent Laid-Open No. 2015-075551

[Problems to be Solved by Invention]

In the photolithography method described above, the following three methods are known for the formation of the laminate including the substrate and the dry film photoresist. Lamination is carried out in the case of liquid (so-called "dry lamination"); method 2, the liquid is applied between the substrate and the dry film photoresist, and the gap between the substrate and the dry film photoresist is filled with liquid (the so-called "wet lamination"). Method 3, lamination at sub-atmospheric pressure (so-called "vacuum lamination").

Among them, it is required to realize the followability and adhesion of the photoresist material to the substrate in the vacuum lamination. It is an especially important subject to take into account the step followability when the photoresist is laminated to the substrate and the adhesion to the Cu substrate when the substrate is a copper (Cu) substrate.

However, the descriptions in Patent Documents 1 to 3 do not focus on the behavior of the photosensitive resin composition and the photoresist obtained from the photosensitive resin composition in vacuum lamination.

Therefore, the objective of this invention is to provide the photosensitive resin composition which can satisfy both the followability and adhesiveness with respect to a board|substrate, the photosensitive element using this photosensitive resin composition, the lamination method, and the manufacturing method of a conductor pattern. [Technical means to solve problems]

{式中，R¹ 及R² 分別獨立地選自由不包含偶氮基之碳數1～20之一價有機基所組成之群} [2] 如項目[1]所記載之感光性樹脂組合物，其中上述化合物(D)於25℃下為固體。 [3] 如項目[1]或[2]所記載之感光性樹脂組合物，其中上述化合物(D)之分子量為100 g/mol以上250 g/mol以下。 [4] 如項目[1]至[3]中任一項所記載之感光性樹脂組合物，其含有相對於上述感光性樹脂組合物之固形物成分之總量為0.0001質量%以上0.0150質量%以下之上述化合物(D)。 [5] 如項目[1]至[4]中任一項所記載之感光性樹脂組合物，其含有相對於上述感光性樹脂組合物之固形物成分之總量為0.0001質量%以上0.0100質量%以下之上述化合物(D)。 [6] 如項目[1]至[5]中任一項所記載之感光性樹脂組合物，其含有相對於上述感光性樹脂組合物之固形物成分之總量為0.0001質量%以上0.0050質量%以下之上述化合物(D)。 [7] 如[1]至[6]中任一項所記載之感光性樹脂組合物，其中上述化合物(D)為下述通式(2A)所表示之化合物。 [化2]

{式中，R¹ 為不包含偶氮基之碳數1～20之一價有機基，且R³ 為不包含偶氮基之碳數1～19之一價有機基} [8] 一種感光性元件，其具備支持體、及形成於上述支持體上且包含如項目[1]至[7]中任一項所記載之感光性樹脂組合物之層。 [9] 如項目[8]所記載之感光性元件，其為乾膜光阻。 [10] 一種於未達大氣壓之氣壓下將如項目[8]或[9]所記載之感光性元件層壓至基板之方法。 [11] 一種導體圖案之製造方法，其包括如下步驟： 於未達大氣壓之氣壓下將如項目[8]或[9]所記載之感光性元件層壓至基板。 [發明之效果]The present inventors found that the above-mentioned problems can be solved by the following technical methods. [1] A photosensitive resin composition comprising: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated double bond; (C) a photopolymerization initiator; and (D) the following general A compound represented by formula (1). [hua 1]

{In the formula, R ¹ and R ² are independently selected from the group consisting of monovalent organic groups having 1 to 20 carbon atoms that do not contain an azo group} [2] The photosensitive resin combination as described in item [1] compound, wherein the above-mentioned compound (D) is solid at 25°C. [3] The photosensitive resin composition according to the 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] The photosensitive resin composition according to any one of the items [1] to [3], which contains 0.0001 mass % or more and 0.0150 mass % with respect to the total amount of the solid content of the photosensitive resin composition. The above-mentioned compound (D) below. [5] The photosensitive resin composition according to any one of the items [1] to [4], which contains 0.0001 mass % or more and 0.0100 mass % with respect to the total amount of the solid content of the photosensitive resin composition. The above-mentioned compound (D) below. [6] The photosensitive resin composition according to any one of the items [1] to [5], which contains 0.0001 mass % or more and 0.0050 mass % with respect to the total amount of the solid content of the photosensitive resin composition. The above-mentioned compound (D) below. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the compound (D) is a compound represented by the following general formula (2A). [hua 2]

{In the formula, R ¹ is a monovalent organic group with 1 to 20 carbon atoms that does not contain an azo group, and R ³ is a monovalent organic group with 1 to 19 carbon atoms that does not contain an azo group} [8] A kind of photosensitive A photosensitive element comprising a support and a layer formed on the support and comprising the photosensitive resin composition as described in any one of the items [1] to [7]. [9] The photosensitive element according to the item [8], which is a dry film photoresist. [10] A method of laminating the photosensitive element as described in item [8] or [9] to a substrate under a pressure below atmospheric pressure. [11] A method of manufacturing a conductor pattern, comprising the steps of: laminating the photosensitive element as described in item [8] or [9] to a substrate under a pressure below atmospheric pressure. [Effect of invention]

ADVANTAGE OF THE INVENTION According to this invention, in the lamination|stacking of a photoresist material and a board|substrate, the followability and adhesiveness with respect to a board|substrate can be made compatible, and the photosensitive element and conductor pattern which have both the followability and adhesiveness can be provided. Furthermore, according to the present invention, it is possible to achieve both the followability to the level difference and the adhesion to the Cu substrate especially under vacuum lamination.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various changes can be made without departing from the gist of the present invention.

<Photosensitive resin composition> One aspect of the present invention is a photosensitive resin composition. The photosensitive resin composition can be used in photolithography, or in the manufacture of photosensitive elements such as dry film resists.

{式中，R¹ 及R² 分別獨立地選自由不包含偶氮基之碳數1～20之一價有機基所組成之群}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). [hua 3]

{In the formula, R ¹ and R ² are independently selected from the group consisting of monovalent organic groups with 1 to 20 carbon atoms that do not include azo groups}

The photosensitive resin composition may further contain various additives, for example, a discoloring agent, a dye, a plasticizer, an antioxidant, an organic halogen compound, a nonionic surfactant, a crosslinking agent, a stabilizer, and the like as necessary.

In addition to being used for the formation of photoresist materials, such as the formation of dry film photoresist, the photosensitive resin composition can also be used for lamination with substrates, exposure using a photomask, or using a direct writing device without using a photomask. Exposure (direct image exposure), and formation of conductor patterns by development. The constituent elements of the photosensitive resin composition will be described below.

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

The photosensitive resin composition requires (A) a carboxyl group in an alkali-soluble polymer in order to have developability and peelability with respect to a developer and a peeling liquid containing an alkaline aqueous solution. The acid equivalent is preferably from 100 to 600, more preferably from 250 to 450. From the viewpoint of ensuring compatibility with the solvent or other components in the photosensitive resin composition, especially the following (b) addition polymerizable monomer, it is preferably 100 or more, and from the viewpoint of maintaining developability and releasability From a viewpoint, 600 or less are preferable. Here, the acid equivalent refers to the mass (g) of the thermoplastic copolymer having 1 equivalent of carboxyl groups therein. In addition, the measurement of the acid equivalent is performed using a titrator (for example, Hiranuma Reporting Titrator (COM-555)) and potentiometric titration with a 0.1 mol/L NaOH aqueous solution.

The weight average molecular weight of the thermoplastic copolymer is preferably 5,000 to 500,000. From the viewpoint of uniformly maintaining the thickness of the dry film photoresist and obtaining the resistance to the developer, it is preferably 5,000 or more, and from the viewpoint of maintaining the developability, it is preferably 500,000 or less. The above-mentioned weight average molecular weight is more preferably 20,000 to 100,000. Furthermore, the measurement conditions of the weight average molecular weight will be described in detail in the following examples.

The thermoplastic copolymer is preferably obtained by copolymerizing a copolymerization component containing one or more of the following first monomer and one or more of the following second monomer.

The first monomer system is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half-ester. Among them, (meth)acrylic acid is particularly preferred. Here, (meth)acrylic acid means acrylic acid or methacrylic acid. The following is the same.

The second monomer system is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-(meth)acrylate Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid ring Hexyl ester, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, vinyl alcohol esters such as vinyl acetate, (meth)acrylonitrile, styrene, and polymerizable styrene derivatives thing. Among them, methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, and benzyl (meth)acrylate are particularly preferred.

