TWI494373B - Resin composition for printed circuit boards - Google Patents

Resin composition for printed circuit boards Download PDF

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Publication number
TWI494373B
TWI494373B TW098138107A TW98138107A TWI494373B TW I494373 B TWI494373 B TW I494373B TW 098138107 A TW098138107 A TW 098138107A TW 98138107 A TW98138107 A TW 98138107A TW I494373 B TWI494373 B TW I494373B
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Taiwan
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circuit board
printed circuit
resin
resin composition
group
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TW098138107A
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Chinese (zh)
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TW201031708A (en
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Hiroshi Orikabe
Takamitsu Aisaka
Hiroyuki Sakauchi
Yuji Hagiwara
Satoru Narizuka
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Ajinomoto Kk
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
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    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/28—Metal sheet
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/163—Metal in the substrate
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    • C09J2463/00—Presence of epoxy resin
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    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions

Description

印刷電路板用樹脂組成物Resin composition for printed circuit boards

本發明係關於含有(A)具有六氟異丙醇基及矽氧烷結構之聚醯亞胺樹脂、及(B)熱硬化性樹脂的印刷電路板用樹脂組成物。The present invention relates to a resin composition for a printed wiring board comprising (A) a polyimine resin having a hexafluoroisopropanol group and a decane structure, and (B) a thermosetting resin.

耐熱性優異的聚醯亞胺樹脂係被廣泛的用於電子領域、航空宇宙領域等。Polyimide resins which are excellent in heat resistance are widely used in the field of electronics and aerospace.

目前為止，已開發在該聚醯亞胺樹脂中導入矽氧烷結構，兼具耐熱性與低彈性的材料(專利文獻1)。但是耐溶劑性仍未必能滿足者。A material having a heat-insulating property and a low elasticity has been developed by introducing a oxime structure into the polyimide resin (Patent Document 1). However, solvent resistance may not be satisfactory.

為了改善此問題，而有含有導入酚性羥基之具有矽氧烷結構的聚醯亞胺樹脂與環氧樹脂的組成物，可作為印刷電路板用的黏著劑等使用(專利文獻2)。但是隨著溫度變化之彈性率的變化仍未必能滿足者。此外，與熱硬化性樹脂之倂用也有印刷電路板之變形或龜裂等疑慮，未必能滿足者。In order to improve the problem, a composition of a polyimine resin having a decyloxy group having a phenolic hydroxyl group and an epoxy resin can be used as an adhesive for a printed circuit board or the like (Patent Document 2). However, the change in the elastic modulus with temperature changes may not be satisfactory. Further, the use of a thermosetting resin may also cause problems such as deformation or cracking of the printed circuit board, and may not be satisfactory.

[先行技術文獻][Advanced technical literature]

[專利文獻][Patent Literature]

[專利文獻1]特開2002-12666號公報[Patent Document 1] JP-A-2002-12666

[專利文獻2]特開2004-51794號公報[Patent Document 2] JP-A-2004-51794

本發明之課題係提供含有具有矽氧烷結構之聚醯亞胺樹脂與熱硬化性樹脂的樹脂組成物，耐熱特性及耐溶劑性更優異，可靠性更高之印刷電路板用的樹脂組成物。An object of the present invention is to provide a resin composition for a printed circuit board having a resin composition containing a polyfluorene-imide resin having a siloxane structure and a thermosetting resin, which is excellent in heat resistance and solvent resistance, and has higher reliability. .

本發明人等為了解決上述課題，而精心研究的結果，發現含有導入六氟異丙醇基之具有矽氧烷結構的聚醯亞胺樹脂、與熱硬化性樹脂的樹脂組成物，隨著溫度變化之彈性率的變化小，耐熱特性及耐溶劑特性優異，作為印刷電路板用之絕緣材料之特性優異，遂完成本發明。In order to solve the above problems, the inventors of the present invention have found that a resin composition containing a fluorinated alkane structure having a fluorinated alkane structure and a thermosetting resin is formed with temperature. The change in the modulus of elasticity is small, the heat resistance and the solvent resistance are excellent, and the properties of the insulating material for a printed circuit board are excellent, and the present invention has been completed.

換言之，本發明係含有以下的內容。In other words, the present invention contains the following contents.

(1)一種印刷電路板用樹脂組成物，其係含有(A)具有六氟異丙醇基及矽氧烷結構的聚醯亞胺樹脂、及(B)熱硬化性樹脂。(1) A resin composition for a printed circuit board comprising (A) a polyimide resin having a hexafluoroisopropanol group and a decane structure, and (B) a thermosetting resin.

(2)如上述(1)項之印刷電路板用樹脂組成物，其係更含有(C)無機填充材。(2) The resin composition for a printed circuit board according to the above (1), which further comprises (C) an inorganic filler.

(3)如上述(1)或(2)項之印刷電路板用樹脂組成物，其中熱硬化性樹脂為環氧樹脂。(3) The resin composition for a printed circuit board according to the above (1) or (2), wherein the thermosetting resin is an epoxy resin.

(4)如上述(1)~(3)項中任一項之印刷電路板用樹脂組成物，其中聚醯亞胺樹脂具有下式(1)及(2)；(4) The resin composition for a printed circuit board according to any one of the above (1), wherein the polyimine resin has the following formulas (1) and (2);

(式中，R1係表示4價之有機基，R2係表示具有六氟異丙醇基之2價之二胺殘基，R3係表示2價之矽氧烷二胺殘基，以式(1)表示之重複單位之一分子中之重複數M係1以上100以下的整數，以式(2)表示之重複單位之一分子中之重複數N係1以上100以下的整數)表示的重複單位。(wherein R1 represents a tetravalent organic group, R2 represents a divalent diamine residue having a hexafluoroisopropanol group, and R3 represents a divalent alkoxyalkyl diamine residue, by formula (1) The repeating unit represented by the number of repetitions M in the molecule of one of the repeating units is an integer of 1 or more and 100 or less, and the number of repetitions in the molecule of the repeating unit represented by the formula (2) is an integer of 1 or more and 100 or less. .

(5)如上述(1)~(4)項中任一項之印刷電路板用樹脂組成物，其中(A)具有六氟異丙醇基及矽氧烷結構之聚醯亞胺樹脂之六氟異丙醇基的官能基當量(以下稱為HFA基當量)為1000~10000g/mol。(5) A resin composition for a printed circuit board according to any one of the above items (1), wherein (A) a polyimine resin having a hexafluoroisopropanol group and a decane structure The functional group equivalent of the fluoroisopropanol group (hereinafter referred to as HFA group equivalent) is from 1,000 to 10,000 g/mol.

(6)如上述(1)~(5)項中任一項之印刷電路板用樹脂組成物，其中(A)具有六氟異丙醇基及矽氧烷結構之聚醯亞胺樹脂的矽氧烷含量為50~80重量%。(A) A resin composition for a printed circuit board according to any one of the above items (1), wherein (A) a fluorene-imide resin having a hexafluoroisopropanol group and a decane structure The oxane content is 50 to 80% by weight.

(7)一種阻焊劑油墨，其係含有上述(1)~(6)項中任一項之印刷電路板用樹脂組成物。(7) A solder resist ink comprising the resin composition for a printed circuit board according to any one of the above items (1) to (6).

(8)一種黏著薄膜，其特徵係在支持體上形成上述(1)~(6)項中任一項之印刷電路板用樹脂組成物層所成。(8) An adhesive film comprising the resin composition layer for a printed circuit board according to any one of the above items (1) to (6).

(9)一種附金屬箔之黏著薄膜，其係在金屬箔上形成上述(1)~(6)項中任一項之印刷電路板用樹脂組成物層所成。(9) A metal foil-attached adhesive film formed by forming a resin composition layer for a printed circuit board according to any one of the above items (1) to (6).

(10)一種預浸體，其係上述(1)~(6)項中任一項之印刷電路板用樹脂組成物含浸於薄片狀纖維基材所成。(10) A prepreg obtained by impregnating a sheet-like fibrous base material with a resin composition for a printed circuit board according to any one of the above items (1) to (6).

(11)一種附金屬箔之預浸體，其係金屬箔被層合於上述(10)項之預浸體所成。(11) A metal foil-containing prepreg obtained by laminating a metal foil to the prepreg of the above item (10).

(12)一種保護層薄膜，其係在耐熱薄膜上形成上述(1)~(6)項中任一項之印刷電路板用樹脂組成物層所成。(12) A protective layer film formed by forming a resin composition layer for a printed circuit board according to any one of the above items (1) to (6).

(13)一種印刷電路板，其特徵係絕緣層含有上述(1)~(6)項中任一項之印刷電路板用樹脂組成物。(13) A printed circuit board comprising the resin composition for a printed circuit board according to any one of the items (1) to (6) above.

(14)如上述(13)項之印刷電路板，其中前述絕緣層含有阻焊劑層、層間絕緣層及保護層。(14) The printed circuit board according to the above (13), wherein the insulating layer contains a solder resist layer, an interlayer insulating layer, and a protective layer.

(15)一種印刷電路板，其係藉由上述(7)項之阻焊劑油墨形成阻焊劑層。(15) A printed circuit board comprising a solder resist layer formed of the solder resist ink of the above item (7).

(16)一種印刷電路板，其係藉由上述(8)項之黏著薄膜形成阻焊劑層。(16) A printed circuit board comprising a solder resist layer formed of the adhesive film of the above item (8).

(17)一種印刷電路板，其係藉由上述(8)項之黏著薄膜形成層間絕緣層。(17) A printed circuit board comprising an interlayer insulating layer formed by the adhesive film of the above item (8).

(18)一種印刷電路板，其係藉由上述(9)項之附金屬箔之黏著薄膜形成層間絕緣層及/或導體層。(18) A printed circuit board comprising an interlayer insulating layer and/or a conductor layer formed of the metal foil-attached adhesive film of the above item (9).

(19)一種印刷電路板，其係藉由上述(10)項之預浸體形成層間絕緣層。(19) A printed circuit board comprising the interlayer insulating layer formed by the prepreg of the above item (10).

(20)一種印刷電路板，其係藉由上述(11)項之附金屬箔之預浸體形成層間絕緣層及/或導體層。(20) A printed circuit board comprising the interlayer insulating layer and/or the conductor layer formed of the metal foil-attached prepreg of the above item (11).

(21)一種印刷電路板，其係藉由上述(12)項之保護層薄膜形成保護層。(21) A printed circuit board comprising a protective layer formed of the protective layer film of the above item (12).

本發明之含有聚醯亞胺樹脂與熱硬化性樹脂的樹脂組成物係低彈性，且具有優異的耐熱性與耐溶劑性，藉由使用該樹脂組成物，可提供耐溶劑性優異，且彈性率之溫度變化小，耐熱特性也優異的印刷電路板用樹脂組成物。The resin composition containing a polyimide resin and a thermosetting resin of the present invention is low in elasticity, and has excellent heat resistance and solvent resistance, and by using the resin composition, it is excellent in solvent resistance and elasticity. A resin composition for a printed circuit board having a small temperature change and excellent heat resistance.

[實施發明之形態][Formation of the Invention]

本發明係關於含有、(A)具有六氟異丙醇基及矽氧烷結構之聚醯亞胺樹脂、及(B)熱硬化性樹脂的印刷電路板用樹脂組成物。The present invention relates to a resin composition for a printed circuit board comprising (A) a polyimine resin having a hexafluoroisopropanol group and a decane structure, and (B) a thermosetting resin.

以下以較佳實施形態說明本發明。Hereinafter, the present invention will be described in terms of preferred embodiments.

本發明之(A)聚醯亞胺樹脂係具有六氟異丙醇基(以下稱為HFA基)及矽氧烷結構。該聚醯亞胺樹脂較佳為具有以下式(1)及(2)表示之重複單位者。The (A) polyimine resin of the present invention has a hexafluoroisopropanol group (hereinafter referred to as HFA group) and a decane structure. The polyimine resin preferably has a repeating unit represented by the following formulas (1) and (2).

式中，R1係表示4價之有機基，R2係表示具有HFA基之2價之二胺殘基，R3係表示2價之矽氧烷二胺殘基。以式(1)表示之重複單位之一分子中之重複數M較佳為1以上100以下(1≦M≦100)的整數。以式(2)表示之重複單位之一分子中之重複數N較佳為1以上100以下(1≦N≦100)的整數。In the formula, R1 represents a tetravalent organic group, R2 represents a divalent diamine residue having an HFA group, and R3 represents a divalent acroxane diamine residue. The number of repetitions M in one of the repeating units represented by the formula (1) is preferably an integer of 1 or more and 100 or less (1≦M≦100). The number of repetitions N in one of the repeating units represented by the formula (2) is preferably an integer of 1 or more and 100 or less (1≦N≦100).

R1表示之4價之有機基，例如有具有以下的結構者。The tetravalent organic group represented by R1 has, for example, the following structure.

式中，A係表示氧原子、硫原子、CO、SO、SO2 、CH2 、CH(CH3 )、C(CH3 )2 、C(CF3 )2 、或C(CCl3 )2 。In the formula, A represents an oxygen atom, a sulfur atom, CO, SO, SO 2 , CH 2 , CH(CH 3 ), C(CH 3 ) 2 , C(CF 3 ) 2 or C(CCl 3 ) 2 .

式中，芳香族環上之氫原子可被鹵素原子、碳數1~8之烷基等取代。In the formula, the hydrogen atom on the aromatic ring may be substituted by a halogen atom, an alkyl group having 1 to 8 carbon atoms or the like.

以R2表示具有HFA基之2價的二胺殘基，例如有以下結構者。The divalent residue having a divalent HFA group is represented by R2, and is, for example, the following structure.

式中，A係與上述同義。J係表示1~4之整數。K係表示1~6之整數。P與Q係分別獨立表示0~2之整數，1≦(P+Q)≦4。In the formula, the A system is synonymous with the above. The J system represents an integer from 1 to 4. The K system represents an integer from 1 to 6. The P and Q systems independently represent an integer of 0~2, and 1≦(P+Q)≦4.

式中，芳香族環上之氫原子可被鹵素原子、碳數1~8之烷基等取代。In the formula, the hydrogen atom on the aromatic ring may be substituted by a halogen atom, an alkyl group having 1 to 8 carbon atoms or the like.

以R3表示之2價之矽氧烷二胺殘基，例如有具有以下結構者。The divalent oxanediamine residue represented by R3 may have, for example, the following structure.

(式中，R4及R5係分別獨立表示碳數1~5之伸烷基、伸苯基或氧伸烷基，R6~R10係分別獨立表示碳數1~5之烷基、碳數1~5之烷氧基、或苯氧基，a、b、c係分別獨立表示0或1以上之整數，b+c≧1、a+b+c≧60。式中，芳香族環上之氫原子可被鹵素原子、碳數1~8之烷基等取代。)(In the formula, R4 and R5 each independently represent an alkylene group having a carbon number of 1 to 5, a phenyl or an alkylene group, and R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms and a carbon number of 1 to 5; a alkoxy group or a phenoxy group, a, b, and c each independently represent an integer of 0 or more, b+c≧1, a+b+c≧60. In the formula, hydrogen on the aromatic ring The atom may be substituted by a halogen atom, an alkyl group having 1 to 8 carbon atoms, etc.)

本發明之聚醯亞胺樹脂可藉由式(3)表示之四元酸二酐與式(4)及(5)表示之二胺化合物反應來製造。The polyimine resin of the present invention can be produced by reacting a tetrabasic dianhydride represented by the formula (3) with a diamine compound represented by the formulas (4) and (5).

(式中，R1、R2及R3係表示與前述同義。)(wherein R1, R2 and R3 are synonymous with the above.)

