JP2016206312A - Photosensitive resin composition, photosensitive film laminate, flexible printed wiring board and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is alkali-developable and excellent in photosensitivity, which can suppress a development residue even when the composition is subjected to film formation using a roll type hot-vacuum laminator, and which can give excellent wire covering property even when the composition is formed into a thin film, a photosensitive film laminate, a flexible printed wiring board and a method for manufacturing the flexible printed wiring board.SOLUTION: The photosensitive resin composition comprises (A) a polyimide precursor, (B) a polymerizable compound having an unsaturated double bond, (C) a photopolymerization initiator, and (D) an antioxidant, in which the (D) antioxidant has a structure represented by general formula (1) below.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition useful as a surface protective film of a semiconductor element, an interlayer insulating film, a protective insulating film for a semiconductor package substrate or a flexible printed circuit board, and a photosensitive film using the photosensitive resin composition The present invention relates to a laminate, a flexible printed wiring board, and a method for manufacturing a flexible printed wiring board.

  In recent years, a film-like printed circuit board called a flexible printed circuit board (hereinafter also referred to as “FPC”) has gained popularity. The FPC has a structure with a coverlay made of polyimide film, etc. on a wiring-processed FCCL (Flexible Copper Clad Laminate), mainly mobile phones, smartphones, tablet terminals, notebook computers, digital cameras It is used in equipment such as. Since FPC maintains its function even when it is bent, it is an indispensable material for reducing the size and weight of equipment. In particular, in recent years, electronic devices represented by smartphones and tablet terminals have been reduced in size and weight. By adopting FPC for such products, the size and weight of the electronic devices are reduced, and the products This contributes to cost reduction and simplification of design.

  The FPC is provided with a cover lay of an insulating material layer that is used to fully or partially cover the conductor pattern on the outer surface of the printed wiring board. The most basic coverlay is a film coverlay composed of a highly reliable non-photosensitive punching material, but the automation of the bonding process is extremely difficult, and even a roll-to-roll attempt is not made. The fact is that it relies on manpower. As a practical solution to the coverlay processing process, the use of screen printing with coverlay ink is being considered, as is the case with solder masks on hard printed circuit boards. Compared to the above, it is inferior in mechanical properties and chemical resistance (particularly plating resistance), and has not been widely used.

  In view of this, development of a photosensitive coverlay for performing microfabrication by lithography has been energetically performed for miniaturization of FPC and labor saving of manufacturing processes. In recent years, materials have been designed to support development with alkaline aqueous solutions for environmental considerations. Among them, photosensitive coverlays using polyimide precursors have mechanical properties such as electrical insulation reliability derived from polyimide and bending resistance. From the viewpoint of heat resistance, chemical resistance and flame retardancy, it is expected as an excellent coverlay. In particular, the dry film type photosensitive cover lay film not only saves labor and time for application and drying compared to the method of applying a liquid photosensitive resin, but also by laminating and lithography on both sides at once. For example, a roll-to-roll production method in which a large number of drilling processes are performed at a time is possible, and shortening of the FPC manufacturing process and labor saving can be achieved.

  In order to obtain photosensitive polyimides that can be developed with these aqueous alkali solutions, alkali-soluble polyimides in which alkali-soluble groups are introduced into polyimides or alkali negatives by a method in which photoreactive groups are introduced into a part of all alkali-soluble groups. Negative photosensitive polyimides in which a polymerizable compound and a photopolymerization initiator are added to a developing photosensitive polyimide precursor have been developed (see, for example, Patent Document 1 and Patent Document 2).

Japanese Patent No. 5092399 JP 2011-59656 A

  However, in the conventional photosensitive resin composition, when a laminated film is formed on both sides at once using a roll-type thermal vacuum laminator, a development residue may be generated after development. In addition, when the photosensitive coverlay is also thinned in response to the need for thinning the process circuit board, the conventional photosensitive resin composition may deteriorate the coating reliability on the wiring.

  The present invention has been made in view of such points, and in particular, when alkali development is possible and photosensitivity is excellent, and development residues can be suppressed even when film formation is performed using a roll-type thermal vacuum laminator. Even if it exists, it aims at providing the photosensitive resin composition which can obtain the outstanding wiring coverage, a photosensitive film laminated body, a flexible printed wiring board, and its manufacturing method.

（式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８は、それぞれ独立して水素原子、１価の有機基、ハロゲン原子のいずれかを表し、同じであっても異なっていてもよい。Ｒ_１とＲ_２の炭素数合計は１〜４であり、かつＲ_７とＲ_８の炭素数合計は１〜４である。Ａ_１は直結あるいは以下の一般式（２）から選択されるいずれかの構造を有する：

式中、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２、Ｒ_１３、Ｒ_１４、Ｒ_１５、Ｒ_１６、Ｒ_１７、Ｒ_１８、Ｒ_１９、Ｒ_２０、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_２４は、それぞれ独立して水素原子、１価の有機基、ハロゲン原子のいずれかを表し、同じであっても異なっていてもよい。ｍ、ｎはそれぞれ１以上１０以下の整数を表す。） The photosensitive resin composition of the present invention comprises (A) a polyimide precursor, (B) a polymerizable compound having an unsaturated double bond, (C) a photopolymerization initiator, (D) an antioxidant, The (D) antioxidant contains a structure represented by the following general formula (1).

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ each independently represents a hydrogen atom, a monovalent organic group, or a halogen atom, The total number of carbon atoms of R ₁ and R ₂ is 1 to 4, and the total number of carbon atoms of R ₇ and R ₈ is 1 to 4. A ₁ is directly connected or Having any structure selected from general formula (2):

In the formula, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ Each independently represents a hydrogen atom, a monovalent organic group or a halogen atom, which may be the same or different. m and n each represent an integer of 1 or more and 10 or less. )

（式中、Ａｒ_１は、芳香族を含んでなる１価の有機基、Ｒ_２５は、アルキル基、又は、アリール基を有する有機基、Ｒ_２６は、分岐鎖アルキル基、直鎖アルキル基、脂環構造を有するアルキル基、又は、芳香族構造を有するアルキル基のいずれかである炭素数３〜５０の１価の炭化水素基である。） In the photosensitive resin composition of this invention, it is preferable that the said (C) photoinitiator is a structure represented by following General formula (3).

(In the formula, Ar ₁ is a monovalent organic group containing an aromatic group, R ₂₅ is an organic group having an alkyl group or an aryl group, R ₂₆ is a branched alkyl group, a linear alkyl group, (It is a C3-C50 monovalent hydrocarbon group which is either an alkyl group having an alicyclic structure or an alkyl group having an aromatic structure.)

（式中、Ｒ_２７、Ｒ_２８、Ｒ_３０、Ｒ_３１、Ｒ_３３、Ｒ_３４、Ｒ_３６、Ｒ_３７、Ｒ_３９、Ｒ_４０はそれぞれ独立して水素原子又は数１〜２０の１価の有機基を表し、同じであっても異なっていても良い。Ｒ_２９、Ｒ_３２、Ｒ_３５、Ｒ_３８、Ｒ_４１は炭素数１〜２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。Ｒ_４２は４価の有機基を表し、Ｒ_４３は炭素数１〜９０の２価の有機基を表し、Ｒ_４４は炭素数１〜５０の４価の有機基を表す。） In the photosensitive resin composition of the present invention, the (A) polyimide precursor repeats a polyimide structure represented by the following general formula (4) and a polyamic acid structure represented by the following general formula (5), respectively. It is preferable to have it as a structural unit.

(In the formula, R ₂₇ , R ₂₈ , R ₃₀ , R ₃₁ , R ₃₃ , R ₃₄ , R ₃₆ , R ₃₇ , R ₃₉ , R ₄₀ are each independently a hydrogen atom or a monovalent organic compound having 1 to 20 numbers. R ₂₉ , R ₃₂ , R ₃₅ , R ₃₈ , R ₄₁ each represents a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p Each independently represents an integer of 0 to 100. R ₄₂ represents a tetravalent organic group, R ₄₃ represents a divalent organic group having 1 to 90 carbon atoms, and R ₄₄ has 1 to 50 carbon atoms. Represents a tetravalent organic group.)

（式中、Ｒ_２７、Ｒ_２８、Ｒ_３０、Ｒ_３１、Ｒ_３３、Ｒ_３４、Ｒ_３６、Ｒ_３７、Ｒ_３９、Ｒ_４０はそれぞれ独立して水素原子又は炭素数１〜２０の１価の有機基を表し、同じであっても異なっていても良い。Ｒ_２９、Ｒ_３２、Ｒ_３５、Ｒ_３８、Ｒ_４１は炭素数１〜２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上３０以下の整数であり、１≦（ｍ＋ｎ＋ｐ）≦３０を満たす。） In the photosensitive resin composition of this invention, it is preferable that the diamine represented by the following general formula (6) is included as a diamine component which comprises the polyimide structure represented by the said General formula (4).

(Wherein R ₂₇ , R ₂₈ , R ₃₀ , R ₃₁ , R ₃₃ , R ₃₄ , R ₃₆ , R ₃₇ , R ₃₉ , R ₄₀ are each independently a hydrogen atom or a monovalent valence having 1 to 20 carbon atoms. R ₂₉ , R ₃₂ , R ₃₅ , R ₃₈ , R ₄₁ each represents an organic group, and may represent a tetravalent organic group having 1 to 20 carbon atoms, m, n, p Are each independently an integer of 0 to 30, which satisfies 1 ≦ (m + n + p) ≦ 30.)

  The photosensitive resin composition of the present invention preferably contains (E) a nitroso compound and / or at least one polymerization inhibitor containing a nitro compound.

  In the photosensitive resin composition of this invention, it is preferable that (di) pentaerythritol (meth) acrylate ester compound is included as said (B) polymeric compound which has an unsaturated double bond.

  In the photosensitive resin composition of this invention, it is preferable that (F) at least 1 type of block isocyanate compound is included.

  The photosensitive resin composition of the present invention preferably contains at least one (G) phosphorus compound.

In the photosensitive resin composition of the present invention, it is preferable that R ₁ , R ₂ , R ₇ and R ₈ in the general formula (1) are all methyl groups.

  The photosensitive film laminated body of this invention has a base material and the photosensitive film formed on the surface of the said base material using the photosensitive resin composition as described above, It is characterized by the above-mentioned.

  In the photosensitive film laminated body of this invention, it is preferable that the said base material is a carrier film.

