JP2011134939A - Printed wiring board, and siloxane-based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printed wiring board, having an insulating protective film formed of a siloxane-based resin composition on a substrate including an insulating base, an adhesive and a wiring pattern, which is improved in electric (insulation) reliability more, and to provide a siloxane-based resin composition capable of suitably improving the electric (insulation) reliability of the printed wiring board. <P>SOLUTION: This invention relates to the printed wiring board which has the insulating protective film formed of the siloxane-based resin composition on the substrate including the insulating base, adhesive and wiring pattern, the siloxane-based resin composition containing 0.5 to 10 parts by mass of a compound having one or more hindered phenol groups in a molecule for 100 parts by mass of a resin component. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a printed wiring board in which an insulating protective film made of a siloxane-based fat composition is formed on a substrate including an insulating base material, an adhesive, and a wiring pattern. This printed wiring board has improved electrical (insulation) reliability. The present invention also relates to a siloxane-based fat composition that can suitably improve electrical (insulation) reliability in the printed wiring board.

  A printed wiring board has, for example, a resin composition in a surface area (pattern surface) excluding connection portions such as lead portions of a wiring pattern on a substrate in which a wiring pattern is formed on an insulating base material such as a polyimide film via an adhesive. It is manufactured by forming an insulating protective film (solder resist) made of a material or the like. As the resin composition for forming this insulating protective film, a siloxane-based resin composition is suitably used.

Patent Documents 1 and 2 disclose that a thermosetting resin composition containing polyimide siloxane is used to form an insulating film protective film such as a flexible printed wiring board.
Patent Document 3 describes a polyaramidsiloxane heat-resistant adhesive, which describes that this modified polyimidesiloxane may contain a crosslinking agent and is also used as a protective film.
Patent Document 4 describes a method for producing a printed circuit board in which an insulating protective film is formed using a polyamic acid solution composition using diaminosiloxane as an amine component.
Patent Document 5 discloses a flexible printed wiring board using a photosensitive resin composition obtained by mixing a terminal tetracarboxylic acid siloxane imide oligomer, a diamino compound, a photosensitive resin, a photopolymerization initiator, and a thermosetting resin. Are listed.

Japanese Patent Laid-Open No. 9-100350 JP 2004-211064 A JP 7-292342 A JP-A-6-232540 JP 2008-197545 A

Electronic devices are becoming smaller, lighter, and finer in pattern, and the demands on the performance of printed wiring boards are increasing. For this reason, even in a printed wiring board in which a wiring pattern is formed on an insulating base material such as a polyimide film via an adhesive, and an insulating protective film made of a siloxane-based resin composition is formed thereon, the characteristics, particularly the electric There is a need to further improve reliability.
An object of the present invention is to improve electrical (insulation) reliability in a printed wiring board in which an insulating protective film made of a siloxane-based fat composition is formed on a substrate comprising an insulating base material, an adhesive, and a wiring pattern. Printed circuit board is provided. Moreover, in the said printed wiring board, it is providing the siloxane type fat composition which can improve electrical (insulation) reliability suitably.

The present invention relates to the following items.
1. In a printed wiring board in which an insulating protective film made of a siloxane-based resin composition is formed on a substrate including an insulating base material, an adhesive, and a wiring pattern,
The siloxane-based resin composition is configured to include 0.5 to 10 parts by mass of a compound having one or more hindered phenol groups in a molecule with respect to 100 parts by mass of a resin component. Wiring board.
2. 2. The printed wiring board according to item 1, wherein the insulating substrate is a polyimide film.
3. The resin component of the siloxane-based resin composition includes polyimide siloxane and at least one curing component selected from the group consisting of an epoxy resin, a compound having two or more phenolic hydroxyl groups, and a polyvalent isocyanate compound. Item 3. The printed wiring board according to any one of Items 1 to 2, wherein

4). A siloxane-based resin composition comprising 0.5 to 10 parts by mass of a compound having at least one hindered phenol group in a molecule with respect to 100 parts by mass of a resin component. Siloxane resin composition.
5. The resin component of the siloxane-based resin composition includes polyimide siloxane and at least one curing component selected from the group consisting of an epoxy resin, a compound having two or more phenolic hydroxyl groups, and a polyvalent isocyanate compound. Item 5. The siloxane-based resin composition according to Item 4, wherein

According to the present invention, electrical (insulation) reliability is further improved in a printed wiring board in which an insulating protective film made of a siloxane-based fat composition is formed on a substrate including an insulating base material, an adhesive, and a wiring pattern. A printed wiring board can be provided.
Moreover, the siloxane type fat composition which can improve suitably the electrical (insulation) reliability of the said printed wiring board can be provided.

