JP5062059B2 - Polymer, photosensitive resin composition - Google Patents

Description

  The present invention relates to a polymer, a photosensitive resin composition, a photosensitive film for permanent resist, a method for forming a resist pattern, a printed wiring board and a method for producing the same, and a surface protective film and an interlayer insulating film.

  Conventionally, with the miniaturization and weight reduction of various electronic devices, a photosensitive solder resist has been used for the purpose of forming a circuit pattern on a package substrate containing a printed wiring board or a semiconductor element. The solder resist is an indispensable material as a protective film for preventing the solder from adhering to unnecessary portions in the soldering process and as a permanent mask. The solder resist material has excellent photosensitive properties such as good developability and high resolution for forming fine patterns, as well as good electrical insulation, high solvent resistance, and high resistance as an excellent insulating material. Characteristics such as alkalinity are required. Such solder resists are also required to have physical properties as a member of a printed wiring board or a package substrate, such as high tensile strength, elongation rate, and electric corrosion resistance.

  With the recent Pb-free soldering, in addition to the above characteristics, especially solder resists used for package substrates have excellent solder heat resistance, high thermal shock resistance, and high temperature and high humidity in a high temperature environment of about 260 ° C. There is also a need for excellent moisture and heat resistance that functions stably as a solder resist even in the environment. Further, a solder resist for a package substrate that requires a particularly fine opening pattern is required to have resistance (thermal shock resistance) to a temperature cycle test (TCT) of, for example, −55 ° C. to 125 ° C.

  As a method of forming a solder resist on a printed wiring board or the like, there is a method using a liquid photoresist. From the viewpoint of production efficiency and uniformity of resist film thickness, so-called dry resist as disclosed in Patent Document 1 is also available. A method using a film (dry film resist) is becoming mainstream. Also, from the viewpoint of work environment conservation and global environment conservation, an alkali development type that can be developed with a weak alkaline solution has become mainstream.

  Patent Document 2 discloses a photosensitive resin that can obtain a cured film excellent in heat resistance, heat and humidity resistance, adhesion, and mechanical properties, and is suitably used for manufacturing printed wiring boards, high-density multilayer boards, semiconductor packages, and the like. Photosensitive resin having a carboxyl group obtained by reacting an esterified product of an epoxy compound (a) and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride for the purpose of providing a composition (A), at least one photosensitive resin (B) selected from a photosensitive polyamide resin having a carboxyl group and a photosensitive polyamideimide resin having a carboxyl group, an elastomer (C), an epoxy curing agent (D), and light A photosensitive resin composition containing a polymerization initiator (E) has been proposed. And it is described in patent document 2 that the solder resist formed from this photosensitive resin composition is excellent in solvent resistance.

  Further, in Patent Document 3, for example, a solder resist film or the like excellent in printability, heat resistance, adhesion to the application surface, chemical resistance, solvent resistance, electrical properties, and mechanical properties on the application surface is formed. A mixture of a novolak epoxy resin having a specific structure and a rubber-modified bisphenol A type epoxy resin having a specific structure, and an epoxy equivalent of 0.2 Reaction product of -1.2 mol of ethylenically unsaturated carboxylic acid with 0.2-1.0 mol of polybasic acid and / or its anhydride per epoxy equivalent of the above mixture. A photosensitive resin composition containing a photosensitive prepolymer having a carboxyl group, (B) a photopolymerizable reactive diluent, (C) a photopolymerization initiator, and (D) a thermosetting component has been proposed. .

  Furthermore, Patent Document 4 discloses a permanent mask resist that exhibits high moisture resistance insulation without lowering flexibility, solder heat resistance, and chemical resistance as a permanent mask resist. In the rinsing step, means for incorporating divalent inorganic ions such as divalent calcium ions into water for rinsing is disclosed.

  On the other hand, conventionally, a photosensitive resin composition using a polyimide precursor having excellent heat resistance and mechanical properties is known as a solder resist material (see, for example, Patent Document 5).

Japanese Patent Laid-Open No. 54-1018 Japanese Patent Laid-Open No. 11-288087 Japanese Patent Laid-Open No. 9-5997 JP 2004-252485 A Japanese Patent Laid-Open No. 11-217414

  However, the present inventors have examined the conventional photosensitive resin composition described in Patent Documents 2 and 3 in detail, and the solder resist obtained from such a conventional photosensitive resin composition is: Furthermore, it has been found that there is a possibility that it cannot sufficiently meet the demand for excellent thermal shock resistance.

  In addition, the present inventors have found that when a dry film is formed from the conventional photosensitive resin compositions described in Patent Documents 2 and 3, sufficient storage stability cannot be obtained. That is, for example, in the conventional photosensitive resin composition disclosed in Patent Document 2, (D) the glycidyl group in the epoxy curing agent and the carboxyl group in the photosensitive resin (A) or (B) are at room temperature. It reacts. Therefore, when this is used as a liquid resist material, a two-part resist material in which the photosensitive resin (A) and (B) and the epoxy curing agent (D) are divided into a main agent and a curing agent, respectively. By doing so, the above reaction is prevented. However, when this photosensitive resin composition is used as a material for a dry film, the photosensitive resin of (A) and (B) and the (D) epoxy curing agent are blended in the same film. The above-described reaction proceeds in the dry film, and it becomes difficult to show sufficient storage stability. The photosensitive resin composition disclosed in Patent Document 3 has similar problems.

  Furthermore, the present inventors have found that using the means disclosed in the above-mentioned Patent Document 4, although there is a certain effect with respect to electric corrosion resistance, it is still insufficient with respect to thermal shock resistance.

  On the other hand, the present inventors have found that a photosensitive resin composition using a polyimide precursor as described in Patent Document 5 is a high alkali concentration condition of 5 wt% heptanoic acid diethanolamide and 0.5 wt% sodium carbonate. It was found that the developability with weak alkalinity is insufficient.

  Accordingly, the present invention provides a weakly alkali developable photosensitive resin composition capable of forming a solder resist having sufficiently high heat resistance and thermal shock resistance and capable of forming a dry film exhibiting sufficiently excellent storage stability. Sensitive to weak alkali development that can form polymers that can be used in products, and can form solder resists with sufficiently high heat resistance and thermal shock resistance, and can form dry films that exhibit sufficiently excellent storage stability. It aims at providing a conductive resin composition. The present invention also provides a photosensitive film for a permanent resist, a method for forming a resist pattern, a printed wiring board and a method for producing the same, and a surface protective film and an interlayer insulating film using the photosensitive resin composition. Objective.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by using a polymer having a specific structure, and the present invention has been completed.

［式中、Ｘは四価の有機基を示し、Ｙ、Ｒ_１及びＲ_２は各々独立に二価の有機基を示し、Ｒは水素原子、フェニル基又は炭素数１〜５のアルキル基を示し、ｎは１以上の整数を示す。］ That is, this invention provides the polymer containing the structure represented by following General formula (1).

[Wherein, X represents a tetravalent organic group, Y, R ₁ and R ₂ each independently represents a divalent organic group, and R represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 5 carbon atoms. N represents an integer of 1 or more. ]

  Since such a polymer is a polyimide precursor (polyamic acid) and imidizes by heating, it can be thermally cured without using a thermosetting agent, and has a sufficiently high 1% weight loss temperature (heat resistance). Moreover, since this polyimide precursor uses a compound having an amide bond in the structure as a diamine component, the amide bond concentration is high and the adhesive strength to various materials is high. Further, since it has a carboxyl group in the structure, it can be developed with a weak alkaline aqueous solution when used as a base polymer of the photosensitive resin composition. As a result, if a photosensitive resin composition containing the polymer of the present invention is used, a solder resist having sufficiently high heat resistance and thermal shock resistance can be formed. In addition, the one-part photosensitive resin composition or dry film containing the polymer of the present invention has high storage stability, and various properties such as coating properties, cured film resolution, and heat resistance even after long-term storage. Can be maintained sufficiently satisfactorily.

  The imidized polymer of the present invention is an imidized polymer obtained by imidizing a polymer containing the structure represented by the general formula (1). Such an imidized polymer has a high 1% weight loss temperature (heat resistance) and has a high adhesive force because it contains a diamine component. Furthermore, when it has the carboxyl group which is not imidized, it can also be used as a base polymer of the photosensitive resin composition in which alkali development is possible.

  The present invention also provides an alkali-developable photosensitive resin composition containing (A) the polymer and / or imidized polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. provide.

  When a predetermined portion of the photosensitive resin composition is irradiated with light, the photopolymerizable compound in the exposed portion is polymerized, and the photosensitive resin composition in the unexposed portion is selectively eluted and removed using an alkaline developer. A predetermined resist pattern can be formed. Furthermore, a cured product having high heat resistance is obtained by imidation of the polymer. As a result, if the photosensitive resin composition of the present invention is used, a solder resist exhibiting sufficiently high heat resistance and thermal shock resistance can be formed. Further, as described above, a dry film exhibiting sufficiently excellent storage stability and high adhesiveness can be formed using such a photosensitive resin composition.