式(3)表示之四元酸二酐之R1表示的4價有機基係與前述相同。R1表示之4價有機基的具體例有苯四甲酸二酐、2,3,6,7-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,3’,4,4’-聯苯四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、3,3’,4,4’-二苯基碸四羧酸二酐、4,4’-(六氟異亞丙基)-雙-(苯二甲酸二酐)、4,4’-氧二苯二甲酸二酐、4,4’-(4,4’-異亞丙基二苯氧基)-雙-(苯二甲酸二酐)、1,3-二氫-1,3-二氧代-5-異苯並呋喃羧酸-(1-甲基亞乙基)-二-4,1-伸苯酯、乙二醇雙脫水偏苯三酸酯、3,4,9,10-苝四羧酸二酐、9,9-雙(3,4-二羧基苯基)芴二酐、1,3-二氫-1,3-二氧代-5-異苯並呋喃羧酸-1,4-伸苯酯、1,2,3,4-環戊烷四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-丁烷四羧酸二酐、4-(2,5-二氧代四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二羧酸酐、5-(2,5-二氧代四氫呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘[1,2-C]呋喃-1,3-二酮等。此等四元酸二酐可組合2種以上使用。The tetravalent organic group represented by R1 of the tetrabasic acid dianhydride represented by the formula (3) is the same as described above. Specific examples of the tetravalent organic group represented by R1 are pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 3,3. ',4,4'-biphenyltetracarboxylic dianhydride, 2,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid Dihydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)-bis-(phthalic anhydride), 4,4 '-Oxydiphthalic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)-bis-(phthalic anhydride), 1,3-dihydro-1, 3-dioxo-5-isobenzofurancarboxylic acid-(1-methylethylidene)-di-4,1-phenylene ester, ethylene glycol double-dehydrated trimellitate, 3,4, 9,10-decane tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)ruthenium anhydride, 1,3-dihydro-1,3-dioxo-5-isobenzo Furancarboxylic acid-1,4-phenylene ester, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-butane tetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5 -(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,3,3a,4,5,9b-hexahydro-5-( Tetrahydro-2,5-dioxo-3-furan Base)-naphthalene [1,2-C]furan-1,3-dione. These tetrabasic acid dianhydrides can be used in combination of 2 or more types.

具有以式(4)表示之HFA基的二胺化合物例如有以下式表示者。The diamine compound having an HFA group represented by the formula (4) is, for example, represented by the following formula.

式中，A係表示與上述同義。J係表示1~4之整數。K係表示1~6之整數。P與Q係分別獨立表示0~2之整數，1≦(P+Q)≦4。In the formula, the A system is synonymous with the above. The J system represents an integer from 1 to 4. The K system represents an integer from 1 to 6. The P and Q systems independently represent an integer of 0~2, and 1≦(P+Q)≦4.

式中，芳香族環上之氫原子可被鹵素原子、碳數1~8之烷基等取代。In the formula, the hydrogen atom on the aromatic ring may be substituted by a halogen atom, an alkyl group having 1 to 8 carbon atoms or the like.

式(4-b)中，萘環上之胺基係分別可鍵結於相同的苯環，或可鍵結於不同的苯環。同樣的，HFA基為複數時，分別可鍵結於相同的苯環，或可鍵結於不同的苯環。In the formula (4-b), the amine groups on the naphthalene ring may be bonded to the same benzene ring, respectively, or may be bonded to different benzene rings. Similarly, when the HFA group is a complex number, it may be bonded to the same benzene ring, or may be bonded to a different benzene ring.

式(4-a)表示之二胺化合物可藉由國際公開第2006/043501號說明書所記載之公知方法來製造。式(4-c)表示之二胺化合物可藉由國際公開第2006/041115號說明書所記載之公知方法來製造。式(4-b)表示之二胺化合物可依據國際公開第2006/043501號說明書、國際公開第2006/041115號說明書所記載之公知方法，使對應之萘二胺化合物與六氟丙酮或六氟丙酮‧3水合物反應，將HFA基導入萘環上而製得。此等具有HFA基的二胺化合物可組合2種類以上使用。The diamine compound represented by the formula (4-a) can be produced by a known method described in the specification of International Publication No. 2006/043501. The diamine compound represented by the formula (4-c) can be produced by a known method described in the specification of International Publication No. 2006/041115. The diamine compound represented by the formula (4-b) can be made into a corresponding naphthalene diamine compound and hexafluoroacetone or hexafluorofluoride according to a known method described in the specification of International Publication No. 2006/043501 and International Publication No. 2006/041115. The acetone ‧3 hydrate is reacted, and the HFA group is introduced into a naphthalene ring to prepare. These diamine compounds having an HFA group can be used in combination of two or more types.

式(5)表示之二胺基矽氧烷例如有以下式表示者。The diamine oxime represented by the formula (5) is, for example, represented by the following formula.

式中，R4及R5係分別獨立表示碳數1~5之伸烷基、伸苯基或氧伸烷基，R6~R10係分別獨立表示碳數1~5之烷基、碳數1~5之烷氧基、或苯氧基，a、b、c係分別獨立表示0或1以上之整數，b+c≧1、a+b+c≧60。式中，芳香族環上之氫原子可被鹵素原子、碳數1~8之烷基等取代。In the formula, R4 and R5 each independently represent an alkylene group having a carbon number of 1 to 5, a phenyl or an alkylene group, and R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms and a carbon number of 1 to 5. The alkoxy group or the phenoxy group, a, b, and c each independently represent an integer of 0 or more, and b+c≧1, a+b+c≧60. In the formula, the hydrogen atom on the aromatic ring may be substituted by a halogen atom, an alkyl group having 1 to 8 carbon atoms or the like.

本發明之矽氧烷結構較佳為以下述(5b)式表示的結構者。The structure of the oxime of the present invention is preferably a structure represented by the following formula (5b).

式中，Re及Rf係分別獨立表示碳數1~5之烷基、碳數1~5之烷氧基、苯基、或苯氧基，m係60以上之整數，各重複單位中，Re或Rf可不同。In the formula, Re and Rf each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and m is an integer of 60 or more, and in each repeating unit, Re Or Rf can be different.

式(5a)表示之二胺基矽氧烷，例如有1,3-雙(3-胺基丙基)-1,1,2,2-四甲基二矽氧烷、1,3-雙(3-胺基丁基)-1,1,2,2-四甲基二矽氧烷、雙(4-胺基苯氧基)二甲基矽烷、1,3-雙(4-胺基苯氧基)四甲基二矽氧烷、1,1,3,3-四甲基-1,3-雙(4-胺基苯基)二矽氧烷、1,1,3,3-四苯氧基-1,3-雙(2-胺基乙基)二矽氧烷、1,1,3,3-四苯基-1,3-雙(2-胺基乙基)二矽氧烷、1,1,3,3-四苯基-1,3-雙(3-胺基丙基)二矽氧烷、1,1,3,3-四甲基-1,3-雙(2-胺基乙基)二矽氧烷、1,1,3,3-四甲基-1,3-雙(3-胺基丙基)二矽氧烷、1,1,3,3-四甲基-1,3-雙(4-胺基丁基)二矽氧烷、1,3-二甲基-1,3-二甲氧基-1,3-雙(4-胺基丁基)二矽氧烷、1,1,3,3,5,5-六甲基-1,5-雙(4-胺基苯基)三矽氧烷、1,1,5,5-四苯基-3,3-二甲基-1,5-雙(3-胺基丙基)三矽氧烷、1,1,5,5-四苯基-3,3-二甲氧基-1,5-雙(4-胺基丁基)三矽氧烷、1,1,5,5-四苯基-3,3-二甲氧基-1,5-雙(5-胺基戊基)三矽氧烷、1,1,5,5-四甲基-3,3-二甲氧基-1,5-雙(2-胺基乙基)三矽氧烷、1,1,5,5-四甲基-3,3-二甲氧基-1,5-雙(4-胺基丁基)三矽氧烷、1,1,5,5-四甲基-3,3-二甲氧基-1,5-雙(5-胺基戊基)三矽氧烷、1,1,3,3,5,5-六甲基-1,5-雙(3-胺基丙基)三矽氧烷、1,1,3,3,5,5-六乙基-1,5-雙(3-胺基丙基)三矽氧烷、1,1,3,3,5,5-六丙基-1,5-雙(3-胺基丙基)三矽氧烷等。此等二胺基矽氧烷可使用單獨使用或組合兩種以上使用。a diamino sulfoxane represented by the formula (5a), for example, 1,3-bis(3-aminopropyl)-1,1,2,2-tetramethyldioxane, 1,3-double (3-Aminobutyl)-1,1,2,2-tetramethyldioxane, bis(4-aminophenoxy)dimethylsilane, 1,3-bis(4-amino group Phenoxy)tetramethyldioxane, 1,1,3,3-tetramethyl-1,3-bis(4-aminophenyl)dioxane, 1,1,3,3- Tetraphenoxy-1,3-bis(2-aminoethyl)dioxane, 1,1,3,3-tetraphenyl-1,3-bis(2-aminoethyl)difluorene Oxane, 1,1,3,3-tetraphenyl-1,3-bis(3-aminopropyl)dioxane, 1,1,3,3-tetramethyl-1,3-double (2-Aminoethyl)dioxane, 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)dioxane, 1,1,3,3 -tetramethyl-1,3-bis(4-aminobutyl)dioxane, 1,3-dimethyl-1,3-dimethoxy-1,3-bis(4-amino group Butyl)dioxane, 1,1,3,3,5,5-hexamethyl-1,5-bis(4-aminophenyl)trioxane, 1,1,5,5- Tetraphenyl-3,3-dimethyl-1,5-bis(3-aminopropyl)trioxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy -1,5-bis(4-aminobutyl)trioxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis(5-amino group Butyl) trioxane, 1,1,5,5-four 3-,3-dimethoxy-1,5-bis(2-aminoethyl)trioxane, 1,1,5,5-tetramethyl-3,3-dimethoxy- 1,5-bis(4-aminobutyl)trioxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(5-aminopenta Trioxane, 1,1,3,3,5,5-hexamethyl-1,5-bis(3-aminopropyl)trioxane, 1,1,3,3,5 ,5-hexaethyl-1,5-bis(3-aminopropyl)trioxane, 1,1,3,3,5,5-hexapropyl-1,5-bis(3-amine Propyl) trioxane and the like. These diaminophthaloxanes can be used singly or in combination of two or more.

式(4)及(5)表示之二胺化合物以外的二胺化合物可使用1種類或組合2種類以上倂用。該二胺化合物例如有以下式(6)表示。The diamine compound other than the diamine compound represented by the formulas (4) and (5) may be used in one type or in combination of two or more types. This diamine compound is represented, for example, by the following formula (6).

(式中，R11係表示具有HFA基之2價之二胺殘基及2價之矽氧烷二胺殘基以外的2價有機基。)(In the formula, R11 represents a divalent organic group other than a divalent diamine residue having a HFA group and a divalent alkoxyalkyl diamine residue.)

該二胺化合物無特別限定，例如有1,4-二胺基苯、1,3-二胺基苯、2,4-二胺基甲苯、2,5-二胺基甲苯、1,4-二胺基-2,5-二甲基苯、1,4-二胺基-2,5-二鹵基苯等含有1個苯環的二胺化合物、4,4’-二胺基二苯醚、3,3’-二胺基二苯醚、3,4’-二胺基二苯醚、4,4’-二胺基二苯甲酮、3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、4,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸、3,4’-二胺基二苯基碸、4,4’-二胺基二苯基甲烷、3,3’-胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基硫醚、3,3’-二胺基二苯基硫醚、3,4’-二胺基二苯基硫醚、2,2-雙(4-胺基苯基)丙烷、2,2-雙(3-胺基苯基)丙烷、2,2’-雙(4-胺基苯基)六氟丙烷、2,2’-雙(3-胺基苯基)六氟丙烷、2,2’-雙(3-胺基-4-甲基苯基)六氟丙烷、1,1’-雙(4-胺基苯基)環己烷、o-二甲氧苯胺、o-聯甲苯胺、2,2’-二甲基-4,4’-二胺基聯苯、2,2’-雙(三氟甲基)-4,4’-二胺基聯苯、4,4’-二胺基苯醯苯胺、3,3’,5,5’-四甲基-4,4’-二胺基聯苯、3,3’,5,5’-四甲基-4,4’-二胺基二苯醚、3,3’,5,5’-四甲基-4,4’-二胺基二苯基甲烷、3,3’,5,5’-四乙基-4,4’-二胺基聯苯、3,3’,5,5’-四乙基-4,4’-二胺基二苯醚、3,3’,5,5’-四乙基-4,4’-二胺基二苯基甲烷、4,4’-甲撐-雙(2,6-二異丙基苯胺)、4,4’-甲撐-雙(2-乙基-6-甲基苯胺)、3,3’-二乙基-4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、3,3’-二甲基-4,4’-二胺基二苯醚、3,3’-二乙基-4,4’-二胺基二苯醚、3,3’-二甲氧基-4,4’-二胺基二苯醚、3,3’-二甲基-4,4’-二胺基二苯基甲烷、3,3’-二乙基-4,4’-二胺基二苯基甲烷、3,3’-二甲氧基-4,4’-二胺基二苯基甲烷、1,5-二胺基萘、2,3-二胺基萘等含有2個苯環的二胺化合物、1,4-雙(4-胺基苯氧基)苯、1,4-雙(3-胺基苯氧基)苯、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、1,4-雙(3-胺基苯基)苯、α,α’-雙(4-胺基苯基)-1,4-二異丙基苯、α,α’-雙(4-胺基苯基)-1,3-二異丙基苯等含有3個苯環的二胺化合物、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]碸、2,2-雙[4-(3-胺基苯氧基)苯基]碸、4,4’-(4-胺基苯氧基)聯苯、4,4’-(3-胺基苯氧基)聯苯、9,9-雙(4-胺基苯基)芴、9,9-雙(3-胺基苯基)芴、9,9-雙(4-胺基-3-甲基苯基)芴、9,9-雙(4-胺基-3-氟苯基)芴、5,10-雙(4-胺基苯基)蒽、1,3-二胺基芘、1,6-二胺基芘等含有4個以上之苯環的二胺化合物、4,4’-甲撐雙(環己胺)、4,4’-甲撐雙(2-甲基環己胺)等具有脂環結構的二胺化合物、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷、1,12-二胺基十二烷等具有線狀烴結構的二胺化合物、商品名Versamine551(cognis Japan(股)製)等具有二聚物二胺結構的二胺化合物、商品名JeffamineD-230、D-400、D-2000、D-4000、XTJ-500、XTJ-501、XTJ-502、HK-511、XTJ-504、XTJ-542、XTJ-533、XTJ-536(huntsman股份公司製)等具有聚氧伸烷二胺結構的二胺化合物等。The diamine compound is not particularly limited, and examples thereof include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 2,5-diaminotoluene, and 1,4-. Diamine compound containing 1 benzene ring such as diamino-2,5-dimethylbenzene or 1,4-diamino-2,5-dihalobenzene, 4,4'-diaminodiphenyl Ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobiphenyl Ketone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 3,4'-diaminodiyl Phenylhydrazine, 4,4'-diaminodiphenylmethane, 3,3'-aminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino Diphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 2,2-bis(4-aminophenyl)propane, 2 , 2-bis(3-aminophenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 1,1'-bis(4-aminophenyl)cyclohexane, o-dimethoxyaniline, o- Toluidine, 2,2'-dimethyl-4,4'-di Biphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminophenylaniline, 3,3',5,5'- Tetramethyl-4,4'-diaminobiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl ether, 3,3',5,5' -tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminobiphenyl, 3,3',5, 5'-Tetraethyl-4,4'-diaminodiphenyl ether, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 4,4' -Methylene-bis(2,6-diisopropylaniline), 4,4'-methylene-bis(2-ethyl-6-methylaniline), 3,3'-diethyl-4, 4'-Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenyl ether , 3,3'-diethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-4,4'-diaminodiphenyl ether, 3,3'-di Methyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4, a diamine compound containing 2 benzene rings such as 4'-diaminodiphenylmethane, 1,5-diaminonaphthalene or 2,3-diaminonaphthalene, 1,4-bis(4-aminobenzene) Oxy)benzene, 1,4-bis(3- Aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminobenzene) Oxy)benzene, 1,4-bis(3-aminophenyl)benzene, α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, α,α'- a diamine compound containing 3 benzene rings such as bis(4-aminophenyl)-1,3-diisopropylbenzene, 2,2-bis[4-(4-aminophenoxy)phenyl] Propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2, 2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]indole, 2,2-double [ 4-(3-Aminophenoxy)phenyl]anthracene, 4,4'-(4-aminophenoxy)biphenyl, 4,4'-(3-aminophenoxy)biphenyl, 9,9-bis(4-aminophenyl)anthracene, 9,9-bis(3-aminophenyl)anthracene, 9,9-bis(4-amino-3-methylphenyl)anthracene, 9,9-bis(4-amino-3-fluorophenyl)anthracene, 5,10-bis(4-aminophenyl)anthracene, 1,3-diaminopurine, 1,6-diamino A diamine compound containing 4 or more benzene rings, 4,4'-methylene bis(cyclohexylamine), 4,4'-methylene bis(2-methylcyclohexylamine), etc., having an alicyclic structure Diamine compound, 1,4-diaminobutane 1,5-Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane a diamine compound having a linear hydrocarbon structure such as 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane, trade name Versamine 551 (cognis Japan ( Diamine compound having a dimer diamine structure, such as Jeffamine D-230, D-400, D-2000, D-4000, XTJ-500, XTJ-501, XTJ-502, HK-511 A diamine compound having a polyoxyalkylene diamine structure, such as XTJ-504, XTJ-542, XTJ-533, and XTJ-536 (manufactured by Huntsman Co., Ltd.).