  The flexible printed wiring board of the present invention includes a circuit board having wiring, and a photosensitive film formed by baking on the surface of the circuit board using the photosensitive resin composition described above. And

  In the method for producing a flexible printed wiring board of the present invention, the above-described photosensitive film laminate is laminated on a wiring surface on a circuit board having wiring using a roll-type thermal vacuum laminator, and then fired to form a film. It is characterized by that. The flexible printed wiring board of the present invention is manufactured by the above manufacturing method.

  According to the photosensitive resin composition of the present invention, alkali development is possible and excellent in photosensitivity, and even when a film is formed using a roll-type thermal vacuum laminator, development residues can be suppressed, and even when the film is thinned. Excellent wiring coverage can be obtained.

  Therefore, by using the photosensitive resin composition of the present invention, a photosensitive film laminate having excellent photosensitivity due to alkali development, no development residue, and excellent wiring coverage, and a flexible printed wiring board Can be obtained.

  Further, according to the method for producing a flexible printed wiring board of the present invention, the photosensitivity by alkali development is excellent, no development residue is generated even when a film is formed using a roll-type thermal vacuum laminator, and the wiring coverage is excellent. The flexible printed wiring board can be manufactured appropriately and easily.

  Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as embodiments) will be described in detail. In addition, this invention is not limited to the following embodiment, It can deform | transform and implement within the range of the summary.

ここで、一般式（１）の式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８は、それぞれ独立して水素原子、１価の有機基、ハロゲン原子のいずれかを表し、同じであっても異なっていてもよい。また、Ｒ_１とＲ_２の炭素数合計は１〜４であり、かつＲ_７とＲ_８の炭素数合計は１〜４である。また、Ａ_１は直結あるいは以下の一般式（２）から選択されるいずれかの構造を有する。

ここで一般式（２）の式中、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２、Ｒ_１３、Ｒ_１４、Ｒ_１５、Ｒ_１６、Ｒ_１７、Ｒ_１８、Ｒ_１９、Ｒ_２０、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_２４は、それぞれ独立して水素原子、１価の有機基、ハロゲン原子のいずれかを表し、同じであっても異なっていてもよい。ｍ、ｎはそれぞれ１以上１０以下の整数を表す。 The photosensitive resin composition according to the present embodiment includes (A) a polyimide precursor, (B) a polymerizable compound having an unsaturated double bond, (C) a photopolymerization initiator, and (D) an antioxidant. The (D) antioxidant contains the structure represented by following General formula (1).

Here, in the formula of the general formula (1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, a monovalent organic group, Represents any of the halogen atoms and may be the same or different. The total carbon number of R ₁ and R ₂ is 1 to 4, and the total carbon number of R ₇ and R ₈ is 1 to 4. A ₁ has a structure directly selected or selected from the following general formula (2).

Here, in the formula of the general formula (2), R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ each independently represent a hydrogen atom, a monovalent organic group, or a halogen atom, and may be the same or different. m and n each represent an integer of 1 or more and 10 or less.

  Since the photosensitive resin composition of this Embodiment contains (A) a polyimide precursor, it becomes alkali developable. Moreover, (C) While containing the photoinitiator and the antioxidant of this Embodiment, the addition amount of antioxidant can be reduced and photosensitivity improves. Moreover, (D) By containing the antioxidant which has a structure represented by said General formula (1), even if it forms into a film using a roll-type thermal vacuum laminator, a development residue does not generate | occur | produce. And since (D) antioxidant has moderate steric hindrance in both ortho positions of a hydroxyl group, it can suppress a development residue effectively with a small addition amount. For this reason, it has a wiring covering property as well as excellent photosensitivity even when it is thinned without inhibiting the curing reaction during exposure. Hereinafter, each component will be described.

(A) Polyimide precursor Although the polyimide precursor in the photosensitive resin composition which concerns on this Embodiment is not specifically limited, For example, it obtains by making tetracarboxylic dianhydride and diamine react. Can do. There is no restriction | limiting in the tetracarboxylic dianhydride to be used, A conventionally well-known tetracarboxylic dianhydride can be used. As the tetracarboxylic dianhydride, aromatic tetracarboxylic acid or aliphatic tetracarboxylic dianhydride can be applied. Moreover, there is no restriction | limiting in the diamine to be used, A conventionally well-known diamine can be used.

  Examples of the tetracarboxylic dianhydride include biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter abbreviated as “BPDA”), benzophenone-3,3 ′, 4,4′-. Tetracarboxylic dianhydride (hereinafter abbreviated as “BTDA”), oxydiphthalic dianhydride (hereinafter abbreviated as “ODPA”), diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride Anhydride, ethylene glycol bis (trimellitic acid monoester acid anhydride) (hereinafter abbreviated as “TMEG”), p-phenylene bis (trimellitic acid monoester acid anhydride), p-biphenylene bis (trimellitic acid) Monoester acid anhydride), m-phenylenebis (tomellitic acid monoester acid anhydride), o-phenylenebis (trimellitic acid monoester acid anhydride) Pentanediol bis (trimellitic acid monoester acid anhydride) (hereinafter abbreviated as “5-BTA”), decanediol bis (trimellitic acid monoester acid anhydride), pyromellitic anhydride, bis (3,4 -Dicarboxyphenyl) ether dianhydride, 4,4 '-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, meta-terphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane- 1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid-2,6: 3,5-dianhydride, 4- (2,5- Geo Sotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene -1,2-dicarboxylic acid anhydride, and the like. The tetracarboxylic dianhydrides described above may be used alone or in combination of two or more. From the viewpoint of developability of the polyimide precursor, BPDA, ODPA, BTDA, TMEG, 5-BTA, and decandiol bis (trimellitic acid monoester acid anhydride) are more preferable.

  Examples of the diamine include 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′- Diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5 5-dioxide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis (4 Aminophenyl) sulfide, 4,4′-diaminobenzanilide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane 9,9-bis (4-aminophenyl) fluorene, 5-amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, , 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene (hereinafter abbreviated as “APB”), 4,4′-bis (4-aminophenoxy) biphenyl, 4, 4′-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane (hereinafter abbreviated as “BAPP”), trimethylene -Bis (4-aminobenzoate) (hereinafter abbreviated as "TMAB"), 4-aminophenyl-4-aminobenzoate, 2-methyl-4-aminophenyl-4-aminobenzoate, bis [4- (4- Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1-amino-3-aminomethyl- 3,5,5-trimethylcyclohexane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3′-dihydroxy-4,4′-diaminobiphenyl, and 1,3-bis (4-aminophenoxybenzene) and the like can be mentioned. Among these, APB, BAPP, and TMAB are preferable from the viewpoint of lowering the glass transition point (Tg) of the polyimide precursor and improving developability. These diamines can also be used as diamine components used for the synthesis of the polyimide structure part of the polyimide precursor described later.

ここで、式中、Ｒ_２７、Ｒ_２８、Ｒ_３０、Ｒ_３１、Ｒ_３３、Ｒ_３４、Ｒ_３６、Ｒ_３７、Ｒ_３９、Ｒ_４０はそれぞれ独立して水素原子又は数１〜２０の１価の有機基を表し、同じであっても異なっていても良い。Ｒ_２９、Ｒ_３２、Ｒ_３５、Ｒ_３８、Ｒ_４１は炭素数１〜２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。Ｒ_４２は４価の有機基を表し、Ｒ_４３は炭素数１〜９０の２価の有機基を表し、Ｒ_４４は炭素数１〜５０の４価の有機基を表す。上記した一般式（４）及び一般式（５）を備えるポリイミド前駆体としては、後述する実施例で示される、ポリイミド前駆体（Ａ１）及びポリイミド前駆体（Ａ２）が該当する。 As a polyimide precursor which concerns on this Embodiment, from a viewpoint of developability and molecular weight stability, the polyimide structure represented by the following general formula (4) and the polyamic acid structure represented by the following general formula (5) are used. It is particularly preferable to have each as a repeating structural unit.

Here, in the formula, R ₂₇ , R ₂₈ , R ₃₀ , R ₃₁ , R ₃₃ , R ₃₄ , R ₃₆ , R ₃₇ , R ₃₉ , R ₄₀ are each independently a hydrogen atom or a monovalent number of 1 to 20 These organic groups may be the same or different. R ₂₉ , R ₃₂ , R ₃₅ , R ₃₈ , and R ₄₁ each represent a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p each independently represent an integer of 0 to 100. R ₄₂ represents a tetravalent organic _{group, R 43} represents a divalent organic group having 1 to 90 carbon _{atoms, R 44} represents a tetravalent organic group having 1 to 50 carbon atoms. As a polyimide precursor provided with above-mentioned General formula (4) and General formula (5), the polyimide precursor (A1) and polyimide precursor (A2) which are shown by the Example mentioned later correspond.

ここで、式中、Ｒ_２７、Ｒ_２８、Ｒ_３０、Ｒ_３１、Ｒ_３３、Ｒ_３４、Ｒ_３６、Ｒ_３７、Ｒ_３９、Ｒ_４０はそれぞれ独立して水素原子又は炭素数１〜２０の１価の有機基を表し、同じであっても異なっていても良い。Ｒ_２９、Ｒ_３２、Ｒ_３５、Ｒ_３８、Ｒ_４１は炭素数１〜２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上３０以下の整数であり、１≦（ｍ＋ｎ＋ｐ）≦３０を満たす。 Moreover, as a polyimide precursor, it is preferable that the diamine represented by following General formula (6) is included as a diamine component which comprises the polyimide structure represented by the said General formula (4).

Here, in the formula, R ₂₇ , R ₂₈ , R ₃₀ , R ₃₁ , R ₃₃ , R ₃₄ , R ₃₆ , R ₃₇ , R ₃₉ , R ₄₀ are each independently a hydrogen atom or 1 to 20 carbon atoms. Represents a valent organic group, which may be the same or different. R ₂₉ , R ₃₂ , R ₃₅ , R ₃₈ , and R ₄₁ each represents a tetravalent organic group having 1 to 20 carbon atoms, m, n, and p are each independently an integer of 0 to 30, and 1 ≦ (M + n + p) ≦ 30 is satisfied.