  Here, the weight average molecular weight of the polymer (A) is preferably 10,000 to 200,000. When the weight average molecular weight is within the above range, it is possible to form a solder resist having good developability with an alkali developer and excellent mechanical properties such as tensile strength and elongation.

  Moreover, it is preferable that the said (B) photopolymerizable compound contains the compound which has an amide bond. Thereby, high compatibility with the said (A) polymer is obtained, and it becomes possible to obtain a uniform cured film. By obtaining a uniform cured film, high tensile strength and elongation can be stably obtained.

  Furthermore, it is preferable that the (B) photopolymerizable compound contains a compound represented by the following general formula (2), (3) or (4). Thereby, high compatibility with the said (A) polymer is obtained, and it becomes possible to obtain the cured film which has high heat resistance, tensile strength, elongation rate, etc. stably.

［式（２）、（３）及び（４）中、Ｒ_３は二価の有機基を示す。］

[In the formulas (2), (3) and (4), R ₃ represents a divalent organic group. ]

  The present invention also provides a photosensitive film for permanent resist comprising a support and a photosensitive layer containing the photosensitive resin composition formed on the support. Such a photosensitive film for a permanent resist exhibits sufficiently excellent storage stability and high adhesiveness, and sufficiently maintains various properties such as coating properties, resolution of cured products and heat resistance even after storage for a long time. be able to.

  The present invention also provides a photosensitive resin composition comprising the above photosensitive resin composition so as to cover the conductive layer on the insulating substrate of a laminated substrate including an insulating substrate and a conductive layer having a circuit pattern formed on the insulating substrate. A method for forming a resist pattern is provided, in which layers are laminated, an exposed portion is formed by irradiating a predetermined portion of the photosensitive layer with an actinic ray, and then a portion other than the exposed portion is removed. Such a resist pattern forming method is suitably used in forming a resist pattern, particularly a permanent resist layer, in a printed wiring board, a semiconductor package, or the like. Resist patterns obtained by such methods exhibit sufficiently high heat resistance and thermal shock resistance, as well as mechanical properties such as tensile strength and elongation, electrical insulation, moisture and heat resistance, alkali resistance, solvent resistance, and solder heat resistance. And excellent resistance to electrolytic Ni / Au plating. Therefore, the obtained permanent resist is preferably used as a surface protective film and an interlayer insulating film.

  The present invention also includes an insulating substrate, a conductor layer having a circuit pattern formed on the insulating substrate, and a cured product of the photosensitive resin composition formed on the insulating substrate so as to cover the conductor layer. A printed wiring board comprising a permanent resist layer.

  The present invention also includes an insulating substrate, a conductor layer having a circuit pattern formed on the insulating substrate, and a permanent resist layer formed on the insulating substrate so as to cover the conductor layer. A photosensitive layer composed of the photosensitive resin composition so as to cover the conductor layer, and irradiating a predetermined portion of the photosensitive layer with an actinic ray to form an exposed portion; A method for manufacturing a printed wiring board is provided, wherein a portion other than an exposed portion is removed.

  The present invention further provides a surface protective film and an interlayer insulating film made of a cured product of the photosensitive resin composition. Such surface protective film and interlayer insulating film have sufficiently high heat resistance and thermal shock resistance, mechanical properties such as tensile strength and elongation, electrical insulation, moisture and heat resistance, alkali resistance, solvent resistance, solder heat resistance And excellent resistance to electrolytic Ni / Au plating.

  According to the present invention, a weakly developable photosensitive resin composition capable of forming a solder resist having sufficiently high heat resistance and thermal shock resistance, and capable of forming a dry film exhibiting sufficiently excellent storage stability. Sensitive to weak alkali development that can form polymers that can be used in products, and can form solder resists with sufficiently high heat resistance and thermal shock resistance, and can form dry films that exhibit sufficiently excellent storage stability. A functional resin composition can be provided. In addition, according to the present invention, there are provided a photosensitive film for a permanent resist, a method for forming a resist pattern, a printed wiring board and a method for producing the same, and a surface protective film and an interlayer insulating film using the photosensitive resin composition. can do.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. In the present specification, “(meth) acrylic acid” means “acrylic acid” and “methacrylic acid” corresponding thereto, and “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto. means.

[polymer]
The polymer of the present invention is a polyimide precursor (polyamic acid) and includes a structure represented by the following general formula (1).

［式（５）中、Ｚは単結合、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−ＳＯ_２−、−ＣＨ_２−、

を示し、Ｒ_４及びＲ_５は各々独立に水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｐ及びｑは各々独立に１〜３の整数を示す。なお、ｐが２以上の場合、複数存在するＲ_４は同一でも異なっていてもよく、ｑが２以上の場合、複数存在するＲ_５は同一でも異なっていてもよい。］ In the general formula (1), X represents a tetravalent organic group, and is preferably a group represented by the following general formula (5), (6), (7), (8) or (9).

[In the formula (5), Z represents a single bond, —O—, —S—, —C (O) —, —SO ₂ —, —CH ₂ —,

R ₄ and R ₅ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and p and q each independently represents an integer of 1 to 3. In addition, when p is 2 or more, a plurality of R ₄ may be the same or different, and when q is 2 or more, a plurality of R ₅ may be the same or different. ]

［式（６）中、Ｒ_６は水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｍは１〜２の整数を示す。なお、ｍが２の場合、複数存在するＲ_６は同一でも異なっていてもよい。］

Wherein (6), _{R 6} represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 6 carbon atoms, m is an integer of 1-2. When m is 2, a plurality of R ₆ may be the same or different. ]

［式（７）中、Ｒ_７は水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｒは１〜４の整数を示す。なお、ｒが２以上の場合、複数存在するＲ_７は同一でも異なっていてもよい。］

Wherein (7), _{R 7} represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 6 carbon atoms, r is an integer of 1-4. When r is 2 or more, a plurality of R ₇ may be the same or different. ]

［式（８）中、Ｒ_８は水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｓは１〜６の整数を示す。なお、ｓが２以上の場合、複数存在するＲ_８は同一でも異なっていてもよい。］

Wherein (8), _{R 8} represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 6 carbon atoms, s is an integer of 1-6. When s is 2 or more, a plurality of R ₈ may be the same or different. ]

［式（９）中、Ｒ_９及びＲ_１０は各々独立に水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｔ及びｕは各々独立に１〜４の整数を示す。なお、ｔが２以上の場合、複数存在するＲ_９は同一でも異なっていてもよく、ｕが２以上の場合、複数存在するＲ_１０は同一でも異なっていてもよい。］

[In Formula (9), R ₉ and R ₁₀ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and t and u each independently represent 1 to 4 carbon atoms. Indicates an integer. When t is 2 or more, a plurality of R ₉ may be the same or different, and when u is 2 or more, a plurality of R ₁₀ may be the same or different. ]

  Among these, general formula (5) or general formula (6) in which Z is a single bond, —O— or —C (O) — is preferable.

  Y represents a divalent organic group, and an arylene group which may have a substituent and an alkylene group which may be branched having 1 to 10 carbon atoms are preferable. Among these, a phenylene group and a pyridylene group are particularly preferable.

R ₁ and R ₂ each independently represent a divalent organic group, preferably an arylene group which may have a substituent, or an alkylene group having 1 to 20 carbon atoms, and particularly preferably a phenylene group.

  R represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 5 carbon atoms, and is preferably a hydrogen atom.

Such a polymer is preferably a polymer having a structure represented by the general formula (1) as a repeating unit. In particular, X is a general formula (wherein Z is a single bond, —O— or —C (O) —). 5), or general formula (6), Y is a phenylene group or pyridylene group, R is a hydrogen atom, R ₁ and R ₂ are phenylene groups, and a polymer having a repeating unit as a structure represented by general formula (1) Preferably used.

［式（１０）中、Ｙは、二価の有機基を示し、Ｒは水素原子、フェニル基又は炭素数１〜５のアルキル基を示す。］そのうち、Ｙは、置換基を有していてもよいアリーレン基、炭素数１〜１０の枝分かれしていてもよいアルキレン基であることが好ましい。 The polymer of the present invention can be obtained by polymerizing a diamine component having an amide bond and a tetracarboxylic dianhydride. The diamine component having an amide bond can be obtained, for example, from a bisoxazoline represented by the following general formula (10) and an amino acid.

[In Formula (10), Y shows a divalent organic group, R shows a hydrogen atom, a phenyl group, or a C1-C5 alkyl group. Among them, Y is preferably an arylene group which may have a substituent or an alkylene group which may have 1 to 10 carbon atoms.

  Examples of the bisoxazoline include 2,2 ′-(1,3-phenylene) bis-2-oxazoline, 2,6-bis (4-isopropyl-2-oxazolin-2-yl) pyridine, and 2-2 ′. -Isopropylidenebis (4-phenyl-2-oxazoline), 2-2'-isopropylidenebis (4-tertiarybutyl-2-oxazoline) and the like. These may be used alone or in combination of two or more.

  Examples of the amino acid include p-aminobenzoic acid, 3-aminobenzoic acid, 2-aminobenzoic acid, glycine, β-alanine, phenylalanine, γ-aminobutyric acid, leucine, and isoleucine. These can be used alone or in combination of two or more.