Regarding the amount of (A) the alkali-soluble polymer contained in the photosensitive resin composition of the present embodiment (it is the ratio with respect to the total amount of the solid content of the photosensitive resin composition; hereinafter, unless otherwise specified) It is the same for each component), from the viewpoint of developability, it is preferably 35% by mass or more, and from the viewpoint of obtaining a balance between alkaline developability and viscosity, it is more preferably 40% by mass to 70% by mass and more preferably 40% by mass to 60% by mass, 41% by mass to 58% by mass, 42% by mass to 57% by mass, or 43% by mass to 56% by mass.

(B) Compounds with ethylenically unsaturated double bonds (B) The compound which has an ethylenically unsaturated double bond can have polymerizability by having an ethylenically unsaturated bis in the structure. From the viewpoint of addition polymerizability, the ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.

{式中，R₁ 及R₂ 分別獨立地表示氫原子或甲基，且m₁ 為滿足2～40之數} (b₂ )下述通式(II)所表示之環氧烷改性雙酚A型二(甲基)丙烯酸酯化合物 [化5]

{式中，R₃ 及R₄ 分別獨立地表示氫原子或甲基，A為C₂ H₄ ，B為C₃ H₆ ，n₁ 、n₂ 、n₃ 及n₄ 為滿足n₁ ＋n₂ ＋n₃ ＋n₄ ＝2～50之關係之整數，-(A-O)-及-(B-O)-之重複單元之排列可為無規，亦可為嵌段，於嵌段之情形時，-(A-O)-與-(B-O)-之任一者可為聯苯基側} (b₃ )下述通式(III)所表示之三(甲基)丙烯酸酯化合物 [化6]

{式中，R₅ ～R₇ 分別獨立地表示氫原子或甲基，X表示碳數2～6之伸烷基，m₂ 、m₃ 及m₄ 分別獨立為0～40之整數，m₂ ＋m₃ ＋m₄ 為1～40，而且於m₂ ＋m₃ ＋m₄ 為2以上之情形時，複數個X可彼此相同或不同} (b₄ )下述通式(IV)所表示之二(甲基)丙烯酸胺基甲酸酯化合物 [化7]

{式中，R₈ 及R₉ 分別獨立地表示氫原子或甲基，Y表示碳數2～6之伸烷基，Z表示二價有機基，且s及t分別獨立為0～40之整數，且s＋t≧1} (b₅ )下述通式(V)所表示之六(甲基)丙烯酸酯化合物 [化8]

{式中，R分別獨立地表示氫原子或甲基，且n為0～30之整數，且所有n之合計值為1以上} (b₆ )下述通式(VI)所表示之鄰苯二甲酸酯化合物 [化9]

{式中，A表示C₂ H₄ ，R₆₁ 表示氫原子或甲基，R₆₂ 表示氫原子、甲基或鹵化甲基，R₆₃ 表示碳數1～6之烷基、鹵素原子或羥基，a為1～4之整數，k為0～4之整數，而且於k為2以上之整數之情形時，複數個R₆₃ 可相同亦可不同} (b₇ )下述式(VII)所表示之環氧(甲基)丙烯酸酯化合物 [化10]

{式中，R₃ 及R₄ 分別獨立地表示氫原子或甲基} (b₈ )除上述(b₁ )～(b₇ )以外之加成聚合性單體(B) a compound having an ethylenically unsaturated double bond may contain the following selected from the group consisting of _{(b 1) ~ (b 8} ) of the group consisting of at least one. (b ₁ ) Ethylene glycol di(meth)acrylate compound represented by the following general formula (I) [Chem. 4]

{In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and m ₁ is a number satisfying 2 to 40} (b ₂ ) The alkylene oxide-modified bismuth represented by the following general formula (II) Phenol A type di(meth)acrylate compound [Chem. 5]

{wherein, R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₁ , n ₂ , n ₃ and n ₄ satisfy n ₁ +n ₂ +n ₃ +n ₄ = an integer in the relationship of 2 to 50, the arrangement of the repeating units of -(AO)- and -(BO)- may be random or block, in the case of block, -(AO)- Any one of )- and -(BO)- may be a side of a biphenyl group} (b ₃ ) A tris(meth)acrylate compound represented by the following general formula (III) [Chem. 6]

{In the formula, R ₅ to R ₇ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, m ₂ , m ₃ and m ₄ are each independently an integer of 0 to 40, and m ₂ +m ₃ +m ₄ is 1 to 40, and when m ₂ +m ₃ +m ₄ is 2 or more, a plurality of X may be the same or different from each other} (b ₄ ) Two (A) represented by the following general formula (IV) base) acrylate urethane compound [Chem. 7]

{In the formula, R ₈ and R ₉ 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} (b ₅ ) a hexa(meth)acrylate compound represented by the following general formula (V) [Chem. 8]

{in the formula, R each independently represents a hydrogen atom or a methyl group, and n is an integer of 0 to 30, and the total value of all n is 1 or more} (b ₆ ) o-phenylene represented by the following general formula (VI) Diformate Compound [Chem. 9]

{In the formula, A represents C ₂ H ₄ , R ₆₁ represents a hydrogen atom or a methyl group, R ₆₂ represents a hydrogen atom, a methyl group or a halogenated methyl group, and 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 when k is an integer of 2 or more, a plurality of R ₆₃ may be the same or different} (b ₇ ) Represented by the following formula (VII) Epoxy (meth)acrylate compound [Chem. 10]

{In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group} (b ₈ ) addition polymerizable monomers other than the above (b ₁ ) to (b _{7 )}

Among (b ₁ ) to (b ₈ ) described above, from the viewpoint of the resolution and peelability of the photoresist pattern, it is preferable to contain a _{component selected from the group consisting of (b 2} ), (b ₃ ) and ( b ₅ ) At least one compound in the group consisting of components.

From the viewpoint of adjusting the peeling time of the photoresist pattern and the size of the peeling sheet, (B) the compound having an ethylenically unsaturated double bond preferably contains (b ₁ ) ethylene glycol di-ethylene represented by the general formula (I). (Meth)acrylate compound.

In the general formula (I), m _{1 is} preferably 2 or more from the viewpoints of peeling time and peeling sheet size, and preferably 20 or more from the viewpoint of the characteristic of suppressing short circuit defects after the etching process. From the viewpoint of resolution, plating resistance, and etching resistance, it is preferably 40 or less. From the viewpoint of the developability or resolution of the photoresist pattern in photolithography including vacuum lamination, m _{1 is} preferably 2-29, 4-20, or 6-15.

As a specific example of the ethylene glycol di(meth)acrylate compound represented by the general formula (I), m ₁ =4-tetraethylene glycol di(meth)acrylate, m ₁ =9-nine Ethylene glycol di(meth)acrylate (for example, dimethacrylate is a product named "SR610" which can be purchased from Arkema Co., Ltd., etc.), polyethylene glycol di(methyl) _{with m 1 =14} Acrylate, _{polyethylene glycol di(meth)acrylate with m 1} =23, polyethylene glycol di(meth)acrylate with m ₁ =30 or polyethylene glycol di(meth)acrylate with m ₁ =40 )Acrylate.

In order to suppress the short circuit after the etching process, (B) the compound having an ethylenically unsaturated double bond preferably contains (b ₂ ) the alkylene oxide-modified bisphenol A type bis(methyl) represented by the general formula (II). ) acrylate compound. B in the general formula (II) can be -CH ₂ CH ₂ CH ₂ - or -CH(CH ₃ )CH ₂ -.

The hydrogen atom on the aromatic ring in the general formula (II) may be substituted with a heteroatom and/or a substituent. Examples of hetero atoms include halogen atoms, and the substituents include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 18 carbon atoms, and benzyl groups. Acyl methyl group, amine group, alkylamine group with 1 to 10 carbon atoms, dialkylamine group with 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkyl mercapto group with 1 to 10 carbon atoms, Aryl, hydroxyl, hydroxyalkyl group with 1-20 carbon atoms, carboxyl group, carboxyalkyl group with 1-10 carbon atoms in alkyl group, acyl group with 1-10 carbon atoms in alkyl group, carboxy group with 1-20 carbon atoms in alkyl group Alkoxy, alkoxycarbonyl having 1-20 carbons, alkylcarbonyl having 2-10 carbons, alkenyl having 2-10 carbons, N-alkylamine carboxyl having 2-10 carbons or containing A heterocyclic group, or an aryl group substituted with these substituents, and the like. The substituents may form a condensed ring, or the hydrogen atoms in the substituents may be replaced by heteroatoms such as halogen atoms. When the aromatic ring in the general formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.

_{R 3} and R ₄ in the general formula (II) may each independently be a hydrogen atom or a methyl group, and from the viewpoint of securing the contrast immediately after exposure of the photosensitive resin layer containing the photosensitive resin composition, R _{3 is preferred One or both of R 4} and R 4 are hydrogen atoms, more preferably _{both R 3} and R ₄ are hydrogen atoms.