式(5)表示之二胺基矽氧烷，較佳為NH2 當量為400~6000g/mol之範圍者，更佳為400~2500g/mol之範圍者，更佳為400~1000g/mol之範圍者。NH2 當量大於此範圍時，矽氧烷結構之分子量大，因此樹脂之疏水性太強，與熱硬化性樹脂之相溶性差，有時樹脂本身，其醯亞胺部與矽氧烷部之極性差太大，很難安定進行樹脂合成。而NH2 當量小於此範圍時，矽氧烷結構之分子量變小，不易得到充分的柔軟性。而含有苯基者，與熱硬化性樹脂之混和性佳，故較佳。The diamino sulfoxane represented by the formula (5) preferably has a NH 2 equivalent of 400 to 6000 g/mol, more preferably 400 to 2500 g/mol, more preferably 400 to 1000 g/mol. Range. When the NH 2 equivalent is larger than this range, the molecular weight of the decane structure is large, so the hydrophobicity of the resin is too strong, and the compatibility with the thermosetting resin is poor, and the resin itself may have a quinone imine portion and a decane portion. The difference in polarity is too large, and it is difficult to stabilize the resin synthesis. On the other hand, when the NH 2 equivalent is less than this range, the molecular weight of the siloxane structure becomes small, and it is difficult to obtain sufficient flexibility. On the other hand, those containing a phenyl group are preferred because they have good adhesion to a thermosetting resin.

倂用式(3)表示之四元酸二酐與式(4)及(5)表示之二胺化合物(式(6)表示之二胺化合物時，式(4)~式(6)表示之二胺化合物之合計)之反應比例，無特別限定，任一方過多也可，較佳為從提高所得之樹脂的分子量，以提高機械特性的觀點，反應所用之全部二胺化合物之官能基當量數的合計與四元酸二酐之官能基當量數大致相等較佳。具體而言，使用之四元酸二酐之酸酐基之官能基當量數為X、使用之胺化合物全部胺基之官能基當量數為Y時，較佳為在0≦∣(X-Y)∣/X≦0.3的條件下進行反應，更佳為在0≦∣(X-Y)∣/X≦0.1的條件下進行反應。When the tetrabasic acid dianhydride represented by the formula (3) and the diamine compound represented by the formula (4) and (5) (the diamine compound represented by the formula (6), the formula (4) to the formula (6) are used. The reaction ratio of the total of the diamine compounds is not particularly limited, and may be any one of them. It is preferred to increase the number of functional groups of all the diamine compounds used for the reaction from the viewpoint of improving the molecular weight of the obtained resin and improving the mechanical properties. The total amount of the functional groups equivalent to the tetrabasic acid dianhydride is preferably equal. Specifically, when the number of functional groups of the acid anhydride group of the tetrabasic acid dianhydride used is X, and the number of functional group equivalents of all the amine groups of the amine compound used is Y, it is preferably 0 ≦∣ (XY) ∣ / The reaction is carried out under the conditions of X ≦ 0.3, more preferably under the conditions of 0 ≦∣ (XY) ∣ / X ≦ 0.1.

酸酐基之官能基當量數X(mol)係當酸酐基之官能基當量為A1(g/mol)、投入量為B1(g)時，可以X=B1/A1的式子求得。換言之，官能基當量係表示官能基1個之化合物的分子量，官能基當量數係表示化合物重量(投入量)之官能基的個數。The functional group equivalent number X (mol) of the acid anhydride group is determined by the formula of X = B1/A1 when the functional group equivalent of the acid anhydride group is A1 (g/mol) and the input amount is B1 (g). In other words, the functional group equivalent system represents the molecular weight of the compound having one functional group, and the functional group equivalent number is the number of functional groups indicating the weight (input amount) of the compound.

同樣的，含有式(4)表示之HFA基之二胺化合物之胺基的官能基當量A2(g/mol)、投入量為B2(g)、式(5)表示之二胺基矽氧烷之胺基的官能基當量A3(g/mol)、投入量為B3、式(6)表示之二胺化合物之胺基的官能基當量A4(g/mol)、投入量為B4(g)時，可以Y=(B2/A2)+(B3/A3)+(B4/A4)的式子求得。式(6)表示之二胺化合物係任意成分，不含有此成分時，上述式中之(B4/A4)=0。Similarly, the functional group equivalent A2 (g/mol) of the amine group of the HFA group-containing diamine compound represented by the formula (4), the input amount is B2 (g), and the diamine oxirane represented by the formula (5) The functional group equivalent A3 (g/mol) of the amine group, the input amount is B3, the functional group equivalent A4 (g/mol) of the amine group of the diamine compound represented by the formula (6), and the input amount is B4 (g). It can be obtained by the formula of Y=(B2/A2)+(B3/A3)+(B4/A4). The diamine compound represented by the formula (6) is an optional component, and when the component is not contained, (B4/A4) = 0 in the above formula.

此外，式(4)與(5)之二胺化合物之投入比例係反映所得之樹脂中之矽氧烷結構的含量與HFA基的含量，因此，藉由任意設定此等2個的值時，式(4)與(5)之二胺化合物的投入比例的範圍自然被決定。首先，所得之樹脂所含的矽氧烷結構的量係重量比例成為40~90重量%較佳，成為50~80重量%更佳。矽氧烷結構之比例大於90重量%時，所得之樹脂的黏著性升高，使用不易，相反的，小於40重量%時，樹脂缺乏柔軟性。Further, the ratio of the input of the diamine compound of the formulae (4) to (5) reflects the content of the decane structure and the content of the HFA group in the obtained resin. Therefore, when these two values are arbitrarily set, The range of the ratio of the ratio of the diamine compounds of the formulae (4) to (5) is naturally determined. First, the amount of the oxymethane structure contained in the obtained resin is preferably from 40 to 90% by weight, more preferably from 50 to 80% by weight. When the proportion of the siloxane structure is more than 90% by weight, the adhesiveness of the obtained resin is increased, and it is difficult to use. On the contrary, when it is less than 40% by weight, the resin lacks flexibility.

矽氧烷結構之含量Z(重量%)係當醯亞胺化產生脫離之水的重量為B5時，可以Z(重量%)={B3/(B1+B2+B3+B4-B5)}×100的式子求得。B5係當前述X或Y之值中較小者當做W時，可以B5=18×W的式子求得。此外，式(6)表示之二胺化合物為任意成分，不含有此成分時，上述式中之B4=0。The content of the oxoxane structure Z (% by weight) is Z (% by weight) = {B3 / (B1 + B2 + B3 + B4 - B5)} when the weight of the yttrium imidized water is B5. The formula of 100 is obtained. B5 is the case where the smaller of the aforementioned values of X or Y is taken as W, and can be obtained by the equation of B5 = 18 × W. Further, the diamine compound represented by the formula (6) is an optional component, and when it is not contained, B4 = 0 in the above formula.

矽氧烷結構之含量的上限值，從維持高溫下之耐熱性的觀點，較佳為80重量%，更佳為75重量%，更佳為70重量%，特佳為65重量%。而矽氧烷結構之含量的下限值，從展現柔軟性的觀點，較佳為50重量%，更佳為54重量%，更佳為58重量%。The upper limit of the content of the decane structure is preferably 80% by weight, more preferably 75% by weight, still more preferably 70% by weight, and particularly preferably 65% by weight, from the viewpoint of maintaining heat resistance at a high temperature. The lower limit of the content of the decane structure is preferably 50% by weight, more preferably 54% by weight, still more preferably 58% by weight, from the viewpoint of exhibiting flexibility.

此外，所得之聚醯亞胺樹脂之HFA基的官能基當量(以下稱為HFA基當量)的上限值，從樹脂中之HFA基的量太少，使用此樹脂之樹脂組成物進行硬化時，防止硬化不完全的觀點，較佳為10000g/mol，更佳為8500g/mol，更佳為6000g/mol，更佳為5000g/mol，特佳為4000g/mol。而所得之聚醯亞胺樹脂之HFA基當量的下限值，從因含有較多HFA基，使得樹脂組成物硬化時之交聯密度升高，矽氧烷結構之含量自然減少，為了防止硬化物之柔軟性降低的觀點，較佳為1000g/mol，更佳為1500g/mol，更佳為2000g/mol，更佳為2500g/mol。聚醯亞胺樹脂之HFA基當量V(g/mol)係當含有HFA基之二胺化合物的HFA基當量為H時，可以V(g/mol)=(B1+B2+B3+B4-B5)÷(B2/H)的式子求得。式(6)表示之二胺化合物係任意成分，不含有此成分時，上述式中之B4=0。Further, the upper limit of the functional group equivalent of the HFA group of the obtained polyimine resin (hereinafter referred to as HFA group equivalent) is too small from the amount of the HFA group in the resin, and the resin composition of the resin is used for hardening. The viewpoint of preventing incomplete hardening is preferably 10,000 g/mol, more preferably 8500 g/mol, still more preferably 6000 g/mol, still more preferably 5000 g/mol, particularly preferably 4000 g/mol. The lower limit of the HFA group equivalent of the obtained polyimine resin is such that the crosslinking density increases when the resin composition is hardened due to the inclusion of a large amount of HFA groups, and the content of the siloxane structure is naturally reduced, in order to prevent hardening. The viewpoint of lowering the softness of the object is preferably 1000 g/mol, more preferably 1500 g/mol, still more preferably 2000 g/mol, still more preferably 2500 g/mol. The HFA group equivalent V (g/mol) of the polyimine resin is such that when the HFA group equivalent of the HFA group-containing diamine compound is H, V(g/mol)=(B1+B2+B3+B4-B5) ) The formula of ÷(B2/H) is obtained. The diamine compound represented by the formula (6) is an optional component, and when it is not contained, B4 = 0 in the above formula.

聚醯亞胺樹脂之末端係因四元酸二酐與二胺化合物的反應比例而異，可能成為胺基、酸酐基或酸酐基產生開環後的二羧基。The terminal of the polyimine resin differs depending on the reaction ratio of the tetrabasic dianhydride to the diamine compound, and may be an amine group, an acid anhydride group or an acid anhydride group to form a dicarboxy group after ring opening.

反應操作無特別限定，例如在聚合溶液中進行加熱脫水醯亞胺化，因作業簡便，故較佳。具體而言，首先，在惰性氣體氣氛下，在具有HFA基之二胺化合物及矽氧烷二胺進行溶解的溶劑中，添加甲苯或二甲苯等與水產生共沸的溶劑。其次，添加四元酸二酐，在80℃以下，較佳為0~50℃，反應1~24小時，得到聚醯胺酸溶液。將所得之聚醯胺酸溶液以100~200℃，較佳為150~200℃進行加熱，此時脫離的水與甲苯共沸除去，同時閉環可得到聚醯亞胺溶液。此時，可確認餾除大致為理論量的水及未發現水流出時點，當作反應完成。此外，與此方法不同，可使用乙酸酐/吡啶混合溶液，以低溫進行聚醯胺酸之脫水閉環反應。The reaction operation is not particularly limited. For example, it is preferred to carry out heat dehydration and imidization in a polymerization solution, which is preferable because it is easy to handle. Specifically, first, a solvent which azeotropes with water, such as toluene or xylene, is added to a solvent in which an HFA-based diamine compound and a decylamine diamine are dissolved in an inert gas atmosphere. Next, a tetrabasic acid dianhydride is added, and the reaction is carried out for 1 to 24 hours at 80 ° C or lower, preferably 0 to 50 ° C, to obtain a polyaminic acid solution. The obtained polyaminic acid solution is heated at 100 to 200 ° C, preferably 150 to 200 ° C, at which time the desorbed water is azeotropically removed with toluene, and the polycyclic imine solution is obtained by ring closure. At this time, it was confirmed that the water was distilled off to a theoretical amount, and the point at which no water was found to flow out was confirmed as completion of the reaction. Further, unlike this method, a dehydration ring-closing reaction of polyglycine can be carried out at a low temperature using an acetic anhydride/pyridine mixed solution.

使用於反應的反應溶劑，只要是不會與原料及所得之樹脂反應者，即無特別限定，例如有四氫呋喃、1,4-二噁烷、環戊酮、環己酮、γ-丁內酯、α-甲基-γ-丁內酯、γ-戊內酯、δ-戊內酯、γ-己內酯、ε-己內酯、乙烯碳酸酯、丙烯碳酸酯、乙基纖維素乙酸酯、丁基纖維素乙酸酯、二乙二醇二甲醚、三乙二醇二甲醚、甲基異丁酮、N-甲基吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲基亞碸等，較佳為環己酮、γ-丁內酯。此等溶劑可單獨使用或組合兩種以上使用。特佳為環己酮、γ-丁內酯等之溶劑與石油腦等的芳香族烴系溶劑倂用。The reaction solvent to be used in the reaction is not particularly limited as long as it does not react with the raw material and the obtained resin, and examples thereof include tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, and γ-butyrolactone. , α-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, ethylene carbonate, propylene carbonate, ethyl cellulose acetate Ester, butyl cellulose acetate, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl isobutyl ketone, N-methyl pyrrolidone, N, N-dimethyl acetamide, N N-dimethylformamide, dimethyl hydrazine, etc., preferably cyclohexanone or γ-butyrolactone. These solvents may be used singly or in combination of two or more. Particularly preferred are solvents such as cyclohexanone and γ-butyrolactone, and aromatic hydrocarbon solvents such as petroleum brain.

將所得之聚醯亞胺樹脂溶液投入於水或甲醇等之弱溶劑中，使聚合物析出沈澱，再經乾燥後，可再溶解於配合用途的溶劑中來使用。The obtained polyimine resin solution is placed in a weak solvent such as water or methanol to precipitate a polymer, and after drying, it can be reused in a solvent for use in combination.

本發明之聚醯亞胺樹脂之數平均分子量(Mn)的上限值，從樹脂組成物之黏度上昇，防止使用性降低的觀點，較佳為50000，更佳為40000，更佳為30000，更佳為25000，特佳為20000。此外，聚醯亞胺樹脂之數平均分子量的下限值，從展現樹脂組成物之柔軟性的觀點，較佳為9000，更佳為10000，更佳為15000。本發明中之聚醯亞胺樹脂之重量平均分子量(Mw)的上限值，從樹脂組成物之黏度上昇，防止使用性降低的觀點，較佳為50000，更佳為40000，更佳為30000。此外，聚醯亞胺樹脂之數平均分子量的下限值，從展現樹脂組成物之柔軟性的觀點，較佳為9000，更佳為10000，更佳為15000，特佳為20000。數平均分子量及重量平均分子量係以凝膠透色譜(GPC)法(聚苯乙烯換算)所測定的值。藉由GPC法的數平均分子量及重量平均分子量，具體而言，測定裝置使用(股)島津製作所製LC-9A/RID-6A，管柱使用昭和電工(股)社製Shodex K-800P/K-804L/K-804L，移動相使用N-甲基吡咯烷酮中溶解0.4重量%之溴化鋰的溶液，並以管柱溫度40℃測定，使用標準聚苯乙烯的校正曲線計算得到。The upper limit of the number average molecular weight (Mn) of the polyimine resin of the present invention is preferably from 50,000, more preferably 40,000, more preferably 30,000, from the viewpoint of increasing the viscosity of the resin composition and preventing the decrease in usability. More preferably 25,000, especially good is 20,000. Further, the lower limit of the number average molecular weight of the polyimide resin is preferably 9000, more preferably 10,000, still more preferably 15,000, from the viewpoint of exhibiting flexibility of the resin composition. The upper limit of the weight average molecular weight (Mw) of the polyimine resin in the present invention is preferably from 50,000, more preferably 40,000, more preferably 30,000, from the viewpoint of increasing the viscosity of the resin composition and preventing the decrease in usability. . Further, the lower limit of the number average molecular weight of the polyimide resin is preferably 9000, more preferably 10,000, still more preferably 15,000, and particularly preferably 20,000, from the viewpoint of exhibiting flexibility of the resin composition. The number average molecular weight and the weight average molecular weight are values measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). By the number average molecular weight and the weight average molecular weight of the GPC method, specifically, the measurement device uses LC-9A/RID-6A manufactured by Shimadzu Corporation, and the column uses Shodex K-800P/K manufactured by Showa Denko Co., Ltd. -804L/K-804L, the mobile phase was prepared by dissolving 0.4% by weight of lithium bromide in N-methylpyrrolidone and measuring at a column temperature of 40 ° C using a calibration curve of standard polystyrene.