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride. 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetra Carboxylic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic anhydride (4,4′-oxydiphthalic dianhydride Product), 2,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,3,3 ′, 4 ′ -Diphenylsulfur Tetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic Examples thereof include acid dianhydride, 2,3,4,7-anthracenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride and the like. These may be used alone or in combination of two or more.

  Moreover, in this polymer, diamine components other than the diamine component obtained from the said oxazoline and an amino acid can be used together. Examples of such a diamine component include polyoxyalkylene diamine (manufactured by Mitsui Chemicals Fine, trade name: “Jeffamine”), [3,4-bis (1-aminoheptyl) -6-hexyru 5- (1 -Octenyl)] cyclohexene (manufactured by Cognis Japan, trade name “Versamine 551”), 1,4-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,4-bis (2-methoxy-4-) Examples of the aminopentyl) benzene and the diamine compound having an aromatic hydrocarbon structure include 4,4′-diaminodibenzyl sulfoxide, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, Bis (4-aminophenyl) ethylphosphine oxide, bis (4-aminophenyl) phenylphosphine Oxide, bis (4-aminophenyl) -N-phenylamine, bis (4-aminophenyl) -N-methylamine, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1, , 6-Diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 1,4-diamino-2-methylnaphthalene, 1,5-diamino 2-methylnaphthalene, 1,3-diamino-2-phenylnaphthalene, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 2,4 -Diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminotoluene, Methoxy-2,4-diaminobenzene, 1,3-diamino-4,6-dimethylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2-methoxy-5-methylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene, o-xylenediamine, m-xylenediamine, p-xylenediamine, 9,10-bis (4-aminophenyl) anthracene, 4-aminophenyl -3-aminobenzoate, 1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane, 1,1-bis [4- (4-aminophenoxy) phenyl] -1 -Phenyl-2,2,2-trifluoroethane, 1,3-bis (3-aminophenyl) decafluoropropane, 2,2-bis (3-amino-4-hydro Xylphenyl) hexafluoropropane, 1,4-bis (3-aminophenyl) but-1-ene-3-yne 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3 , 3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-5,5 '-Diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'diethoxy-4,4'-diaminodiphenylmethane, bis (3-aminophenyl) ether, Bis (4-aminophenyl) ether, 3,4′-diaminodiphenyl ether, 3,3′-diethyl-4,4′-diamino Phenyl ether, 3,3′-dimethoxy-4,4′-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, 3,3′-dimethyl-4,4′-diaminodiphenyl sulfone, 3, 3'-diethyl-4,4'-diaminodiphenylsulfone, 3,3'-dimethoxy-4,4'-diaminodiphenylsulfone, 3,3'-diethoxy-4,4'-diaminodiphenylsulfone, 3,3 ' -Dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diethyl-4,4'-diaminodiphenylpropane, 3,3'-dimethoxy-4,4'-diaminodiphenylpropane, 3,3'-diethoxy -4,4'-diaminodiphenylpropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane 1,3-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl sulfide, 3,3′-dimethyl-4,4′-diaminodiphenyl sulfide 3,3′-diethyl-4,4′-diaminodiphenyl sulfide, 3,3′-dimethoxy-4,4′-diaminodiphenyl sulfide, 3,3′-diethoxy-4,4′-diaminodiphenyl sulfide, 2, , 4′-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis ( 4-aminophenyl) ethane, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, bis (4-toluidine) sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene, 4, 4′-diaminobiphenyl, 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, 9,9-bis [4- (3-aminophenoxy) phenyl] fluorene, 3,3′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,4′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4′- Bis (4-aminophenoxy) biphenyl, 1,4-bis (4-aminophenoxy) benzene, 3,3′-diaminobenzophenone, 4,4′-dia Nobenzophenone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis-4- (4-aminophenoxy) phenylpropane, 1,3-bis (3-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (5-amino-4-methylphenyl) hexafluoropropane, and the like. These diamine components may be used alone or in combination of two or more.

  In the synthesis of such a polymer, an appropriate amount of solvent is usually used. Specific examples include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and γ-butyrolactone. In order to control the drying property of the coating film, a poor solvent having high volatility can be used in combination with such a solvent so that the polymer does not precipitate. For example, ketone compounds such as methyl isobutyl ketone, cyclohexanone or methylcyclohexanone, aromatic hydrocarbon compounds such as toluene, xylene or tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol Monomethyl ether, dipropylene glycol monomethyl ether, glycol ether compounds such as dipropylene glycol diethyl ether or triethylene glycol monoethyl ether, ester compounds such as acetate compounds of the above glycol ether compounds, alcohol compounds such as ethylene glycol or propylene glycol, Or petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha or sorbene Petroleum solvents such as naphtha, which may be used alone or in combination of two or more thereof.

The weight average molecular weight (Mw) of the polymer that is the polyimide precursor can be measured by gel permeation chromatography (GPC) (in terms of standard polystyrene). The conditions for GPC are as follows.
(GPC conditions)
Pump: Hitachi L-7100 [manufactured by Hitachi, Ltd.]
Detector: UV Hitachi L-4000 type UV [manufactured by Hitachi, Ltd.]
RI: Hitachi L-7490 type [manufactured by Hitachi, Ltd.]
Column: Gelpack GL-S300MDT-5 (two in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
Column size: 8mmφ × 300mm
Eluent: DMF / THF = 1/1 + phosphoric acid 0.06M + lithium bromide 0.06M
Sample concentration: 5 mg / 1 mL
Injection volume: 5 μL
Pressure: 343 Pa (35 kgf / cm ² )
Flow rate: 1.0 mL / min

  The Mw of the polyimide precursor obtained by this measurement method, when used as a base polymer of a photosensitive resin composition, develops with a developer such as a dilute alkaline aqueous solution, and mechanical properties such as tensile strength and elongation. From the viewpoint, it is preferably 10,000 to 200,000, more preferably 15,000 to 150,000, and particularly preferably 30,000 to 100,000.

  In addition, the imidized polymer of this invention is an imidized polymer formed by imidating the polymer containing the structure represented by the said General formula (1). This imidized polymer includes those obtained by imidizing a part of the polymer including the structure represented by the general formula (1). Although different depending on the structure, the imidization temperature is in the range of 100 to 300 ° C.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention contains (A) a polymer containing a structure represented by the general formula (1), (B) a photopolymerizable compound, and (C) a photopolymerization initiator. . Hereinafter, each component of the photosensitive resin composition of this invention is demonstrated in detail.

<(A) component>
(A) The polymer is the polymer and / or imidized polymer described in [Polymer] above. This (A) polymer is used as a base polymer in the photosensitive resin composition. In addition, (A) polymer can be used individually by 1 type or in combination of 2 or more types.

<(B) component>
Although it does not specifically limit as a photopolymerizable compound which is (B) component, What has an ethylenically unsaturated group in a molecule | numerator is used preferably. For example, a (meth) acrylate compound having an amide bond in the molecule; a bisphenol A (meth) acrylate compound; a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid; a glycidyl group-containing compound , Compounds obtained by reacting β-unsaturated carboxylic acids; urethane monomers or urethane oligomers such as (meth) acrylate compounds having a urethane bond in the molecule; in addition to these, nonylphenoxy polyoxyethylene acrylate; Phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxyalkyl-o-phthalate; ) Acrylic acid alkyl ester, EO-modified nonylpheny (Meth) acrylate or the like can be exemplified. These may be used alone or in combination of two or more.

  Among these, from the viewpoint of compatibility with the polymer (A), a compound having an amide bond or a urethane bond is particularly preferably used. More preferably, a (meth) acrylate compound having an amide bond in the molecule is preferable from the viewpoint of heat resistance. Of these, compounds represented by the following general formula (2), (3) or (4) are particularly preferably used.

である。 In the above general formulas (2), (3) and (4), R ₃ represents a divalent organic group, preferably an alkylene group having 1 to 10 carbon atoms and an arylene group which may have a substituent. ,

It is.

The compounds represented by the general formula (2) and the general formula (3) can be obtained from the bisoxazoline and (meth) acrylic acid.
Moreover, the compound represented by General formula (4) can be obtained from 2-vinyl-2-oxazoline and dicarboxylic acid.
Examples of the dicarboxylic acid include ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, phthalic acid, isophthalic acid, Examples include terephthalic acid, biphenyl-2,2′-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the like.

  Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). ) Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Can be mentioned. These can be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy nonaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexa) Decaethoxy) phenyl) propane and the like. These can be used alone or in combination of two or more.

  Of these, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.). -Bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). These can be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Xinonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meth)) And acryloxyhexadecapropoxy) phenyl) propane. These may be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, Examples include 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane. These can be used alone or in combination of two or more.

  Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups. Polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO / PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) A Examples thereof include acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.

“EO” refers to “ethylene oxide”, and “PO” refers to “propylene oxide”. Further, “EO modified” means having a block structure of ethylene oxide units (—CH ₂ —CH ₂ —O—), and “PO modified” means propylene oxide units (—CH ₂ —CH (CH ₃ )). -O-) having a block structure.