From the viewpoint of both the suppression of etching short-circuit defects and the resolution, it is preferable to add 10 moles of the alkylene oxide-modified bisphenol A type di(meth)acrylate compound represented by the general formula (II) _{to (b 2 ).} above the ear of alkylene oxides. More specifically, in the general formula (II), n ₁ , n ₂ , n ₃ and n ₄ preferably satisfy the relationship of n ₁ +n ₂ +n ₃ +n ₄ =4 to 50, more preferably n ₁ +n ₂ +n ₃ +n ₄ =6 to 40, more preferably n ₁ +n ₂ +n ₃ +n ₄ =8 to 30, more preferably n ₁ +n ₂ +n ₃ +n ₄ =10 to 20 relation.

In the general formula (II), from the viewpoint of photosensitivity, developability or resolution in photolithography including vacuum lamination, n ₁ +n ₃ forms (B1) monomer in (b _{2 ) component} when the case is preferably 3 to 30 or 5 to 20, in (b ₂₎ the case of forming the component (B2) of the monomer, preferably from 3 to 30, more preferably from 5 to 20.

(b ₂ ) Preferred specific examples of the alkylene oxide-modified bisphenol A-type di(meth)acrylate compound represented by the general formula (II) include: adding an average amount to both ends of bisphenol A, respectively. Di(meth)acrylate of polyethylene glycol obtained by 1 mol of ethylene oxide, and the second of polyethylene glycol obtained by adding an average of 2 mol of ethylene oxide to both ends of bisphenol A (Meth)acrylate (for example, dimethacrylate is a product named "Blemmer PDBE-200" which can be purchased from NOF Corporation, etc.), add an average of 2 moles to both ends of bisphenol A Di(meth)acrylate of polyethylene glycol obtained from ethylene oxide, and di(methyl) polyethylene glycol obtained by adding an average of 5 mol of ethylene oxide to both ends of bisphenol A respectively. ) Acrylate (for example, diacrylate is a product named "A-BPE-10" which can be purchased from Shin-Nakamura Chemical Industry Co., Ltd., etc., and dimethacrylate is a product named "A-BPE-10" which can be purchased from Hitachi Chemical Co., Ltd. "FA-321" products, and "BPE-500" products that can be purchased from Shin Nakamura Chemical Industry Co., Ltd., etc.), add an average of 7 moles of ethylene oxide to both ends of bisphenol A. Di(meth)acrylate of polyethylene glycol obtained from alkane, polyalkylene obtained by adding an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A, respectively Di(meth)acrylate of diol, di(meth)acrylate of polyalkylene glycol obtained by adding an average of 15 moles of ethylene oxide to both ends of bisphenol A, respectively, to bisphenol Di(meth)acrylate of polyalkylene glycol obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of A, respectively.

From the viewpoint of resolution, (B) the compound having an ethylenically unsaturated double bond preferably contains (b ₃ ) a tris(meth)acrylate compound represented by the general formula (III). X in the general formula (III) is an alkylene group having 2 to 6 carbon atoms, for example, it can be -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )CH ₂ - and the like. When the _{component (b 3} ) is used as the monomer having an EO (ethylene oxide, ethylene oxide) unit as described above, the carbon number of at least one X in the general formula (III) is 2.

(b ₃ ) Preferable specific examples of the tris(meth)acrylate compound represented by the general formula (III) include ethylene oxide (EO)-modified trimethylolpropane tri(meth)acrylic acid Esters (EO average added moles: 2 to 40, 3 to 35, 3 to 20 or 30 to 35), propylene oxide (PO) modified trimethylolpropane tri(meth)acrylate (PO average The number of added moles: 10 to 40) and so on.

Regarding the EO-modified trimethylolpropane tri(meth)acrylate with an EO average added molar number of 3, for example, the triacrylate can be purchased from Shin-Nakamura Chemical Industry Co., Ltd. under the name "A-TMPT" -3EO" products, etc. Regarding the EO-modified trimethylolpropane tri(meth)acrylate with an EO average added molar number of 9, for example, the triacrylate can be a product named "Miramer M3160" which can be purchased from Miwon Specialty Chemical Co., Ltd. .

From the viewpoint of resolution, (B) the compound having an ethylenically unsaturated double bond preferably contains (b ₄ ) a di(meth)acrylate urethane compound represented by the general formula (IV).

In the general formula (IV), Z represents a divalent organic group, such as an alkylene group having 1 to 10 carbon atoms, an epoxy alkyl group having 2 to 10 carbon atoms, or a substituted group having 3 to 10 carbon atoms. Divalent alicyclic group, etc. In the general formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, for example, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )CH ₂ - and the like can be used.

For the sake of shielding, the -(YO) _s - and -(YO) _t - moieties in the general formula (IV) are preferably each independently composed of -(C ₂ H ₄ O)-(C ₃ H ₆ O) ₉ -substituted. In order to suppress the short circuit after the etching process, it is preferable that s+t=20-40 in the general formula (IV).

(b ₄ ) Preferable specific examples of the di(meth)acrylate urethane compound represented by the general formula (IV) include (meth)acrylic monomers having a hydroxyl group at the β-position and isophor. Addition reaction products of diisocyanate compounds such as ketone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate and 1,6-hexamethylene diisocyanate, tris((meth)acryloyloxy Tetraethylene glycol isocyanate) hexamethylene isocyanurate, EO modified di(meth)acrylate urethane, and EO, PO modified di(meth)acrylate urethane. Among them, the urethane product of hexamethylene diisocyanate and polypropylene glycol mono(meth)acrylate is preferable. Furthermore, EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. In addition, PO represents propylene oxide, and the compound modified with PO has a block structure of a propylene oxide group.

As an EO modified|denatured di(meth)acrylate urethane, the brand name "UA-11" by Shin-Nakamura Chemical Industry Co., Ltd. etc. is mentioned, for example. Moreover, as an EO, PO modified|denatured di(meth)acrylate urethane, the brand name "UA-13" by Shin-Nakamura Chemical Industry Co., Ltd. etc. is mentioned, for example. These can be used individually by 1 type or in combination of 2 or more types.

From the viewpoint of resolution, (B) the compound having an ethylenically unsaturated double bond preferably contains (b ₅ ) a hexa(meth)acrylate compound represented by the general formula (V).

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 of n is 1 or more. The total value of n in the general formula (V) is preferably 180 or less, more preferably 30 to 180, 30-36, 1-29 or 6-29.

(b ₅ ) Preferable specific examples of the hexa(meth)acrylate compound represented by the general formula (V) include dipentaerythritol hexa(meth)acrylate and the sum of additions to the six terminals of dipentaerythritol. Hexa(meth)acrylate obtained by adding 1-36 mol of ethylene oxide and hexa(meth)acrylic acid obtained by adding a total of 1-10 mol of ε-caprolactone to the six terminals of dipentaerythritol ester.

From the viewpoint of resolution, (B) the compound having an ethylenically unsaturated double bond may contain (b ₆ ) a phthalate compound represented by the general formula (VI). As the phthalate compound represented by the general formula (VI), for example, phthalate-γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl, Phthalate-β-hydroxyethyl-β'-(meth)acryloyloxyethyl ester, and phthalate-β-hydroxypropyl-β'-(meth)acryloyloxyethyl ester Wait. Among them, phthalate-γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate is preferred. These are used individually by 1 type or in combination of 2 or more types.

From the viewpoint of photosensitivity, developability and resolution in photolithography including vacuum lamination, (B) the compound having an ethylenically unsaturated double bond preferably contains (b ₇ ) the general formula (VII) The epoxy (meth)acrylate compound represented by ) is more preferably a _{component (b 7} ) and trimethylolpropane tri(meth)acrylate which is a component _{(b 8 ) described below.} Without wishing to be bound by theory, it is believed that in _{the general formula (VII) of the component (b 7} ), the hydroxyl groups present at sites other than the polymerizable terminal contribute to the peelability of the photoresist pattern.

The mixing ratio of the component (b ₇ ) and trimethylolpropane tri(meth)acrylate as the component (b ₈ ) below is preferably the mass of the component _{(b 7 )/trimethylolpropane tri(} The mass of meth)acrylate=50-80/50-20, More preferably, it is 55-75/45-25, More preferably, it is 60/40.

(B) a compound having an ethylenically unsaturated double bond may in addition comprise _{(b 1) ~ (b 7} ) an addition polymerizable monomer other than as a component (b ₈₎ component.