  In the polyimide precursor represented by the general formula (4) and the general formula (5), the molecular chain of the polyimide precursor has an appropriate flexibility due to the oxyalkylene skeleton introduced into the molecular chain of the polyimide precursor. Therefore, the developability of the photosensitive resin composition can be improved. Here, when an oxyalkylene skeleton is introduced into the polyamic acid structure part of the polyimide precursor by the diamine represented by the general formula (6), a secondary amino group derived from the diamine is introduced into the polyamic acid structure part. Is done. This secondary amino group has a high basicity and has a problem in that the depolymerization of the polyamic acid structure portion is promoted and the molecular weight of the polyimide precursor is significantly lowered as compared with the conventional polyamic acid. For this reason, in this Embodiment, the basicity of the secondary amino group mentioned above is introduce | transduced by introduce | transducing an oxyalkylene skeleton with the diamine represented by the said General formula (6) into the polyimide structure part of a polyimide precursor. The developability of the photosensitive resin composition can be improved while preventing the adverse effects of the composition and stabilizing the molecular weight.

  M, n, and p in the general formula (6) are each independently an integer of 0 or more and 30 or less. From the viewpoint of insulation reliability, 1 ≦ (m + n + p) ≦ 30 is preferable, and 3 ≦ (m + n + p) ≦ 10 is more preferable. If it is within the range of 1 ≦ (m + n + p) ≦ 30, the skeleton having an oxyalkylene group is shortened, so that the elastic modulus of the polyimide precursor is increased and the insulation reliability is estimated to be improved.

  The diamine represented by the general formula (6) is not limited as long as the polyimide structure represented by the general formula (4) is obtained. Such diamines include polyoxyethylene diamine compounds such as 1,8-diamino-3,6-dioxyoctane, and polyoxyalkylene diamine compounds such as Huntsman's Jeffamine (registered trademark) EDR-148 and EDR-176. , Jeffamine D-230, D-400, D-2000, D-4000, polyoxypropylene diamine compounds such as polyetheramine D-230, D-400, D-2000 manufactured by BASF, and HK-511 , ED-600, ED-900, ED-2003, XTJ-542 and other compounds having different oxyalkylene groups. The skeleton having these oxyalkylene groups can reduce the warpage of FPC after baking of the polyimide.

  The end of the main chain of the polyimide precursor is not particularly limited as long as it does not affect performance. A terminal structure derived from an acid dianhydride or a diamine used for producing a polyimide precursor may be used, or a structure in which the terminal is sealed with another acid anhydride or an amine compound may be used.

  The weight average molecular weight of the polyimide precursor is preferably 1000 or more and 1000000 or less. Here, the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography using polystyrene having a known weight average molecular weight as a standard. The weight average molecular weight is preferably 1000 or more from the viewpoint of the strength of the resin layer obtained by the photosensitive resin composition, and preferably 1000000 or less from the viewpoint of the viscosity and moldability of the photosensitive resin composition. . The weight average molecular weight is more preferably from 5,000 to 500,000, particularly preferably from 10,000 to 300,000, and most preferably from 15,000 to 80,000.

  A polyimide precursor having a polyimide structure and a polyamic acid structure as repeating units, respectively, is a step of reacting acid dianhydride and diamine in a non-equal molar amount to synthesize a first-stage polyimide site (step 1), followed by 2 It can be prepared by the step of synthesizing the polyamic acid moiety at the stage (Step 2). Hereinafter, each process will be described.

(Process 1)
The process of synthesizing the first-stage polyimide site will be described. The step of synthesizing the first-stage polyimide site is not particularly limited, and a known method can be applied. More specifically, it is obtained by the following method. First, diamine is dissolved and / or dispersed in a polymerization solvent, acid dianhydride powder is added thereto, a solvent azeotropic with water is added, and a by-product water is removed azeotropically using a mechanical stirrer. And stirring for 0.5 to 96 hours, preferably 0.5 to 30 hours. In this case, the monomer concentration is 0.5% by mass or more and 95% by mass or less, preferably 1% by mass or more and 90% by mass or less.

  When manufacturing a polyimide site | part, it can obtain even by adding a well-known imidation catalyst or without a catalyst. The imidization catalyst is not particularly limited, but an acid anhydride such as acetic anhydride, a lactone compound such as γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin, and γ-phthalido acid, Examples thereof include tertiary amines such as pyridine, quinoline, N-methylmorpholine, and triethylamine. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. Among these, a mixed system of γ-valerolactone and pyridine and a non-catalyst are particularly preferable from the viewpoint of high reactivity and influence on the next reaction.

  The amount of the imidization catalyst added is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less, based on 100 parts by mass of the polyamic acid.

  As a reaction solvent used in the production of the polyimide portion, dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and the like having 2 to 9 carbon atoms. Ether compounds; ketone compounds having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; benzene Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as toluene, xylene, mesitylene and tetralin; methyl acetate, ethyl acetate, γ-butyrolacto An ester compound having 3 to 12 carbon atoms such as methyl benzoate; a halogen-containing compound having 1 to 10 carbon atoms such as chloroform, methylene chloride, and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone; and sulfur-containing compounds such as dimethyl sulfoxide. These may be one kind or a mixture of two or more kinds as necessary. Particularly preferred solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms. Can be mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

  In the production of the polyimide part, the reaction temperature is preferably 15 ° C. or higher and 250 ° C. or lower. If it is 15 degreeC or more, reaction will be started, and if it is 250 degrees C or less, there will be no deactivation of a catalyst. Preferably they are 20 degreeC or more and 220 degrees C or less, More preferably, they are 20 degreeC or more and 200 degrees C or less.

  The time required for the reaction varies depending on the purpose or reaction conditions, but is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.

(Process 2)
Next, the process for synthesizing the second stage polyamic acid moiety will be described. The synthesis of the polyamic acid moiety in the second step can be carried out by using the polyimide moiety obtained in Step 1 as a starting material and adding diamine and / or acid dianhydride to cause polymerization. The polymerization temperature for producing the second stage polyamic acid moiety is preferably 0 ° C. or higher and 250 ° C. or lower, more preferably 0 ° C. or higher and 100 ° C. or lower, and particularly preferably 0 ° C. or higher and 80 ° C. or lower.

  The time required for the reaction of the polyamic acid varies depending on the purpose or reaction conditions, but is usually within 96 hours, and particularly preferably 30 minutes to 30 hours.

  As the reaction solvent, the same solvent as used for the production of the polyimide moiety in Step 1 can be used. In that case, the reaction solution of step 1 can be used as it is. Moreover, you may use the solvent different from what was used for manufacture of a polyimide site | part.

  Examples of the solvent include ether compounds having 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; carbons such as acetone and methyl ethyl ketone. A ketone compound having 2 to 6 carbon atoms; a saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin; such as benzene, toluene, xylene, mesitylene, and tetralin Aromatic hydrocarbon compounds having 6 to 10 carbon atoms; 3 or more carbon atoms such as methyl acetate, ethyl acetate, γ-butyrolactone, methyl benzoate 12 or less ester compounds; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride, 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms such as 2-pyrrolidone; sulfur-containing compounds such as dimethyl sulfoxide.

  These may be one kind or a mixture of two or more kinds as necessary. Particularly preferred solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms. Can be mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

  The polyimide precursor after the production may be used as it is dissolved in the reaction solvent, or may be recovered and purified by the following method. The polyimide precursor after the production can be recovered by distilling off the solvent in the reaction solution under reduced pressure.

  Examples of the method for purifying the polyimide precursor include a method of removing insoluble acid dianhydride and diamine in the reaction solution by vacuum filtration, pressure filtration, or the like. In addition, a so-called reprecipitation purification method in which the reaction solution is precipitated by adding it to a poor solvent can be carried out. Furthermore, when a highly pure polyimide precursor is required, an extraction method by a carbon dioxide supercritical method is also possible.

(B) Polymerizable compound The photosensitive resin composition in this Embodiment contains the polymeric compound which has an unsaturated double bond. The polymerizable compound having an unsaturated double bond in the present embodiment includes a polymerizable unsaturated functional group such as a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. Those having a vinyl group, acryloyl group, and methacryloyl group of the mold are preferred in view of polymerizability. Further, the number of polymerizable unsaturated functional groups in the polymerizable compound is preferably 2 or more from the viewpoint of polymerizability. In this case, the polymerizable unsaturated functional group may not necessarily be the same functional group. Moreover, as molecular weight of a polymeric compound, 100-5000 are preferable. In particular, when the molecular weight is in the range of 60 to 2500, the compatibility with the alkali-soluble resin is good and the storage stability is excellent.

  The polymerizable compound having an unsaturated double bond according to the present embodiment contributes to the property that the solubility of the photosensitive resin composition in an alkaline developer changes due to the change in structure caused by light irradiation. In the photosensitive resin composition according to the present embodiment, since a crosslinked product is formed by light irradiation by including a polymerizable compound having an unsaturated double bond and a photopolymerization initiator, the developer resistance is high. improves.

  Examples of the polymerizable compound having an unsaturated double bond include tricyclodecane dimethylol diacrylate, ethylene oxide (EO) -modified bisphenol A dimethacrylate, EO-modified hydrogenated bisphenol A diacrylate, and 1,6-hexanediol (meth) acrylate. 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, tris (2-acryloxy) Ethyl) isocyanurate, ε-caprolactone modified tris (acryloxyethyl) isocyanurate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxy Ropil trimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether (meth) acrylate, bisphenol A diglycidyl ether di ( (Meth) acrylate, β-hydroxypropyl-β ′-(acryloyloxy) -propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta / hex (Meth) acrylate. Among them, EO-modified bisphenol A dimethacrylate, EO-modified hydrogenated bisphenol A diacrylate, and pentaerythritol tri / tetra (meth) acrylate are preferable from the viewpoint of developability and warpage after firing. These may be used alone or in combination of two or more.

  As a particularly preferable form as the polymerizable compound having an unsaturated double bond, it is preferable that a (di) pentaerythritol (meth) acrylate ester compound is included from the viewpoint of wiring coverage. The (di) pentaerythritol (meth) acrylate ester compound means a dipentaerythritol methacrylate ester compound, a dipentaerythritol acrylate ester compound, a pentaerythritol methacrylate ester compound, and a pentaerythritol acrylate ester compound. Examples of the polymerizable compound having an unsaturated double bond including a (di) pentaerythritol (meth) acrylate ester compound include ethoxylated pentaerythritol tetraacrylate.