In a substrate comprising an insulating base material, an adhesive, and a wiring pattern, an insulating protective film (solder resist) made of a resin composition or the like is formed on the surface region (pattern surface) excluding connection portions such as lead portions of the wiring pattern. A printed wiring board obtained by forming, particularly a flexible printed wiring board, is typically manufactured by the following method.
In other words, press punched perforation holes (sprocket holes) for tape feeding and device holes for forming inner leads for joining semiconductor chips to an insulating base material made of an insulating film with an adhesive layer, if necessary. Then, a conductive metal foil such as a copper foil is heat-bonded to the substrate made of the insulating film with the adhesive layer. Thereafter, a photosensitive resin resist is applied to the surface of the metal foil, and a wiring pattern is formed on an insulating substrate made of an insulating film with an adhesive layer by baking, developing, and etching. The wiring pattern is formed with inner leads for joining semiconductor chips and outer leads for joining with other components at the ends. The surface of the wiring pattern may be subjected to surface treatment by tin plating, gold plating, solder plating, or the like. Next, most of the surface region (pattern surface) except for the connecting portion such as the inner lead and outer lead in the region where the wiring pattern is formed is protected by an insulating protective film. Thereafter, the surface of the wiring pattern including connection portions such as inner leads and outer leads, on which the insulating protective film is not formed on the surface, may be subjected to surface treatment by tin plating, gold plating, solder plating, or the like, as necessary.
The printed wiring board manufactured as described above is usually used as an electronic component by mounting an electronic component such as a semiconductor chip on an inner lead.

  The present invention relates to a printed wiring board in which an insulating protective film made of a siloxane-based resin composition is formed on a substrate including an insulating base material, an adhesive, and a wiring pattern, wherein the siloxane-based resin composition is a resin component 100. The present invention relates to a printed wiring board, preferably a flexible printed wiring board, comprising 0.5 to 10 parts by mass of a compound having one or more hindered phenol groups in the molecule with respect to parts by mass.

  As the insulating base material, any base material having excellent electrical insulation properties may be used. For example, a rigid insulating base material using an epoxy resin may be used, but a flexible insulating base material made of an insulating film having a thickness of about 5 to 100 μm. Is preferred. Insulating films include aromatic polyimide films, aromatic polyamideimide films, aromatic polyester films, etc. Especially, aromatic polyimide films are electrically insulating (for example, having high dielectric breakdown strength and low dielectric loss tangent). In addition, high heat resistance, flexibility, moderate rigidity, chemical resistance, low thermal shrinkage, and excellent dimensional stability against moisture absorption are preferable. Specifically, an upilex film manufactured by Ube Industries, Ltd., a Kapton film manufactured by DuPont, and the like can be preferably exemplified.

  The adhesive is used to bond the insulating substrate and the wiring pattern, and has excellent adhesive strength, insulation reliability, heat resistance and chemical resistance, small warpage after curing, and excellent flatness. Epoxy adhesives or phenolic adhesives, particularly modified epoxy resin adhesives excellent in flexibility can be suitably used. Especially in the case of flexible printed wiring boards, it can be easily used as a polyimide film with an adhesive in which an adhesive layer is laminated on an insulating film in advance, or a copper-clad polyimide film in which a copper foil is laminated on an insulating film through an adhesive in advance. It can be obtained. As the polyimide film with an adhesive, specifically, polyimide films # 7100, # 8200, # 8600, etc. with an adhesive manufactured by Toray Industries, Inc. can be preferably mentioned. Specific examples of the copper-clad polyimide film include F-type and K-type copper-clad polyimide films manufactured by Toray Industries, Inc. The adhesive layer is preferably used in a thickness of 1 to 30 μm, particularly 2 to 20 μm, usually about 10 μm.

  The wiring pattern is formed of a conductive metal foil. As the metal foil, a copper foil or an aluminum foil is suitable. The copper foil may be a rolled copper foil or an electrolytic copper foil. The thickness of the wiring pattern is preferably 10 to 100 μm, usually 18 μm, 25 μm, or 35 μm. The wiring pattern having a line width of about 10 to 500 μm, particularly about 30 to 300 μm, and a line interval of about 10 to 500 μm, particularly about 40 to 400 μm, is preferably used.

In this invention, an insulating protective film is 0.5-10 mass parts (preferably 2 mass parts or more, Furthermore, 4 masses) the compound which has 1 or more of hindered phenol groups in a molecule | numerator with respect to 100 mass parts of resin components. Part or more and 8 parts by mass or less, and further 7 parts by mass or less).
Here, the siloxane-based resin is a resin containing a polysiloxane segment or a siloxane oligomer segment (hereinafter sometimes referred to as a siloxane segment) having a siloxane bond in the molecule, and preferably a siloxane having the following chemical formula (1) A resin containing segments.

ただし、化学式（１）において、Ｒは炭素数が１〜１０の１価の炭化水素基、ｍは１〜１００の整数を表す。

However, in Chemical formula (1), R represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and m represents an integer of 1 to 100.

  Specific examples of the siloxane-based resin include, but are not limited to, polyimide siloxane, polyamide imide siloxane, polyamide siloxane, polyester imide siloxane, polyester siloxane, polyurethane siloxane, polyamic acid containing siloxane segments, and siloxane segments. Preferred examples include imide oligomers. Among these, polyimidesiloxane is preferable because high electrical reliability is easily obtained. In addition, these resins are suitably modified with segments having a thermosetting or photosensitive reactive group for the purpose of imparting thermosetting properties or photocuring properties.