As the _{component (b 8 ), di(meth)acrylates other than the components (b 1} ), (b ₂ ), and (b ₇ ), for example, polypropylene glycol-polyethylene glycol di(meth)acrylate, can be mentioned. , Polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate and other polyalkylene glycol di(meth)acrylates. More specifically, as the _{component (b 8} ), di(meth)acrylate of polyalkylene glycol can be used, and the di(meth)acrylate of polyalkylene glycol is 12 per addition average. The polypropylene glycol obtained by molar propylene oxide is obtained by adding an average of 3 molar ethylene oxide to both ends respectively.

Further, as the _{component (b 8} ), the following examples can be given: - Mono(meth)acrylate, for example, 4-nonylphenyl-heptaethylene glycol-dipropylene glycol (meth)acrylate (for example, acrylate can be A product named "DISPANOL LS-100A" purchased from NOF Co., Ltd.), etc.; _{Tri(meth)acrylates other than (b 3} ) components, such as trimethylolpropane tri(meth)acrylic acid Esters (for example, triacrylate is a product named "A-TMPT" which can be purchased from Shin Nakamura Chemical Industry Co., Ltd., etc.), ethoxylated glycerol tri(meth)acrylate, ethoxylated isocyanuric acid tris( meth)acrylate, pentaerythritol tri(meth)acrylate, etc.; Tetra(meth)acrylate, such as di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, Dipentaerythritol tetra(meth)acrylate, pentaerythritol (poly)alkoxytetra(meth)acrylate, etc.; Penta(meth)acrylate, such as dipentaerythritol penta(meth)acrylate, etc.; Compounds obtained by reacting ,β-unsaturated carboxylic acids with polyhydric alcohols; and · Compounds obtained by reacting α,β-unsaturated carboxylic acids with compounds containing glycidyl groups.

From the viewpoint of resolution and the property of suppressing short-circuit failure 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, more preferably 4% by mass to 39% by mass, particularly preferably 15% by mass to 38% by mass , within the range of 20% by mass to 35% by mass or 30% by mass to 34% by mass.

(C) Photopolymerization initiator As the (C) photopolymerization initiator, a photopolymerization initiator generally used in the field of photosensitive resins can be used. The quantity of the (C) photopolymerization initiator in the photosensitive resin composition is 0.1 mass % - 20 mass %. This amount is 0.1 mass % or more in terms of sensitivity, and 20 mass % or less in terms of resolution. A preferable content is 0.1 mass % - 15 mass %, More preferably, it is 0.9 mass % - 10 mass %. As the (C) photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.

In one embodiment of the present invention, (C) the photopolymerization initiator is preferably at least one selected from the group consisting of an acridine derivative, an anthracene derivative, and a pyrazoline derivative. By using at least one selected from the group consisting of acridine derivatives, anthracene derivatives and pyrazoline derivatives, it is possible to achieve higher sensitivity of the photosensitive composition to ultraviolet rays, and during the vacuum lamination process. The followability and adhesion tend to become better. From such a viewpoint, among the photopolymerization initiators (C), an acridine derivative is more preferable. (C) The photopolymerization initiator may contain any combination of acridine derivatives, anthracene derivatives, and pyrazoline derivatives, and these derivatives and other photopolymerization initiators may be used in combination.

Examples of acridine derivatives include 9-phenylacridine, 1,6-bis(9-acridinyl)hexane, 1,7-bis(9-acridinyl)heptane, 1,6-bis(9-acridinyl)heptane, 8-Bis(9-acridinyl)octane, 1,9-bis(9-acridinyl)nonane, 1,10-bis(9-acridinyl)decane, 1,11-bis(9 -acridinyl)undecane, 1,12-bis(9-acridinyl)dodecane, etc. Among them, 9-phenylacridine is preferred.

From the viewpoint of improvement of sensitivity and/or resolution, and good followability and adhesiveness, it is preferable to use the above-mentioned acridine derivative and N-arylamino acid together. Examples of N-arylamino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like, wherein Preferred is N-phenylglycine.

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, and 9,10-dibutoxyanthracene , 9,10-diphenylanthraquinone, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, etc.

Examples of pyrazoline derivatives include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1- -(4-(Benzoxazol-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline , 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5 -(4-Third-octyl-phenyl)-pyrazoline and the like.

As the (C) photopolymerization initiator that can be used in the present embodiment, the above-mentioned derivatives and a hexaarylbisimidazole derivative (hereinafter also referred to as a dimer of a triarylimidazolyl derivative, or a triaryl imidazolyl dimer). Examples of triarylimidazolyl dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimers (hereinafter also referred to as 2,2′-bis(2-chlorobenzene) base)-4,4',5,5'-tetraphenyl-1,1'-bisimidazole), 2,2',5-tri-(o-chlorophenyl)-4-(3,4-di Methoxyphenyl)-4',5'-diphenylimidazolyl dimer, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)- Diphenylimidazolyl dimer, 2,4,5-tris-(o-chlorophenyl)-diphenylimidazolyl dimer, 2-(o-chlorophenyl)-bis-4,5-(3 ,4-Dimethoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetra-(3-methoxy Phenyl)-imidazolyl dimer, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetra-(3-methoxyphenyl) )-imidazolyl dimer, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2' -Bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis -(2,3,5-Trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-( 2,3,6-Trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2, 4,5-Trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,4, 6-Trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,3,4, 5-Tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,3,4, 6-Tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, and 2,2'-bis-(2,3,4 ,5,6-pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer. In particular, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer is a photopolymerization initiator that has a high effect on the resolution and the strength of the cured film, and can preferably be used as a photopolymerization initiator. use.

等9-氧硫𠮿

類與烷基胺基苯甲酸之組合；以及1-苯基-1,2-丙二酮-2-O-安息香肟、及1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)肟等肟酯類。As a compound which can be used as the (C) photopolymerization initiator other than the above, for example, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,4-naphthoquinone, Quinones such as 3-dimethylanthraquinone and 3-chloro-2-methylanthraquinone; Benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone] , and 4,4'-bis (diethylamino) benzophenone and other aromatic ketones; benzoin, benzoin ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin and other benzoin ethers; Methyl ketal, benzil diethyl ketal, 2,4-diethyl 9-oxothioate

Wait for 9-oxysulfur 𠮿

and alkylaminobenzoic acid; and 1-phenyl-1,2-propanedione-2-O-benzoin oxime, and 1-phenyl-1,2-propanedione-2-(O - Oxime esters such as ethoxycarbonyl) oxime.

類與烷基胺基苯甲酸之組合，例如可列舉：乙基9-氧硫𠮿

與二甲基胺基苯甲酸乙酯之組合、2-氯9-氧硫𠮿

與二甲基胺基苯甲酸乙酯之組合、及異丙基9-氧硫𠮿

與二甲基胺基苯甲酸乙酯之組合。又，較佳為六芳基雙咪唑衍生物與芳香族酮類之組合。Furthermore, as the above-mentioned 9-oxysulfur 𠮿

The combination of sulfhydryl and alkylamino benzoic acid, for example: ethyl 9-oxothioate

In combination with ethyl dimethylaminobenzoate, 2-chloro-9-oxothioate

Combination with ethyl dimethylaminobenzoate, and isopropyl 9-oxothioate

In combination with ethyl dimethylaminobenzoate. Moreover, a combination of a hexaarylbisimidazole derivative and an aromatic ketone is preferable.

{式中，R¹ 及R² 分別獨立地選自由不包含偶氮基之碳數1～20之一價有機基所組成之群}(D) The compound represented by general formula (1) The photosensitive resin composition of one Embodiment of this invention contains the compound represented by following general formula (1) as a compound (D). [Chemical 11]

{In the formula, R ¹ and R ² are independently selected from the group consisting of monovalent organic groups with 1 to 20 carbon atoms that do not include azo groups}

The compound represented by the general formula (1) contains a cyano group (-CN) and does not contain an azo group (R-N=N-R'). The dipole moment of the C≡N bond in the cyano group of the compound represented by the general formula (1) is large, and it is easy to interact with copper (Cu). Therefore, when the photosensitive resin composition contains the components (A) to (C) and contains the compound represented by the general formula (1), there is a tendency that the photosensitive resin composition can interact with the Cu surface of a copper (Cu) substrate and the like to improve Adhesion, so that when it is laminated with the substrate, both the followability and adhesion to the substrate are taken into account. This tendency is remarkable when the substrate has a step difference or the substrate contains copper (Cu).

If the lamination of the laminate of the support and the photosensitive resin composition and the substrate has good followability, there is an advantage in that no gap is formed between the photoresist and the substrate, so that the wiring formation step after lamination is not easy. defects in. On the other hand, in lamination, there is an advantage that the better the adhesion, the thinner the photoresist pattern can be formed.