本發明之樹脂組成物係含有(B)熱硬化性樹脂。藉由在上述所得之(A)具有矽氧烷結構的醯亞胺樹脂中混合熱硬化性樹脂，可得到硬化收縮小，富有柔軟性，顯示高的耐熱性、黏著性的熱硬化性樹脂組成物。熱硬化性樹脂例如有環氧樹脂、酚系化合物、羧酸系化合物、酸酐系化合物、胺系化合物、苯並噁嗪系化合物、胺醯亞胺系化合物、氰酸酯系化合物。此時，選擇具有可與樹脂(A)骨架中所含有之HFA基反應之官能基的熱硬化性樹脂，其中更佳為具有2個以上之縮水甘油基的環氧樹脂。也可添加環氧樹脂之硬化劑、硬化促進劑等。The resin composition of the present invention contains (B) a thermosetting resin. By mixing the thermosetting resin with the yttrium imine resin having the oxyalkylene structure obtained as described above, it is possible to obtain a thermosetting resin having a small heat-shrinkable shrinkage and having high flexibility and exhibiting high heat resistance and adhesion. Things. Examples of the thermosetting resin include an epoxy resin, a phenol compound, a carboxylic acid compound, an acid anhydride compound, an amine compound, a benzoxazine compound, an amine quinone compound, and a cyanate compound. In this case, a thermosetting resin having a functional group reactive with the HFA group contained in the skeleton of the resin (A) is selected, and among them, an epoxy resin having two or more glycidyl groups is more preferable. A hardener for an epoxy resin, a hardening accelerator, or the like may also be added.

本發明之實施態樣所使用的環氧樹脂，只要含有2個以上之縮水甘油基時，則無特別限定。例如有雙酚A、雙酚F、雙酚S、間苯二酚、苯酚酚醛、甲酚酚醛等之酚類的縮水甘油醚、丁二醇、聚乙二醇、聚丙二醇等之醇類的縮水甘油醚、苯二甲酸、間苯二甲酸、四氫苯二甲酸等之羧酸類的縮水甘油醚、苯胺、三聚異氰酸等之氮原子所鍵結的活性氫以縮水甘油基取代者等之縮水甘油型(也包括甲基縮水甘油型)環氧樹脂、分子內之烯烴鍵經環氧化所得之乙烯基環己烯二環氧化物、3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯、2-(3,4-環氧基)環己基-5,5-螺(3,4-環氧基)環己烷-m-二噁烷等之脂環型環氧樹脂、對二甲苯變性酚樹脂之縮水甘油醚、間二甲苯.對二甲苯變性酚樹脂之縮水甘油醚、萜烯變性酚樹脂之縮水甘油醚、二環戊二烯變性酚樹脂之縮水甘油醚、環戊二烯變性酚樹脂之縮水甘油醚、多環芳香環變性酚樹脂之縮水甘油醚、含有萘環之酚樹脂的縮水甘油醚、聯苯型環氧樹脂等，可單獨使用或組合兩種以上使用。The epoxy resin used in the embodiment of the present invention is not particularly limited as long as it contains two or more glycidyl groups. For example, there are phenolic glycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, resorcinol, phenol novolac, cresol novolac, and the like, and alcohols such as butanediol, polyethylene glycol, and polypropylene glycol. An active hydrogen bonded to a nitrogen atom such as a glycidyl ether such as glycidyl ether, phthalic acid, isophthalic acid or tetrahydrophthalic acid, or a nitrogen atom such as aniline or trimeric isocyanate is substituted with a glycidyl group. Glycidyl type (also including methyl glycidol type) epoxy resin, vinyl cyclohexene diepoxide obtained by epoxidation of intramolecular olefin bonds, 3,4-epoxycyclohexylmethyl-3 , 4-epoxycyclohexane carboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, etc. An alicyclic epoxy resin, a glycidyl ether of a p-xylene modified phenol resin, a meta-xylene, a glycidyl ether of a p-xylene-modified phenol resin, a glycidyl ether of a terpene-modified phenol resin, and a dicyclopentadiene denaturation Glycidyl ether of phenol resin, glycidyl ether of cyclopentadiene-modified phenol resin, glycidyl ether of polycyclic aromatic ring-modified phenol resin, shrinkage of phenol resin containing naphthalene ring Ether or biphenyl type epoxy resin may be used singly or in combination of two or more.

單環氧化合物可適當與上述1分子中至少具有2個環氧基的環氧化合物倂用，此單環氧化合物例如有、苯乙烯氧化物、環己烯氧化物、丙烯氧化物、甲基縮水甘油醚、乙基縮水甘油醚、苯基縮水甘油醚、烯丙基縮水甘油醚、辛烯氧化物、十二烯氧化物等。使用的環氧樹脂不限於1種類，可倂用2種或2種以上。The monoepoxy compound may suitably be used in combination with an epoxy compound having at least two epoxy groups in the above one molecule, and the monoepoxy compound is, for example, a styrene oxide, a cyclohexene oxide, a propylene oxide, or a methyl group. Glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octene oxide, dodecene oxide, and the like. The epoxy resin to be used is not limited to one type, and two or more types may be used.

本發明之實施態樣所用的環氧樹脂硬化劑，只要是使環氧樹脂硬化者時，即無特別限定，例如有酚系化合物、羧酸系化合物、酸酐系化合物、胺系化合物、苯並噁嗪系樹脂、胺醯亞胺系樹脂、氰酸酯系化合物等。此等硬化劑中，特佳為酚系化合物。The epoxy resin hardener used in the embodiment of the present invention is not particularly limited as long as it cures the epoxy resin, and examples thereof include a phenol compound, a carboxylic acid compound, an acid anhydride compound, an amine compound, and benzo An oxazine-based resin, an amine quinone-based resin, a cyanate-based compound, or the like. Among these hardeners, a phenolic compound is particularly preferred.

酚系化合物較佳為具有2個以上之酚基者。例如有雙酚A、雙酚F、雙酚S、間苯二酚、苯酚酚醛樹脂、甲酚酚醛樹脂、對二甲苯變性酚樹脂、間二甲苯‧對二甲苯變性酚樹脂、萜烯變性酚樹脂、二環戊二烯變性酚樹脂、環戊二烯變性酚樹脂、多環芳香環變性酚樹脂、含有萘環之酚樹脂、聯苯型環氧樹脂、含有三嗪結構的酚醛樹脂等，可單獨使用或混合兩種類以上使用。The phenolic compound is preferably one having two or more phenol groups. For example, there are bisphenol A, bisphenol F, bisphenol S, resorcinol, phenol novolac resin, cresol novolac resin, p-xylene modified phenol resin, meta-xylene ‧ p-xylene modified phenol resin, terpene modified phenol Resin, dicyclopentadiene-modified phenol resin, cyclopentadiene-modified phenol resin, polycyclic aromatic ring-modified phenol resin, phenol resin containing naphthalene ring, biphenyl type epoxy resin, phenol resin containing triazine structure, etc. It can be used alone or in combination of two or more types.

羧酸系化合物較佳為具有2個以上之羧基者。例如有對苯二甲酸、間苯二甲酸、六氫苯二甲酸、四氫苯二甲酸、苯四甲酸、偏苯三酸、甲基納迪克酸、十二烷基琥珀酸、六氯雙環庚烯二羧酸、馬來酸、己二酸等之有機酸等，可單獨或混合兩種以上使用。The carboxylic acid compound preferably has two or more carboxyl groups. For example, terephthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, pyromellitic acid, trimellitic acid, methyl nadic acid, dodecyl succinic acid, hexachlorobicycloheptane An organic acid such as an enedicarboxylic acid, maleic acid or adipic acid may be used singly or in combination of two or more.

酸酐系化合物較佳為具有1個以上之酸酐基者。例如有苯二甲酸酐、六氫苯二甲酸酐、四氫苯二甲酸酐、苯四甲酸酐、偏苯三酸酐、甲基納迪克酸酐、十二烷基琥珀酸酐、六氯雙環庚烯二羧酸酐、馬來酸酐等，可單獨或混合兩種以上使用。The acid anhydride compound is preferably one having one or more acid anhydride groups. For example, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, hexachlorobicycloheptene dicarboxylic anhydride, Maleic anhydride or the like may be used alone or in combination of two or more.

胺系化合物可作為與環氧樹脂之加成反應、或環氧樹脂本身產生陰離子聚合的硬化劑使用。例如有苄基二甲胺、2-(二甲基胺基甲基)酚、2,4,6-(二甲基胺基甲基)酚等之三級胺類或、2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-苯基咪唑、1-苄基-2-甲基咪唑、1-氰乙基-2-甲基咪唑等之咪唑類、及同時具有咪唑部位與矽烷醇部位的咪唑矽烷化合物的IM-1000(日鑛金屬(股))或IS-1000(日鑛金屬(股))、及4,4’-二胺基二苯醚、3,3’-二胺基二苯醚、3,4’-二胺基二苯醚、4,4’-二胺基二苯甲酮、3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、4,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸、3,4’-二胺基二苯基碸、4,4’-二胺基二苯基甲烷、3,3’-胺基二苯基甲烷、3,4’-二胺基二苯基甲烷等的芳香族胺系化合物或、m-二甲苯二胺、二乙撐三胺、四乙撐五胺等的脂肪族胺系化合物、三聚氰胺樹脂、2-乙烯基-4,6-二胺基-s-三嗪等之三嗪化合物、脒基脲等。The amine compound can be used as a curing agent for an addition reaction with an epoxy resin or an anionic polymerization of an epoxy resin itself. For example, there are tertiary amines such as benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-(dimethylaminomethyl)phenol, or 2-methylimidazole. , 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, etc. IM-1000 (Nippon Mining Metals) or IS-1000 (Nippon Mining Metals) and 4,4'-diamino groups of imidazoles and imidazolium compounds having both an imidazole moiety and a stanol moiety Diphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diamino group Benzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 3,4'-diamine Aromatic amine compounds such as diphenyl hydrazine, 4,4'-diaminodiphenylmethane, 3,3'-aminodiphenylmethane, 3,4'-diaminodiphenylmethane Or an aliphatic amine compound such as m-xylylenediamine, diethylenetriamine or tetraethylenepentamine, a melamine resin, or a 2-vinyl-4,6-diamino-s-triazine or the like. Triazine compounds, guanyl urea, and the like.

苯並噁嗪系化合物較佳為具有2個以上之苯並噁嗪部位者，例如有B-a型苯並噁嗪、B-b型苯並噁嗪(四國化成工業(股)製)等。The benzoxazine-based compound is preferably one having two or more benzoxazine sites, and examples thereof include a B-a type benzoxazine and a B-b type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd.).

胺醯亞胺系化合物係使馬來醯亞胺化合物與胺化合物反應所得者，特佳為具有2個以上之二級胺基者，例如有techmite E2020((股)printech製)等。The amine quinone imine compound is obtained by reacting a maleimide compound with an amine compound, and particularly preferably a secondary amine group having two or more, for example, techmite E2020 (manufactured by Printech).

氰酸酯系化合物較佳為具有2個以上之氰酸酯基者，例如有lonza Japan(股)製之Primaset BADCY、Primaset BA230S、Primaset LECY等。The cyanate ester-based compound preferably has two or more cyanate groups, and examples thereof include Primaset BADCY, Primaset BA230S, Primaset LECY, and the like manufactured by lonza Japan Co., Ltd.

本發明之實施態樣使用的環氧樹脂硬化促進劑，無特別限定。例如有三苯基膦、三苯基鏻三苯基硼酸酯、四苯基鏻四苯基硼酸酯等之磷系化合物或苄基二甲基胺、2-(二甲基胺基甲基)酚、2,4,6-(二甲基胺基甲基)酚等之三級胺類、2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-苯基咪唑、1-苄基-2-甲基咪唑、1-氰乙基-2-甲基咪唑等之咪唑類、脒基脲等。The epoxy resin hardening accelerator used in the embodiment of the present invention is not particularly limited. For example, a phosphorus compound such as triphenylphosphine, triphenylsulfonium triphenyl borate or tetraphenylphosphonium tetraphenyl borate or benzyldimethylamine or 2-(dimethylaminomethylmethyl) a tertiary amine such as phenol or 2,4,6-(dimethylaminomethyl)phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole An imidazole such as 2-phenylimidazole, 1-benzyl-2-methylimidazole or 1-cyanoethyl-2-methylimidazole, or guanylurea.

樹脂組成物中之熱硬化性樹脂的調配量係因其具體的種類，較佳的調配量也不同，一般而言，相對於(A)聚醯亞胺樹脂100質量份時，(B)熱硬化性樹脂為1~200質量份，更佳為5~100質量份。熱硬化性樹脂之調配量太少時，硬化不足，有時耐藥品性、耐熱性等較差，太多時，有時柔軟性不足。此外，相對於環氧樹脂時，環氧樹脂硬化劑與骨架中具有HFA基之含有矽氧烷之聚醯亞胺樹脂之總和的化學當量比無特別限定，較佳為設定為0.7~1.3的範圍，更佳為0.8~1.2。設定在此範圍，可將官能基各自未反應分壓低，更能提高耐藥品性及電特性等。不含有HFA基及矽氧烷之聚醯亞胺樹脂與熱硬化性樹脂中即使以另外方式添加矽氧烷樹脂，相溶性有不佳的傾向，使用含有HFA基及矽氧烷結構的聚醯亞胺樹脂時，與熱硬化性樹脂之相溶性有變得更好的傾向。The blending amount of the thermosetting resin in the resin composition is preferably a specific amount depending on the specific type thereof. In general, (B) heat is relative to 100 parts by mass of the (A) polyimine resin. The curable resin is 1 to 200 parts by mass, more preferably 5 to 100 parts by mass. When the amount of the thermosetting resin is too small, the curing is insufficient, and the chemical resistance and heat resistance may be inferior. When the amount is too large, the flexibility may be insufficient. Further, in the case of the epoxy resin, the stoichiometric ratio of the epoxy resin hardener to the sum of the hafnoid-containing polyfluorene-containing resin having an HFA group in the skeleton is not particularly limited, and is preferably set to 0.7 to 1.3. The range is preferably 0.8 to 1.2. When it is set in this range, the unreacted partial pressure of the functional groups can be lowered, and the chemical resistance and electrical properties can be further improved. In the polyiminoimine resin and the thermosetting resin which do not contain an HFA group and a siloxane, even if a sulfoxane resin is added separately, the compatibility may be inferior, and the polyfluorene which has an HFA group and a oxoxane structure is used. In the case of an imide resin, compatibility with a thermosetting resin tends to be better.

本發明之樹脂組成物中較佳為添加(C)無機填充劑。藉由添加無機填充劑，可發揮調整硬化前的黏度特性及調整硬化後之彈性率，提高強度、降低熱膨張率等的效果。無機填充材例如有氧化矽、氧化鋁、雲母、雲母(mica)、矽酸鹽、硫酸鋇、氫氧化鎂、氧化鈦等，較佳為氧化矽、氧化鋁，特佳為氧化矽。從絕緣可靠性的觀點來看，無機填充劑的平均粒徑較佳為3μm以下，平均粒徑更佳為1.5μm以下，平均粒徑更佳為1μm以下。平均粒徑可藉由用雷射繞射/散射式粒度分佈測量裝置LA-500((股)堀場製作所製)來測定。樹脂組成物中之無機充填劑的含量係當樹脂組成物之不揮發成分為100重量%時，較佳為5~60重量%，更佳為5~30重量%。無機充填劑之含量未達5重量%時，無法充分發揮調整黏度、調整彈性率、提高強度、降低熱膨張率等效果的傾向，無機充填劑之含量超過60重量%時，影響樹脂組成物之硬化物之柔軟性，有變脆的傾向。It is preferred to add (C) an inorganic filler to the resin composition of the present invention. By adding an inorganic filler, it is possible to exhibit an effect of adjusting the viscosity characteristics before curing and adjusting the elastic modulus after curing, and improving the strength and the thermal expansion rate. The inorganic filler is, for example, cerium oxide, aluminum oxide, mica, mica, cerate, barium sulfate, magnesium hydroxide, titanium oxide or the like, preferably cerium oxide or aluminum oxide, and particularly preferably cerium oxide. The inorganic filler preferably has an average particle diameter of 3 μm or less, an average particle diameter of 1.5 μm or less, and an average particle diameter of preferably 1 μm or less from the viewpoint of insulation reliability. The average particle diameter can be measured by a laser diffraction/scattering particle size distribution measuring device LA-500 (manufactured by Horiba, Ltd.). The content of the inorganic filler in the resin composition is preferably from 5 to 60% by weight, more preferably from 5 to 30% by weight, based on 100% by weight of the nonvolatile component of the resin composition. When the content of the inorganic filler is less than 5% by weight, the effect of adjusting the viscosity, adjusting the modulus of elasticity, improving the strength, and lowering the thermal expansion rate tends not to be sufficiently exhibited. When the content of the inorganic filler exceeds 60% by weight, the resin composition is affected. The softness of the hardened material tends to become brittle.