The siloxane-based resin composition of the present invention includes 0.5 to 10 parts by mass of a compound having one or more hindered phenol groups in the molecule with respect to 100 parts by mass of the resin component together with the siloxane-based resin. It is characterized by being.
The compound having at least one hindered phenol group in the molecule is not limited, but is preferably a compound having at least one hindered phenol group represented by the following chemical formula (2) in the molecule.

ただし、化学式（２）において、Ｚは炭素数が２〜１０の一価の基、好ましくはｔ−ブチル基を表す。

However, in chemical formula (2), Z represents a monovalent group having 2 to 10 carbon atoms, preferably a t-butyl group.

  Specific examples of the compound having one or more hindered phenol groups in the molecule include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1330, IRGANOX 259, IRGANOX MD 1024 and the like manufactured by Ciba Japan. .

  In the siloxane-based resin composition of the present invention, the content of the compound having one or more hindered phenol groups in the molecule is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin component. More preferably, it is 2 parts by mass or more, further 4 parts by mass or more, 8 parts by mass or less, and further 7 parts by mass or less. By containing the amount within this range, the printed wiring board of the present invention can suitably improve the electrical reliability. Specifically, in a printed wiring board in which an insulating protective film made of a siloxane-based resin composition is formed on a printed wiring board including an insulating base material, an adhesive, and a wiring pattern, in the insulating protective film, By containing a compound having one or more hindered phenol groups in the molecule, migration of copper ions to the adhesive layer can be suppressed, and as a result, the electrical (insulation) reliability of the printed wiring board is preferably improved. can do. If the amount of the compound having one or more hindered phenol groups in the molecule is less than 0.5 parts by mass, the electrical reliability of the printed wiring board cannot be suitably improved, and it exceeds 10 parts by mass. If contained, the compound having one or more hindered phenol groups in the molecule is not suitable because it tends to bleed out to the surface of the insulating protective film and is not economical.

Hereinafter, the resin composition of the present invention will be described. The resin composition of the present invention includes, for example, polyimide siloxane, polyamide imide siloxane, polyamide siloxane, polyester imide siloxane, polyester siloxane, polyurethane siloxane, polyamic acid containing siloxane segments, imide oligomers configured to contain siloxane segments, and the like. It is configured to include a resin containing a siloxane segment having a siloxane bond in the molecule.
Such a composition may be either thermosetting or photocurable, and already known ones can be suitably used. Here, the siloxane-based resin composition is not limited, but a thermosetting resin composition using polyimidesiloxane will be described as a representative example.

  A thermosetting resin composition using polyimidesiloxane is suitably formed by combining polyimidesiloxane and an epoxy compound, a compound having two or more phenolic hydroxyl groups, or a curable resin component such as a polyvalent isocyanate compound. For example, a polyimide siloxane, an epoxy compound, and a compound having two or more phenolic hydroxyl groups may be combined, and a polyvalent isocyanate compound may be added as necessary.

  Polyimide siloxane uses a tetracarboxylic acid component and a diamine component containing diaminopolysiloxane in an approximately equimolar amount, preferably in a ratio of about 1.0 to 1.2 mol of tetracarboxylic acid component per 1 mol of diamine component. It can be obtained by reacting in an organic solvent.

  Examples of the tetracarboxylic acid component include 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, and 2,2 ′, 3,3′-biphenyl. Tetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetra Carboxylic acid, 2,2-bis (3,4-benzenedicarboxylic acid) hexafluoropropane, pyromellitic acid, 1,4-bis (3,4-benzenedicarboxylic acid) benzene, 2,2-bis [4- ( 3,4-phenoxydicarboxylic acid) phenyl] propane, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalene Arocarboxylic tetracarboxylic acids such as tracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,1-bis (2,3-dicarboxyphenyl) ethane, or their acid dianhydrides or lower Alcohol esterified products and fats such as cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3-methyl-4-cyclohexene-1,2,4,5-tetracarboxylic acid Preferable examples include cyclic tetracarboxylic acids, or acid dianhydrides and esterified products of lower alcohols. As the tetracarboxylic acid component of polyimidesiloxane, it is preferable to use a tetracarboxylic dianhydride that can be easily reacted with a diamine.

The diamine component preferably contains diaminopolysiloxane as an essential component, and if necessary, an aromatic diamine having a reactive group and an aromatic diamine other than the above can be used in combination.
The diaminopolysiloxane is preferably a compound represented by the following chemical formula (3).

化学式（３）において、Ｒ_１は２価の炭化水素基又は芳香族基を示し、Ｒ_２は独立に１価の炭素水素基又は芳香族基を示し、ｎ１は３〜５０の整数を示す。但し、化学式（３）中、Ｒ_１は炭素数１〜６の２価の炭化水素基又はフェニレン基、特にプロピレン基が好ましく、Ｒ_２は独立に炭素数１〜５のアルキル基又はフェニル基が好ましく、ｎ１は３〜５０、特に３〜２０が好ましい。尚、ジアミノポリシロキサンが２種以上の混合物からなる場合は、ｎ１はアミノ当量から計算される。

In the chemical formula (3), R ₁ represents a divalent hydrocarbon group or an aromatic group, R ₂ independently represents a monovalent carbon hydrogen group or an aromatic group, and n1 represents an integer of 3 to 50. However, in chemical formula (3), R ₁ is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms or a phenylene group, particularly a propylene group, and R ₂ is independently an alkyl group having 1 to 5 carbon atoms or a phenyl group. N1 is preferably from 3 to 50, particularly preferably from 3 to 20. In addition, when diaminopolysiloxane consists of 2 or more types of mixtures, n1 is calculated from an amino equivalent.