The compound represented by the general formula (1) is preferably solid at 25°C. It is thought that the compound which is solid at 25 degreeC softens by heating at the time of lamination with a board|substrate, and shows flexibility, and the followability to a board|substrate becomes favorable by this. Furthermore, when the compound represented by the general formula (1) is liquid or waxy at 25° C., it is considered that there is no temperature responsiveness at the time of lamination with a substrate.

As a method for making the compound represented by the general formula (1) solid at 25°C, it is preferable to control the molecular weight of the compound represented by the general formula (1) within an appropriate range, and it is more preferable to control the molecular weight to 100 g/mol or more within the range of 250 g/mol or less, and more preferably controlled within the range of 111 g/mol or more and 240 g/mol or less.

The molecular weight of the compound represented by the general formula (1) is preferably 100 g from the viewpoint of being in a solid state at 25°C as described above, and from the viewpoint of the followability of the photosensitive resin composition or photosensitive element to the substrate /mol or more and 250 g/mol or less. When the molecular weight is 100 g/mol or more, the compound represented by the general formula (1) is solid at 25° C., and temperature responsiveness is easily obtained during lamination with a substrate. On the other hand, when the molecular weight is 250 g/mol or less, the softening point of the compound represented by the general formula (1) and the photosensitive resin composition containing the compound is lowered, whereby flexibility is easily expressed.

Furthermore, when the photosensitive resin composition contains a compound having a molecular weight in the range of not less than 100 g/mol and not more than 250 g/mol in advance, the compound that is solid at 25°C tends to be degraded by heating during lamination. By softening and expressing flexibility, the followability to the substrate becomes good. From such a viewpoint, the molecular weight of the compound represented by the general formula (1) is more preferably in the range of 111 g/mol or more and 240 g/mol or less.

The specific structure of the compound represented by general formula (1) is demonstrated below.

In the general formula (1), both R ¹ and R ² do not contain an azo group (RN=N-R'). The azo group has the property of being decomposed by heating and light irradiation to generate free radicals. Therefore ^{, since at least one of R 1} and R ^{2 in} the general formula (1) does not contain an azo group, the present invention during storage and use can be suppressed. Unexpected polymerization of the photosensitive resin composition.

In the general formula (1), R ¹ and R ² are each independently one that does not contain an azo group and is selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms. The number of carbon atoms of the groups R ¹ and R ² is preferably 1 to 19 from the viewpoint of adhesion and followability to the substrate during lamination, and more preferably 1 to 16 in the case of a chain group. 1-14, 1-12, 1-10, 1-9, 1-8 or 1-7, in the case of a cyclic group, more preferably 3-19, 3-18, 3-15, 3-12 , 3~9, 3~8, 3~7, 6~18 or 6~12.

{式中，R＝C_{1 ～ 9} 烷基} ・具有氰基及C_{1 ～ 19} 支鏈烴基之基、例如下述式所表示之基等。 [化13]

{式中，R＝C_{1 ～ 9} 或C_{1 ～ 8} 烷基}The monovalent organic group having 1 to 20 carbon atoms may have a substituent, a hetero atom or a halogen atom as necessary. Examples of the monovalent organic group having 1 to 20 carbon atoms include the following groups: - For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl , n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and other straight-chain or branched alkyl groups; For example, vinyl, allyl, propenyl, 3- Butenyl, 2-butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl , butynyl, pentynyl, hexynyl and other unsaturated aliphatic hydrocarbon groups; ・For example, alkoxy, epoxy and other heteroatom-containing groups; ・For example, monofluoromethyl, difluoromethyl or trifluoromethyl halogen-containing groups such as cyclopropyl, monochloromethyl, dichloromethyl or trichloromethyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;・Aromatic groups such as phenyl, aryl, benzyl, phenoxy, benzyl, naphthyl, anthracenyl, phenanthryl, and halides of these: ・Has an amide bond and C _{1 to 19} A branched chain hydrocarbon group, such as a group represented by the following formula, etc.; [Chem. 12]

{In the formula, R = C _{1 ~ 9}} · alkyl group having C _{1 ~ 19} cyano group and a branched hydrocarbon group of, for example, the group represented by the following formula and the like. [Chemical 13]

{In the formula, R = C _{1 ~ 9} alkyl or C _{1 ~ 8}}

^{When R 1} and R ² in the general formula (1) are the same, ^{preferable combinations of R 1} and R ² include aromatic groups, for example, benzyl and phenyl.

^{When R 1} and R ² in the general formula (1) are different from each other, ^{the preferred combination of R 1} and R ² can be as follows: - Combination of straight-chain alkyl groups with different carbon numbers; in combination with a branched chain alkyl group of the alkyl group; a straight-chain alkyl group-composition and the aromatic group; composition-branched alkyl group of the aromatic; straight-chain alkyl group, acyl having amine bond and C _{1 ~ Combination of 19-} branched-chain hydrocarbon groups; ·Combination of straight-chain alkyl groups and groups having cyano groups and C _{1 to 19-} branched-chain hydrocarbon groups.

{式中，R¹ 及R² 分別獨立地選自由不包含偶氮基之碳數1～20之一價有機基所組成之群} [化15]

{式中，R¹ 為不包含偶氮基之碳數1～20之一價有機基，且R³ 為不包含偶氮基之碳數1～19之一價有機基}The compound (D) is preferably a compound in which R ₁ and/or R ₂ in the general formula (1) have an amide bond, and more preferably a compound represented by the following general formula (2) or (2A). [Chemical 14]

{In the formula, R ¹ and R ² are each independently selected from the group consisting of monovalent organic groups with 1 to 20 carbon atoms that do not include an azo group} [Chem. 15]

{In the formula, R ¹ is a monovalent organic group with 1 to 20 carbon atoms that does not contain an azo group, and R ³ is a monovalent organic group with 1 to 19 carbon atoms that does not contain an azo group}

The compound represented by the general formula (2) or (2A) has an amide bond in addition to a cyano group, whereby the interaction force with the Cu surface such as a Cu substrate increases, and the adhesion to the substrate tends to be excellent .

The groups R ¹ and R ² in the general formula (2) and the groups R ¹ in the general formula (2A) may be the same as ^{the groups R 1} and R ² defined in the general formula (1), respectively. ^{In addition, the group R 3} in the general formula (2A) may be the same as ^{the group R 2} defined in the general formula (1) as long as the number of carbon atoms is 1 to 19.

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 mass % or more and 0.0150 mass % or less with respect to the total amount of the solid content of the photosensitive resin composition, More preferably, the compound (D) is contained in an amount of 0.0001 mass % or more and 0.0100 mass % or less, and more preferably the compound (D) is contained in an amount of 0.0001 mass % or more and 0.0050 mass % or less. When the content of the compound (D) is adjusted within the range of 0.0001 to 0.0150 mass %, there is a tendency that both when the photosensitive element formed from the photosensitive resin composition is laminated on a copper (Cu) substrate having a step difference Step followability and Cu adhesion.

other ingredients In addition to the components (A) to (D) described above, the photosensitive resin composition may further contain various additives such as discoloration agents, dyes, plasticizers, antioxidants, organohalogen compounds, and nonionic interfacial activity agents, cross-linking agents and stabilizers.

discoloration agent As a color changing agent, a leuco dye and a fluoran dye are mentioned. As a leuco dye, a leuco crystal violet, a leuco malachite green, etc. are mentioned, for example. The content of the discoloring agent in the photosensitive resin composition is preferably 0.01 mass % or more from the viewpoint of recognizing good colorability (that is, color rendering property), and from the viewpoint of hue stability and obtaining a good image From the viewpoint of image characteristics, it is preferably 5 mass % or less.

dye Examples of dyes include basic green 1 [CAS: 633-03-4] (eg, trade name: Aizen Diamond Green GH; manufactured by Hodogaya Chemical Industry Co., Ltd.), malachite green oxalate [2437-29- 8] (eg trade name: Aizen Malachite Green; 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] (eg trade name: Aizen Victoria Pure Blue BOH; 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 which basic green 1, malachite green oxalate, and basic blue 7 are preferred.

The amount of the dye in the photosensitive resin composition is preferably within a range of 0.001 mass % to 0.3 mass %, more preferably within a range of 0.01 mass % to 0.12 mass %. The amount of the dye is preferably 0.001 mass % or more from the viewpoint of recognizing good colorability, and preferably 0.3 mass % or less from the viewpoint of maintaining sensitivity.

Plasticizer Examples of plasticizers include polyethylene glycol, polypropylene glycol (for example, Mw≒2000), polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxyethylene Glycol-esters such as propylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether; phthalates such as diethyl phthalate; o-toluenesulfonic acid Sulfonamides such as acetamide and p-toluenesulfonamide; tributyl citrate, triethyl citrate, acetonitrile triethyl citrate, acetonitrile tri-n-propyl citrate, and acetonitrile tri-n-propyl citrate Butyl ester. Among them, sulfonamides are preferred.