  (Di) pentaerythritol (meth) acrylate ester compounds include pentaerythritol tri / tetraacrylate (trade name: Aronix (registered trademark) M-303, 305, 306, 450, 452, manufactured by Toagosei Co., Ltd.), pentaerythritol tetra Acrylate (trade name: A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxylated pentaerythritol tetraacrylate (trade name: SARTOMER (registered trademark) SR-494, manufactured by Sartomer), dipentaerythritol penta / hexaacrylate (product) Name: Aronix M-400, 402, 403, 404, 405, 406, manufactured by Toagosei Co., Ltd.).

  The amount of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is from 5 parts by weight to 100 parts by weight from the viewpoint of developability when the amount of the polyimide precursor is 100 parts by weight. Is preferably 10 parts by mass or more and 80 parts by mass or less.

ここで、式中、Ａｒ_１は、芳香族を含んでなる１価の有機基、Ｒ_２５は、アルキル基、又は、アリール基を有する有機基、Ｒ_２６は、分岐鎖アルキル基、直鎖アルキル基、脂環構造を有するアルキル基、又は、芳香族構造を有するアルキル基のいずれかである炭素数３〜５０の１価の炭化水素基である。 (C) Photopolymerization initiator The photopolymerization initiator according to the present embodiment is preferably represented by the following general formula (3).

Here, in the formula, Ar ₁ is a monovalent organic group containing an aromatic group, R ₂₅ is an organic group having an alkyl group or an aryl group, and R ₂₆ is a branched alkyl group or a linear alkyl group. It is a C3-C50 monovalent hydrocarbon group which is either a group, an alkyl group having an alicyclic structure, or an alkyl group having an aromatic structure.

  The photopolymerization initiator in this embodiment generates radicals by light irradiation, and the polymerization reaction of a polymerizable compound having an unsaturated double bond changes the solubility of the photosensitive resin composition in an alkaline developer. Contributes to the nature of

In particular, when R ₂₆ is a branched chain alkyl group, a straight chain alkyl group, an alkyl group having an alicyclic structure, or an alkyl group having an aromatic structure, it has a hydrophobic or bulky skeleton, thereby being unsaturated. The compatibility with the polymerizable compound having a double bond is improved, and the polymerization reactivity is improved. In particular, it shows a remarkable effect when combined with a polymerizable compound having an unsaturated double bond having a quaternary carbon, such as a (di) pentaerythritol (meth) acrylate ester compound, and is a highly sensitive photosensitive resin. Even when the composition is thinned, it exhibits excellent wiring coverage. From the viewpoint of polymerization reactivity, R ₂₆ is preferably an alkyl group having an alicyclic structure, and more preferably an alkyl group having an alicyclic structure having 5 to 7 carbon atoms.

By having a monovalent organic group comprising an aromatic as Ar ₁ , high photosensitivity from i-line (365 nm) to g-line (436 nm), which is an exposure wavelength widely used industrially as photolithography technology Indicates.

  The amount of the photopolymerization initiator is preferably 0.01 parts by weight or more and 40 parts by weight or less, and 0.1 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the polyimide precursor from the viewpoint of photosensitivity and lithography characteristics. It is more preferable that the amount is not more than parts. Examples of the photopolymerization initiator having the above general formula (3) include 1,2-propanedione-3-cyclopentyl-1- [4- (phenylthio) phenyl] -2-2, which is used in experiments described later. (O-benzoyloxime), 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), and 1,2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furanylcarbonyl) -9H-carbazol-3-yl]-, 2- (O-acetyloxime) is relevant.

  The photopolymerization initiator according to the present embodiment can also be used in combination with other known photopolymerization initiators. Other known photopolymerization initiators include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, benzyl dipropyl ketals, benzyl diphenyl ketals, and benzoin methyl ethers. , Benzoin ethyl ether, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-isopropylthioxanthone, 2-fluorothioxanthone, 4-fluorothioxanthone, 2- Chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, benzophenone, 4,4′-bis (dimethylamino) benzophenone [Michler's ketone], 4,4′-bis ( Ethylamino) benzophenone, aromatic ketone compounds such as 2,2-dimethoxy-2-phenylacetophenone, triarylimidazole dimers such as lophine dimer, acridine compounds such as 9-phenylacridine, α, α-dimethoxy- Oxime ester compounds such as α-morpholino-methylthiophenylacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, N-aryl-α-amino acid, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylamino Benzoic acid, p-diisopropylaminobenzoic acid, p-benzoic acid ester, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) ) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4-[(2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane Α-hydroxyalkylphenones such as -1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methyl Α-aminoalkylphenones such as phenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6) -Acylphosphine oxides such as trimethylbenzoyl) -phenylphosphine oxide, photocationic polymerization of sulfonium salts And an iodonium salt-based photocationic polymerization initiator. These may be used alone or in combination of two or more.

ここで、式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８は、それぞれ独立して水素原子、１価の有機基、ハロゲン原子のいずれかを表し、同じであっても異なっていてもよい。Ｒ_１とＲ_２の炭素数合計は１〜４であり、かつＲ_７とＲ_８の炭素数合計は１〜４である。また、Ａ_１は直結あるいは以下の一般式（２）から選択されるいずれかの構造を有する。

ここで式中、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２、Ｒ_１３、Ｒ_１４、Ｒ_１５、Ｒ_１６、Ｒ_１７、Ｒ_１８、Ｒ_１９、Ｒ_２０、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_２４は、それぞれ独立して水素原子、１価の有機基、ハロゲン原子のいずれかを表し、同じであっても異なっていてもよい。ｍ、ｎはそれぞれ１以上１０以下の整数を表す。 (D) Antioxidant The photopolymerization initiator according to the present embodiment includes a structure represented by the following general formula (1).

Here, in the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ are each independently a hydrogen atom, a monovalent organic group, or a halogen atom. May be the same or different. The total carbon number of R ₁ and R ₂ is 1 to 4, and the total carbon number of R ₇ and R ₈ is 1 to 4. A ₁ has a structure directly selected or selected from the following general formula (2).

Here, in the formula, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ each independently represents a hydrogen atom, a monovalent organic group or a halogen atom, and may be the same or different. m and n each represent an integer of 1 or more and 10 or less.

  When the photopolymerization initiator generates radicals by heat, the antioxidant in the present embodiment inhibits the start of the polymerization reaction of the polymerizable compound having an unsaturated double bond by capturing the generated radicals. . This contributes to the suppression of development residue even in situations where development residue is more likely to occur, such as laminating with a roll-type thermal vacuum laminator.

In particular, when R ₁ , R ₂ , R ₇ and R ₈ are all methyl groups in the above general formula (1), they have a moderate steric hindrance with respect to the hydroxyl groups capturing the radicals. Can suppress the development residue. For this reason, the curing reaction at the time of exposure can be suppressed to the minimum, and as a result, the wiring coverage as the alkaline developer resistance of the cured film is also improved. For example, 4,4 ′-(1-methylethylidene) bis [2,6-dimethylphenol]), 4,4′-methylenebis (2,6-dimethylphenol), 4,4 used in the experiments described below. '-[1,4-phenylenebis (1-methylethylidene)] bis (2,6-dimethylphenol) and bis (4-hydroxy-3,5-dimethylphenyl) sulfone are applicable.

  Other antioxidants include 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4′-thiobis [3 -Methyl-6- (1,1-dimethylethyl) phenol], 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,3 ′, 5,5′-tetramethyl-1,1 '-Biphenyl-4,4'-diol, 4,4'-oxybis (2,6-dimethylphenol), 4,4'-thiobis (2,6-dimethylphenol), 3,3'-dimethyl-1, 1'-biphenyl-4,4'-diol, 4,4'-methylenebis (o-cresol), 2,2 ', 3,3', 5,5'-hexamethylbiphenyl-4,4'-diol preferable. These may be used alone or in combination of two or more.

  The addition amount of the antioxidant is preferably 0.01 parts by mass or more and 10 parts by mass or less from the viewpoint of the development residue suppressing effect, photosensitivity, and wiring coverage when the amount of the polyimide precursor is 100 parts by mass. 1 part by mass or more and 4 parts by mass or less are more preferable, and 0.1 part by mass or more and 2 parts by mass or less are particularly preferable.

(E) Nitroso compound and / or nitro compound In the photosensitive resin composition according to the present embodiment, at least one nitroso compound and / or nitro compound is used as a polymerization inhibitor used for thermal stability. It is particularly preferable to include it. The nitroso compound contains a nitroso group in the structural formula, and the nitro compound contains a nitro group.

  Examples of the nitroso compound include nitroso aromatic hydrocarbons such as nitrosobenzene, nitrosotoluene, p-nitrosophenol, nitrosolesorcinol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, N-nitrosodiphenylamine, N-nitroso such as N-nitroso-N-methylaniline, N-nitroso-N-phenylaniline, N-nitrosophenylhydroxylamine, N-nitrosophenylhydroxylamine salt (metal salt, ammonium salt, etc.) can be mentioned.

  Examples of the nitro compound include o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrochlorobenzene, 1,5-dinitronaphthalene, 2,4-dinitro-1-naphthol, 2, Such as 4-dinitrophenol, 2,5-dinitrophenol, 2,4-dinitro-6-secondary-butyl-phenol, 4,6-dinitro-o-cresol, and 1,3,5-trinitrobenzene A nitro aromatic compound is mentioned.

  Among these, in consideration of the ability to inhibit polymerization and availability, it is preferable to select N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, and 2,4-dinitrophenol.

  The addition amount of the polymerization inhibitor is preferably 1 ppm to 100,000 ppm, more preferably 100 ppm to 10000 ppm with respect to the mass of the alkali-soluble resin. Further, the addition amount is preferably 1 ppm or more from the viewpoint of sufficiently exhibiting the polymerization inhibition effect, and preferably 100000 ppm or less from the viewpoint of maintaining photosensitivity.

(F) Blocked isocyanate In the photosensitive resin composition in this Embodiment, it is preferable that block isocyanate is included. The blocked isocyanate is a compound obtained by reacting a blocking agent with an isocyanate having two or more isocyanate groups in the molecule.

  Examples of the isocyanate include 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. -Xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-hydroxylated diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 4, 4-diphenyl diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, phenylene 1,4-diisocyanate, phenylene 2,6-diisocyanate, 1,3,6-hexamethylene triisocyanate And hexamethylene diisocyanate.