  Examples of diaminopolysiloxanes include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (4-aminophenyl) poly Dimethylsiloxane, α, ω-bis (4-amino-3-methylphenyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, α, ω-bis (4-aminobutyl) polydimethyl Examples thereof include siloxane.

  The diamine having a reactive group is a diamine having a reactive group capable of reacting with a curing component such as an epoxy resin in the molecule, and a diamine represented by the following chemical formula (4) is preferable.

化学式（４）において、Ｘ及びＹは、それぞれ独立に、直接結合、ＣＨ_２、Ｃ（ＣＨ_３）_２、Ｃ（ＣＦ_３）_２、Ｏ、ベンゼン環、ＳＯ_２を示し、ｒ１はＣＯＯＨ又はＯＨを示し、ｎ２は１又は２であり、ｎ３、ｎ４はそれぞれ独立に０、１又は２、好ましくは０又は１であり、ｎ３及びｎ４の少なくとも一方は１又は２である。

In the chemical formula (4), X and Y each independently represent a direct bond, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , O, a benzene ring, SO ₂ , and r1 is COOH or OH N2 is 1 or 2, n3 and n4 are each independently 0, 1 or 2, preferably 0 or 1, and at least one of n3 and n4 is 1 or 2.

  Examples of the diamine compound represented by the chemical formula (4) include diaminophenol compounds such as 2,4-diaminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4 '-Diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino-2,2', 5,5'-tetrahydroxybiphenyl, etc. Hydroxybiphenyl compounds, 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′- Dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydride Hydroxydiphenylalkane compounds such as xylphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylmethane 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2 ′ Hydroxydiphenyl ether compounds such as dihydroxydiphenyl ether, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenyl ether, 3,3′-diamino-4, 4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, 4,4 Hydroxydiphenyl sulfone compounds such as -diamino-2,2'-dihydroxydiphenyl sulfone, 4,4'-diamino-2,2 ', 5,5'-tetrahydroxydiphenyl sulfone, 2,2-bis [4- Bis (hydroxyphenoxy) phenyl such as (4-amino-3-hydroxyphenoxy) phenyl] propane, bis (hydroxyphenoxy) biphenyl such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl Examples thereof include diamine compounds having an OH group such as compounds and bis (hydroxyphenoxyphenyl) sulfone compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone.

  Furthermore, examples of the diamine compound represented by the chemical formula (4) include benzene carboxylic acids such as 3,5-diaminobenzoic acid and 2,4-diaminobenzoic acid, 3,3′-diamino-4,4′-di Carboxybiphenyl, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-2,2′-dicarboxybiphenyl, 4,4′-diamino-2,2 ′, 5,5 Carboxyphenyl compounds such as' -tetracarboxybiphenyl, 3,3'-diamino-4,4'-dicarboxydiphenylmethane, 4,4'-diamino-3,3'-dicarboxydiphenylmethane, 4,4'-diamino -2,2'-dicarboxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4-amino- -Carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, carboxydiphenylalkanes such as 4,4'-diamino-2,2 ', 5,5'-tetracarboxybiphenyl Compounds, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-dicarboxydiphenyl ether, 4,4′-diamino-2, Carboxydiphenyl ether compounds such as 2′-dicarboxydiphenyl ether, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenyl ether, 3,3′-diamino- 4,4′-dicarboxydiphenylsulfone, 4,4′-diamino-3,3′-dicarboxydiphenylsulfone, 4,4′-diamino- , 2 ′, 5,5′-tetracarboxydiphenylsulfone and other carboxydiphenylsulfone compounds, bis (carboxyphenoxyphenyl) such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane Alkane compounds, bis (carboxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino-3-carboxyphenoxy) biphenyl, 2,2-bis [4- (4-amino-3-carboxyphenoxy) And diamine compounds having a COOH group such as bis (carboxyphenoxyphenyl) sulfone compounds such as phenyl] sulfone.

  The diamine other than the diaminopolysiloxane constituting the diamine component of the polyimidesiloxane and the diamine having the reactive group is not particularly limited, but a diamine represented by the following chemical formula (5) is preferable.

化学式（５）において、Ｘ及びＹは、それぞれ独立に、直接結合、ＣＨ_２、Ｃ（ＣＨ_３）_２、Ｃ（ＣＦ_３）_２、Ｏ、ベンゼン環、ＳＯ_２を示し、ｎ５は１又は２である。

In the chemical formula (5), X and Y each independently represent a direct bond, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , O, a benzene ring, or SO ₂ , and n5 is 1 or 2 It is.