The amount of the plasticizer in the photosensitive resin composition is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass to 20% by mass, and still more preferably 3% by mass to 10% by mass. The amount of the plasticizer is preferably 0.1 mass % or more from the viewpoint of securing viscosity stability, suppressing the development time delay, and imparting flexibility or releasability to the cured film, and suppressing insufficient curing and cooling From the viewpoint of flow, it is preferably 50 mass % or less.

Antioxidants Examples of antioxidants include triphenyl phosphite (for example, manufactured by ADEKA Co., Ltd.; trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (for example, ADEKA Co., Ltd. manufactured by the company; trade name: 2112), tris(mononylphenyl) phosphite (for example, manufactured by ADEKA Co., Ltd., trade name: 1178), and bis(mononylphenyl)-dinonylbenzene phosphite Esters (eg, manufactured by ADEKA Co., Ltd.; trade name: 329K). The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01 to 0.8 mass %, more preferably in the range of 0.01 to 0.3 mass %. When the said content is 0.01 mass % or more, the effect which is excellent in the hue stability of the photosensitive resin composition is exhibited well, and the sensitivity at the time of exposure of the photosensitive resin composition is favorable. Moreover, when the said content is 0.8 mass % or less, the color developability is suppressed, and the hue stability is favorable by this, and adhesiveness is also favorable.

organohalogen compounds Examples of the organic halogen compound include bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, 1,2-dibromoethane, diphenylbromomethane, benzyl bromide, and dibromomethane. , Tribromomethylbenzene, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro -2,2-bis(p-chlorophenyl)ethane, and chlorinated tris(II) compounds, among them, tribromomethylbenzene is particularly preferably used. The amount of the organic halogen compound 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, or 0.01% by mass to 1.0% by mass.

nonionic surfactant As the nonionic surfactant, sorbitan fatty acid compounds such as polyoxyethylene sorbitan trioleate (such as A product named "Newcol 3-85" purchased from Nippon Emulsifier Co., Ltd., etc.). The amount of the nonionic surfactant in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 2.5% by mass, and still more preferably 0.5% by mass to 2.0% by mass or 1 mass % to 2 mass %.

cross-linking agent As the crosslinking agent, from the viewpoint of water resistance or heat resistance, a dithiol compound having a tris' skeleton, such as 2-(dibutylamino)-1,3,5-tris'-4, is preferable. 6-Dithiol (for example, a product named "BSH" which can be purchased from Kawaguchi Chemical Industry Co., Ltd.). 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.

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

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di- Tributyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tertiary butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), nitrosophenylhydroxylamine aluminum salt (eg, amine addition molar: 3), and N - Nitrosodiphenylamine.

Examples of thiazoles include 2-mercaptobenzothiazole, 6-amino-2-mercaptobenzothiazole, 2-mercapto-5-methoxybenzothiazole, and 5-chloro-2-mercaptobenzothiazole Wait. As thiadiazoles, 2-amino-5-mercapto-1,3,4-thiadiazole etc. are mentioned, for example.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminoidene Methyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolutriazole, bis(N-2-hydroxyethyl) ) aminomethylene-1,2,3-benzotriazole, 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,3-benzotriazole, etc. .

Examples of 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)aminoethylidene carboxybenzotriazole, and 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-normal 1:1 mixture of butylaminomethyl)-6-carboxybenzotriazole.

Examples of cresols include 4,4'-butylenebis(6-tert-butyl-m-cresol), and specific examples include "Antage W-300" available from Kawaguchi Chemical Industry Co., Ltd. "products, etc.

The total amount of the 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 still more preferably 0.05% by mass to 1.9% by mass. The total amount is preferably 0.001 mass % or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and preferably 4.0 mass % or less from the viewpoint of maintaining the sensitivity well .

<Photosensitive resin composition preparation solution> The photosensitive resin composition of this invention can also be used as a photosensitive resin composition preparation liquid which added a solvent to it. As a preferable solvent, ketones represented by methyl ethyl ketone (MEK), and alcohols, such as methanol, ethanol, and isopropanol, are mentioned. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of a photosensitive resin composition preparation liquid may become 500 mPa·sec - 4000 mPa·sec at 25 degreeC.

<Photosensitive element (photosensitive resin laminate)> Another aspect of the present invention provides a photosensitive resin laminate (hereinafter also referred to as a photosensitive element) having a support and a photosensitive resin layer, the photosensitive resin layer being laminated on the support, and comprising the present invention described above The photosensitive resin composition. In addition to the photosensitive resin layer and the support which supports the photosensitive resin layer, the photosensitive element may have a protective layer on the surface of the photosensitive resin layer opposite to the side where the support is formed, if necessary. From the viewpoint of being used in photolithography, the photosensitive element is preferably a photoresist having a dry film form (hereinafter also referred to as dry film photoresist).

As a support, the transparent support which transmits the light radiated from a self-exposure light source is preferable. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polyvinylidene chloride film, and a polyvinylidene chloride film. Methyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film and cellulose derivative film, etc. Extensions of these films can also be used as supports if desired. In addition, the haze of the film used as the support is preferably 5 or less, and from the viewpoints of image forming properties and economical efficiency, the thinner the thickness is, the more advantageous it is, but the thickness is preferred from the viewpoint of maintaining strength 10 μm to 30 μm.

In addition, an important characteristic of the protective layer used in the photosensitive element is that the adhesive force between the protective layer and the photosensitive resin layer is smaller than the adhesive force between the support and the photosensitive resin layer, so that the protective layer can be easily peeled off. For example, polyethylene films, polypropylene films, etc. are preferable as the protective layer. Moreover, as a protective layer, the film excellent in peelability shown in Unexamined-Japanese-Patent No. 59-202457, for example can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

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. The thinner the photosensitive resin layer, the higher the resolution, and the higher the thickness, the higher the film strength, so it can be appropriately selected according to the application.

As a method of laminating a support body, a photosensitive resin layer, and an optional protective layer in this order to produce a photosensitive element, a conventionally known method can be employed. For example, after the photosensitive resin composition for forming the photosensitive resin layer is previously formed in the form of the above-mentioned photosensitive resin composition preparation, it is first applied to the support using a bar coater or a roll coater. The photosensitive resin layer containing the photosensitive resin composition is laminated on the support body and dried. Then, if necessary, a photosensitive element can be produced by laminating a protective layer on the photosensitive resin layer.

＜Lamination＞ Another aspect of the present invention is a method of laminating the above-mentioned photosensitive element of the present invention to a substrate.

From the viewpoint of suppressing the generation of air bubbles (voids) or wrinkles in the laminate of the photosensitive element and the substrate, the lamination of the photosensitive element and the substrate is preferably vacuum lamination, and specifically, preferably in a place where the atmospheric pressure is not high. under air pressure. Vacuum lamination can be performed using, for example, a diaphragm type laminator, a hydraulic type laminator, or the like.

In the case where the photosensitive element is a dry film photoresist, the lamination of the dry film photoresist and the substrate can be: dry lamination, which is performed in the absence of liquid; or wet lamination, which involves liquid lamination. It is suitable for filling the gap between the substrate and the dry film photoresist, and filling the gap between the substrate and the dry film photoresist; vacuum lamination, which is carried out under the pressure below atmospheric pressure; among them, the followability of the dry film photoresist to the substrate From the viewpoint of adhesiveness, vacuum lamination is preferable. In addition, the vacuum lamination can be performed, for example, at a vacuum degree of 1 to 1000 Pa, preferably 50 to 500 Pa.

<Method for forming a photoresist pattern> After the lamination described above, a method for forming a photoresist pattern can be provided, which sequentially performs an exposure step and a development step, the exposure step is to expose the photosensitive resin layer of the photosensitive element, and the development step uses a developing solution The photosensitive resin layer after exposure is developed to form a photoresist pattern. An example of a specific method of forming a photoresist pattern using the dry lamination and/or vacuum lamination described above is shown.