  Examples of the blocking agent include alcohols, phenols, ε-caprolactam, oximes, active methylenes, mercaptans, amines, imides, acid amides, imidazoles, ureas, and carbamine. Examples include acid salts, imines, and sulfites.

  Specific examples of the blocked isocyanate include trade names Duranate (registered trademark) SBN-70D, TPA-B80E, TPA-B80X, 17B-60PX, MF-B60X, E402-B80T, ME20-B80S, MF- manufactured by Asahi Kasei Chemicals Corporation. Hexamethylene diisocyanate (hereinafter also referred to as “HDI”) block isocyanates such as K60X and K6000, trade names of Mitsui Chemicals polyurethane products Takenate (registered trademark) B-882N, products that are tolylene diisocyanate block isocyanates Name Takenate B-830, trade name Takenate B-815N, which is 4,4′-diphenylmethane diisocyanate block isocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane block isocyanate Takenate B-846N which is an acrylate, trade name Coronate (registered trademark) AP-M, 2503, 2515, 2507, 2513 and Millionate (registered trademark) MS-50 manufactured by Nippon Polyurethane Industry Co., Ltd., isophorone diisocyanate block isocyanate No. 7950, 7951, 7990 and the like manufactured by Baxenden. These blocked isocyanates may be used alone or in combination of two or more. By using the blocked isocyanate, it is possible to achieve the effects of improving the insulation reliability after firing and suppressing warpage.

  In the present embodiment, the example of using the blocked isocyanate as the polyfunctional isocyanate has been described. However, it is also possible to use a polyfunctional isocyanate having two or more isocyanate groups as long as the effects of the present embodiment are exhibited. is there.

(G) Phosphorus compound In the photosensitive resin composition in this Embodiment, it is preferable that a phosphorus compound is included from a viewpoint which the flame retardance of the photosensitive resin composition improves. As a phosphorus compound, it is especially preferable that a phosphazene compound is included. Thereby, especially the flame retardance of the photosensitive resin composition improves. The phosphazene compound is a compound having a phosphazene structure in the molecule. As the phosphorus compound, one type of phosphorus compound may be used, or two or more types of phosphorus compounds may be used in combination.

Examples of the phosphazene compound include those having a structure represented by the following general formula (7) and the following general formula (8).

R ₄₂ , R ₄₃ , R ₄₄ , and R ₄₅ in the phosphazene compound represented by the general formula (7) and the general formula (8) are not limited as long as they are organic groups having 1 to 20 carbon atoms. A carbon number of 1 or more is preferable because flame retardancy tends to be exhibited. A carbon number of 20 or less is preferred because it tends to be compatible with the polyimide precursor.

As R ₄₂ , R ₄₃ , R ₄₄ , and R ₄₅ , a functional group derived from an aromatic compound having 6 to 18 carbon atoms is particularly preferable from the viewpoint of flame retardancy. Examples of such a functional group include a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2 -Functional groups having a phenyl group such as cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, functional groups having a naphthyl group such as 1-naphthyl group, 2-naphthyl group, pyridine, imidazole, triazole, tetrazole And functional groups derived from nitrogen-containing heterocyclic compounds such as These compounds may be used alone or in combination of two or more as required. Among these, it is preferable to select a compound having a phenyl group, a 3-methylphenyl group, a 4-hydroxyphenyl group, and a 4-cyanophenyl group in view of availability.

  V in the phosphazene compound represented by the general formula (7) is not limited as long as it is 3 or more and 25 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 25 or less, the solubility in an organic solvent is high. Among these, it is preferable that v is 3 or more and 10 or less because of availability.

  The w in the phosphazene compound represented by the general formula (8) is not limited as long as it is 3 or more and 10,000 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 10,000 or less, the solubility in organic solvents is high. Among these, 3 or more and 100 or less are preferable in view of availability.

D and E in the phosphazene compound represented by the general formula (8) are not limited as long as they are organic groups having 3 to 30 carbon atoms. In this, D is _{-N = P (OC 6 H 5} ) 3, -N = P (OC 6 H 5) 2, (OC 6 H 4 OH) 3, -N = P (OC 6 H 5) ( _{OC 6 H 4 OH) 2,} -N = P (OC 6 H 4 OH) 3, -N = P (O) OC 6 H 5, -N = P (O) (OC 6 H 4 OH) are preferred. E is _{-P (OC 6 H 5) 4} , -P (OC 6 H 5) 3 (OC 6 H 4 OH), - P (OC 6 H 5) 2 (OC 6 H 4 OH) 2, -P ( _{OC 6 H 5) (OC 6} H 4 OH) 3, -P (OC 6 H 4 OH) 4, -P (O) (OC 6 H 5) 2, -P (O) (OC 6 H 4 OH) _2, such as _{-P (O) (OC 6 H} 5) (OC 6 H 4 OH) are preferred. A phosphorus compound may be used alone or in combination of two or more.

  In the photosensitive resin composition, the addition amount of the phosphorus compound is preferably 50 parts by mass or less from the viewpoint of developability and the like when the amount of the polyimide precursor is 100 parts by mass. From the viewpoint of flame retardancy of the cured product, 45 parts by mass or less is more preferable. Moreover, if it is 5 mass parts or more, an effect is exhibited.

(G) Other compound In the photosensitive resin composition in this Embodiment, another compound can be included in the range which does not have a bad influence on the performance. Specifically, other compounds include alkali-soluble resins such as thermosetting resins and polyimide precursors used to improve the toughness, solvent resistance, and heat resistance (thermal stability) of the film after firing. Examples thereof include reactive compounds, heterocyclic compounds used for improving adhesion, and coloring substances such as pigments and dyes used for coloring films formed using the photosensitive resin composition.

  Examples of the thermosetting resin include epoxy resins, cyanate ester resins, unsaturated polyester resins, benzoxazine resins, benzoxazolines, phenol resins, melamine resins, and maleimide compounds.

  Examples of the compound having reactivity with the alkali-soluble resin include a compound that reacts with a carboxyl group and an amino group in a polymer and a terminal having a structure derived from an acid anhydride to form a three-dimensional crosslinked structure. Among these, a so-called thermal base generator, which is a compound that generates an amino group as a base by heating, is preferable. Examples of the thermal base generator include compounds obtained by forming a salt structure between an amino group of a base compound such as amine and an acid such as sulfonic acid and protecting it as a dicarbonate compound or an acid chloride compound. . For this reason, the thermal base generator does not exhibit basicity at room temperature and is stable, and can be deprotected by heating to generate a base.

  The heterocyclic compound is not limited as long as it is a cyclic compound containing a hetero atom. Heteroatoms include oxygen, sulfur, nitrogen, and phosphorus. Examples of the heterocyclic compound include N-alkyl group substitution such as 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, imidazole such as 2-phenylimidazole, and 1,2-dimethylimidazole. Aromatic group-containing imidazole such as imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, cyano group-containing imidazole such as 1-cyanoethyl-2-phenylimidazole, imidazole compounds such as silicon-containing imidazole such as imidazolesilane, 5-methylbenzotriazole, 1- (1 ' 2'-di-carboxyethyl benzotriazole), 1- (2-ethyl-F carboxymethyl aminomethyl benzotriazole) triazole compounds such as, and, oxazole compounds such as 2-methyl-5-phenyl-benzoxazole and the like.

  Examples of coloring substances include anthraquinone compounds, phthalocyanine compounds such as phthalocyanine green, fuchsin, auramine base, chalcoxide green S, paramagenta, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green, basic blue. 20 and diamond green.

  Further, as the coloring substance, a coloring dye that develops color when irradiated with light can also be used. Such coloring dyes include a combination of a leuco dye or a fluorane dye and a halogen compound. Examples of such combinations include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet] and tris (4-dimethylamino-2-methylphenyl) methane [leucomalachichi green]. . Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, and triazine compounds. Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. .

  The addition amount of another compound will not be limited if it is 0.01 mass part or more and 30 mass parts or less with respect to 100 mass parts of alkali-soluble resin. If the addition amount is 0.01 parts by mass or more, the added effect tends to be sufficiently exerted, and if it is 30 parts by mass or less, there is no adverse effect on photosensitivity.

  The photosensitive resin composition in the present embodiment may further contain an organic solvent. The organic solvent is not limited as long as it can uniformly dissolve and / or disperse the alkali-soluble resin. Examples of such organic solvents include alcohol compounds having 1 to 9 carbon atoms such as methyl alcohol, ethyl alcohol, normal propyl alcohol, and isopropyl alcohol; dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene An ether compound having 2 to 9 carbon atoms such as glycol dimethyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether; a ketone compound having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; Saturated hydrocarbon compounds having 5 to 10 carbon atoms such as cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin An aromatic hydrocarbon compound having 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene, and tetralin; a carbon number such as methyl acetate, ethyl acetate, γ-butyrolactone, and methyl benzoate; An ester compound having 3 to 9 carbon atoms; a halogen-containing compound having 1 to 10 carbon atoms such as chloroform, methylene chloride, and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N, N -Nitrogen-containing compounds having 2 to 10 carbon atoms such as dimethylacetamide and N-methyl-2-pyrrolidone; and sulfur-containing compounds such as dimethylsulfoxide.

  These may be used alone or as a mixed solvent of two or more as required. Particularly preferable organic solvents include alcohol compounds having 1 to 9 carbon atoms, ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 9 carbon atoms, 6 to 10 carbon atoms. Examples include the following aromatic hydrocarbon compounds, nitrogen-containing compounds having 2 to 10 carbon atoms, and a mixed solvent of two or more thereof. Further, from the viewpoint of solubility of the alkali-soluble resin, triethylene glycol dimethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable.

  In the photosensitive resin composition having an alkali-soluble resin and an organic solvent, the concentration of the alkali-soluble resin is not particularly limited as long as it can form a resin molded body. The concentration of the alkali-soluble resin is preferably 1% by mass or more from the viewpoint of the film thickness of the resin molded body to be produced, and the concentration of the alkali-soluble resin is 90% by mass or less from the uniformity of the film thickness of the resin molded body. Is preferable, and 2 mass% or more and 80 mass% or less are more preferable.