Examples of the aromatic diamine represented by the chemical formula (5) include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 1,4-diamino-2,5-dihalogenobenzene, and the like. Diamines containing one benzene, bis (4-aminophenyl) ether, bis (3-aminophenyl) ether, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) methane, bis (3-aminophenyl) methane, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfide, 2,2-bis (4-aminophenyl) propane, 2, 2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, o-dianisidine, o-to Diamines containing two benzenes such as gin and tolidine sulfonic acids, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-amino) Phenyl) benzene, 1,4-bis (3-aminophenyl) benzene, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, α, α′-bis (4-aminophenyl)- Diamines containing three benzenes such as 1,3-diisopropylbenzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4 ′-(4-aminophenoxy) biphenyl, 9,9-bi Examples thereof include diamine compounds such as diamines containing 4 or more benzenes such as su (4-aminophenyl) fluorene and 5,10-bis (4-aminophenyl) anthracene.
In addition, aliphatic diamine compounds such as hexamethylene diamine and diaminododecane can be used together with the diamine.

Polyimidesiloxane can be obtained, for example, by the following method.
(A) A method in which a tetracarboxylic acid component and a diamine component are used in approximately equimolar amounts, and polymerized and imidized continuously in an organic polar solvent at 15 to 250 ° C. to obtain polyimidesiloxane.
(B) A tetracarboxylic acid component and a diamine component are separated from each other, and an excess amount of a tetracarboxylic acid component and a diamine component (for example, diaminopolysiloxane) are first polymerized and imidized at 15 to 250 ° C. in an organic polar solvent. An imidosiloxane oligomer having an acid anhydride group (or acid, esterified product thereof) at the terminal having an average degree of polymerization of about 1 to 10 is prepared, and a tetracarboxylic acid component and an excess amount of a diamine component are separately added in an organic polar solvent 15 Polymerize and imidize at ˜250 ° C. to prepare an imide oligomer having an amino group at an average degree of polymerization of about 1 to 10, and then mix the two so that the acid component and the diamine component are approximately equimolar. Then, the reaction is carried out at 15 to 60 ° C., and the temperature is further raised to 130 to 250 ° C. for reaction to obtain polyimide siloxane.
(C) A tetracarboxylic acid component and a diamine component are used in approximately equimolar amounts, and after first polymerizing at 20 to 80 ° C. in an organic polar solvent to obtain a polyamic acid, the polyamic acid is imidized to obtain a polyimide siloxane. Method.

  Examples of the organic polar solvent used in obtaining the polyimidesiloxane by the above method include nitrogen-containing solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethyl. Solvents containing sulfur atoms such as formamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethyl Such as sulforamide, phenolic solvents such as cresol, phenol, xylenol, diglyme solvents such as diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraglyme , The solvent having an oxygen atom in the molecule, such as acetone, methanol, ethanol, ethylene glycol, dioxane, tetrahydrofuran, and other pyridine, and the like tetramethylurea. Moreover, you may use together other organic solvents, such as aromatic hydrocarbon type solvents, such as benzene, toluene, and xylene, solvent naphtha, and benzonitrile, as needed.

  The polyimide siloxane may be obtained by any method such as the above (a) to (c), but at least 3% by weight or more in an organic solvent, preferably at a high concentration of about 5 to 60% by weight. It can be dissolved, and the solution viscosity at 25 ° C. (E-type rotational viscometer) is preferably 1 to 10000 poise, particularly 1 to 100 poise. In addition, it is preferable that the polyimidesiloxane has a high imidization rate. The logarithmic viscosity (measurement concentration: 0.5 g / 100 ml, solvent: N-methyl-2-pyrrolidone, measurement temperature: 30 ° C.) as a measure of molecular weight is 0.15 or more, particularly 0.16 to 2. This is preferable from the viewpoint of mechanical properties such as strength and elongation of the cured product. Further, the imidation ratio obtained from the infrared absorption spectrum is preferably 90% or more, particularly 95% or more, and substantially 100%.

  The epoxy resin is preferably liquid or solid having an epoxy equivalent of about 100 to 4000 and a molecular weight of about 300 to 10,000. For example, bisphenol A type or bisphenol F type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: Epicoat 806, Epicoat 825, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1055, Epicoat 1004AF, Epicoat 1007, Epicoat 1009, Epicoat 1010, etc.) Trifunctional or higher epoxy resin (manufactured by Japan Epoxy Resins Co., Ltd .: Epicoat 152, Epicoat 154, Epicoat 180 series, Epicoat 157 series, Epicoat 1032 series, Ciba-Geigy: MT0163, etc. ), Hibe ETBN 1300 × 40 manufactured by Ube Industries, Ltd., Denarex R-45EPT manufactured by Nagase ChemteX Corporation, bifunctional bifeni Type epoxy resin (Japan Epoxy Resins Co., Ltd.: YX4000 series), epoxy-modified polysiloxane (Shin-Etsu Chemical Co., Ltd., etc. KF105) and the like.