  Examples of the compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4- (meth) acryloxy- 2-hydroxy-propyloxy) phenyl and the like. These can be used alone or in combination of two or more.

  Examples of the α, β-unsaturated carboxylic acid include (meth) acrylic acid. These can be used alone or in combination of two or more.

  Examples of urethane monomers include (meth) acrylic monomers having an OH group at the β-position and diisocyanate compounds such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Additional reaction products, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO or PO-modified urethane di (meth) acrylate, and the like can be mentioned. These can be used alone or in combination of two or more.

  Furthermore, examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and the like. It is done. These can be used alone or in combination of two or more.

  These (B) components are used individually by 1 type or in combination of 2 or more types.

<(C) component>
Examples of the photopolymerization initiator (C) include benzophenone; N, N′-tetraalkyl-4,4′-diaminobenzophenone; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). Aromatic ketones such as butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; quinones such as alkylanthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin Benzoin compounds such as alkylbenzoin; benzyl derivatives such as benzyldimethyl ketal; 2,4,5-triarylimidazole dimer; 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc. Acridine derivatives; N-phenylglycine, N-phenylglycine derivatives Coumarin compounds, acylphosphine oxide derivatives. These can be used singly or in combination of two or more.

<Diluent>
The photosensitive resin composition is usually used for production of a photosensitive film, formation of a resist pattern, or the like in a state dissolved or dispersed in a diluent. The diluent is not particularly limited as long as it can dilute the components (A) to (C). Examples include N-methylpyrrolidone, γ-butyrolactone, dimethylformamide, dimethylacetamide, aliphatic alcohols, cyclic hydrocarbons, ketones, ketoalcohols, alkylene glycols, alkylene glycol alkyl ethers, acetate compounds thereof, and carboxylic acid esters. . These can be used alone or in combination of two or more.

  Examples of the aliphatic alcohol include methanol, ethanol, n-propanol, iso-propanol, n-butanol, n-pentanol, and n-hexanol. Examples of the cyclic hydrocarbon include benzyl alcohol, cyclohexane, and toluene. These can be used alone or in combination of two or more.

  Examples of the ketone include acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, methyl hexyl ketone, ethyl butyl ketone, dibutyl ketone, cyclopentanone and cyclohexanone. Examples of keto alcohols include diacetone alcohol, 3-hydroxy-2-butanone, 4-hydroxy-2-pentanone, and 6-hydroxy-2-hexanone. These can be used alone or in combination of two or more.

  Examples of the alkylene glycol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and propylene glycol. Examples of the alkylene glycol alkyl ether include diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, triethylene glycol alkyl ether, propylene glycol alkyl ether and dipropylene glycol alkyl ether. More specifically, for example, 3-methoxy- Examples include 1-butanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, methyl cellosolve, ethyl cellosolve, and butyl cellosolve. The acetate compound of alkylene glycol or alkylene glycol alkyl ether may be any of the above-mentioned alkylene glycol or alkylene glycol alkyl ether acetate compounds, such as ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, propylene glycol diacetate. Examples include acetate, methyl cellosolve acetate, and ethyl cellosolve acetate. These can be used alone or in combination of two or more.

  Examples of the carboxylic acid ester include ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate and ethyl butyrate. These can be used alone or in combination of two or more.

<Thermosetting compound>
In addition, although it is not essential, you may use the thermosetting compound which can be thermoset between 120-200 degreeC. For example, a blocked isocyanate compound, a bismaleimide compound, an oxetane compound, a benzoxazine compound, a melamine resin, and the like that can be subjected to a thermosetting reaction at 120 to 200 ° C. Among these, from the viewpoint of solder heat resistance, electroless Ni / Au plating resistance, electric corrosion resistance, thermal shock resistance, etc., a block isocyanate compound, an epoxy compound having two or more glycidyl groups in one molecule, a bismaleimide compound, and One or more compounds selected from oxetane compounds are preferred, and one or more compounds selected from blocked isocyanate compounds, bismaleimide compounds and oxetane compounds are more preferred from the viewpoint of the stability of the resin varnish or the photosensitive film. . Even more preferred are compounds having (meth) acrylate moieties and blocked isocyanate moieties in the structure.

  A blocked isocyanate compound is a compound that is generated by the reaction of an isocyanate compound and a blocking agent and is temporarily inactivated by a group derived from the blocking agent. When heated to a predetermined temperature, the group derived from the blocking agent is dissociated. To generate isocyanate groups. Specific examples of isocyanate compounds that can react with the blocking agent include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, and o-xylylene diene. Aromatic polyisocyanates such as isocyanate, m-xylylene diisocyanate, 2,4-tolylene dimer, aliphatic polyisocyanates such as hexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, etc. Of alicyclic polyisocyanate.

  As a blocking agent, what has active hydrogen is preferable, and an active methylene compound, a diketone compound, an oxime compound, a phenol compound, an alkanol compound, a caprolactam compound, etc. are mentioned. Specifically, methyl ethyl ketone oxime, ε-caprolactam and the like can be used.

  The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2957, TPLS-2078. , TPLS-2117, Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., trade name) and the like. It is done.

  The bismaleimide compound is a compound having two or more maleimide groups in the molecule.

  Specific examples of the bismaleimide compound include 1-methyl-2,4-bismaleimide benzene, N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide, N, N′-m- Toluylene bismaleimide, N, N′-4,4′-biphenylenebismaleimide, N, N′-4,4 ′-[3,3′-dimethyl-biphenylene] bismaleimide, N, N′-4,4 '-[3,3'-dimethyldiphenylmethane] bismaleimide, N, N'-4,4'-[3,3'-diethyldiphenylmethane] bismaleimide, N, N'-4,4'-diphenylmethane bismaleimide, N, N′-4,4′-diphenylpropane bismaleimide, N, N′-4,4′-diphenyl ether bismaleimide, N, N′-3,3′-diphenylsulfone Bismaleimide, N, N′-4,4′-diphenylsulfone bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-tert-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-s-butyl-4- (4-maleimidophenoxy) phenyl] propane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] Decane, 1,1-bis [2-methyl-4- (4-maleimidophenoxy) -5-tert-butylphenyl] -2-methylpropane, 4,4′-cyclohexylidene-bis [1- (4- Maleimidophenoxy) -2- (1,1-dimethylethyl) benzene], 4,4′-methylene-bis [1- (4-maleimidophenoxy) -2,6-bis (1,1- Methylethyl) benzene], 4,4′-methylene-bis [1- (4-maleimidophenoxy) -2,6-di-s-butylbenzene], 4,4′-cyclohexylidene-bis [1- ( 4-maleimidophenoxy) -2-cyclohexylbenzene, 4,4′-methylenebis [1- (maleimidophenoxy) -2-nonylbenzene], 4,4 ′-(1-methylethylidene) -bis [1- (maleimidophenoxy) ) -2,6-bis (1,1-dimethylethyl) benzene], 4,4 ′-(2-ethylhexylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4 ′-( 1-methylheptylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4′-cyclohexylidene-bis [1- (maleimidophenoxy) -3-methylbenzene 2, 2-bis [4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-Methyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3 , 5-Dimethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-ethyl -4- (4-maleimidophenoxy) phenyl] hexafluoropropane, bis [3-methyl- (4-maleimidophenoxy) phenyl Methane, bis [3,5-dimethyl- (4-maleimidophenoxy) phenyl] methane, bis [3-ethyl- (4-maleimidophenoxy) phenyl] methane, 3,8-bis [4- (4-maleimidophenoxy) Phenyl] -tricyclo [5.2.1.02,6] decane, 4,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 3, 9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 4,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5. 2.1.02,6] decane, 1,8-bis [4- (4-maleimidophenoxy) phenyl] menthane, 1,8-bis [3-methyl-4- (4-maleimidophenoxy) Phenyl] menthane, 1,8-bis [3,5-dimethyl-4- (4-maleimide phenoxy) phenyl] menthane and the like. These bismaleimide compounds may be synthesized by a conventional method, or commercially available products may be used.

  Among these bismaleimide compounds, a compound having no halogen atom in the molecule is preferable from the viewpoint of further suppressing the generation of harmful substances.

  Moreover, as a compound which has a (meth) acrylate part and a blocked isocyanate part in a structure, methacrylic acid-2- [0- [1'methylpropylideneamino] carboxyamino] ethyl, acrylic acid-2- [0- [1 ′ methylpropylideneamino] carboxyamino] ethyl and the like. Examples of commercially available compounds include, but are not limited to, Karenz MOI-BM (manufactured by Showa Denko KK, trade name).

  These can be used individually by 1 type or in combination of 2 or more types.

<Content of each component>
In the photosensitive resin composition, the content ratio of the component (A) is a viewpoint for preventing exudation from the end face of a photosensitive element such as a photosensitive film for permanent resist having a photosensitive layer made of the photosensitive resin composition, In addition, from the viewpoint of obtaining superior solder heat resistance and photosensitivity, it is preferably 30 to 70 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), and 45 to 55 parts by mass. More preferably, it is a part.