After dry lamination/vacuum lamination, in the exposure step, the photosensitive resin composition in the photosensitive resin layer is exposed to active light using an exposure machine. The exposed part of the photosensitive resin layer is polymerized and cured (when the photosensitive resin composition is negative type) or solubilized with respect to the developer (when the photosensitive resin composition is positive type). If necessary, exposure can be performed after peeling off the support. In the case of exposure through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and can be measured using a light meter. In the exposure step, a maskless exposure method can be used. In maskless exposure, exposure is performed on the substrate by a direct writing device without using a mask. As a light source, a semiconductor laser with a wavelength of 350 nm to 410 nm, an ultra-high pressure mercury lamp, or the like is used. The writing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Then, in the developing step, the unexposed part (when the photosensitive resin composition is negative) or the exposed part (in the photosensitive resin layer) in the exposed photosensitive resin layer is removed by a developing device and a developing solution. when the composition is positive). When a support exists on the photosensitive resin layer after exposure, the support is removed. Then, the unexposed portion or the exposed portion is developed and removed using a developer containing an alkaline aqueous solution to obtain a photoresist image. The alkaline aqueous solution is preferably an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ or the like. These are selected according to the characteristics of the photosensitive resin layer, and are usually Na ₂ CO ₃ aqueous solutions with a concentration of 0.2 to 2 mass %. The alkaline aqueous solution can be mixed with surfactants, defoaming agents, and a small amount of organic solvents for promoting development. Furthermore, the temperature of the developing solution in the developing step is preferably kept constant within the range of 20°C to 40°C.

The photoresist pattern is obtained by the above steps, and a heating step of 100°C to 300°C may be further performed depending on the situation. By carrying out this heating step, the chemical resistance of the pattern can be further improved. Heating can use hot air, infrared or far infrared heating furnace.

<Manufacturing method of conductor pattern> Another aspect of this invention is the manufacturing method of the conductor pattern which comprises the lamination of the said photosensitive element and a board|substrate. In the manufacture of the conductor pattern, from the viewpoint of suppressing generation of voids or wrinkles in the laminate of the photosensitive element and the substrate, the lamination of the photosensitive element and the substrate is preferably performed under a pressure lower than atmospheric pressure. An example of the manufacturing method of the conductor pattern using the dry lamination and/or vacuum lamination demonstrated above is shown below.

The manufacturing method of the conductor pattern according to one embodiment of the present invention can be implemented by using a metal plate or a metal film insulating plate as a substrate, after forming a photoresist pattern by the above-mentioned photoresist pattern forming method, and then going through a conductor pattern forming step. For example, after the above dry lamination/vacuum lamination, the following steps can be performed in sequence: an exposure step, which exposes the photosensitive resin layer; a development step, which uses a developer to develop the exposed photosensitive resin layer , thereby forming a photoresist pattern; and a step of forming a conductor pattern, which is to perform etching or plating on the substrate on which the photoresist pattern is formed.

In the conductor pattern forming step, in the substrate on which the photoresist pattern is formed by the above-mentioned method, conductors can be formed on the substrate surface (eg copper surface) exposed by development using a known etching method or plating method pattern.

Furthermore, the present invention is preferably applied to, for example, the following applications.

<Manufacture of printed wiring boards> Furthermore, according to the present invention, after the conductor pattern is produced by the above-mentioned method, a printed wiring board with the desired wiring pattern can be obtained by further performing the peeling step, which utilizes an alkali stronger than the developing solution. The aqueous solution peels the photoresist pattern from the substrate. In the manufacture of printed circuit boards, it is preferable to use a copper foil laminate or a flexible substrate as a substrate. There is no particular limitation on the alkaline aqueous solution for peeling (hereinafter, also referred to as "peeling liquid"), and an aqueous solution of NaOH or KOH with a concentration of 2 to 5 mass % is usually used. A small amount of water-soluble solvent can be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably in the range of 40°C to 70°C.

<Manufacture of lead frame> Using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate, after forming a photoresist pattern by the above-described photoresist pattern forming method, a lead frame can be manufactured through the following steps. First, a step of forming a conductor pattern by etching the substrate exposed by the development is performed. After that, a peeling step of peeling off the photoresist pattern by the same method as the manufacturing method of the above-mentioned printed wiring board is performed to obtain a desired lead frame.

<Manufacture of the base material with uneven|corrugated pattern> The photoresist pattern formed by the photoresist pattern formation method of this invention can be used as a protective mask member when a board|substrate is processed by sandblasting method. Examples of the substrate in this case include glass, silicon wafer, amorphous silicon, polysilicon, ceramics, sapphire, and metal materials. On these substrates, photoresist patterns are formed by the same method as the above-mentioned photoresist pattern formation method. After that, through a sandblasting step and a peeling step, a substrate with a fine concave-convex pattern on the substrate can be produced. The sandblasting step is to blow a blasting material from the formed photoresist pattern and cut it to a target depth. The peeling step Part of the photoresist pattern remaining on the substrate is removed from the substrate by an alkaline stripping solution or the like. As the blasting material used in the sandblasting step, known ones can be used, for example, fine particles of 2 μm to 100 μm in diameter _{such as SiC, SiO 2} , Al ₂ O ₃ , CaCO _{3 , ZrO, glass, stainless steel, etc. can be used.}

<Manufacture of semiconductor packages> A semiconductor package can be manufactured by using a wafer on which a large scale integrated circuit (LSI) is formed as a substrate, and after forming a photoresist pattern on the substrate by the above-mentioned photoresist pattern forming method, through the following steps. First, a step of forming a conductor pattern by applying columnar plating of copper, solder, or the like to the opening exposed by the development is performed. After that, a peeling step of peeling off the photoresist pattern by the same method as the above-mentioned manufacturing method of the printed wiring board is performed, and further a step of removing the thin metal layer except for the columnar plating by etching is performed, thereby The desired semiconductor package can be obtained. [Example]

The present invention will be described in detail in the following examples, but the present invention is not limited to these examples.

The production methods of the samples for evaluation of Examples 1 to 15 and Comparative Examples 1 to 2, and the evaluation methods and evaluation results of the obtained samples are shown.

<Method for preparing samples for evaluation> Samples for evaluation were prepared as follows.

＜Production of photosensitive element＞ The components shown in the following Table 1 (wherein, the numbers of each component represent the compounding amount (parts by mass) as solid content) and methyl ethyl ketone measured so that the solid content concentration becomes 55% are fully stirred. It mixed and obtained the photosensitive resin composition preparation liquid. Details of the components shown in Table 1 are shown in Tables 2 and 3. A 16 μm-thick polyethylene terephthalate film (16FB40 manufactured by Toray Co., Ltd.) was used as a support film, and the mixture was uniformly coated on its surface using a bar coater, and the mixture was heated at 95°C. The photosensitive resin layer was formed by drying for 2 minutes and 30 seconds in a drier. The dry thickness of the photosensitive resin layer was 25 μm. Next, a 19 μm-thick polyethylene film (GF-18, manufactured by Tamapoly Co., Ltd.) was attached as a protective layer to the surface of the photosensitive resin layer on the side on which the polyethylene terephthalate film was not laminated to obtain a photosensitive element. In addition, content of the compound (D) in Table 1 means the density|concentration based on the solid content total amount in a photosensitive resin composition.

<Substrate surface trimming> A 0.4 mm thick copper foil with a 35 μm rolled copper foil layered as a substrate for evaluation of image properties was applied with an abrasive (#400 manufactured by Uji Electrochemical Co., Ltd.) under a spray pressure of 0.2 MPa. After the laminated board was sandblasted and brushed, the substrate surface was washed _{with a 10 mass % H 2} SO _{4 aqueous solution.}

＜Lamination＞ While peeling off the polyethylene film (protective layer) of the photosensitive element, the photosensitive element was laminated to a preheated surface at a roll temperature of 105°C by a heating roll laminating machine (AL-700 manufactured by Asahi Kasei Co., Ltd.). Copper foil laminates to 50°C. The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m/min.

＜Exposure＞ The substrate for evaluation after 2 hours after lamination was exposed by a direct writing exposure machine (INPREX IP-8 8000 manufactured by ADTEC Engineering Co., Ltd.) using a Stuffier 41-stage exposure meter. Exposure was performed with the above-mentioned Stuffy 41-stage exposure meter as a mask, and the maximum residual film level during development was 14 levels of exposure.

<Development> After peeling the polyethylene terephthalate film (support film) from the photosensitive element, using an alkaline developing machine (developer for dry film by Fuji Kiko Co., Ltd.) The 1 mass % Na ₂ CO ₃ aqueous solution was sprayed and developed. The time of developing spray was set as twice the shortest developing time, and the time of water washing spray after developing was set as twice the shortest developing time. At this time, the shortest time required for the photosensitive resin layer of the unexposed part to melt|dissolve completely was made into the shortest developing time.

＜Assessment＞ The evaluation method of the sample is described below.