本發明之樹脂組成物中，必要時可添加有機填充劑。有機填充劑例如有丙烯酸橡膠粒子、聚矽氧粒子等。有機填充劑較佳為平均粒徑為3μm以下者，更佳為平均粒徑為1.5μm以下者，更佳為平均粒徑為1μm以下者。In the resin composition of the present invention, an organic filler may be added as necessary. Examples of the organic filler include acrylic rubber particles, polyoxyn oxide particles, and the like. The organic filler preferably has an average particle diameter of 3 μm or less, more preferably an average particle diameter of 1.5 μm or less, and more preferably an average particle diameter of 1 μm or less.

本發明之樹脂組成物中，在可發揮、本發明效果的範圍內，可添加各種樹脂添加劑或成分(A)及(B)以外的樹脂成分等。樹脂添加劑例如有Orben(白石工業(股)製)、Bentone(Rheox公司製)等之增黏劑、聚矽氧系、氟系或丙烯酸系的消泡劑、平坦劑、咪唑系、噻唑系、***系等密著賦予劑、矽烷偶合劑等的表面處理劑、酞花青藍、酞花青綠、碘綠、二重氮黃、碳黑等的著色劑、含磷化合物、含溴化合物、氫氧化鋁、氫氧化鎂等難燃劑、磷系抗氧化劑、酚系抗氧化劑等的抗氧化劑。In the resin composition of the present invention, various resin additives or resin components other than the components (A) and (B) may be added within the range in which the effects of the present invention can be exhibited. Examples of the resin additive include a tackifier such as Orben (manufactured by Shiraishi Kogyo Co., Ltd.) and Bentone (manufactured by Rheox Co., Ltd.), a polyfluorene-based system, a fluorine-based or acrylic-based antifoaming agent, a flattening agent, an imidazole-based compound, and a thiazole system. a surface treatment agent such as a triazole-based adhesion imparting agent or a decane coupling agent, a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black, a phosphorus-containing compound, a bromine-containing compound, or the like. An antioxidant such as a flame retardant such as aluminum hydroxide or magnesium hydroxide, a phosphorus-based antioxidant, or a phenol-based antioxidant.

本發明之樹脂組成物可用於阻焊劑油墨、黏著薄膜、附金屬箔的黏著薄膜、保護層薄膜、預浸體、附金屬箔的預浸體。The resin composition of the present invention can be used for a solder resist ink, an adhesive film, a metal foil-attached adhesive film, a protective layer film, a prepreg, and a metal foil-containing prepreg.

(阻焊劑油墨)(solder resist ink)

將本發明之樹脂組成物溶解或分散於各種有機溶劑中形成膏狀，可製作形成印刷電路基板之絕緣保護膜用所需要的阻焊劑油墨。此處所用的有機溶劑無特別限定，較佳為使用沸點為150℃以上的溶劑，更佳為使用沸點為180℃以上的溶劑。使用沸點低於150℃的溶劑時，在油墨塗佈作業時，在網板上，阻焊劑油墨乾燥，可能產生網板網目阻塞。沸點為150℃以上的溶劑例如有N,N’-二甲基甲醯胺、N,N’-二乙基甲醯胺、N,N’-二甲基乙醯胺、N-甲基-2-吡咯烷酮、四甲基脲等之含氮化合物系溶媒、二甲基亞碸等之含硫化合物系溶媒、γ-丁內酯之環狀酯化合物系溶媒、環己酮、甲基環己酮、異爾氟酮等之酮系溶媒、二甘醇二甲醚、三甘醇二甲醚等之醚系溶媒、卡必醇乙酸酯、丙二醇單***乙酸酯等酯系溶媒等之極性溶媒。此等溶媒可混組合兩種以上使用。必要時，可適當混合芳香族烴等之非極性溶媒使用，例如有沸點為160℃以上的石油腦等。The resin composition of the present invention is dissolved or dispersed in various organic solvents to form a paste, and a solder resist ink required for forming an insulating protective film for a printed circuit board can be produced. The organic solvent to be used herein is not particularly limited, and a solvent having a boiling point of 150 ° C or higher is preferably used, and a solvent having a boiling point of 180 ° C or higher is more preferably used. When a solvent having a boiling point of less than 150 ° C is used, the solder resist ink is dried on the screen during the ink coating operation, which may cause stencil mesh clogging. The solvent having a boiling point of 150 ° C or higher is, for example, N,N'-dimethylformamide, N,N'-diethylformamide, N,N'-dimethylacetamide, N-methyl- A solvent containing a nitrogen-containing compound such as 2-pyrrolidone or tetramethylurea, a solvent containing a sulfur compound such as dimethyl hydrazine, a solvent of a cyclic ester compound of γ-butyrolactone, a cyclohexanone, and a methylcyclohexane. a ketone-based solvent such as a ketone or an isopropanone, an ether-based solvent such as diglyme or triglyme, an ester-based solvent such as carbitol acetate or propylene glycol monoethyl ether acetate, or the like. Polar solvent. These solvents may be used in combination of two or more kinds. If necessary, a nonpolar solvent such as an aromatic hydrocarbon may be appropriately mixed, and for example, a petroleum brain having a boiling point of 160 ° C or higher may be used.

對於本發明之樹脂組成物任意使用有機溶劑欲形成膏狀時，將含有(A)含有矽氧烷結構之聚醯亞胺樹脂及(B)熱硬化性樹脂、溶劑、硬化劑、硬化促進劑、填充材、添加材等的調配成分，使用行星式混合機、3輥、珠磨機等，進行混練、溶解或分散來調製。混合固形樹脂時，預先製作將固形樹脂溶解於有機溶劑的溶液，然後進行前述的混練操作。When the organic solvent is used arbitrarily in the form of a paste, the resin composition of the present invention contains (A) a polyfluorene-containing resin having a siloxane structure and (B) a thermosetting resin, a solvent, a hardener, and a hardening accelerator. The blending component of the filler, the additive, and the like is prepared by kneading, dissolving, or dispersing using a planetary mixer, a three-roller, a bead mill, or the like. When the solid resin is mixed, a solution in which the solid resin is dissolved in an organic solvent is prepared in advance, and then the above-described kneading operation is performed.

(黏著薄膜)(adhesive film)

本發明之樹脂組成物可以含有作為電路基板製造用之較佳形態之樹脂組成物層(A層)及支持體薄膜(B層)之黏著薄膜的形態來使用。黏著薄膜係熟悉該項技藝者可依據公知方法來製造。例如與前述阻焊劑油墨製作法同樣，首先調配含有(A)含有矽氧烷結構之聚醯亞胺樹脂及(B)熱硬化性樹脂、溶劑、硬化劑、硬化促進劑、填充材、添加材等的成分。再將此等成分使用行星式混合機、3輥、珠磨機等進行混練、溶解或分散來調製樹脂組成物清漆。接著，在支持體薄膜上塗佈此樹脂清漆，最後藉由加熱或吹熱風等，使有機溶劑乾燥，形成樹脂組成物層，可製造黏著薄膜。支持體薄膜係成為製造黏著薄膜時的支持體，在製造、印刷電路基板時，最終被剝離或除去者。支持體薄膜例如有聚乙烯、聚氯乙烯等之聚烯烴、聚對苯二甲酸乙二酯(以下有時簡稱為「PET」)、聚萘二甲酸乙二酯等之聚酯、聚碳酸酯、脫模紙或銅箔等的金屬箔等。The resin composition of the present invention may be used in the form of an adhesive film of a resin composition layer (layer A) and a support film (layer B) which are preferred forms for manufacturing a circuit board. Adhesive films are familiar to those skilled in the art and can be made according to known methods. For example, in the same manner as the above-described method for producing a solder resist ink, first, a polyfluorene-containing imide resin containing (A) a decane structure and (B) a thermosetting resin, a solvent, a curing agent, a hardening accelerator, a filler, and an additive are prepared. The ingredients of etc. Further, these components are kneaded, dissolved or dispersed using a planetary mixer, a three-roller, a bead mill or the like to prepare a resin composition varnish. Next, the resin varnish is applied onto the support film, and finally, the organic solvent is dried by heating or blowing hot air to form a resin composition layer, whereby an adhesive film can be produced. The support film is a support when the adhesive film is produced, and is finally peeled off or removed when the circuit board is manufactured or printed. The support film is, for example, a polyolefin such as polyethylene or polyvinyl chloride, a polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), a polyester such as polyethylene naphthalate, or a polycarbonate. , metal foil such as release paper or copper foil.

樹脂組成物層(A層)之厚度係因黏著薄膜之用途而異。用於藉由增層法(Build-Up Process)製造多層軟質電路板時，形成電路之導體層的厚度為5~70μm，因此，相當於層間絕緣層之A層的厚度較佳為10~100μm的範圍。此外，支持體薄膜的厚度無特別限定，較佳為10~150μm，更佳為25~50μm。The thickness of the resin composition layer (layer A) varies depending on the use of the adhesive film. When the multilayer flexible circuit board is manufactured by the Build-Up Process, the thickness of the conductor layer forming the circuit is 5 to 70 μm, and therefore, the thickness of the A layer corresponding to the interlayer insulating layer is preferably 10 to 100 μm. The scope. Further, the thickness of the support film is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

清漆調製用的溶劑無特別限定。例如有丙酮、甲基乙基酮、環己酮等之酮系溶劑、乙酸乙酯、乙酸丁酯、2-乙氧基乙醇乙酸酯、丙二醇單甲醚乙酸酯、卡必醇乙酸酯等之乙酸酯類、2-乙氧基乙醇、丁基卡必醇等之卡必醇類、γ-丁內酯等之環狀酯化合物類、甲苯、二甲苯、石油腦等之芳香族烴類、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮等。其中從提高薄膜製作時溶劑之乾燥性的觀點，較佳為沸點為160℃以下者，更佳為沸點為100℃以下者。此外，此等溶劑可組合2種類以上使用。The solvent for varnish preparation is not particularly limited. For example, a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone, ethyl acetate, butyl acetate, 2-ethoxyethanol acetate, propylene glycol monomethyl ether acetate, carbitol acetic acid Acetate such as esters, carbitols such as 2-ethoxyethanol and butyl carbitol, cyclic ester compounds such as γ-butyrolactone, aromatics such as toluene, xylene, and petroleum brain Hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. Among them, from the viewpoint of improving the drying property of the solvent at the time of film production, those having a boiling point of 160 ° C or less are preferable, and those having a boiling point of 100 ° C or less are more preferable. Further, these solvents may be used in combination of two or more types.

乾燥條件無特別限定，為了保持黏著能力，在乾燥時，僅可能不要使熱硬化性樹脂組成物進行硬化是很重要的。此外，黏著薄膜內殘留許多有機溶劑時，會成為在硬化後產生膨脹的原因，因此，樹脂組成物層中之有機溶劑的比例較佳為乾燥至5重量%以下，更佳為3重量%以下。具體的乾燥條件係因熱硬化性樹脂組成物之硬化性或清漆中溶劑的量或沸點而異，例如含有30~60重量%之溶劑的清漆時，較佳為以80~120℃，乾燥3~15分鐘。熟悉該項技藝者可藉由簡單實驗，適當設定較佳的乾燥條件。The drying conditions are not particularly limited, and in order to maintain the adhesion ability, it is important that the thermosetting resin composition is not hardened during drying. Further, when a large amount of the organic solvent remains in the adhesive film, the expansion occurs after curing. Therefore, the ratio of the organic solvent in the resin composition layer is preferably 5% by weight or less, more preferably 3% by weight or less. . The specific drying conditions vary depending on the curability of the thermosetting resin composition or the amount or boiling point of the solvent in the varnish. For example, when the varnish contains 30 to 60% by weight of the solvent, it is preferably dried at 80 to 120 ° C. ~15 minutes. Those skilled in the art can appropriately set the preferred drying conditions by simple experimentation.

(附金屬箔之黏著薄膜)(adhesive film with metal foil)

本發明之樹脂組成物係可以含有作為電路基板製造用之較佳形態之樹脂組成物層(A層)及金屬箔(C層)之黏著薄膜的形態來使用。附金屬箔之黏著薄膜係熟悉該項技藝者可依據公知方法來製造。例如將上述黏著薄膜與金屬箔進行層合即可。或上述說明之黏著薄膜之支持體薄膜的支持體以金屬箔構成，可在形成金屬箔上之樹脂組成物層(A層)上層合其他的支持體。用於本發明之附金屬箔之黏著薄膜所用的金屬箔的種類無特別限定，可使用銅、鎳、鋁、不鏽鋼、氦-銅合金、磷青銅等，但是作為形成印刷電路用的金屬箔，較佳為銅箔。銅箔可使用壓延銅箔或電解銅箔，也可使用附或體之極薄銅箔。The resin composition of the present invention may be used in the form of an adhesive film of a resin composition layer (layer A) and a metal foil (layer C) which are preferred forms for manufacturing a circuit board. Adhesive films with metal foil are familiar to those skilled in the art and can be made according to known methods. For example, the adhesive film and the metal foil may be laminated. The support of the support film of the adhesive film described above is made of a metal foil, and another support can be laminated on the resin composition layer (layer A) on which the metal foil is formed. The type of the metal foil used for the adhesive film with metal foil of the present invention is not particularly limited, and copper, nickel, aluminum, stainless steel, bismuth-copper alloy, phosphor bronze or the like can be used. However, as a metal foil for forming a printed circuit, It is preferably a copper foil. The copper foil may be a rolled copper foil or an electrolytic copper foil, or an extremely thin copper foil attached to the body.

(保護層薄膜)(protective film)

使用本發明之樹脂組成物，以形成含有作為電路基板製造用之較佳形態之樹脂組成物層(A層)及耐熱薄膜(D層)之黏著薄膜的形態，可製作形成印刷電路基板之絕緣保護膜所必要的保護層薄膜。該保護層薄膜係熟悉該項技藝者可依據公知方法，例如調製將本發明之樹脂組成物溶解於有機溶劑的清漆，將此樹脂清漆塗佈於耐熱薄膜上，藉由加熱或吹熱風等，使有機溶劑乾燥，形成樹脂組成物層而製得。耐熱薄膜係成為製造保護層薄膜時之支持體，但是與前述黏著薄膜不同，在製造印刷電路基板時，最終被層合於電路基板之最外層電路上者。耐熱薄膜例如有PET、聚萘二甲酸乙二酯等之聚酯、聚醯亞胺、聚醚醯亞胺、聚醯胺醯亞胺、聚醚醚酮、聚醚碸、液晶聚合物等。By using the resin composition of the present invention to form an adhesive film containing a resin composition layer (layer A) and a heat-resistant film (layer D) which are preferable forms for manufacturing a circuit board, insulation for forming a printed circuit board can be produced. A protective film necessary for the protective film. The protective layer film is familiar to those skilled in the art, for example, by preparing a varnish in which the resin composition of the present invention is dissolved in an organic solvent, and applying the resin varnish to a heat-resistant film by heating or blowing hot air or the like. The organic solvent is dried to form a resin composition layer. The heat-resistant film is a support for producing a protective layer film. However, unlike the above-mentioned adhesive film, when a printed circuit board is manufactured, it is finally laminated on the outermost circuit of the circuit board. Examples of the heat-resistant film include polyesters such as PET and polyethylene naphthalate, polyimine, polyetherimine, polyamidoximine, polyetheretherketone, polyether oxime, liquid crystal polymer, and the like.