  The content ratio of the component (B) is preferably 10 to 70 parts by mass and more preferably 35 to 55 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). . If this content is less than 10 parts by mass, the photosensitivity tends to be insufficient, and if it exceeds 70 parts by mass, the resulting cured product tends to be brittle.

  (C) The content rate of a component is 0.1-20 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component from a viewpoint of obtaining the more outstanding photosensitivity and solder heat resistance. It is preferable that it is 0.2 to 10 parts by mass.

  In addition, the photosensitive resin composition of the present embodiment includes a melamine resin or isocyanate block, a thermosetting component such as bismaleimide, a dye such as malachite green, tribromophenyl sulfone or leuco crystal violet as necessary. Photo-coloring agent, thermo-coloring inhibitor or plasticizer such as p-toluenesulfonamide, phthalocyanine-based such as phthalocyanine green or phthalocyanine blue, azo-based organic pigments or inorganic pigments such as titanium dioxide, silica, alumina, talc, Component (A) includes fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances or imaging agents made of inorganic pigments such as calcium carbonate or barium sulfate. And (B) each with respect to 100 parts by mass in total It can contain about 0.01 to 20 parts by weight. These can be used alone or in combination of two or more. Moreover, you may use together polymer components other than (A) component, such as an acryl-type copolymer and an acid-modified vinyl group containing epoxy resin.

  According to the photosensitive resin composition of the present embodiment, it is possible to form a good coating film having excellent photosensitivity such as good developability and high resolution and with reduced stickiness. Thereby, it is possible to form a solder resist having sufficiently high heat resistance and thermal shock resistance, and it is possible to form a dry film exhibiting sufficiently excellent storage stability.

  The photosensitive resin composition of the present embodiment has characteristics and reliability required for a solder resist, an interlayer insulating film, a semiconductor surface protective film, etc. provided in a printed wiring board such as a rigid wiring board and a flexible wiring board and a package substrate. Can satisfy the sex. The solder resist obtained from the photosensitive resin composition of the present embodiment is sufficiently excellent in thermal shock resistance, and in addition to alkali resistance, solder heat resistance, and electrolytic Ni / Au plating due to the same factors. It has excellent mechanical properties such as properties, elongation and tensile strength, and electric corrosion resistance.

[Photosensitive film for permanent resist]
The photosensitive film for permanent resists of this invention is equipped with a support body and the photosensitive layer containing the said photosensitive resin composition formed on this support body. Hereinafter, a preferred embodiment of the photosensitive film for permanent resist of the present invention will be described with reference to FIG. The photosensitive film 1 for permanent resist shown in FIG. 1 includes a support 11, a photosensitive layer 12 containing the photosensitive resin composition formed on the support, and a protective film laminated on the photosensitive layer 12. 13.

  The photosensitive layer 12 is prepared by dissolving the above-described photosensitive resin composition in a solvent (diluent) or a mixed solvent (diluent) to obtain a solution having a solid content of about 30 to 70% by mass, and then applying the solution on the support 11. It is preferable to form by coating. Although the thickness of a photosensitive layer changes with uses, it is the thickness after drying which removed the diluent by heating and / or hot air spraying, and it is preferable that it is 10-100 micrometers, and it is more preferable that it is 20-60 micrometers. If the thickness is less than 10 μm, there is a tendency that it is difficult to apply (apply) industrially. If the thickness exceeds 100 μm, the above-described effect produced by the present invention tends to be small, and in particular, physical properties such as mechanical properties and resolution are low. It tends to decrease.

  Examples of the protective film 13 include polyethylene film, polypropylene film, Teflon (registered trademark) film, and surface-treated paper. The protective film 13 preferably has a smaller adhesive force between the photosensitive layer 12 and the protective film 13 than the adhesive force between the photosensitive layer 12 and the support 11.

  Examples of the support 11 provided in the photosensitive film 1 for permanent resist include polymer films having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester.

  The thickness of the support 11 is preferably 5 to 100 μm, and more preferably 10 to 30 μm. If the thickness is less than 5 μm, the support 11 tends to be broken when the support 11 is peeled off from the photosensitive film 1 for permanent resist before development, and if it exceeds 100 μm, the resolution and flexibility are lowered. Tend. In the present embodiment, since the photosensitive layer 12 is formed using the polyester resin as described above, when the thickness of the support 11 is larger than that of the conventional one, for example, when the thickness is more than 25 μm and not more than 100 μm. Can maintain its flexibility and resolution.

  The photosensitive film 1 for permanent resist composed of three layers of the support 11, the photosensitive layer 12, and the protective film 13 as described above may be stored as it is, or wound with the protective film 13 interposed therebetween, for example. The core can be wound into a roll and stored.

  Since the photosensitive film for permanent resist of this embodiment does not contain a thermosetting agent that reacts with the base polymer at room temperature, various properties such as coating properties, resolution of cured products, and thermal shock resistance even after storage for a long time. Sufficient storage stability that can maintain the characteristics sufficiently good can be exhibited. Further, since the surface of the photosensitive layer is less sticky, it is possible to efficiently produce a high-resolution and high-density printed wiring board.

[Method of forming resist pattern]
According to another aspect of the present invention, there is provided a method for forming a resist pattern, the method comprising: forming the photosensitive resin on the insulating substrate of a laminated substrate including an insulating substrate and a conductor layer having a circuit pattern formed on the insulating substrate so as to cover the conductor layer. A photosensitive layer made of the composition is laminated, an actinic ray is irradiated to a predetermined portion of the photosensitive layer to form an exposed portion, and then a portion other than the exposed portion of the photosensitive layer is removed.

  In one Embodiment, the photosensitive layer of the said photosensitive film for permanent resists is used as a photosensitive layer which consists of the said photosensitive resin composition. Examples of the method for laminating the photosensitive layer include a method in which the photosensitive layer in the above-described permanent resist photosensitive film is laminated by pressing onto the insulating substrate while heating. When the photosensitive resin composition contains a volatile component such as a solvent, the photosensitive layer formed on the substrate is mainly composed of components after most of the solvent is removed. Moreover, when the photosensitive film for permanent resist is provided with a protective film, the protective film is peeled off from the photosensitive film for permanent resist before the formation of the photosensitive layer.

  The surface of the insulating substrate on which the photosensitive layer is laminated is usually the surface of the conductor layer, but may be a surface other than the conductor layer. In the case where the photosensitive layer in the photosensitive film for permanent resist is heated and laminated on the insulating substrate while being laminated, the heating temperature of the photosensitive layer is preferably 70 to 110 ° C., and the pressure is about 0.1 to 1.0 MPa. The ambient pressure is more preferably 4 kPa or less, but these conditions are not particularly limited. Further, if the photosensitive layer is heated to 70 to 110 ° C. as described above, it is not necessary to pre-heat the insulating substrate and the conductor layer in advance. However, in order to further improve the laminating property, the pre-heat treatment is performed. You can also.

  After the lamination of the photosensitive layer is completed in this way, an exposure part is formed by irradiating a predetermined portion of the photosensitive layer with an actinic ray in an exposure step. Examples of the method for forming the exposed portion include a method of irradiating actinic rays in an image form through a negative or positive mask pattern called an artwork. At this time, when the support on the photosensitive layer is transparent, it can be irradiated with actinic rays as it is, but when it is opaque, it is irradiated with actinic rays after removing the support.

  As the light source of actinic light, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp that emits ultraviolet rays effectively is used. Moreover, what emits visible light effectively, such as a photographic flood light bulb and a solar lamp, is also used.

After the exposure, if a support is present on the photosensitive layer, the support is removed. Thereafter, a portion other than the exposed portion of the photosensitive layer is developed and removed by wet development or the like to form a resist pattern made of a cured product of the photosensitive resin composition. In the case of wet development, development is performed using a developer by a known method such as spraying, rocking immersion, brushing, or scraping. In addition, you may further perform post-curing by 1-5 J / cm < ² > exposure or / and the heating (post-heating process) of 100-200 degreeC and 30 minutes-12 hours after resist pattern formation.

  The developer used in the development process is not particularly limited as long as it does not damage the exposed area and selectively elutes the unexposed area. The alkaline developer is safe and stable, and has good operability. Therefore, it is preferably used. Examples of the alkali developer include dilute alkali aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, sodium 4-borate, ammonia, amines, or dilute alkaline aqueous solutions. An emulsion developer with an organic solvent can also be used. For example, a dilute solution of sodium carbonate (1 to 5 wt% aqueous solution) at 20 to 50 ° C. is used.

  The resist pattern obtained by the resist pattern forming method of the present embodiment is composed of a cured product (cured film) of the photosensitive resin composition of the present invention, and the circuit wiring after the circuit wiring is soldered to the substrate It is also useful as a permanent mask (solder resist) for semiconductor packages. Further, it is useful as an interlayer insulating film and / or a surface protective layer of an electronic component such as a semiconductor element, and further as a cover coat layer. This resist pattern exhibits sufficiently high thermal shock resistance, mechanical properties such as tensile strength and elongation, electrical insulation, wet heat resistance, alkali resistance, solvent resistance, solder heat resistance, and electrolytic Ni / Au plating resistance Also excellent.