  The amount used in the case of using an epoxy resin is preferably 0.1 parts by mass or more, further 0.3 parts by mass or more, particularly 0.5 parts by mass or more and 30 parts by mass or less, further 15 parts by mass with respect to 100 parts by mass of polyimidesiloxane. Less than or equal to 7 parts by weight, in particular.

  The compound having two or more phenolic hydroxyl groups may be any compound as long as it has two or more phenolic hydroxyl groups in the molecule. Examples thereof include phenol resins such as hydroquinone, 4,4'-dihydroxybiphenyl, phenol novolac, and cresol novolac. As phenol resins, Meiwa Kasei Co., Ltd. phenol novolac resins H-1, H-2, H-3, H-4, H-5, orthocresol novolac MER-130, triphenolmethane type MEH-7500, tetrakisphenol Type MEH-7600, naphthol type MEH-7700, phenol aralkyl type MEH-7800, MEH-7851, triphenol type R-3, bisphenol novolac type MEP-6309, MEP-6309E, liquid phenol novolac MEH-8000H, MEH-8005 , MEH-8010, MEH-8015, MEH-8205, and the like.

  The amount used in the case of using a compound having two or more phenolic hydroxyl groups is preferably 0.1 parts by mass or more, preferably 0.3 parts by mass or more, particularly 0.5 parts by mass or more, relative to 100 parts by mass of polyimidesiloxane. And 20 parts by mass or less, preferably 15 parts by mass or less, particularly less than 10 parts by mass.

Any polyvalent isocyanate may be used as long as it has two or more isocyanate groups in one molecule. Examples of such polyvalent isocyanate compounds include aliphatic, alicyclic or aromatic diisocyanates, such as 1,4-tetramethylene diisocyanate and 1,5-pentamethylene diisocyanate. Net, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, lysine diisocyanate, 3-isocyanate methyl 3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate Neat, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diene Soshiane - door, and the like can be given.
Further, as the polyvalent isocyanate compound, those derived from aliphatic, alicyclic or aromatic polyvalent isocyanates such as isocyanurate-modified polyisocyanate, burette-modified polyisocyanate, It may be a urethane-modified polyvalent isocyanate.
As the polyvalent isocyanate compound, a block polyvalent isocyanate in which the isocyanate group of the polyvalent isocyanate is blocked with a blocking agent is preferably used.
Examples of the block polyvalent isocyanate include Burnock D-500 (tolylene diisocyanate blocked) and D-550 (1,6-hexamethylene diisocyanate blocked) manufactured by Dainippon Ink and Chemicals, Inc. ), Takenate Takenate B-830 (tolylene diisocyanate blocked), B-815N (4,4′-methylenebis (cyclohexyl isocyanate) blocked), B-842N (made by Mitsui Takeda Chemical Co., Ltd.) 1,3-bis (isocyanatemethyl) cyclohexane blocked), B-846N (1,3-bis (isocyanatemethyl) cyclohexane blocked), B-874N (isophorone diisocyanate blocked), first Elastolone BN-P17 (4,4'-diphenylmethane manufactured by Kogyo Seiyaku Co., Ltd. Isocyanate block), Elastron BN-04, Elastron BN-08, Elastron BN-44, Elastron BN-45 (above, 3 to 5 functional groups per molecule of urethane-modified polyvalent isocyanate block, all water emulsion (It can be used after being dried and isolated with a product).

  When the polyvalent isocyanate compound is used, the amount used is from 0.1 to 40 parts by weight, preferably from 2 to 30 parts by weight, particularly from 5 to 30 parts by weight, based on 100 parts by weight of the polyimidesiloxane.

  In the resin composition of the present invention, the organic solvent used in the reaction for preparing polyimidesiloxane can be used as it is as the organic solvent.

  Furthermore, the resin composition of the present invention may contain an additive having a siloxane skeleton in the component, such as a silicone-based antifoaming agent. Specific examples of additives having a siloxane skeleton include self-emulsifying anti-foaming agents KS-508, KS-530, KS-531, KS-537, KS-538, KS-540, compound type manufactured by Shin-Etsu Chemical Co., Ltd. Examples thereof include antifoaming agents KS-69, KS-66, oil type antifoaming agents KF-69, KS-604, FA-600, DB-100 manufactured by Toray Dow Corning.

Furthermore, the resin composition of the present invention can suitably contain a morpholine compound having a monovalent group as a curing accelerator.
Specific examples of the morpholine compound include morpholine, 2,2′-dimorpholinodiethyl ether, di (2,6-dimethylmorpholinoethyl) ether, bis {2- (2,6-dimethyl-4-morpholino) ethyl. }-{2- (4-morpholino) ethyl} amine, bis {2- (2,6-dimethyl-4-morpholino) ethyl}-{2- (2,6-diethyl-4-morpholino) ethyl} amine, Tris {2- (4-morpholino) ethyl} amine, tris {2- (4-morpholino) propyl} amine, tris {2- (4-morpholino) butyl} amine, tris {2- (2,6-dimethyl- 4-morpholino) ethyl} amine, tris {2- (2,6-diethyl-4-morpholino) ethyl} amine, tris {2- (2-ethyl-4-morpholino) ethyl} a Min etc. can be illustrated. Among them, a compound having a boiling point of 100 ° C. or higher, such as 2,2′-dimorpholinodiethyl ether (in another nomenclature, bis [(2-morpholino) ethyl]), which is chemically stable in the process of being cured by heating. It is preferable to use ether.