樹脂組成物層(A)之厚度係因形成電路之導體層的厚度而異，導體層的厚度為5~70μm時，相當於層間絕緣層之A層的厚度較佳為10~100μm的範圍。此外，耐熱薄膜的厚度無特別限定，較佳為10~100μm，更佳為15~50μm的範圍。清漆調製用的溶劑無特別限定，例如有丙酮、甲基乙基酮、環己酮等之酮系溶劑、乙酸乙酯、乙酸丁酯、2-乙氧基乙醇乙酸酯、丙二醇單甲醚乙酸酯、卡必醇乙酸酯等之乙酸乙酯類、2-乙氧基乙醇、丁基卡必醇等之卡必醇類、γ-丁內酯等之環狀酯化合物類、甲苯、二甲苯、石油腦等之芳香族烴類、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮等。其中從提高薄膜製作時溶劑之乾燥性的觀點，較佳為沸點為160℃以下者，更佳為沸點為100℃以下者。此外，此等溶劑可組合2種類以上使用。The thickness of the resin composition layer (A) varies depending on the thickness of the conductor layer forming the circuit. When the thickness of the conductor layer is 5 to 70 μm, the thickness of the layer A corresponding to the interlayer insulating layer is preferably in the range of 10 to 100 μm. Further, the thickness of the heat-resistant film is not particularly limited, but is preferably in the range of 10 to 100 μm, more preferably 15 to 50 μm. The solvent for preparing the varnish is not particularly limited, and examples thereof include a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone, ethyl acetate, butyl acetate, 2-ethoxyethanol acetate, and propylene glycol monomethyl ether. Ethyl acetates such as acetates and carbitol acetates, carbitols such as 2-ethoxyethanol and butyl carbitol, cyclic ester compounds such as γ-butyrolactone, and toluene An aromatic hydrocarbon such as xylene or petroleum brain, dimethylformamide, dimethylacetamide or N-methylpyrrolidone. Among them, from the viewpoint of improving the drying property of the solvent at the time of film production, those having a boiling point of 160 ° C or less are preferable, and those having a boiling point of 100 ° C or less are more preferable. Further, these solvents may be used in combination of two or more types.

乾燥條件無特別限定，為了保持黏著能力，在乾燥時，僅可能不要使熱硬化性樹脂組成物進行硬化是很重要的。此外，黏著薄膜內殘留許多有機溶劑時，會成為在硬化後產生膨脹的原因，因此，樹脂組成物層中之有機溶劑的比例較佳為乾燥至5重量%以下，更佳為3重量%以下。具體的乾燥條件係因熱硬化性樹脂組成物之硬化性或清漆中溶劑的量或沸點而異，例如含有30~60重量%之溶劑的清漆時，較佳為以80~120℃，乾燥3~15分鐘。熟悉該項技藝者可藉由簡單實驗，適當設定較佳的乾燥條件。The drying conditions are not particularly limited, and in order to maintain the adhesion ability, it is important that the thermosetting resin composition is not hardened during drying. Further, when a large amount of the organic solvent remains in the adhesive film, the expansion occurs after curing. Therefore, the ratio of the organic solvent in the resin composition layer is preferably 5% by weight or less, more preferably 3% by weight or less. . The specific drying conditions vary depending on the curability of the thermosetting resin composition or the amount or boiling point of the solvent in the varnish. For example, when the varnish contains 30 to 60% by weight of the solvent, it is preferably dried at 80 to 120 ° C. ~15 minutes. Those skilled in the art can appropriately set the preferred drying conditions by simple experimentation.

(預浸體)(prepreg)

本發明之預浸體可藉由熱熔法或溶劑法將本發明之熱硬化性樹脂組成物含浸於含有纖維的薄片狀補強基材中，以加熱產生半硬化來製造。換言之，可形成本發明之熱硬化性樹脂組成物含浸於含有纖維之薄片狀補強基材之狀態的預浸體。此外，如後述，將含有熱硬化性樹脂組成物的黏著薄膜由薄片狀補強材之兩面層合來調製。含有纖維之薄片狀補強基材，可使用例如玻璃布或芳香族聚醯胺纖維等，常作為預浸體用纖維使用者。The prepreg of the present invention can be produced by impregnating a thermosetting resin composition of the present invention into a sheet-like reinforcing substrate containing fibers by a hot melt method or a solvent method, and heating and semi-curing. In other words, the prepreg in which the thermosetting resin composition of the present invention is impregnated with the flaky reinforcing substrate containing the fibers can be formed. Further, as will be described later, an adhesive film containing a thermosetting resin composition is prepared by laminating both surfaces of a sheet-like reinforcing material. As the flaky reinforcing base material containing fibers, for example, a glass cloth or an aromatic polyamide fiber can be used, and it is often used as a fiber user for a prepreg.

熱熔法係不必將本發明之熱硬化性樹脂組成物溶解於有機溶劑，而是將樹脂塗佈於剝離性較佳的塗佈紙上，然後將其層合於薄片狀補強基材，或藉由模塗佈機直接塗佈等，製造預浸體的方法。此外，溶劑法係與黏著薄膜同樣，將薄片狀補強基材浸漬於將本發明之熱硬化性樹脂組成物溶解於有機溶劑的樹脂清漆中，使樹脂清漆含浸於薄片狀補強基材中，然後乾燥的方法。In the hot melt method, the thermosetting resin composition of the present invention is not required to be dissolved in an organic solvent, but the resin is applied onto a coated paper having a good release property, and then laminated on a sheet-like reinforcing substrate, or borrowed. A method of producing a prepreg by directly coating or the like by a die coater. Further, in the solvent method, the sheet-like reinforcing substrate is immersed in a resin varnish in which the thermosetting resin composition of the present invention is dissolved in an organic solvent, and the resin varnish is impregnated into the sheet-like reinforcing substrate, and then the solvent method is applied. Dry method.

(附金屬箔之預浸體)(prepreg with metal foil)

附金屬箔之預浸體係於金屬箔上層合含浸有本發明之樹脂組成物的預浸體者。其製造方法無特別限定。例如可將含浸樹脂清漆之薄片狀補強基材與金屬箔貼合後，進行乾燥。此外，將預先製作後的預浸體層合於脫模性薄膜與金屬箔之間，也可製作附金屬箔之預浸體。在此，本發明之附金屬箔之預浸體所用的金屬箔的種類無特別限定，可使用銅、鎳、鋁、不鏽鋼、氦-銅合金、磷青銅等。一般而言，金屬箔較常使用銅箔，而銅箔可使用壓延銅箔、電解銅箔及附載體之極薄銅箔中任一種。A prepreg system with a metal foil is laminated on a metal foil to a prepreg impregnated with the resin composition of the present invention. The manufacturing method is not particularly limited. For example, a sheet-like reinforcing substrate impregnated with a resin varnish may be bonded to a metal foil and then dried. Further, a prepreg prepared in advance is laminated between the release film and the metal foil, and a prepreg with a metal foil can also be produced. Here, the type of the metal foil used for the metal foil-containing prepreg of the present invention is not particularly limited, and copper, nickel, aluminum, stainless steel, bismuth-copper alloy, phosphor bronze or the like can be used. In general, a metal foil is often used as a copper foil, and a copper foil may be any one of a rolled copper foil, an electrolytic copper foil, and an extremely thin copper foil with a carrier.

黏著薄膜、附金屬箔之黏著薄膜、保護層薄膜、預浸體、附金屬箔之預浸體，其樹脂組成物層之支持體未密著的面上可再層合依據支持體的保護薄膜。保護薄膜之厚度無特別限定，較佳為1~40μm，更佳為10~30μm。藉由層合保護薄膜，可防止污垢等附著於樹脂組成物層的表面或防止受傷。此外，此等可捲繞成滾筒狀來儲藏。Adhesive film, adhesive film with metal foil, protective layer film, prepreg, prepreg with metal foil, and the surface of the resin composition layer on which the support is not adhered can be further laminated with a protective film according to the support . The thickness of the protective film is not particularly limited, but is preferably 1 to 40 μm, more preferably 10 to 30 μm. By laminating the protective film, it is possible to prevent dirt or the like from adhering to the surface of the resin composition layer or to prevent injury. Further, these can be wound into a drum shape for storage.

阻焊劑油墨、保護層薄膜、黏著薄膜可用於形成最外層的絕緣保護膜。而黏著薄膜、附金屬箔之黏著薄膜、預浸體、附金屬箔之預浸體可用於製作最外層以外的多層基板。The solder resist ink, the protective layer film, and the adhesive film can be used to form the outermost insulating protective film. Adhesive films, metal foil-attached adhesive films, prepregs, and metal foil-containing prepregs can be used to make multilayer substrates other than the outermost layer.

(製造在最外層形成絕緣保護膜的印刷電路基板)(Manufacturing a printed circuit board in which an insulating protective film is formed on the outermost layer) <藉由阻焊劑油墨製作絕緣保護膜><Insulation Protective Film Made of Solder Resist Ink>

本發明之阻焊劑油墨特別適用於製造軟質電路基板。具體而言，將本發明之阻焊劑油墨塗佈於軟質印刷電路板的所定部分，藉由使塗佈面乾燥，可得到全表面或一部份的表面被本發明之阻焊劑保護的軟質印刷電路板。乾燥條件係因使用的阻焊劑的種類，熟悉該項技藝者可適當輕易設定，但是至少必須為使構成阻焊劑油墨的溶劑充分乾燥，且樹脂組成物充分熱硬化的條件。較佳為以100~200℃，乾燥1~120分鐘。形成之表面保護膜的厚度無特別限定，較佳為5~100μm。藉由本發明之樹脂組成物保護表面之軟質印刷電路板的種類，無特別限定。例如保護TAB用軟質印刷電路板、COF用軟質印刷電路板、多層軟質印刷電路板、導電性膏印刷軟質印刷電路板等的各種軟質印刷電路板時，可使用本發明之樹脂組成物。本發明之樹脂組成物特別適用於作為TAB用軟質印刷電路板、COF用軟質印刷電路板之保護塗膜用。The solder resist ink of the present invention is particularly suitable for the manufacture of flexible circuit substrates. Specifically, by applying the solder resist ink of the present invention to a predetermined portion of the flexible printed circuit board, by drying the coated surface, it is possible to obtain a soft print in which the entire surface or a part of the surface is protected by the solder resist of the present invention. Circuit board. The drying conditions are appropriately set by the person skilled in the art depending on the kind of the solder resist to be used, but at least the conditions for sufficiently drying the solvent constituting the solder resist ink and sufficiently curing the resin composition are required. It is preferably dried at 100 to 200 ° C for 1 to 120 minutes. The thickness of the surface protective film to be formed is not particularly limited, but is preferably 5 to 100 μm. The type of the flexible printed circuit board that protects the surface by the resin composition of the present invention is not particularly limited. For example, when various soft printed circuit boards such as a flexible printed circuit board for TAB, a flexible printed circuit board for COF, a multilayer flexible printed circuit board, and a conductive paste printed flexible printed circuit board are used, the resin composition of the present invention can be used. The resin composition of the present invention is particularly suitably used as a protective coating film for a flexible printed circuit board for TAB or a flexible printed circuit board for COF.

<藉由保護層薄膜之絕緣保護膜之製作><Production of insulating protective film by protective layer film>

本發明之保護層薄膜特別適用於製造軟質電路基板。具體而言，首先，使用以真空層合機之層合、或以金屬板之壓製層合等方法，將本發明之保護層薄膜貼合於軟質印刷電路板之所定部分。接著，使樹脂組成物層(A)硬化，可得到全表面或一部份表面被本發明之保護層薄膜保護的軟質印刷電路板。此時，壓黏條件係因使用之保護層薄膜的種類，熟悉該項技藝者可適當輕易設定。在溫度為100~200℃、壓力為1~40kgf/cm2 、空氣壓20mmHg以下的減壓下進行層合較佳。此外，層合的方式可為分批式或滾筒之連續式。硬化條件係因使用之樹脂組成物層(A)的種類，熟悉該項技藝者可適當輕易設定，但是至少必須為樹脂組成物充分熱硬化的條件，較佳為以100~200℃硬化1~120分鐘。The protective layer film of the present invention is particularly suitable for the manufacture of flexible circuit substrates. Specifically, first, the protective layer film of the present invention is bonded to a predetermined portion of the flexible printed circuit board by lamination using a vacuum laminator or by press lamination of a metal plate. Next, the resin composition layer (A) is cured to obtain a soft printed circuit board having a full surface or a part of the surface protected by the protective layer film of the present invention. At this time, the pressure-bonding conditions are due to the type of the protective film used, and those skilled in the art can appropriately set them. The lamination is preferably carried out under reduced pressure at a temperature of 100 to 200 ° C, a pressure of 1 to 40 kgf/cm 2 , and an air pressure of 20 mmHg or less. In addition, the lamination may be in the form of a batch or a continuous drum. The curing conditions are due to the type of the resin composition layer (A) to be used, and those skilled in the art can appropriately set them, but at least the resin composition must be sufficiently thermally cured, preferably at 100 to 200 ° C for 1~. 120 minutes.

<藉由黏著薄膜之絕緣保護膜之製作><Production of insulating protective film by adhesive film>

本發明之黏著薄膜係與前述阻焊劑油墨或保護層薄膜同樣，適合作為電路基板之最外層的絕緣保護膜使用。具體而言，首先，使用以真空層合機之層合、或以金屬板之壓製層合等方法，將本發明之黏著薄膜貼合於軟質印刷電路板之所定部分。接著，將支持體薄膜(B)剝離後，使樹脂組成物層(A)硬化，可得到全表面或一部份表面被本發明之黏著薄膜保護的軟質印刷電路板。此時之壓黏條件係因使用之保護層薄膜的種類，熟悉該項技藝者可適當輕易設定，在溫度為100~200℃、壓力為1~40kgf/cm2 、空氣壓20mmHg以下的減壓下進行層合較佳。此外，層合的方式可為分批式或滾筒之連續式。硬化條件係因使用之樹脂組成物層(A)的種類，熟悉該項技藝者可適當輕易設定，但是至少必須為樹脂組成物充分熱硬化的條件，較佳為以100~200℃硬化1~120分鐘。The adhesive film of the present invention is suitable for use as an insulating protective film of the outermost layer of a circuit board, similarly to the above-mentioned solder resist ink or protective layer film. Specifically, first, the adhesive film of the present invention is bonded to a predetermined portion of the flexible printed circuit board by lamination using a vacuum laminator or by press lamination of a metal plate. Next, after the support film (B) is peeled off, the resin composition layer (A) is cured to obtain a soft printed circuit board having a full surface or a part of the surface protected by the adhesive film of the present invention. The pressure-bonding condition at this time is due to the type of the protective layer film used, and those skilled in the art can appropriately set the pressure at a temperature of 100 to 200 ° C, a pressure of 1 to 40 kgf/cm 2 , and an air pressure of 20 mmHg or less. It is preferred to carry out the lamination below. In addition, the lamination may be in the form of a batch or a continuous drum. The curing conditions are due to the type of the resin composition layer (A) to be used, and those skilled in the art can appropriately set them, but at least the resin composition must be sufficiently thermally cured, preferably at 100 to 200 ° C for 1~. 120 minutes.

(多層基板之製作)(production of multilayer substrate) <使用黏著薄膜的情形><The case of using an adhesive film>

本發明之黏著薄膜係特別適用於製造多層軟質電路基板。具體而言，首先，使用以真空層合機之層合、或以金屬板之壓製層合等方法，將本發明之黏著薄膜貼合於預先製作之兩面軟質印刷電路基板之單面或兩面。接著，使用真空層合機，將支持體薄膜層(B)剝離，露出後之樹脂組成物層(A)面，與預先製作之另外的兩面軟質電路板進行貼合。接著，使樹脂組成物層(A)硬化，最後藉由形成穿孔，得到層間之導通，可得到多層軟質印刷電路板。此時，壓黏條件係因使用之黏著薄膜的種類，熟悉該項技藝者可適當輕易設定。在溫度為100~200℃、壓力為1~40kgf/cm2 、空氣壓20mmHg以下的減壓下進行層合較佳。此外，層合的方式可為分批式或滾筒之連續式。硬化條件係因使用之樹脂組成物層(A)的種類，熟悉該項技藝者可適當輕易設定，但是至少必須為樹脂組成物充分熱硬化的條件，較佳為以100~200℃硬化1~120分鐘。此外，以重複同樣的操作可得到高度多層化的電路基板。使用的電路基板可同時組合單面電路基板、兩面電路基板，也可製造使用玻璃環氧基板等之剛性(Rigid)電路基板與軟質電路板複合之軟硬(Rigid Flex)電路基板。The adhesive film of the present invention is particularly suitable for the production of a multilayer flexible circuit substrate. Specifically, first, the adhesive film of the present invention is bonded to one side or both sides of a pre-made two-sided flexible printed circuit board by lamination using a vacuum laminator or by press lamination of a metal plate. Next, the support film layer (B) was peeled off using a vacuum laminator, and the exposed resin composition layer (A) surface was bonded to another double-sided flexible circuit board prepared in advance. Next, the resin composition layer (A) is cured, and finally, a perforation is formed to obtain conduction between the layers, whereby a multilayer flexible printed circuit board can be obtained. At this time, the pressure-bonding condition is suitable for the person skilled in the art due to the type of the adhesive film to be used. The lamination is preferably carried out under reduced pressure at a temperature of 100 to 200 ° C, a pressure of 1 to 40 kgf/cm 2 , and an air pressure of 20 mmHg or less. In addition, the lamination may be in the form of a batch or a continuous drum. The curing conditions are due to the type of the resin composition layer (A) to be used, and those skilled in the art can appropriately set them, but at least the resin composition must be sufficiently thermally cured, preferably at 100 to 200 ° C for 1~. 120 minutes. Further, a highly multilayered circuit substrate can be obtained by repeating the same operation. The circuit board to be used can simultaneously combine a single-sided circuit board and a double-sided circuit board, and can also manufacture a Rigid Flex circuit board in which a rigid (Rigid) circuit board such as a glass epoxy board and a flexible circuit board are combined.