<Photosensitive film laminate>
The photosensitive film laminate according to the present embodiment has a base material, and a photosensitive film formed on the surface of the base material using the above-described photosensitive resin composition according to the present embodiment. Configured. Thus, the photosensitive resin composition which concerns on this Embodiment can be used suitably for formation of a photosensitive film. By using the product form of the photosensitive film, a solvent drying and volatilization process at the printed wiring board production site is not required, and the working environment is improved as compared with the liquid product form. In addition, since both sides can be processed simultaneously, it contributes to productivity improvement. Further, there is an advantage that a product excellent in surface smoothness of the cover material on the wiring can be easily produced. Moreover, in the photosensitive film laminated body which concerns on this Embodiment, it forms on this photosensitive resin and the photosensitive film containing the base material, said photosensitive resin composition provided on this base material. It is preferable to make a photosensitive film laminate comprising an antifouling or protective cover film.

  The substrate is not particularly limited as long as it is a substrate that does not damage the photosensitive film when forming the photosensitive film laminate. Examples of such a substrate include a silicon wafer, glass, ceramic, heat resistant resin, and carrier film. Among these, a carrier film is preferable from the viewpoint of compatibility in a roll-to-roll production method and ease of handling.

  As the carrier film, a transparent film that transmits ultraviolet light is desirable. Examples of carrier films that transmit ultraviolet light are, for example, polyethylene terephthalate (PET) film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, and polymethacrylic acid. Examples include a methyl copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. Among these, a PET film is preferable from the viewpoint of circuit board pressure bonding and peelability after exposure. As these films, those stretched as necessary can also be used. The thinner these films are, the more advantageous in terms of image forming properties and economic efficiency, but those having a thickness of about 10 μm to 30 μm are generally used because the strength needs to be maintained.

  Next, the manufacturing method of the photosensitive film laminated body is demonstrated. First, the solution of the photosensitive resin composition according to the present embodiment is applied on an arbitrary substrate by an arbitrary method. Next, the photosensitive resin composition is dried to form a dry film. Thereby, the photosensitive film laminated body which has a carrier film and a photosensitive film, for example can be manufactured. Application of the photosensitive resin composition onto the base material is, for example, bar coating, roller coating, die coating, blade coating, dip coating, doctor knife, spray coating, flow coating, spin coating, slit coating, and brush coating. Various coating methods such as these can be used. After the coating, if necessary, a heat treatment called pre-baking may be performed with a hot plate or the like.

<Flexible printed wiring board>
The photosensitive film which concerns on this Embodiment can be used suitably for manufacture of a flexible printed wiring board. A flexible printed wiring board according to the present embodiment includes a circuit board having wiring, a photosensitive film formed by baking on the surface of the circuit board using the photosensitive resin composition according to the present embodiment, It is comprised. The wiring is, for example, a copper wiring, but is not particularly limited. This flexible printed wiring board can be obtained by press-bonding a photosensitive film on a circuit board having wiring, developing it with an alkali, and performing baking. At this time, after laminating the above photosensitive film on a wiring surface on a circuit board having wiring using a roll-type thermal vacuum laminator, firing film formation enables efficient mass production of flexible printed wiring boards To preferred. By using the photosensitive resin composition of the present embodiment, it is possible to obtain a flexible printed wiring board that is excellent in photosensitivity by alkali development, does not generate a development residue, and has excellent wiring coverage.

  Examples of the circuit board having wiring in the flexible printed wiring board include a hard board such as a glass epoxy board and a glass maleimide board, and a flexible board such as a copper clad laminate. Among these, a flexible substrate is preferable from the viewpoint of bendability.

  The manufacturing method of a flexible printed wiring board will not be specifically limited if a photosensitive film is provided on a circuit board so that wiring may be covered. As such a manufacturing method, in a state where the wiring side of the circuit board having wiring and the photosensitive film laminate according to the present embodiment are in contact, hot pressing, thermal laminating, thermal vacuum pressing, thermal vacuum laminating, etc. The method of performing etc. is mentioned. Among these, from the viewpoint of embedding the photosensitive film between the wirings, the thermal vacuum pressing method and the thermal vacuum laminating method are preferable, and it is particularly preferable to laminate using a roll type thermal vacuum laminator. According to the method for producing a flexible printed wiring board of the present embodiment, it has excellent photosensitivity due to alkali development, development residue does not occur even when film formation is performed using a roll-type thermal vacuum laminator, and wiring coverage is improved. An excellent flexible printed wiring board can be manufactured appropriately and easily.

  The heating temperature when laminating the photosensitive film laminate on the circuit board having wiring is not limited as long as the photosensitive film can be in close contact with the circuit board. From the viewpoint of adhesion to the circuit board and from the viewpoint of decomposition of the photosensitive film and side reactions, 30 ° C. or higher and 400 ° C. or lower is preferable. More preferably, it is 50 degreeC or more and 150 degrees C or less.

  The surface treatment of the circuit board having wiring is not particularly limited, and examples thereof include hydrochloric acid treatment, sulfuric acid treatment, and sodium persulfate aqueous solution treatment.

  The photosensitive film laminate can be subjected to negative photolithography by selecting a light-irradiated portion with an arbitrary photomask and dissolving the portion other than the light-irradiated portion by alkali development after light irradiation. In this case, it is preferable to irradiate light after the circuit board reaches room temperature. In addition, the carrier film is peeled off after the light irradiation and the alkali development treatment is performed, thereby preventing the radical generated by the photopolymerization initiator (C) from being deactivated due to the influence of oxygen inhibition, and stabilizing the photosensitivity. From the viewpoint of improving the property. Examples of the light source used for the light irradiation include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium cadmium laser. Among these, a high pressure mercury lamp and an ultrahigh pressure mercury lamp are preferable.

  The aqueous alkali solution used for development is not particularly limited as long as it is a solution capable of dissolving other than the light irradiation site. Examples of such a solution include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous tetramethylammonium hydroxide solution. From the viewpoint of developability, an aqueous sodium carbonate solution and an aqueous sodium hydroxide solution are preferred. Examples of the development method include spray development, immersion development, and paddle development. If necessary, a water washing treatment or a drying treatment can be performed.

  Next, a flexible printed wiring board is obtained by baking the printed wiring board which pressure-bonded the photosensitive film. Firing is preferably performed at a temperature of 30 ° C. or higher and 400 ° C. or lower, more preferably 100 ° C. or higher and 300 ° C. or lower, from the viewpoints of solvent removal, side reactions, decomposition, and the like.

  The reaction atmosphere in the firing can be performed in an air atmosphere or an inert gas atmosphere. In the production of a printed wiring board, the time required for firing varies depending on the reaction conditions, but is usually within 24 hours, and particularly preferably in the range of 1 to 8 hours.

  The photosensitive film laminate using the photosensitive film according to the present embodiment has good warpage after firing and good developability, and exhibits chemical resistance when used as a cured product. Printed wiring boards used for operation panels of various electronic devices in the electronics field, formation of protective layers on circuit boards, formation of insulating layers on laminated boards, silicon wafers used in semiconductor devices, semiconductor chips, and components around semiconductor devices It is used for film formation on electronic components for use in protection, insulation and adhesion of semiconductor mounting substrates, heat sinks, lead pins, semiconductors, etc.

  Moreover, the photosensitive film laminated body using the photosensitive film which concerns on this Embodiment is a board | substrate for flexible printed wiring circuits (FPC), a board | substrate for tape automation bonding (TAB), and electrical insulation in various electronic devices. It can also be used for membrane and liquid crystal display substrates, organic-luminescence (EL) display substrates, electronic paper substrates, solar cell substrates, especially silicon wafers, copper-clad laminates, and flexible printed wiring. It can be suitably used as a cover lay which is a protective film for protecting circuits and the like.

  Examples carried out to clarify the effects of the present invention will be described below, but the present invention is not limited to these examples. In addition, the measurement methods and definitions of various physical properties and characteristics in the examples are as follows.

<Reagent>
In the examples and comparative examples, the reagents used are as follows. In addition, in each description part of the following Example 1 to Example 11 and Comparative Example 1 to Comparative Example 5, the abbreviations of the following reagents are appropriately described.

(A) Polyimide precursor BPDA (Mitsui Chemicals)
APB (trade name: APB-N, manufactured by Mitsui Chemicals)
Diamine represented by the general formula (6): polyetheramine (trade name: polyetheramine D-400 (hereinafter simply referred to as “D-400”), manufactured by BASF, represented by the general formula (6) m + n + p = 6.1), Jeffamine (trade name: Jeffamine D-230 (hereinafter simply referred to as “D-230”), manufactured by Huntsman, m + n + p = 2.5 represented by the general formula (6))

(B) Polymerizable compound having an unsaturated double bond EO-modified bisphenol A dimethacrylate (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Ethoxylated pentaerythritol tetraacrylate (trade name: SARTOMER SR-494 (hereinafter simply referred to as “SR-494”), manufactured by Sartomer)
Trimethylolpropane PO-modified triacrylate (trade name: Aronix M-310 (hereinafter simply referred to as “M-310”), manufactured by Toagosei Co., Ltd.)

(C) Photopolymerization initiator 1,2-propanedione-3-cyclopentyl-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (trade name: PBG-305, manufactured by Changzhou Koki Electronics Co., Ltd. )
1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01 (hereinafter simply referred to as “OXE-01”) And made by Ciba Japan)
1,2-propanedione, 3-cyclohexyl-1- [9-ethyl-6- (2-furanylcarbonyl) -9H-carbazol-3-yl]-, 2- (O-acetyloxime) (oxime ester compound) (C3))

(D) Antioxidant 4,4 ′-(1-methylethylidene) bis [2,6-dimethylphenol] (trade name: Bis26X-A, manufactured by Honshu Chemical Industry Co., Ltd.)
4,4′-methylenebis (2,6-dimethylphenol) (trade name: TM-BPF, manufactured by Honshu Chemical Industry Co., Ltd.)
4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bis (2,6-dimethylphenol) (trade name: BIS-2,6-XYLENOL-P, manufactured by Mitsui Chemicals Fine)
Bis (4-hydroxy-3,5-dimethylphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.)
2,2-bis (3-allyl-4-hydroxyphenyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd.)
2,2-bis (4-hydroxy-3-methylphenyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd.)
4,4′-thiobis [3-methyl-6- (1,1-dimethylethyl) phenol] (manufactured by Tokyo Chemical Industry Co., Ltd.)
4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (trade name: NOCRACK NS-30, manufactured by Ouchi Shinsei Chemical Co., Ltd.)
2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
4,4'-methylenediphenol (Tokyo Chemical Industry Co., Ltd.)