In addition, when the resist pattern is used as, for example, a solder resist for a printed wiring board, a flexible wiring board, or a semiconductor package substrate, the solder heat resistance, chemical resistance, etc. are improved after completion of development in the resist pattern forming method. For this purpose, it is preferable to perform ultraviolet irradiation or heating with a high-pressure mercury lamp. In the case of irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary. For example, the irradiation can be performed at an irradiation amount of about 0.2 to 10 J / cm ² . Moreover, when heating a resist pattern, it is preferable to carry out for about 15 to 90 minutes in the range of about 100-170 degreeC. Furthermore, ultraviolet irradiation and heating can be performed at the same time, and after either one is performed, the other can be performed. When performing ultraviolet irradiation and heating simultaneously, it is more preferable to heat to 60 to 150 ° C. from the viewpoint of effectively imparting solder heat resistance, chemical resistance and the like. In the case of a resist pattern obtained by both light irradiation and heating, the above-described effects can be more effectively exhibited.

  Further, the resist pattern can be used for a package substrate including an insulating substrate and an insulating film formed on the insulating substrate. In this case, a resist pattern made of a cured product of the photosensitive resin composition may be used as the insulating film. The substrate provided with the resist pattern in this manner is then mounted with a semiconductor element or the like (for example, wire bonding or solder connection), and is mounted on an electronic device such as a personal computer.

[Printed wiring board and manufacturing method thereof]
The printed wiring board of the present invention comprises an insulating substrate, a conductor layer having a circuit pattern formed on the insulating substrate, and the photosensitive resin composition formed on the insulating substrate so as to cover the conductor layer. And a permanent resist layer made of a cured product. Hereinafter, a preferred embodiment of the printed wiring board of the present invention will be described with reference to FIG. FIG. 2 is a schematic cross-sectional view showing the printed wiring board of the present embodiment.

  The printed wiring board 2 shown in FIG. 2 has an insulating substrate 22, a conductor layer 23 having a circuit pattern formed on one surface of the insulating substrate 22, and a circuit pattern formed on the other surface of the insulating substrate 22. And a solder resist 241 formed on the insulating substrate 22 so as to cover the conductor layer 23 having a circuit pattern. The solder resist 241 is made of a cured product of the photosensitive resin composition, and the solder resist 241 has an opening 26 so that at least a part of the conductor layer 23 having a circuit pattern is exposed.

  Since the printed wiring board 2 has the opening 26, a mounting component such as CSP or BGA can be joined to the conductor layer 23 having a circuit pattern by solder or the like, and so-called surface mounting becomes possible. The solder resist 241 has a role as a solder resist for preventing the solder from adhering to unnecessary portions of the conductor layer during soldering for joining. Functions as a permanent mask for protecting the conductor layer 23.

  Next, an example of a method for manufacturing the printed wiring board 2 will be schematically described. FIG. 3 is a process diagram schematically showing a method of manufacturing the printed wiring board 2 shown in FIG. FIG. 3A shows a printed wiring board substrate 3 including a conductor layer 23 having a circuit pattern on one side and a conductor layer 21 having no circuit pattern on the other side, and FIG. 3 (c) and 3 (d) show the printed wiring board substrate 4 after the photosensitive layer 24 is laminated on the insulating substrate 22, the state in which the photosensitive layer 24 is irradiated with actinic rays, and the printed wiring after development. The plate 2 is shown.

  First, the pattern of the conductor layer 23 is formed on the insulating substrate 22 as shown in FIG. 3A by a known method of etching one side of a double-sided metal-clad laminate (for example, a double-sided copper-clad laminate). Then, the printed wiring board substrate 3 on which the conductor layer 23 is formed is obtained. Next, as shown in FIG. 3B, a photosensitive layer made of the photosensitive resin composition according to the present invention on the printed wiring board substrate 3 on which the conductor layer 23 is formed so as to cover the conductor layer 23. 24 is obtained, and the printed wiring board substrate 4 on which the photosensitive layer 24 is laminated is obtained. Next, as shown in FIG. 3C, a predetermined portion of the photosensitive layer 24 is cured by irradiating the laminated photosensitive layer 24 with actinic rays through the photomask 5 having a predetermined pattern. Finally, the printed wiring board 2 is obtained by removing a non-exposed portion (for example, alkali development) to form a solder resist 241 having an opening 26 as shown in FIG. In addition, when the photosensitive resin composition contains volatile components, such as an organic solvent, the soldering resist 241 is a cured product of the photosensitive resin composition after most of the volatile components are removed.

  In addition, lamination | stacking of the photosensitive layer 24 on the insulated substrate 22, irradiation of actinic light, and removal of an unexposed part can be performed by the method similar to the case in the formation method of the above-mentioned resist pattern.

  The solder resist 241 in the printed wiring board 2 obtained in this way is made of a cured product (cured film) of the photosensitive resin composition of the present embodiment, and exhibits sufficiently high thermal shock resistance, as well as tensile strength. Excellent mechanical properties such as strength and elongation, electrical insulation, heat and humidity resistance, alkali resistance, solvent resistance, solder heat resistance and electrolytic Ni / Au plating resistance. If the solder resist 241 is obtained by both light irradiation and heating, effects such as solder heat resistance and chemical resistance can be more effectively exhibited.

[Surface protective film and interlayer insulating film]
The surface protective film and interlayer insulating film of the present invention are made of a cured product (cured film) of the photosensitive resin composition of the present invention. In one embodiment, the surface protective film and the interlayer insulating film are formed on the surface of the semiconductor element (surface protective film), and between the layers (interlayer insulating film) such as a multilayer wiring board and a semiconductor package by the resist pattern forming method of the present invention. be able to.

  FIG. 4 is a schematic cross-sectional view showing an example of a semiconductor package using a cured product of the photosensitive resin composition of the present invention as an interlayer insulating film. In the semiconductor package 100 shown in FIG. 4, an electrode 20 made of a metal such as aluminum is provided on a silicon wafer (substrate) 10. Although the silicon wafer 10 and the electrode 20 are covered with the interlayer insulating film 3, a part of the interlayer insulating film 30 on the electrode 20 is removed and is made of a metal such as copper connected to the electrode 2 from the part. The rewiring 40 is drawn out. The rewiring 40 is connected to a post portion 5 made of a metal such as copper. The interlayer insulating film 30, the rewiring 40, and the post portion 50 are sealed with a sealing resin 60 so that only one end of the post portion 50 is exposed.

  In the semiconductor package 100, the interlayer insulating film 30 is formed using the above-described photosensitive resin composition of the present invention. Therefore, the interlayer insulating film 30 has been increased in thickness with high resolution, and has sufficiently high heat resistance and thermal shock resistance, as well as excellent insulating properties.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  For example, in another embodiment of the photosensitive film for permanent resist of the present invention, the protective film 13 may not be provided, and only the photosensitive layer 12 and the support 11 in FIG. The printed wiring board of the present invention may be a multilayer printed wiring board in which a plurality of conductive layers and insulating layers are alternately laminated on the insulating substrate or on both sides of the insulating substrate. The cured product of the product functions as an interlayer insulating film for reliably insulating the conductive layers.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

  The polyimide precursor (component (A)) and photopolymerizable compound (component (B)) of the present invention were prepared by the following method.

(Synthesis Example 1) Synthesis of polyimide precursor (component (A)) (P1)
44. Fully dried 2,2 ′-(1,3-phenylene) bis-2-oxazoline (manufactured by Mikuni Pharmaceutical Co., Ltd.) in a flask equipped with a stirrer, reflux condenser, thermometer and dry nitrogen gas inlet tube. 1 g (0.204 mol), 55.9 g (0.408 mol) of p-aminobenzoic acid and 60 g of dehydrated γ-butyrolactone (hereinafter referred to as GBL) are charged and stirred at 150 ° C. for 8 hours to have an amide bond. A diamine monomer was obtained. This reaction solution was reprecipitated and purified with purified water, ethanol, or the like, and then vacuum-dried to obtain a diamine monomer (M1) having an amide bond as a target product in a powder form.

A flask equipped with a stirrer and reflux condenser was charged with 3.06 g of a sufficiently dried diamine monomer (M1) having an amide bond, 1.94 g of oxydiphthalic dianhydride (ODPA), and 5 g of dimethylacetamide at room temperature. Was stirred for 8 hours to obtain a polyimide precursor (P1) having an amide bond as component (A). The obtained polyimide precursor had the repeating structure shown below, and its weight average molecular weight was 69000.

(Synthesis Example 2) Synthesis of polyimide precursor (component (A)) (P2)
In a flask equipped with a stirrer and a reflux condenser, 2.17 g of the sufficiently dried diamine monomer (M1) having an amide bond, 1.96 g of oxydiphthalic dianhydride (ODPA), Jeffamine D400 (Mitsui Chemicals) Fine) 0.86 g and dimethylacetamide 5 g were charged and stirred at room temperature for 8 hours to obtain a polyimide precursor (P2) having an amide bond as component (A). The obtained polyimide precursor had the repeating structure shown below, and its weight average molecular weight was 70000.