<使用附金屬箔之黏著薄膜的情形><The case of using an adhesive film with a metal foil>

本發明之附金屬箔之黏著薄膜係特別適用於製造多層軟質電路基板。具體而言，首先，使用以真空層合機之層合、或以金屬板之壓製層合等方法，將本發明之附銅箔之黏著薄膜貼合於預先製作之兩面軟質印刷電路基板之單面或兩面。接著，使樹脂組成物層(A)硬化，最後，在最外層之銅箔上形成圖型電路，形成穿孔，得到層間之導通，可得到多層軟質印刷電路板。此時，壓黏條件係因使用之黏著薄膜的種類，熟悉該項技藝者可適當輕易設定，在溫度為100~200℃、壓力為1~40kgf/cm2 、空氣壓20mmHg以下的減壓下進行層合較佳。此外，層合的方式可為分批式或滾筒之連續式。硬化條件係因使用之樹脂組成物層(A)的種類，熟悉該項技藝者可適當輕易設定，但是至少必須為樹脂組成物充分熱硬化的條件，較佳為以100~200℃硬化1~120分鐘。此外，以重複同樣的操作可得到高度多層化的電路基板。此外，形成製造多層電路基板所必要之層間絕緣層的手段為可同時使用附金屬箔之黏著薄膜與前述黏著薄膜，而形成在多層基板之最外層所形成之電路之絕緣保護膜的手段為可使用前述阻焊劑油墨、或保護層薄膜或黏著薄膜中任一種。The metal foil-attached adhesive film of the present invention is particularly suitable for the manufacture of a multilayer flexible circuit substrate. Specifically, first, the adhesive film of the copper foil of the present invention is bonded to a preformed two-sided flexible printed circuit board by lamination by a vacuum laminator or by press lamination of a metal plate. Face or two sides. Next, the resin composition layer (A) is cured, and finally, a pattern circuit is formed on the outermost copper foil to form perforations, and conduction between the layers is obtained, whereby a multilayer flexible printed circuit board can be obtained. At this time, the pressure-bonding condition is due to the type of the adhesive film used, and those skilled in the art can appropriately set it at a reduced pressure of 100 to 200 ° C, a pressure of 1 to 40 kgf/cm 2 , and an air pressure of 20 mmHg or less. It is preferred to carry out lamination. In addition, the lamination may be in the form of a batch or a continuous drum. The curing conditions are due to the type of the resin composition layer (A) to be used, and those skilled in the art can appropriately set them, but at least the resin composition must be sufficiently thermally cured, preferably at 100 to 200 ° C for 1~. 120 minutes. Further, a highly multilayered circuit substrate can be obtained by repeating the same operation. Further, a means for forming an interlayer insulating layer necessary for manufacturing a multilayer circuit substrate is a method in which an adhesive film with a metal foil and the above-mentioned adhesive film can be simultaneously used, and a means for forming an insulating protective film of a circuit formed on the outermost layer of the multilayer substrate is Any of the aforementioned solder resist inks, or a protective layer film or an adhesive film is used.

<使用預浸體的情形><The case of using a prepreg>

其次說明使用本發明之預浸體製造本發明之多層印刷電路板的方法。將本發明之預浸體層合於預先製作之兩面軟質電路板之單面或兩面的法，例如有將該預浸體1片或必要時複數片重疊，其上介於脫膜薄膜，配置金屬板，藉由加壓及加熱條件下層合壓製機進行層合的方法。此時，同時進行預浸體對電路基板之層合與硬化，壓力較佳為1~40kgf/cm2 ，溫度較佳為100~200℃，在1~120分鐘的範圍進行層合‧硬化較佳。此外，藉由真空層合機，可將預浸體層合於電路基板，然後進行加熱硬化。如此，在電路基板上，形成作為預浸體之硬化物的絕緣層後，必要時，絕緣層上形成穿孔或通孔(via hole)或穿孔((Through Hole))，使絕緣層表面粗化後，藉由電鍍形成導體層，製造多層印刷電路板。Next, a method of manufacturing the multilayered printed circuit board of the present invention using the prepreg of the present invention will be described. The method of laminating the prepreg of the present invention on one side or both sides of a pre-made two-sided flexible circuit board, for example, one piece of the prepreg or a plurality of sheets if necessary, which is interposed between the release film and the metal A method of laminating a plate by a laminating press under pressure and heating. At this time, the prepreg is laminated and hardened to the circuit substrate at the same time, the pressure is preferably 1 to 40 kgf/cm 2 , the temperature is preferably 100 to 200 ° C, and the lamination and hardening are performed in the range of 1 to 120 minutes. good. Further, the prepreg can be laminated on the circuit substrate by a vacuum laminator and then heat-hardened. In this manner, after forming an insulating layer as a cured product of the prepreg on the circuit board, if necessary, a via hole or a via hole or a through hole is formed on the insulating layer to roughen the surface of the insulating layer. Thereafter, a conductor layer is formed by electroplating to fabricate a multilayer printed circuit board.

<使用附金屬箔之預浸體的情形><Case of using prepreg with metal foil>

使用本發明之附金屬箔之預浸體，製造本發明之多層印刷電路板的方法係與上述使用預浸體之多層軟質電路板的製造方法同樣。藉由使用附金屬箔之預浸體，可將金屬箔直接作為導體層使用。The method of producing the multilayer printed wiring board of the present invention using the metal foil-containing prepreg of the present invention is the same as the above-described method of manufacturing a multilayer flexible circuit board using a prepreg. The metal foil can be directly used as a conductor layer by using a prepreg with a metal foil.

以下，舉實施例及比較例，具體說明本發明，但是本發明不限於下述實施例。Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples.

(聚醯亞胺樹脂之合成)(Synthesis of Polyimine Resin) [合成例1][Synthesis Example 1]

在具備連結回流冷卻器之水分定量受器、氮導入管、攪拌器之500mL的可分離燒瓶中加入4,4’-(六氟異亞丙基)-雙-(苯二甲酸二酐)(以下稱為6FDA)25質量份、γ丁內酯69.9質量份、甲苯7質量份、二胺基矽氧烷X-22-9409(信越化學工業(股)製)55.7質量份(胺當量665)、2,6-雙(1-羥基-1-三氟甲基-2,2,2-三氟乙基)-1,5-萘二胺(以下稱為HFA-NAP)6.7質量，在氮氣流下以45℃攪拌2小時進行反應。接著，使此反應溶液昇溫，在保持約160℃的狀態，氮氣流下，將縮合水與甲苯一同共沸除去。確認水分定量受器蓄積所定量的水及未見水流出時，再昇溫，以200℃攪拌1小時。然後進行冷卻、結束，製作含有具有HFA基之聚醯亞胺樹脂(A1)55重量%的清漆。此時之樹脂中的矽氧烷結構含量為65.2重量%，HFA基當量為3313g/mol。4,4'-(hexafluoroisopropylidene)-bis-(phthalic anhydride) was added to a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a stirrer connected to a reflux condenser ( Hereinafter, it is referred to as "6FDA" 25 parts by mass, γ-butyrolactone 69.9 parts by mass, 7 parts by mass of toluene, and diamine-based decane X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) 55.7 parts by mass (amine equivalent: 665) 2,6-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-1,5-naphthalenediamine (hereinafter referred to as HFA-NAP) 6.7 mass in nitrogen The reaction was carried out by stirring at 45 ° C for 2 hours. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water did not flow out, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour. Then, the mixture was cooled and finished to prepare a varnish containing 55 wt% of the polyimine resin (A1) having an HFA group. The content of the decane structure in the resin at this time was 65.2% by weight, and the HFA group equivalent was 3313 g/mol.

將所得之聚醯亞胺樹脂清漆塗佈於銅板上，由75℃~120℃以12分鐘昇溫，再以180℃加熱90分鐘使其乾燥。對於此塗膜，藉由反射法測定紅外線吸光光譜時，未發現基於顯示有未反應之官能基之聚醯胺酸的吸收，在1780cm-1 及1720cm-1 確認基於醯亞胺基的吸收，在3300~3500cm-1 確認源自HFA基之羥基的吸收。此外，秤取所得之聚醯亞胺樹脂清漆36mg與溶解有溴化鋰0.4重量%的N-甲基吡咯烷酮混合，調製成全體成為5g。使用此調製溶液進行GPC測定，測得Mn=11064、Mw=18769。The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. When the infrared absorption spectrum was measured by the reflection method, the absorption of the polyaminic acid based on the unreacted functional group was not observed, and the absorption based on the quinone imine group was confirmed at 1780 cm -1 and 1720 cm -1 . The absorption of the hydroxyl group derived from the HFA group was confirmed at 3,300 to 3,500 cm -1 . Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was adjusted to 5 g. GPC measurement was carried out using this preparation solution, and Mn=11064 and Mw=18769 were measured.

[合成例2][Synthesis Example 2]

在具備連結回流冷卻器之水分定量受器、氮導入管、攪拌器之500mL的可分離燒瓶中加入6FDA 32質量份、γ丁內酯28.6質量份、ipzole150 28.6質量份、甲苯7質量份、二胺基矽氧烷KF-8010(信越化學工業(股)製)50.1質量份(胺當量430)、HFA-NAP 6.3質量份，在氮氣流下以45℃攪拌2小時進行反應。接著，使此反應溶液昇溫，在保持約160℃的狀態，氮氣流下，將縮合水與甲苯一同共沸除去。確認水分定量受器蓄積所定量的水及未見水流出時，再昇溫，以200℃攪拌1小時。然後進行冷卻、結束，製作含有具有HFA基之聚醯亞胺樹脂(A2)55重量%的清漆。ipzole係出光興產(股)製之芳香族系高沸點溶劑。此時之樹脂中的矽氧烷結構含量為58.4重量%、HFA基當量為3316g/mol。In a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a stirrer connected to a reflux condenser, 32 FDA 32 parts by mass, γ-butyrolactone 28.6 parts by mass, ipzole 150 28.6 parts by mass, toluene 7 parts by mass, and two were added. 50.1 parts by mass (amine equivalent: 430) and HFA-NAP (6.3 parts by mass) of an amine-based oxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.) were stirred at 45 ° C for 2 hours under a nitrogen stream to carry out a reaction. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water did not flow out, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour. Then, the mixture was cooled and finished to prepare a varnish containing 55 wt% of the polyimine resin (A2) having an HFA group. Ipzole is an aromatic high-boiling solvent manufactured by Idemitsu Kosan Co., Ltd. The content of the decane structure in the resin at this time was 58.4% by weight, and the HFA group equivalent was 3316 g/mol.

將所得之聚醯亞胺樹脂清漆塗佈於銅板上，由75℃~120℃以12分鐘昇溫，再以180℃加熱90分鐘使其乾燥。對於此塗膜，藉由反射法測定紅外線吸光光譜時，未發現基於顯示有未反應之官能基之聚醯胺酸的吸收，在1780cm-1 及1720cm-1 確認基於醯亞胺基的吸收，在3300~3500cm-1 確認源自HFA基之羥基的吸收。此外，秤取所得之聚醯亞胺樹脂清漆36mg與溶解有溴化鋰0.4重量%的N-甲基吡咯烷酮混合，調製成全體成為5g。使用此調製溶液進行GPC測定，測得Mn=23086、Mw=35970。The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. When the infrared absorption spectrum was measured by the reflection method, the absorption of the polyaminic acid based on the unreacted functional group was not observed, and the absorption based on the quinone imine group was confirmed at 1780 cm -1 and 1720 cm -1 . The absorption of the hydroxyl group derived from the HFA group was confirmed at 3,300 to 3,500 cm -1 . Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was adjusted to 5 g. GPC measurement was carried out using this preparation solution, and Mn = 23086 and Mw = 35970 were measured.

[合成例3][Synthesis Example 3]

在具備連結回流冷卻器之水分定量受器、氮導入管、攪拌器之500mL的可分離燒瓶中投入3,3’,4,4’-二苯甲酮四羧酸二酐(以下稱為BTDA)23質量份、γ丁內酯30.9質量份、ipzole150 30.9質量份、甲苯7質量份、二胺基矽氧烷KF-8010(信越化學工業(股)製)49.0質量份(胺當量430)，在氮氣流下以45℃攪拌1小時進行反應，接著添加3,3’-雙(1-羥基-1-三氟甲基-2,2,2-三氟乙基)-4,4’-甲撐二苯胺(以下稱為HFA-MDA)6.1質量份加，45℃攪拌2小時進行反應。接著，使此反應溶液昇溫，在保持約160℃的狀態，氮氣流下，將縮合水與甲苯一同共沸除去。確認水分定量受器蓄積所定量的水及未見水流出時，再昇溫，以200℃攪拌1小時。然後進行冷卻、結束，製作含有具有HFA基之聚醯亞胺樹脂(A3)55重量%的清漆。此時之樹脂中的矽氧烷結構含量為64.9重量%、HFA基當量為3271g/mol。3,3',4,4'-benzophenonetetracarboxylic dianhydride (hereinafter referred to as BTDA) was placed in a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a stirrer connected to a reflux condenser. 23 parts by mass, 30.9 parts by mass of γ-butyrolactone, 30.9 parts by mass of ipzole 150, 7 parts by mass of toluene, and 49.0 parts by mass of diamine sulfoxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.) (amine equivalent 430), The reaction was carried out by stirring at 45 ° C for 1 hour under a nitrogen stream, followed by the addition of 3,3'-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-4,4'- 6.1 parts by mass of diphenylamine (hereinafter referred to as HFA-MDA) was added, and the mixture was stirred at 45 ° C for 2 hours to carry out a reaction. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water did not flow out, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour. Then, the mixture was cooled and finished, and a varnish containing 55 wt% of the polyimine resin (A3) having an HFA group was prepared. The content of the oxime structure in the resin at this time was 64.9 wt%, and the HFA group equivalent was 3271 g/mol.

將所得之聚醯亞胺樹脂清漆塗佈於銅板上，由75℃~120℃以12分鐘昇溫，再以180℃加熱90分鐘使其乾燥。對於此塗膜，藉由反射法測定紅外線吸光光譜時，未發現基於顯示有未反應之官能基之聚醯胺酸的吸收，在1780cm-1 及1720cm-1 確認基於醯亞胺基的吸收，在3300~3500cm-1 確認源自HFA基之羥基的吸收。此外，秤取所得之聚醯亞胺樹脂清漆36mg與溶解有溴化鋰0.4重量%的N-甲基吡咯烷酮混合，調製成全體成為5g。使用此調製溶液進行GPC測定，測得Mn=18914、Mw=38256。The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. When the infrared absorption spectrum was measured by the reflection method, the absorption of the polyaminic acid based on the unreacted functional group was not observed, and the absorption based on the quinone imine group was confirmed at 1780 cm -1 and 1720 cm -1 . The absorption of the hydroxyl group derived from the HFA group was confirmed at 3,300 to 3,500 cm -1 . Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was adjusted to 5 g. GPC measurement was carried out using this preparation solution, and it was found that Mn was 18914 and Mw was 38,256.

[合成例4][Synthesis Example 4]

在具備連結回流冷卻器之水分定量受器、氮導入管、攪拌器之500mL的可分離燒瓶中加入BTDA 20質量份、γ丁內酯70.9質量份、甲苯7質量份、二胺基矽氧烷X-22-9409(信越化學工業(股)製)61.5質量份(胺當量665)、HFA-NAP 7.4質量份，在氮氣流下以45℃攪拌2小時進行反應。接著，使此反應溶液昇溫，在保持約160℃的狀態，氮氣流下，將縮合水與甲苯一同共沸除去。確認水分定量受器蓄積所定量的水及未見水流出時，再昇溫，以200℃攪拌1小時。然後進行冷卻、結束，製作含有具有HFA基之聚醯亞胺樹脂(A4)55重量%的清漆。此時之樹脂中的矽氧烷結構含量為70.9重量%、HFA基當量為2881g/mol。20 parts by mass of BTDA, 70.9 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, and diamine sulfoxane were placed in a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a stirrer connected to a reflux condenser. X.sub.2-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) 61.5 parts by mass (amine equivalent 665) and HFA-NAP 7.4 parts by mass, and the mixture was stirred at 45 ° C for 2 hours under a nitrogen stream to carry out a reaction. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water did not flow out, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour. Then, the mixture was cooled and finished, and a varnish containing 55 wt% of the polyimine resin (A4) having an HFA group was prepared. The content of the decane structure in the resin at this time was 70.9 wt%, and the HFA group equivalent was 2881 g/mol.