(E) Nitroso compound and / or nitro compound (polymerization inhibitor)
N-nitrosophenylhydroxylamine aluminum (trade name: Q-1301, manufactured by Wako Pure Chemical Industries, Ltd.)

(F) Blocked isocyanate Blocked isocyanate (trade name: Duranate (registered trademark) SBN-70D (hereinafter simply referred to as “SBN-70D”), manufactured by Asahi Kasei Chemicals)

(G) Phosphorus compound component 4-cyanophenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
Phenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
Dichlorophosphazene oligomer (manufactured by Tokyo Chemical Industry Co., Ltd.)

(H) Other compounds Solvent Green-3 (trade name: OPLAS (registered trademark) GREEN533, manufactured by Orient Chemical Industries)
Toluene (Wako Pure Chemical Industries, for organic synthesis)
γ-Butyrolactone (Wako Pure Chemical Industries)
Sodium carbonate (Wako Pure Chemical Industries)
Sodium hydroxide (Wako Pure Chemical Industries)
Chlorbenzene (Wako Pure Chemical Industries, Ltd.)

<Weight average molecular weight measurement>
Gel permeation chromatography (GPC), which is a method for measuring the weight average molecular weight, was measured under the following conditions. Using N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) as a solvent, 24.8 mmol / L of lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity before measurement) 99.5%) and 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) were used.
Column: Shodex (registered trademark) KD-806M (manufactured by Showa Denko KK)
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Pump: PU-2080 Plus (manufactured by JASCO)
Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO)
UV-2075 Plus (UV-VIS: UV-Visible Absorber, manufactured by JASCO)

  Moreover, the calibration curve for calculating the molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

<Production of photosensitive film roll>
The coating method of the photosensitive resin composition was performed using a comma coater (manufactured by Hirano Tech Seed). It apply | coated so that the film thickness after drying might be set to 15 micrometers on PET film (The Teijin DuPont Films company make, brand name; G2, film thickness = 16 micrometers). Next, after drying the dryer zone at 95 ° C. for 6 minutes, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name: GF-818, film thickness = 19 μm) was bonded as a protective layer to obtain a photosensitive film roll. The film thickness was measured using a film thickness meter (ID-C112B, manufactured by Mitutoyo).

<Manufacture of flexible printed wiring boards>
Migration resistance test wiring (conductor width / between conductors) on copper surface of flexible substrate roll (Espanex (registered trademark): MC12-20-00CEM, manufactured by Nippon Steel Chemical Co., Ltd.) according to JPCA-2006-DG2 Annex 2. A test roll substrate on which a 50/50 μm beak and a pattern number of 10) and a solid copper foil portion (5 cm × 5 cm) were formed was prepared.

  Next, using a roll type thermal vacuum laminator (MC VR, MVR-250), the roll temperature was set to 80 ° C., the cylinder pressure was 0.4 MPa, the degree of vacuum was 100 Pa, and the speed was 1 m / min. A photosensitive film (film thickness = 15 μm) was laminated on the copper wiring surface of the roll substrate to obtain a flexible printed wiring board.

<Practical property evaluation>
Practical characteristics were observed visually or using a microscope in the process of preparing a lithography pattern of the photosensitive film, and the practical characteristics of the photosensitive film laminate were evaluated based on the quality. For the following three evaluations, ◎ or ○ was regarded as acceptable.

(Light sensitivity evaluation)
A solid copper foil portion (5 cm × 5 cm) of the flexible printed wiring board obtained above was cut out, and a step tablet (Stuffer (registered trademark) 21) was arranged. And after making both adhere to a vacuum, it exposed at 50 mJ / cm < ² > using the ultrahigh pressure mercury lamp (HMW-201KB, the Oak Manufacturing company make). Thereafter, the PET film is peeled off from the obtained laminate, spray development treatment and water rinsing with 30 ° C., 1.0 mass% sodium carbonate aqueous solution for 30 seconds, and then drying and photosensitive resin composition. A photolithographic pattern was prepared. By the obtained photolithography pattern, the number of steps of the step tablet was observed at a portion where the copper surface was not completely exposed without being removed by development.
◎: 8 steps or more ○: 6-7 steps ×: 5 steps or less

(Development residue evaluation)
A flexible printed wiring board roll having a length of 50 m was prepared using the above-described method for producing a flexible printed wiring board. A solid copper foil portion (5 cm × 5 cm) located at 0 m, 15 m, 30 m, and 45 m of the obtained flexible wiring board roll was cut out, and the PET film was peeled off from the obtained laminate, at 30 ° C. and 1.0 mass%. Spray development treatment, rinsing with water and drying were performed for 60 seconds with an aqueous sodium carbonate solution. The obtained board | substrate was visually observed and the color of the copper surface of an untreated test board | substrate was compared.
○: There is no difference in the color of the copper surface in all the substrates of 0 m, 15 m, 30 m, and 45 m. ×: The developed and removed copper surface is discolored in any of the substrates of 0 m, 15 m, 30 m, and 45 m.

(Evaluation of wiring coverage under over-development conditions)
Cut out the migration resistance test wiring of the flexible printed wiring board obtained above (the conductor width / conductor spacing is 50/50 μm, the number of patterns is 10), and use an ultra-high pressure mercury lamp (HMW-201KB, manufactured by Oak Manufacturing Co., Ltd.). And was exposed at 50 mJ / cm ² . Thereafter, the PET film was peeled off from the obtained laminate, spray-developed with a 1.0 mass% sodium carbonate aqueous solution at 30 ° C. for 80 seconds and rinsed with water, and then dried. The state of the photosensitive film on the obtained migration resistance test wiring was observed with an optical microscope (50 times). The criteria for evaluation are as follows.
A: Swelling or peeling of the photosensitive film on the wiring is not observed. ○: Swelling of the photosensitive film on the end of the wiring is observed, but it is not peeled off and the copper wiring is not exposed. The photosensitive film is peeled off and the copper wiring is exposed.

<Synthesis example>
(Polyimide precursor (A1))
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (255 g), toluene (51.0 g), polyetheramine D-400 (86.8 g (201.9 mmol)), BPDA. (120 g (407.9 mmol)) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 40 ° C., APB-N (48.4 g (165.7 mmol)) was added, and the mixture was stirred at 40 ° C. for 4 hours to obtain a polyimide precursor (A1). A solution was obtained. The weight average molecular weight of the obtained polyimide precursor (A1) was 23,000.

(Polyimide precursor (A2))
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (80.0 g), toluene (16.0 g), and polyetheramine D-230 (16.8 g (73.04 mmol)). BPDA (30.0 g (102.0 mmol)) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene which is an azeotropic solvent, the solution was cooled to 40 ° C., APB-N (5.60 g (19.16 mmol)) was added, and the mixture was stirred at 40 ° C. for 4 hours to obtain a polyimide precursor (A2). A solution was obtained. The weight average molecular weight of the obtained polyimide precursor (A2) was 21,000.

(Phosphazene Compound (G1))
The phosphazene compound (G1) was synthesized by the method described in Synthesis Example 17 of JP-A No. 2002-114981.

  4-cyanophenol 1.32 mol (157.2 g), phenol 2.20 mol (124.2 g), hydroxylation in a 2 liter four-necked flask equipped with a stirrer, heating device, thermometer and dehydrator Sodium 2.64 mol (105.6 g) and 1000 ml toluene were added. This mixture was heated to reflux, water was removed from the system, and a toluene solution of cyanophenol and a sodium salt of phenol was prepared. 580 g of a 20% chlorobenzene solution containing 1 unit mol (115.9 g) of dichlorophosphazene oligomer was added dropwise to the toluene solution of cyanophenol and sodium salt of phenol at an internal temperature of 30 ° C. or lower while stirring. After the mixed solution was refluxed for 12 hours, a 5% aqueous sodium hydroxide solution was added to the reaction mixture and washed twice. Next, the organic layer was neutralized with dilute sulfuric acid, and then washed twice with water. The organic layer was filtered, concentrated, and dried under vacuum to obtain the target product (phosphazene compound (G1)).

<Abbreviation of each component>
Hereinafter, Example 1 to Example 11 and Comparative Example 1 to Comparative Example 5 were prepared using each component shown in Table 1. The abbreviations shown in Table 1 are as follows. In addition, in Table 1, the compounding quantity is represented by mass solid content ratio.
(A) Component: Polyimide precursor A1: Polyimide precursor (A1)
A2: Polyimide precursor (A2)
(B) component: polymerizable compound having an unsaturated double bond B1: BPE-500 (EO-modified bisphenol A dimethacrylate)
B2: SR-494 (ethoxylated pentaerythritol tetraacrylate)
B3: M-310 (trimethylolpropane PO-modified triacrylate)
Component (C): Photopolymerization initiator C1: PBG-305 (1,2-propanedione-3-cyclopentyl-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime))
C2: OXE-01 (1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime))
C3: Oxime ester compound (C3) (1,2-propanedione, 3-cyclohexyl-1- [9-ethyl-6- (2-furanylcarbonyl) -9H-carbazol-3-yl]-, 2- ( O-acetyloxime))
(D) Component: Antioxidant D1: Bis26X-A (4,4 ′-(1-methylethylidene) bis [2,6-dimethylphenol])
D2: TM-BPF (4,4′-methylenebis (2,6-dimethylphenol))
D3: BIS-2,6-XYLENOL-P (4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bis (2,6-dimethylphenol))
D4: Bis (4-hydroxy-3,5-dimethylphenyl) sulfone D5: 2,2-bis (3-allyl-4-hydroxyphenyl) propane D6: 2,2-bis (4-hydroxy-3-methylphenyl) Propane D7: 4,4′-thiobis [3-methyl-6- (1,1-dimethylethyl) phenol]
D8: 4,4′-butylidenebis (3-methyl-6-tert-butylphenol)
D9: 2,6-di-t-butyl-4-methylphenol D10: 4-methoxyphenol D11: 4,4′-methylenediphenol (E) Component: nitroso compound and / or nitro compound (polymerization inhibitor) )
E1: Q-1301 (N-nitrosophenylhydroxylamine aluminum)
(F) Component: Blocked isocyanate F1: SBN-70D (Blocked isocyanate)
(G) Component: Phosphorus compound G1: Phosphazene compound (G1)
(H) Component: Other compounds H1: OPLAS GREEN533 (Solvent Green-3)

Here, D1 to D11 described above are represented by the following general formulas (9) to (19).