  Furthermore, imidazoles or tertiary amines can be contained. Examples of imidazoles or tertiary amines include imidazoles such as 2-ethyl-4-methylimidazole, 2-methylimidazole, and 2-phenylimidazole, and 1,8-diazabicyclo [5.4.0] -7-undecene. (May be abbreviated as DBU; the same shall apply hereinafter), N, N-dimethylbenzylamine, N, N, N ′, N′-tetramethylhexanediamine, triethylenediamine (TEDA), 2-dimethylaminomethylphenol (DMP) -10), tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30), 1,4-dimethylpiperazine, and cyclohexyldimethylamine.

  The amount of such a curing accelerator is about 0.01 to 25 parts by mass, particularly about 0.1 to 15 parts by mass with respect to 100 parts by mass of the resin component.

  Further, the resin composition of the present invention can suitably contain known additives and fillers such as pigments such as inorganic fillers, organic color pigments, and inorganic color pigments.

The siloxane-based resin composition of the present invention includes, for example, polyamideimide siloxane, polyamide siloxane, polyester imide siloxane, polyester siloxane, polyurethane siloxane, polyamic acid containing siloxane segments, and siloxane segments instead of polyimide siloxane. A siloxane-based resin composition using a resin containing a siloxane segment having a siloxane bond in the molecule, such as an imide oligomer, may also be used. Even in these cases, as a component other than the siloxane-based resin component, an epoxy compound, a compound having two or more phenolic hydroxyl groups, a polyvalent isocyanate compound, or another curable resin component can be suitably combined.
Moreover, the siloxane-based resin composition of the present invention may be a siloxane-based resin composition into which a photosensitive reactive group is introduced.

In the printed wiring board of the present invention, an insulating protective film made of the aforementioned siloxane-based resin composition is formed on a substrate including an insulating base material, an adhesive, and a wiring pattern.
When the siloxane-based resin composition is thermosetting, the dry film has a thickness of about 3 to 60 μm on the pattern surface of the substrate having a wiring pattern formed of, for example, metal foil. After printing and applying by screen printing, etc., it is obtained by forming an insulating protective film by removing the solvent and curing by heat treatment at a temperature of about 100 to 180 ° C. for about 5 minutes to 3 hours. Can do.
When the siloxane-based resin composition is photocurable, for example, the dry film has a thickness of about 3 to 60 μm on the pattern surface of the base material having a wiring pattern formed of a metal foil. After printing and applying by screen printing, etc., irradiate with light such as ultraviolet rays, and if necessary, heat treatment at a temperature of about 100 to 180 ° C. for about 5 minutes to 3 hours to remove the solvent and cure. Thus, it can be obtained by forming an insulating protective film.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example.

The evaluation method of the present invention will be described.
[Electrical Reliability Test HAST]
Wiring pattern of comb substrate for electrical reliability test comprising three layers of substrate including 75 μm thick polyimide film as insulating base material, 10 μm thick modified epoxy resin adhesive and 15 μm thick copper foil wiring pattern (40 μm pitch) The resin composition of the sample was applied to the surface, and heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 60 minutes to obtain a printed wiring board having an insulating protective film thickness of about 20 μm. This printed wiring board was used as an electrical reliability test sample.
Using this sample, an electrical reliability test was performed under HAST conditions (130 ° C., 85% RH, DC 100 V). The determination was made as follows according to the time until the short circuit. ×: Short circuit occurred in less than 48 hours Δ: Short circuit occurred in 48 hours or more and less than 72 hours ○: Short circuit occurred in 72 hours or more and less than 96 hours ◎: No short circuit occurred in less than 96 hours

A compound having one or more hindered phenol groups in the molecule used in the following examples will be described.
IRGANOX 3114: manufactured by Ciba Japan. It is a hindered phenol type antioxidant in which three hindered phenol groups are bonded via a methylene group with an isocyanurate ring as a center.

[Reference Example 1] [Preparation of polyimide siloxane]
A glass flask with a capacity of 500 ml was charged with 61.79 g (0.21 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 100 g of solvent triglyme and heated at 80 ° C. in a nitrogen atmosphere. Stir. 122.24 g (0.145 mol) of α, ω-bis (3-aminopropyl) polydimethylsiloxane (amine equivalent 422) and 40 g of triglyme were added, and the mixture was heated and stirred at 175 ° C. for 60 minutes. Furthermore, 13.29 g (0.033 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 8.29 g (0 of bis (3-carboxy-4-aminophenyl) methane were added to this reaction solution. 0.029 mol) and 50 g of triglyme were added, and the mixture was heated and stirred at 175 ° C. for 20 hours and then filtered. The resulting polyimidesiloxane reaction solution was a solution having a polymer solid content concentration of 52% by weight and ηinh of 0.20. The imidization rate was substantially 100%.