(Synthesis Example 3) Synthesis of polyimide precursor (component (A)) (P3)
In a flask equipped with a stirrer and a reflux condenser, 2.14 g of a sufficiently dried diamine monomer having an amide bond (M1), 2.01 g of benzophenone tetracarboxylic dianhydride (BTDA), and Jeffamine D400 ( Mitsui Chemicals Fine) 0.85 g and dimethylacetamide 5 g were charged and stirred at room temperature for 8 hours to obtain a polyimide precursor (P3) having an amide bond as component (A). The obtained polyimide precursor had the repeating structure shown below, and its weight average molecular weight was 40000.

(Synthesis Example 4) Synthesis of Polyimide Precursor (Comparative Example) (P4)
In a flask equipped with a stirrer and a reflux condenser, 1.96 g of sufficiently dried 4,4 ′-[isopropylidenebis (p-phenyleneoxy)] dianiline (BAPP) and oxydiphthalic dianhydride (ODPA) were added. 2.11 g, Jeffamine D400 (Mitsui Chemicals) 0.93 g, and dimethylacetamide 5 g were charged and stirred at room temperature for 8 hours to obtain a polyimide precursor (P4) having an amide bond. The obtained polyimide precursor had the repeating structure shown below, and its weight average molecular weight was 45,000.

(Synthesis Example 5) Synthesis of a polyimide precursor (Comparative Example) (P5)
In a flask equipped with a stirrer and a reflux condenser, 1.93 g of sufficiently dried 4,4 ′-[isopropylidenebis (p-phenyleneoxy)] dianiline (BAPP), benzophenone tetracarboxylic dianhydride (BTDA) ) 2.16 g, Jeffamine D400 (Mitsui Chemicals) 0.91 g, and dimethylacetamide 5 g were stirred at room temperature for 8 hours to obtain a polyimide precursor (P5) having an amide bond. The weight average molecular weight of the obtained polyimide precursor was 43,000.

(Synthesis Example 6) Synthesis of photopolymerizable compound (component (B)) (PM1)
In a flask equipped with a stirrer, reflux condenser, thermometer, and dry air introduction tube, 21.6 g of 2,2 ′-(1,3-phenylene) bis-2-oxazoline (manufactured by Mikuni Pharmaceutical Co., Ltd.) that was sufficiently dried. (0.1 mol), 17.2 g (0.2 mol) of methacrylic acid and 0.02 g of hydroquinone were added, and after heating and stirring at 100 ° C. for 8 hours, a dimethacrylate monomer (PM1) having an amide bond was obtained. It was.

(Synthesis Example 7) Synthesis of photopolymerizable compound (component (B)) (PM2)
In a flask equipped with a stirrer, reflux condenser, thermometer, and dry air introduction tube, 21.6 g of 2,2 ′-(1,3-phenylene) bis-2-oxazoline (manufactured by Mikuni Pharmaceutical Co., Ltd.) that was sufficiently dried. (0.1 mol), 14.4 g (0.2 mol) of acrylic acid and 0.02 g of hydroquinone were added, and after heating and stirring at 100 ° C. for 8 hours, a diacrylate monomer (PM2) having an amide bond was obtained. It was.

(Synthesis Example 8) Synthesis of Photopolymerizable Compound (Component (B)) (PM3)
In a flask equipped with a stirrer, reflux condenser, thermometer and dry air introduction tube, 16.6 g (0.1 mol) of sufficiently dried terephthalic acid (manufactured by Wako Pure Chemical Industries), 2-vinyl-2-oxazoline Was charged with 19.4 g (0.2 mol) and 0.02 g of hydroquinone and heated and stirred at 100 ° C. for 8 hours to obtain a divinyl monomer (PM3) having an amide bond.

(Examples 1-5)
The photosensitive resin composition of Examples 1-5 was obtained by mixing a material according to the compounding component and compounding ratio (unit: mass part) shown in Table 1.

(Comparative Example 1)
A photosensitive resin composition of Comparative Example 1 was obtained in the same manner as in Example 2 except that the component (A) was changed to P4 of Synthesis Example 4.

(Comparative Example 2)
A photosensitive resin composition of Comparative Example 2 was obtained in the same manner as in Example 2 except that the component (A) was changed to P5 of Synthesis Example 5.

(Comparative Example 3)
The component (A) is 100 parts by weight (nonvolatile content 50% by weight) of a copolymer of methyl methacrylate (85% by weight) and methacrylic acid (15% by weight), and the component (B) is only 50 parts by weight of FA-321M. did. Otherwise, the photosensitive resin composition of Comparative Example 3 was obtained in the same manner as in Example 1.

(Comparative Example 4)
The component (A) is 100 parts by weight of tetrahydrophthalic anhydride modified phenolic resin (non-volatile content 50% by weight), the component (B) is only 50 parts by weight of FA-321M, and an epoxy resin (manufactured by Japan Epoxy Resin, No. 1001) A photosensitive resin composition of Comparative Example 4 was obtained in the same manner as in Example 1 except that 20 parts by weight were used.

[Evaluation of light sensitivity]
Applying the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 uniformly onto a 16 μm-thick polyethylene terephthalate (PET) film (trade name: G2-16, manufactured by Teijin Limited) as a support. Then, a photosensitive layer was formed by using a hot air convection dryer at 100 ° C. for about 10 minutes. The film thickness after drying of the photosensitive layer was 25 μm. Subsequently, a polyethylene film (trade name: NF-13, manufactured by Tamapoly Co., Ltd.) is bonded as a protective film on the surface of the photosensitive layer opposite to the side in contact with the support, and a photosensitive film for permanent resist is attached. Obtained.

  The copper surface of a printed wiring board substrate (trade name: E-679, manufactured by Hitachi Chemical Co., Ltd.) in which a 12 μm thick copper foil was laminated on a glass epoxy substrate was polished with an abrasive brush, washed with water, and dried. Using a continuous vacuum laminator (trade name: HLM-V570, manufactured by Hitachi Chemical Co., Ltd.) on the polished copper foil of the printed wiring board substrate, a heat shoe temperature of 100 ° C., a laminating speed of 0.5 m / min, atmospheric pressure Under the conditions of 4 kPa or less and pressure bonding pressure of 0.3 MPa, the photosensitive film for permanent resist was laminated while peeling the polyethylene film so that the photosensitive layer and the copper foil were in close contact with each other to obtain a laminate for evaluation. .

  A photo tool having a stove 21-step tablet as a negative is closely attached to the obtained PET film of the laminate for evaluation, and the stove 21-step is used by using an HMW-201GX type exposure machine manufactured by Oak Manufacturing Co., Ltd. The exposure was performed with an energy amount such that the number of steps remaining after development of the tablet was 8.0. Subsequently, the evaluation laminate was allowed to stand at room temperature for 1 hour, the PET film was peeled off, developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 60 seconds, and further heated at 80 ° C. for 10 minutes ( Dried). The above energy amount was used as a numerical value for evaluating the photosensitivity. The lower this value, the higher the photosensitivity. The results are shown in Table 2. In Table 2, “Undevelopable” means that the unexposed photosensitive resin composition could not be eluted with a 1% by mass aqueous sodium carbonate solution, and development was not possible. (Please check it

[Resolution evaluation]
On the PET film of the laminate for evaluation described above, a photo tool having a 21-step stove tablet and a wiring pattern having a line width / space width of 30/30 to 200/200 (unit: μm) as a negative for resolution evaluation The photo tool was closely adhered, and exposure was performed using an HMW-201GX type exposure machine manufactured by Oak Seisakusho Co., Ltd. with an energy amount such that the number of remaining step steps after development of the stove 21-step step tablet was 8.0. Subsequently, the evaluation laminate was allowed to stand at room temperature for 1 hour, the PET film was peeled off, developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 60 seconds, and further heated at 80 ° C. for 10 minutes ( Dried). The resolution was evaluated based on the smallest value (unit: μm) of the space width between the line widths in which a rectangular resist shape was obtained by development processing. It shows that it is excellent in the resolution, so that this value is small. The results are shown in Table 2.

[Evaluation of coating properties]
Without exposing the said evaluation laminated body, the PET film of this evaluation laminated body was peeled, the finger | toe was lightly pressed on the exposed photosensitive layer surface, and the sticking degree with respect to the finger was evaluated on the following references | standards. That is, “A” indicates that sticking to the finger is not recognized or hardly recognized, and “B” indicates that sticking to the finger is recognized. The results are shown in Table 2.

[Evaluation of solder heat resistance]
On the PET film of the evaluation laminate, a phototool having a stove 21-step tablet and a phototool having a 2 mm square rectangular pattern as a negative are brought into close contact, and an HMW-201GX type exposure machine manufactured by Oak Manufacturing Co., Ltd. is used. In use, exposure was performed with an energy amount such that the number of remaining step steps after development of the stove 21-step tablet was 8.0. Next, after standing at room temperature for 1 hour, the PET film of the laminate was peeled off, spray development was performed under the same developer and development conditions as in the photosensitivity evaluation, and heated (dried) at 80 ° C. for 10 minutes. . Subsequently, the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Seisakusho. Further, the photosensitive layer was heat-treated at 160 ° C. for 60 minutes to obtain an evaluation package substrate on which a solder resist having a 2 mm square opening was formed.