  Table 2 is a table showing the number of parts by mass of the antioxidant with respect to 100 parts by mass of the polyimide precursor in Examples 1 to 11 and Comparative Examples 1 to 5.

  The production methods of Examples 1 to 11 and Comparative Examples 1 to 5 will be specifically described below.

[Example 1]
BPE-500 (B1) (18 parts by mass), SR-494 (B2) (10 parts by mass), PBG-305 (C1) (0.6 parts by mass) with respect to 47 parts by mass of the polyimide precursor (A1). , Oxime ester compound (C3) (0.5 part by mass), Bis26X-A (D1) (0.8 part by mass), Q-1301 (E1) (0.1 part by mass), SBN-70D (F1) ( 10 parts by mass), a phosphazene compound (G1) (18 parts by mass), and OPLAS GREEN533 (H1) (0.2 parts by mass) were mixed to prepare a photosensitive resin composition. And the photosensitive film of 15 micrometers thickness was produced by the method mentioned above using the obtained photosensitive resin composition. The photosensitive film was evaluated for photosensitivity, development residue, and wiring coverage by the methods described above. The evaluation results are shown in Table 3 below.

[Example 2]
A photosensitive film having a thickness of 15 μm was prepared in the same manner as in Example 1 except that the antioxidant was added in the amount shown in Table 1. The photosensitive film was evaluated for photosensitivity, development residue, and wiring coverage by the methods described above. The evaluation results are shown in Table 3 below.

[Example 3]
A photosensitive film having a thickness of 15 μm was prepared in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the polyimide precursor and the photopolymerization initiator. The photosensitive film was evaluated for photosensitivity, development residue, and wiring coverage by the methods described above. The evaluation results are shown in Table 3 below.

[Example 4 to Example 6 and Example 8 to Example 11]
A photosensitive film having a thickness of 15 μm was prepared in the same manner as in Example 1 except that the compounds shown in Table 1 were added in the amounts shown in Table 1 as antioxidants. The photosensitive film was evaluated for photosensitivity, development residue, and wiring coverage by the methods described above. The evaluation results are shown in Table 3 below.

[Example 7]
A photosensitive film having a thickness of 15 μm was prepared in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the polymerizable compound having an unsaturated double bond and the antioxidant. The photosensitive film was evaluated for photosensitivity, development residue, and wiring coverage by the methods described above. The evaluation results are shown in Table 3 below.

[Comparative Example 1]
A photosensitive film having a thickness of 15 μm was obtained in the same manner as in Example 1 except that the antioxidant was not added. The photosensitive film was evaluated for photosensitivity, development residue, and wiring coverage by the methods described above. The evaluation results are shown in Table 3 below.

[Comparative Example 2 and Comparative Example 3]
A photosensitive film having a thickness of 15 μm was prepared in the same manner as in Example 1 except that the compounds shown in Table 1 were added as photopolymerization initiators and antioxidants in the amounts shown in Table 1. The photosensitive film was evaluated for photosensitivity, development residue, and wiring coverage by the methods described above. The evaluation results are shown in Table 3 below.

[Comparative Example 4 and Comparative Example 5]
A photosensitive film having a thickness of 15 μm was prepared in the same manner as in Example 1 except that the compounds shown in Table 1 were added in the amounts shown in Table 1 as antioxidants. The photosensitive film was evaluated for photosensitivity, development residue, and wiring coverage by the methods described above. The evaluation results are shown in Table 3 below.

  The wiring protective film using the photosensitive film roll obtained in Example 1 to Example 11 is more sensitive to photosensitivity and development than the wiring protective film using the photosensitive film roll of Comparative Example 1 to Comparative Example 5. Both the residue and the wiring coverage under over-development conditions were good. Moreover, the wiring protective film using the photosensitive film roll obtained in Example 1 to Example 6 has particularly excellent wiring coverage. This is presumably because the effect of inhibiting the development residue of the antioxidant is high, the amount added can be reduced, and the inhibition of the curing reaction during exposure can be minimized. In Examples 1 to 6, 4,4 ′-(1-methylethylidene) bis [2,6-dimethylphenol]), 4,4′-methylenebis (2,6-dimethylphenol) were used as antioxidants. 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bis (2,6-dimethylphenol) or bis (4-hydroxy-3,5-dimethylphenyl) sulfone was used. These antioxidants have a methyl group at the 2- and 6-positions of phenol, thereby increasing the development residue inhibiting effect more effectively. In Examples other than Example 7, SR-494 (ethoxylated pentaerythritol tetraacrylate) was used as the polymerizable compound having the component (B): unsaturated double bond. It was found to have an improvement effect. In Example 3, since the component (C): photopolymerization initiator was changed to C2, the photosensitivity was slightly lowered. It was.

  On the other hand, since the antioxidant was not added to the photosensitive film roll described in Comparative Example 1, it was found that the development residue could not be suppressed. Further, in the photosensitive film roll described in Comparative Example 2, the development residue can be suppressed by increasing the amount of the antioxidant, but the curing reaction at the time of exposure is inhibited, and the photosensitivity and wiring coverage cannot be satisfied. all right. Furthermore, in the photosensitive film roll described in Comparative Example 3, the photosensitivity and wiring coverage were satisfied by reducing the amount of the antioxidant compared to Comparative Example 2, but the addition amount of the antioxidant was sufficient. Therefore, it was found that a development residue was generated. In the photosensitive film rolls described in Comparative Example 4 and Comparative Example 5, it was found that the development residue could not be suppressed because the effect of the antioxidant was low, and that the wiring coverage was also deteriorated by increasing the addition amount. It was.

  From the above, the photosensitive resin composition of this example has good photosensitivity, development residue inhibiting effect and wiring coverage, and the photosensitive film made of the photosensitive resin composition of this example is roll-to-roll. It was confirmed that this was a wiring protective film suitable for a flexible printed wiring board that contributed to improvement in compatibility and productivity in the roll production method.

  In the present invention, it is possible to obtain a wiring protective layer (photosensitive film) having excellent photosensitivity and high reliability, and in particular, a surface protective film for semiconductor elements, an interlayer insulating film, a semiconductor package substrate, and a protective insulation for a flexible printed circuit board. It can be suitably used in the field of membranes.

Claims (14)

(A) a polyimide precursor, (B) a polymerizable compound having an unsaturated double bond, (C) a photopolymerization initiator, and (D) an antioxidant. The photosensitive resin composition characterized by an agent containing the structure represented by following General formula (1).

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ each independently represents a hydrogen atom, a monovalent organic group, or a halogen atom, The total number of carbon atoms of R ₁ and R ₂ is 1 to 4, and the total number of carbon atoms of R ₇ and R ₈ is 1 to 4. A ₁ is directly connected or Having any structure selected from general formula (2):

In the formula, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ Each independently represents a hydrogen atom, a monovalent organic group or a halogen atom, which may be the same or different. m and n each represent an integer of 1 or more and 10 or less. ) The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (C) has a structure represented by the following general formula (3).

(In the formula, Ar ₁ is a monovalent organic group containing an aromatic group, R ₂₅ is an organic group having an alkyl group or an aryl group, R ₂₆ is a branched alkyl group, a linear alkyl group, (It is a C3-C50 monovalent hydrocarbon group which is either an alkyl group having an alicyclic structure or an alkyl group having an aromatic structure.) The (A) polyimide precursor has a polyimide structure represented by the following general formula (4) and a polyamic acid structure represented by the following general formula (5) as repeating structural units, respectively. The photosensitive resin composition of Claim 1 or Claim 2.

(In the formula, R ₂₇ , R ₂₈ , R ₃₀ , R ₃₁ , R ₃₃ , R ₃₄ , R ₃₆ , R ₃₇ , R ₃₉ , R ₄₀ are each independently a hydrogen atom or a monovalent organic compound having 1 to 20 numbers. R ₂₉ , R ₃₂ , R ₃₅ , R ₃₈ , R ₄₁ each represents a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p Each independently represents an integer of 0 to 100. R ₄₂ represents a tetravalent organic group, R ₄₃ represents a divalent organic group having 1 to 90 carbon atoms, and R ₄₄ has 1 to 50 carbon atoms. Represents a tetravalent organic group.) The photosensitive resin composition according to claim 3, comprising a diamine represented by the following general formula (6) as a diamine component constituting the polyimide structure represented by the general formula (4).

(Wherein R ₂₇ , R ₂₈ , R ₃₀ , R ₃₁ , R ₃₃ , R ₃₄ , R ₃₆ , R ₃₇ , R ₃₉ , R ₄₀ are each independently a hydrogen atom or a monovalent valence having 1 to 20 carbon atoms. R ₂₉ , R ₃₂ , R ₃₅ , R ₃₈ , R ₄₁ each represents an organic group, and may represent a tetravalent organic group having 1 to 20 carbon atoms, m, n, p Are each independently an integer of 0 to 30, which satisfies 1 ≦ (m + n + p) ≦ 30.)   (E) The photosensitive resin composition according to any one of claims 1 to 4, comprising at least one kind of a polymerization inhibitor containing a nitroso compound and / or a nitro compound.   The photosensitive resin according to any one of claims 1 to 5, wherein (B) a polymerizable compound having an unsaturated double bond includes (di) pentaerythritol (meth) acrylate ester compound. Composition. (F) The photosensitive resin composition in any one of Claims 1-6 containing at least 1 type of block isocyanate compound. (G) At least 1 type of phosphorus compound is contained, The photosensitive resin composition in any one of the Claims 1-7 characterized by the above-mentioned. 9. The photosensitive resin composition according to claim ₁ , wherein R ₁ , R ₂ , R ₇ and R ₈ in the general formula (1) are all methyl groups.   A photosensitive film comprising: a base material; and a photosensitive film formed on the surface of the base material using the photosensitive resin composition according to claim 1. Laminated body.   The photosensitive film laminate according to claim 10, wherein the substrate is a carrier film.   It has a circuit board which has wiring, and a photosensitive film formed by baking on the surface of the circuit board using the photosensitive resin composition according to any one of claims 1 to 9. Flexible printed wiring board.   A flexible film characterized by laminating the photosensitive film laminate according to claim 10 or 11 on a wiring surface on a circuit board having wiring, using a roll-type thermal vacuum laminator, and then baking the film. Manufacturing method of printed wiring board.   A flexible printed wiring board manufactured by the manufacturing method according to claim 13.