[Example 1]
In the polyimidesiloxane solution obtained in Reference Example 1, 1.2 parts by mass of epoxy resin Epicoat 157S70, 1.2 parts by mass of epoxy resin YX4000HK, and 3.3 parts of phenolic resin H-1 were added to 100 parts by mass of polyimidesiloxane. 0 parts by mass, 10.0 parts by mass of finely divided silica Aerosil 50, 80.0 parts by mass of talc SG-95, and 1.6 parts by mass of silane coupling agent KBE-402 were added and stirred uniformly. A polyimidesiloxane composition was obtained.
In the polyimide siloxane composition, with respect to 100 parts by mass of the total amount of polyimide siloxane and epoxy compound, 0.8 parts by mass of bis [(2-molyforno) ethyl] ether as a curing accelerator, 0.2 parts by mass of 2E4MZ, molecules 5 parts of IRGANOX 3114 of a compound having one or more hindered phenol groups therein is dissolved in 27 g of a cyclohexanone and diglyme mixed solvent (cyclohexanone: diglyme = 1: 6) and mixed with the polyimidesiloxane composition at a ratio of 20: 1. The mixture was stirred to obtain a thermosetting resin composition.
Using this thermosetting resin composition, screen printing is performed on the wiring pattern surface of the comb substrate for electrical reliability test, and the insulating protective film is formed by heating and curing in a hot air oven at 80 ° C. for 30 minutes and 120 ° C. for 60 minutes. A printed wiring board was obtained. Using this printed wiring board as an electrical reliability test sample, an electrical reliability test was performed under HAST conditions.
The evaluation results are shown in Table 1.

[Example 2]
In the thermosetting resin composition of Example 1, a printed wiring board was obtained in the same manner as in Example 1 except that the amount of IRGANOX 3114 added as a compound having one or more hindered phenol groups in the molecule was 3 parts. It was. Using this printed wiring board as an electrical reliability test sample, an electrical reliability test was performed under HAST conditions.
The evaluation results are shown in Table 1.

Example 3
In the thermosetting resin composition of Example 1, a printed wiring board was obtained in the same manner as in Example 1 except that the amount of IRGANOX3114 added as a compound having one or more hindered phenol groups in the molecule was 1 part. It was. Using this printed wiring board as an electrical reliability test sample, an electrical reliability test was performed under HAST conditions.
The evaluation results are shown in Table 1.

[Comparative Example 1]
In the thermosetting resin composition of Example 1, a printed wiring board was obtained in the same manner as in Example 1 except that IRGANOX 3114 which is a compound having one or more hindered phenol groups in the molecule was not added. Using this printed wiring board as an electrical reliability test sample, an electrical reliability test was performed under HAST conditions.
The evaluation results are shown in Table 1.

[Reference Example 1]
Printed in the same manner as in Comparative Example 1 except that a comb-type printed wiring board for electric reliability test comprising a two-layer wiring board having no adhesive layer was used as the comb-type printed wiring board for electric reliability test. A wiring board was obtained. Using this printed wiring board as an electrical reliability test sample, an electrical reliability test was performed under HAST conditions.
The evaluation results are shown in Table 1.

[Reference Example 2]
Printing was performed in the same manner as in Example 3 except that a comb-type printed wiring board for electric reliability test comprising a two-layer wiring board having no adhesive layer was used as the comb-type printed wiring board for electric reliability test. A wiring board was obtained. Using this printed wiring board as an electrical reliability test sample, an electrical reliability test was performed under HAST conditions.
The evaluation results are shown in Table 1.

According to the present invention, electrical (insulation) reliability is further improved in a printed wiring board in which an insulating protective film made of a siloxane-based fat composition is formed on a substrate including an insulating base material, an adhesive, and a wiring pattern. A printed wiring board can be provided.
Moreover, the siloxane type fat composition which can improve suitably the electrical (insulation) reliability of the said printed wiring board can be provided.

Claims (5)

In a printed wiring board in which an insulating protective film made of a siloxane-based resin composition is formed on a substrate including an insulating base material, an adhesive, and a wiring pattern,
The siloxane-based resin composition is configured to include 0.5 to 10 parts by mass of a compound having one or more hindered phenol groups in a molecule with respect to 100 parts by mass of a resin component. Wiring board.   The printed wiring board according to claim 1, wherein the insulating base material is a polyimide film.   The resin component of the siloxane-based resin composition includes polyimide siloxane and at least one curing component selected from the group consisting of an epoxy resin, a compound having two or more phenolic hydroxyl groups, and a polyvalent isocyanate compound. The printed wiring board according to claim 1, wherein the printed wiring board is provided.   A siloxane-based resin composition comprising 0.5 to 10 parts by mass of a compound having at least one hindered phenol group in a molecule with respect to 100 parts by mass of a resin component. Siloxane resin composition.   The resin component of the siloxane-based resin composition includes polyimide siloxane and at least one curing component selected from the group consisting of an epoxy resin, a compound having two or more phenolic hydroxyl groups, and a polyvalent isocyanate compound. The siloxane-based resin composition according to claim 4, wherein