  Next, after applying a rosin flux (trade name: MH-820V, manufactured by Tamura Kaken Co., Ltd.) to the evaluation package substrate, it was immersed in a solder bath at 260 ° C. for 30 seconds for soldering.

  In this way, the crack generation state of the solder resist on the evaluation package substrate subjected to the solder plating and the degree of lifting and peeling of the solder resist from the substrate were visually observed and evaluated according to the following criteria. That is, “A” was given when no cracking of the solder resist was observed and no solder resist was lifted or peeled off, and “B” was given when any of them was observed. The results are shown in Table 2.

[Evaluation of thermal shock resistance]
After the evaluation package substrate subjected to solder plating used for the evaluation of solder heat resistance is exposed to the atmosphere of −55 ° C. for 15 minutes, the temperature is increased at a temperature increase rate of 180 ° C./min, and then the temperature of 125 ° C. After being exposed to the atmosphere for 15 minutes, a heat cycle in which the temperature was lowered at a rate of temperature reduction of 180 ° C./min was repeated 1500 times. The crack and peeling degree of the solder resist on the evaluation package substrate after being exposed to such an environment were observed with a 100-fold metal microscope and evaluated according to the following criteria. That is, “A” indicates that the solder resist could not be cracked and peeled, and “B” indicates that any of them could be confirmed. The results are shown in Table 2.

[Evaluation of electric corrosion resistance]
Etching is performed on the copper foil of a printed wiring board substrate (trade name: E-679, manufactured by Hitachi Chemical Co., Ltd.) in which a 12 μm thick copper foil is laminated on a glass epoxy substrate, and the line width / space width is 50 μm / A comb-shaped electrode on the same surface opposed to each other was obtained, which was 50 μm and the lines were not in contact with each other. Using a continuous vacuum laminator (trade name: HLM-V570, manufactured by Hitachi Chemical Co., Ltd.) on the comb-shaped electrode of this substrate, a heat shoe temperature of 100 ° C., a laminating speed of 0.5 m / min, an atmospheric pressure of 4 kPa or less, and a pressure of pressure 0 .3 MPa under the condition of 3 MPa, the above-mentioned photosensitive film for permanent resist was laminated while peeling off the polyethylene film so that the photosensitive layer and the comb-shaped electrode were in close contact with each other. Got.

A phototool having a stove 21-step tablet as a negative is brought into close contact with the PET film of the obtained laminate for evaluation of electric corrosion resistance, and the stove 21 is used using an HMW-201GX type exposure machine manufactured by Oak Manufacturing Co., Ltd. The exposure was performed with an energy amount such that the number of steps remaining after development of the stepped tablet was 8.0. Subsequently, the laminate for evaluation of electric corrosion resistance was allowed to stand at room temperature for 1 hour, the PET film was peeled off, developed by spraying with a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 60 seconds, and further at 80 ° C. for 10 hours. Heated (dried) for minutes. Subsequently, using a UV irradiation device manufactured by Oak Manufacturing Co., Ltd., the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm ² and further subjected to heat treatment at 160 ° C. for 60 minutes to form a solder resist.

  After connecting the polytetrafluoroethylene shield wire to the comb electrodes with Sn / Pb solder so that a voltage is applied between the comb electrodes of the laminate for evaluation of electric corrosion resistance after heating, In a state where a voltage of 5 V was applied, the laminate for evaluation was allowed to stand in a super accelerated high temperature high humidity life test (HAST) bath at 130 ° C. and 85% RH for 200 hours. The degree of migration of the solder resist in the subsequent evaluation laminate was observed with a 100-fold metal microscope and evaluated according to the following criteria. That is, “A” indicates that the solder resist migration could not be confirmed, and “B” indicates that it was not confirmed. The results are shown in Table 2.

[Evaluation of storage stability]
As described above, the photosensitive film for permanent resist obtained using the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 was allowed to stand at 5 ° C. for 1 month in the air. Subsequently, the evaluation laminated body was obtained like the case of light sensitivity evaluation using the photosensitive film for permanent resists after stationary. And the board | substrate for evaluation which formed the soldering resist which has a 2 mm square rectangular opening part similarly to the thing in the solder heat resistance evaluation was obtained. The pattern of the solder resist formed on the evaluation substrate was observed with a stereomicroscope, and “A” indicates that no resin remains in the unexposed area, and “B” indicates that resin remains. The results are shown in Table 2.

[Evaluation of glass transition temperature]
As described above, the photosensitive film for permanent resist obtained using the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 is exposed and heated under the same conditions as described above to cure the photosensitive layer. A cured film was obtained. The glass transition temperature of the cured film was measured by using TMA (TMA-1 type manufactured by Seiko Instruments Inc.) in a tensile mode, a temperature rising rate of 5 ° C./min, and a load of 5 g. The results are shown in Table 2.

[Evaluation of physical properties of cured film]
As described above, the photosensitive film for permanent resist obtained using the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 is exposed and heated under the same conditions as described above to cure the photosensitive layer. A cured film was obtained. The 1% thermogravimetric decrease temperature of the cured film was measured by a thermobalance (TG-DTA300 manufactured by Seiko Instruments Inc.) at a temperature at which the weight decreased by 1% at a heating rate of 10 ° C./min in an air atmosphere. In addition, the tensile strength and elongation rate of a sample having a film thickness of 20 μm, a width of 10 mm, and a length between chucks of 20 mm were measured with a Tensilon tensile tester (UCT-5T type manufactured by Orientec Co., Ltd.) at a test temperature of 25 ° C. and a tensile speed of 5 mm / min. It was measured. The results are shown in Table 2.

It is a schematic cross section which shows one Embodiment of the photosensitive film for permanent resists of this invention. It is a schematic cross section which shows one Embodiment of the printed wiring board of this invention. It is a schematic process drawing which shows one Embodiment of the manufacturing method of the printed wiring board of this invention. It is a schematic cross section which shows an example of the semiconductor package which used the hardened | cured material of the photosensitive resin composition of this invention as an interlayer insulation film.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive film for permanent resists, 2 ... Printed wiring board, 3, 4 ... Base material for printed wiring boards, 5 ... Photomask, 11 ... Support body, 12, 24 ... Photosensitive layer, 13 ... Protective film, 21 ... Conductor layer having no circuit pattern, 22 ... insulating substrate, 23 ... conductor layer having circuit pattern, 26 ... opening, 241 ... solder resist, 10 ... silicon wafer (substrate), 20 ... electrode, 30 ... interlayer insulating film, 40: rewiring, 50: post portion, 60: sealing resin, 100: semiconductor package.

Claims (12)

A polymer comprising a structure represented by the following general formula (1).

[Wherein, X represents a tetravalent organic group, Y, R ₁ and R ₂ each independently represents a divalent organic group, and R represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 5 carbon atoms. N represents an integer of 1 or more. ]   An imidized polymer obtained by imidizing the polymer according to claim 1. (A) the polymer according to claim 1 and / or 2,
(B) a photopolymerizable compound;
(C) A photosensitive resin composition containing a photopolymerization initiator and capable of alkali development.   The photosensitive resin composition of Claim 3 whose weight average molecular weights of the said (A) polymer are 10,000-200000.   The photosensitive resin composition of Claim 3 or 4 in which the said (B) photopolymerizable compound contains the compound which has an amide bond. The photosensitive resin composition as described in any one of Claims 3-5 in which the said (B) photopolymerizable compound contains the compound represented by the following general formula (2), (3) or (4).

[In the formulas (2), (3) and (4), R ₃ represents a divalent organic group. ]   A photosensitive film for permanent resist, comprising: a support; and a photosensitive layer made of the photosensitive resin composition according to any one of claims 3 to 6 formed on the support.   The photosensitive property as described in any one of Claims 3-6 so that the said conductor layer may be covered on the said insulated substrate of a laminated substrate provided with the insulated substrate and the conductor layer which has a circuit pattern formed on this insulated substrate. Laminating a photosensitive layer made of a resin composition, irradiating a predetermined portion of the photosensitive layer with actinic rays to form an exposed portion, and then removing portions other than the exposed portion of the photosensitive layer And a resist pattern forming method.   The photosensitive resin according to claim 3, formed on the insulating substrate so as to cover the insulating substrate, a conductor layer having a circuit pattern formed on the insulating substrate, and the conductor layer. A printed wiring board comprising: a permanent resist layer made of a cured product of the composition. A printed wiring board manufacturing method comprising: an insulating substrate; a conductor layer having a circuit pattern formed on the insulating substrate; and a permanent resist layer formed on the insulating substrate so as to cover the conductor layer. And
A photosensitive layer made of the photosensitive resin composition according to any one of claims 3 to 6 is laminated on the insulating substrate so as to cover the conductor layer, and a predetermined portion of the photosensitive layer is irradiated with actinic rays. Forming an exposed portion, and then removing portions other than the exposed portion.   The surface protection film which consists of hardened | cured material of the photosensitive resin composition as described in any one of Claims 3-6. The interlayer insulation film which consists of a hardened | cured material of the photosensitive resin composition as described in any one of Claims 3-6.

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