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

＜Followability＞ For the copper foil laminate, a commercially available dry film resist (DFR) was used for lamination, exposure, development, etching and peeling to produce a pit substrate with circular depressions with a diameter of 310 μm and a depth of about 10 μm. The photosensitive element obtained above was subjected to a roll temperature of 80°C, a cylinder pressure of 0.4 MPa, a degree of vacuum = 100 Pa, and a speed of 1 m/min using a roll-type thermal vacuum laminating machine (MVR-250 manufactured by MCK Co., Ltd.). The surface of the photosensitive element (film thickness=25 μm) from which the protective film was peeled was laminated to the pit substrate under the same conditions. At this time, the average value of the air remaining in the pits without sufficient tracking of the photosensitive element at a diameter of 10 was calculated, and evaluated according to the following criteria. If the evaluation is "Yes" or higher, it will be regarded as pass. (assessment benchmark) Excellent: below 100 μm Good: Over 100 μm and 150 μm or less Possible: Over 150 μm and 200 μm or less Impossible: Over 200 μm

＜Adhesion＞ In the above-mentioned exposure step, exposure is performed using the writing data having a line pattern, and the width of the exposed portion and the unexposed portion in the line pattern is a ratio of x μm:200 μm. The minimum line width at which hardened photoresist lines are normally formed by developing in accordance with the above-mentioned developing conditions is determined by optical microscopy. This measurement was performed for four lines, the average value of the four line widths was obtained as the value of the adhesiveness, and the evaluation was performed according to the following criteria. If the evaluation is "Yes" or higher, it will be regarded as pass. (assessment benchmark) Excellent: Below 7 μm Good: Over 7 μm and 9 μm or less Possible: Over 9 μm and 11 μm or less No: more than 12 μm

＜Evaluation results＞ The evaluation results of Examples 1 to 15 and Comparative Examples 1 to 2 are shown in Tables 1 to 3.

[Table 1-1] compound Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 A-1 20 35 20 20 25 25 A-2 55 55 35 35 50 25 25 A-3 20 15 B-1 10 15 15 25 10 10 B-2 5 10 10 5 5 B-3 10 10 10 30 10 10 B-4 10 10 B-5 5 5 5 5 5 B-6 5 B-7 5 B-8 5 5 5 B-9 15 15 15 B-10 5 5 B-11 5 C-1 2.5 2.5 2.5 3.5 3.5 3.5 C-2 0.14 0.14 0.25 0.25 C-3 0.25 C-4 0.8 0.8 0.8 C-5 0.1 0.1 0.1 C-6 0.7 0.7 0.7 E-1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 E-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 E-3 0.05 0.05 E-4 0.05 0.05 0.05 E-5 0.1 E-6 3 3 3 E-7 4 4 4 4 E-8 2 2 E-9 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 E-10 0.2 D-1 0.01 0.005 0.002 D-2 0.01 D-3 0.005 0.001 D-4 0.015 D-5 0.005 0.001 D-6 D-7 D-8 D-9 total 82.4 98.3 98.3 96.5 99.3 99.3 112.1 81.2 81.2 Compound (D) content/mass % 0.0121 0.0051 0.0020 0.0104 0.0050 0.0010 0.0134 0.0062 0.0012 following Can good excellent Can good excellent Can good excellent tightness Can good good good good excellent Can excellent excellent

[Table 1-2] compound Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Comparative Example 1 Comparative Example 2 A-1 20 30 30 30 30 30 20 20 A-2 35 A-3 20 20 20 25 20 20 20 B-1 10 25 10 B-2 5 5 B-3 10 10 10 10 B-4 10 10 5 10 B-5 5 5 5 15 15 5 5 B-6 5 B-7 B-8 5 5 5 5 10 10 5 5 B-9 15 15 15 B-10 5 5 5 B-11 C-1 2.5 2.5 2.5 3 3.5 3.5 2.5 3.5 C-2 0.25 0.25 0.25 0.25 0.25 0.25 C-3 0.25 0.25 C-4 C-5 C-6 E-1 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 E-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 E-3 E-4 0.05 0.05 0.05 0.05 0.05 E-5 0.1 E-6 3 3 E-7 4 4 4 E-8 E-9 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 E-10 0.2 D-1 D-2 D-3 D-4 D-5 D-6 0.01 D-7 0.005 0.001 D-8 0.015 D-9 0.006 0.001 total 82.4 93.4 93.4 103.2 92.31 92.305 82.4 99.3 Compound (D) content/mass % 0.0121 0.0054 0.0011 0.0145 0.0065 0.0011 0.0000 0.0000 following Can good excellent Can good excellent not possible not possible tightness Can good good good good good Can Can

[Table 2] compound structure A-1 Methacrylic acid/methyl methacrylate/styrene = 29/19/52 A-2 Methacrylic acid/methyl methacrylate/styrene = 25/50/25 A-3 Methacrylic acid/methyl methacrylate/styrene = 21/39/40 B-1 Dimethacrylate of polyethylene glycol obtained by adding an average of 5 moles of ethylene oxide to both ends of bisphenol A B-2 Dimethacrylate of polyalkylene glycol obtained by adding an average of 12 moles of propylene oxide to both ends of the polypropylene glycol obtained by adding an average of 3 moles of ethylene oxide to each B-3 Nonaethylene glycol diacrylate B-4 Dimethacrylate of polyalkylene glycol obtained by adding an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A B-5 Triacrylate obtained by adding an average of 3 moles of ethylene oxide to trimethylolpropane B-6 Diacrylate of polyalkylene glycol obtained by adding an average of 5 moles of ethylene oxide to both sides of bisphenol A B-7 Triacrylate obtained by adding trimethylolpropane to an average of 9 moles of ethylene oxide B-8 Urethane compound of hexamethylene diisocyanate and polypropylene glycol monomethacrylate B-9 Dimethacrylate of polyethylene glycol obtained by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A B-10 Trimethylolpropane triacrylate B-11 4-Nonylphenyl heptaethylene glycol dipropylene glycol acrylate C-1 2-(o-Chlorophenyl)-4,5-diphenylimidazole dimer C-2 4,4'-Bis(diethylamino)benzophenone C-3 9,10-Diphenylanthracene C-4 9-Phenylacridine C-5 N-Phenylglycine C-6 Tribromomethylbenzene E-1 diamond green E-2 leuco crystal violet E-3 2-(Dibutylamino)-1,3,5-tris-4,6-dithiol E-4 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole E-5 Carboxybenzotriazole E-6 Polypropylene glycol with weight average molecular weight of 2000 E-7 p-toluenesulfonamide E-8 Polyoxyethylene sorbitan trioleate E-9 Addition of 3 molar aluminum salt of nitrosophenylhydroxylamine E-10 4,4'-Butylenebis(6-tert-butyl-m-cresol)

D-4 154 -CH₃

D-5 164 -C₂ H₅

D-6 182 -C₂ H₅

D-7 207

D-8 220 -CH(CH₃ )₂

D-9 240 -CH₃

[table 3] compound Molecular weight (g/mol) The base in formula (1) R ¹ R ² D-1 111 -CH ₃ -C ₃ H ₇ D-2 125 -CH ₃ -CH ₃ (CH ₂ ) ₃ D-3 136 -CH ₃

D-4 154 -CH ₃

D-5 164 -C ₂ H ₅

D-6 182 -C ₂ H ₅

D-7 207

D-8 220 -CH (CH _{3) 2}

D-9 240 -CH ₃

Claims (10)

A photosensitive resin composition comprising: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated double bond; (C) a photopolymerization initiator; and (D) the following general formula (1) ) represented by the compound

{in the formula, R ¹ and R ² are independently selected from the group consisting of monovalent organic groups with 1 to 20 carbon atoms that do not include an azo group, a thiol group, and/or a thiocarbonyl group}, and contain relative to The total amount of the solid content of the said photosensitive resin composition is 1 ppm or more and 150 ppm or less of the said compound (D). The photosensitive resin composition according to claim 1, wherein the compound (D) is solid at 25°C. 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. The photosensitive resin composition according to claim 1 or 2, which contains the above-mentioned photosensitive resin composition in an amount of 0.0001 mass % or more and 0.0100 mass % or less with respect to the total amount of the solid content of the photosensitive resin composition. Compound (D). The photosensitive resin composition of Claim 1 or 2 containing the said compound (D) with respect to the total amount of the solid content of the said photosensitive resin composition 0.0001 mass % or more and 0.0050 mass % or less. 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 formula, R ¹ is a monovalent organic group with 1 to 20 carbon atoms that does not include an azo group, a thiol group, and/or a thiocarbonyl group, and R ³ is an organic group that does not include an azo group, a thiol group, and/ Or a monovalent organic group with 1 to 19 carbon atoms in the thiocarbonyl group}. A photosensitive element comprising a support and a layer formed on the support and comprising the photosensitive resin composition according to any one of claims 1 to 6. As claimed in claim 7, the photosensitive element is a dry film photoresist. A method of laminating the photosensitive element as claimed in claim 7 or 8 to a substrate under a sub-atmospheric pressure. A method for manufacturing a conductor pattern, comprising the steps of laminating the photosensitive element as claimed in claim 7 or 8 to a substrate under a pressure below atmospheric pressure.