將所得之聚醯亞胺樹脂清漆塗佈於銅板上，由75℃~120℃以12分鐘昇溫，再以180℃加熱90分鐘使其乾燥。對於此塗膜，藉由反射法測定紅外線吸光光譜時，未發現基於顯示有未反應之官能基之聚醯胺酸的吸收，在1780cm-1 及1720cm-1 確認基於醯亞胺基的吸收，在3300~3500cm-1 確認源自HFA基之羥基的吸收。此外，秤取所得之聚醯亞胺樹脂清漆36mg與溶解有溴化鋰0.4重量%的N-甲基吡咯烷酮混合，調製成全體成為5g。使用此調製溶液進行GPC測定，測得Mn=13135、Mw=35245。The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. When the infrared absorption spectrum was measured by the reflection method, the absorption of the polyaminic acid based on the unreacted functional group was not observed, and the absorption based on the quinone imine group was confirmed at 1780 cm -1 and 1720 cm -1 . The absorption of the hydroxyl group derived from the HFA group was confirmed at 3,300 to 3,500 cm -1 . Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was adjusted to 5 g. GPC measurement was carried out using this preparation solution, and Mn = 13135 and Mw = 35245 were measured.

[合成例5][Synthesis Example 5]

在具備連結回流冷卻器之水分定量受器、氮導入管、攪拌器之500mL的可分離燒瓶中投入3,3’,4,4’-二苯基碸四羧酸二酐(以下稱為DSDA)19質量份、γ丁內酯22.7質量份、ipzole150 22.7質量份、甲苯7質量份、二胺基矽氧烷KF-8010(信越化學工業(股)製)30.9質量份(胺當量430)，在氮氣流下以45℃攪拌1小時進行反應，接著添加HFA-NAP 7.5質量份，以45℃攪拌2小時進行反應。接著，使此反應溶液昇溫，在保持約160℃的狀態，氮氣流下，將縮合水與甲苯一同共沸除去。確認水分定量受器蓄積所定量的水及未見水流出時，再昇溫，以200℃攪拌1小時。然後進行冷卻、結束，製作含有具有HFA基之聚醯亞胺樹脂(A5)55重量%的清漆。此時之樹脂中的矽氧烷結構含量為55.7重量%、HFA基當量為1810g/mol。3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride (hereinafter referred to as DSDA) was placed in a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a stirrer connected to a reflux condenser. 19 parts by mass, 22.7 parts by mass of γ-butyrolactone, 22.7 parts by mass of ipzole 150, 7 parts by mass of toluene, and 30.9 parts by mass of diamine sulfoxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.) (amine equivalent 430), The reaction was carried out by stirring at 45 ° C for 1 hour under a nitrogen stream, followed by the addition of 7.5 parts by mass of HFA-NAP, and the mixture was stirred at 45 ° C for 2 hours to carry out a reaction. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water did not flow out, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour. Then, the mixture was cooled and finished to prepare a varnish containing 55 wt% of the polyimine resin (A5) having an HFA group. The content of the siloxane structure in the resin at this time was 55.7 wt%, and the HFA group equivalent was 1810 g/mol.

將所得之聚醯亞胺樹脂清漆塗佈於銅板上，由75℃~120℃以12分鐘昇溫，再以180℃加熱90分鐘使其乾燥。對於此塗膜，藉由反射法測定紅外線吸光光譜時，未發現基於顯示有未反應之官能基之聚醯胺酸的吸收，在1780cm-1 及1720cm-1 確認基於醯亞胺基的吸收，在3300~3500cm-1 確認源自HFA基之羥基的吸收。此外，秤取所得之聚醯亞胺樹脂清漆36mg與溶解有溴化鋰0.4重量%的N-甲基吡咯烷酮混合，調製成全體成為5g。使用此調製溶液進行GPC測定，測得Mn=27337、Mw=50713。The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. When the infrared absorption spectrum was measured by the reflection method, the absorption of the polyaminic acid based on the unreacted functional group was not observed, and the absorption based on the quinone imine group was confirmed at 1780 cm -1 and 1720 cm -1 . The absorption of the hydroxyl group derived from the HFA group was confirmed at 3,300 to 3,500 cm -1 . Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was adjusted to 5 g. GPC measurement was carried out using this preparation solution, and Mn = 27337 and Mw = 50713 were measured.

[合成例6][Synthesis Example 6]

在具備連結回流冷卻器之水分定量受器、氮導入管、攪拌器之500mL的可分離燒瓶中加入6FDA 25質量份、γ丁內酯68.1質量份、甲苯7質量份、二胺基矽氧烷X-22-9409(信越化學工業(股)製)58.4質量份(胺當量665)、1,5-二胺基萘(以下稱為NDA)1.8質量份，在氮氣流下以45℃攪拌2小時進行反應。接著，使此反應溶液昇溫，在保持約160℃的狀態，氮氣流下，將縮合水與甲苯一同共沸除去。確認水分定量受器蓄積所定量的水及未見水流出時，再昇溫，以200℃攪拌1小時。然後進行冷卻、結束，製作含有不具有酚基及HFA基之聚醯亞胺樹脂(B1)55重量%的清漆。此時，樹脂中的矽氧烷結構含量為70.2重量%。6 mL of 25 parts by mass, 68.1 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, and diamine-based decane were placed in a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a stirrer connected to a reflux condenser. 58.4 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd.), 58.4 parts by mass (amine equivalent: 665), 1.8 parts by weight of 1,5-diaminonaphthalene (hereinafter referred to as NDA), and stirred at 45 ° C for 2 hours under a nitrogen stream. Carry out the reaction. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water did not flow out, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour. Then, the mixture was cooled and finished, and a varnish containing 55 wt% of the polyamidimide resin (B1) having no phenol group and HFA group was produced. At this time, the content of the decane structure in the resin was 70.2% by weight.

將所得之聚醯亞胺樹脂清漆塗佈於銅板上，由75℃~120℃以12分鐘昇溫，再以180℃加熱90分鐘使其乾燥。對於此塗膜，藉由反射法測定紅外線吸光光譜時，未發現基於顯示有未反應之官能基之聚醯胺酸的吸收，在1780cm-1 及1720cm-1 確認基於醯亞胺基的吸收。此外，秤取所得之聚醯亞胺樹脂清漆36mg與溶解有溴化鋰0.4重量%的N-甲基吡咯烷酮混合，調製成全體成為5g。使用此調製溶液進行GPC測定，測得Mn=15974、Mw=30002。The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. When the infrared absorption spectrum was measured by the reflection method, the absorption of the polyaminic acid based on the unreacted functional group was not observed, and the absorption by the quinone imine group was confirmed at 1780 cm -1 and 1720 cm -1 . Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was adjusted to 5 g. GPC measurement was carried out using this preparation solution, and Mn = 15974 and Mw = 30002 were measured.

[合成例7][Synthesis Example 7]

在具備連結回流冷卻器之水分定量受器、氮導入管、攪拌器之500mL的可分離燒瓶中投入6FDA 36質量份、γ丁內酯19.6質量份、ipzole150 29.3質量份、甲苯7質量份、二胺基矽氧烷KF-8010(信越化學工業(股)製)51.5質量份(胺當量430)，氮氣流下以45℃攪拌1小時進行反應，接著添加NDA 3.2質量份、γ丁內酯16.4質量份及6.7質量份的ipzole150，以45℃攪拌2小時進行反應。接著，使此反應溶液昇溫，在保持約160℃的狀態，氮氣流下，將縮合水與甲苯一同共沸除去。確認水分定量受器蓄積所定量的水及未見水流出時，再昇溫，以200℃攪拌1小時。然後進行冷卻、結束，製作含有不具有酚基及HFA基之聚醯亞胺樹脂(B2)55重量%的清漆。此時，樹脂中的矽氧烷結構含量為58.6重量%。In a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a stirrer connected to a reflux condenser, 36 FDA 36 parts by mass, γ-butyrolactone 19.6 parts by mass, ipzole 150 29.3 parts by mass, toluene 7 parts by mass, and two were charged. 51.5 parts by mass (amine equivalent: 430) of amino methoxy oxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.), and stirred at 45 ° C for 1 hour under a nitrogen stream, followed by addition of 3.2 parts by mass of NDA and 6.4 mass of γ-butyrolactone The reaction was carried out by stirring with 6.7 parts by mass of ipzole 150 at 45 ° C for 2 hours. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water did not flow out, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour. Then, the mixture was cooled and finished, and a varnish containing 55 wt% of a polyamidimide resin (B2) having no phenol group and HFA group was produced. At this time, the content of the decane structure in the resin was 58.6 wt%.

將所得之聚醯亞胺樹脂清漆塗佈於銅板上，由75℃~120℃以12分鐘昇溫，再以180℃加熱90分鐘使其乾燥。對於此塗膜，藉由反射法測定紅外線吸光光譜時，未發現基於顯示有未反應之官能基之聚醯胺酸的吸收，在1780cm-1 及1720cm-1 確認基於醯亞胺基的吸收。此外，秤取所得之聚醯亞胺樹脂清漆36mg與溶解有溴化鋰0.4重量%的N-甲基吡咯烷酮混合，調製成全體成為5g。使用此調製溶液進行GPC測定，測得Mn=33046、Mw=67573。The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. When the infrared absorption spectrum was measured by the reflection method, the absorption of the polyaminic acid based on the unreacted functional group was not observed, and the absorption by the quinone imine group was confirmed at 1780 cm -1 and 1720 cm -1 . Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was adjusted to 5 g. GPC measurement was carried out using this preparation solution, and Mn = 33046 and Mw = 67573 were measured.

[合成例8][Synthesis Example 8]

在具備連結回流冷卻器之水分定量受器、氮導入管、攪拌器之500mL的可分離燒瓶中、投入BTDA 23質量份、γ丁內酯29.5質量份、ipzole150 29.5質量份、甲苯7質量份、二胺基矽氧烷KF-8010(信越化學工業(股)製)49.1質量份(胺當量430)，在氮氣流下以45℃攪拌1小時進行反應，接著添加4,4’-二胺基-3,3’-二甲基二苯基甲烷(以下稱為C-100)2.6質量份，以45℃攪拌2小時進行反應。接著，使此反應溶液昇溫，在保持約160℃的狀態，氮氣流下，將縮合水與甲苯一同共沸除去。確認水分定量受器蓄積所定量的水及未見水流出時，再昇溫，以200℃攪拌1小時。然後進行冷卻、結束，製作含有不具有酚基及HFA基之聚醯亞胺樹脂(B3)50重量%的清漆。此時，樹脂中的矽氧烷結構含量為68.0重量%。In a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a stirrer connected to a reflux condenser, 23 parts by mass of BTDA, 29.5 parts by mass of γ-butyrolactone, 29.5 parts by mass of ipzole 150, and 7 parts by mass of toluene were charged. Diamine methoxy oxane KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.) 49.1 parts by mass (amine equivalent 430), and stirred at 45 ° C for 1 hour under a nitrogen stream to carry out a reaction, followed by the addition of 4,4 '-diamino group- 2.6 parts by mass of 3,3'-dimethyldiphenylmethane (hereinafter referred to as C-100) was stirred at 45 ° C for 2 hours to carry out a reaction. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water did not flow out, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour. Then, the mixture was cooled and finished, and a varnish containing 50% by weight of the polyimine resin (B3) having no phenol group and HFA group was produced. At this time, the content of the decane structure in the resin was 68.0% by weight.

將所得之聚醯亞胺樹脂清漆塗佈於銅板上，由75℃~120℃以12分鐘昇溫，再以180℃加熱90分鐘使其乾燥。對於此塗膜，藉由反射法測定紅外線吸光光譜時，未發現基於顯示有未反應之官能基之聚醯胺酸的吸收，在1780cm-1 及1720cm-1 確認基於醯亞胺基的吸收。此外，秤取所得之聚醯亞胺樹脂清漆36mg與溶解有溴化鋰0.4重量%的N-甲基吡咯烷酮混合，調製成全體成為5g。使用此調製溶液進行GPC測定，測得Mn=38052、Mw=110120。The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. When the infrared absorption spectrum was measured by the reflection method, the absorption of the polyaminic acid based on the unreacted functional group was not observed, and the absorption by the quinone imine group was confirmed at 1780 cm -1 and 1720 cm -1 . Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was adjusted to 5 g. GPC measurement was carried out using this preparation solution, and Mn = 38052 and Mw = 11020 were measured.

[合成例9][Synthesis Example 9]

在具備連結回流冷卻器之水分定量受器、氮導入管、攪拌器之500mL的可分離燒瓶中投入DSDA 19質量份、γ丁內酯55.2質量份、甲苯7質量份、二胺基矽氧烷X-22-9409(信越化學工業(股)製)44.1質量份(胺當量665)，氮氣流下以45℃攪拌1小時進行反應，接著添加1,3-雙(4-胺基-3-羥基苯氧基)苯(以下稱為AHPB)6.3質量份，以45℃攪拌2小時進行反應。接著，使此反應溶液昇溫，在保持約160℃的狀態，氮氣流下，將縮合水與甲苯一同共沸除去。確認水分定量受器蓄積所定量的水及未見水流出時，再昇溫，以200℃攪拌1小時。然後進行冷卻、結束，製作含有不具有酚基及HFA基之聚醯亞胺樹脂(B4)55重量%的清漆。此時，樹脂中的矽氧烷結構含量為65.3重量%，OH當量為1744g/mol。In a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a stirrer connected to a reflux condenser, 19 parts by mass of DSDA, 55.2 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, and diamine-based decane were charged. 4-22 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd.) 44.1 parts by mass (amine equivalent: 665), and stirred at 45 ° C for 1 hour under a nitrogen stream to carry out a reaction, followed by addition of 1,3-bis(4-amino-3-hydroxyl) 6.3 parts by mass of phenoxy)benzene (hereinafter referred to as AHPB) was stirred at 45 ° C for 2 hours to carry out a reaction. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water did not flow out, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour. Then, the mixture was cooled and finished, and a varnish containing 55 wt% of a polyamidimide resin (B4) having no phenol group and HFA group was produced. At this time, the content of the decane structure in the resin was 65.3% by weight, and the OH equivalent was 1,744 g/mol.

將所得之聚醯亞胺樹脂清漆塗佈於銅板上，由75℃~120℃以12分鐘昇溫，再以180℃加熱90分鐘使其乾燥。對於此塗膜，藉由反射法測定紅外線吸光光譜時，未發現基於顯示有未反應之官能基之聚醯胺酸的吸收，在1780cm-1 及1720cm-1 確認基於醯亞胺基的吸收，在3300~3500cm-1 確認源自酚性羥基的吸收。此外，秤取所得之聚醯亞胺樹脂清漆36mg與溶解有溴化鋰0.4重量%的N-甲基吡咯烷酮混合，調製成全體成為5g。使用此調製溶液進行GPC測定，測得Mn=14430、Mw=28630。The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. When the infrared absorption spectrum was measured by the reflection method, the absorption of the polyaminic acid based on the unreacted functional group was not observed, and the absorption based on the quinone imine group was confirmed at 1780 cm -1 and 1720 cm -1 . The absorption from the phenolic hydroxyl group was confirmed at 3,300 to 3,500 cm -1 . Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was adjusted to 5 g. GPC measurement was carried out using this preparation solution, and it was found that Mn = 14430 and Mw = 28,630.

[合成例10][Synthesis Example 10]

在具備連結回流冷卻器之水分定量受器、氮導入管、攪拌器之500mL的可分離燒瓶中投入DSDA 19質量份、γ丁內酯54.5質量份、甲苯7質量份、二胺基矽氧烷X-22-9409(信越化學工業(股)製)44.1質量份(胺當量665)，氮氣流下以45℃攪拌1小時進行反應，接著添加3,3’-二胺基-4,4’-二羥基二苯基碸(以下稱為DABS)5.4質量份，以45℃攪拌2小時進行反應。接著，使此反應溶液昇溫，在保持約160℃的狀態，氮氣流下，將縮合水與甲苯一同共沸除去。確認水分定量受器蓄積所定量的水及未見水流出時，再昇溫，以200℃攪拌1小時。然後進行冷卻、結束，製作含有不具有酚基及HFA基之聚醯亞胺樹脂(B5)55重量%的清漆。此時，樹脂中的矽氧烷結構含量為66.2重量%，OH當量為1722g/mol。In a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a stirrer connected to a reflux condenser, 19 parts by mass of DSDA, 54.5 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, and diamine-based decane were charged. 4-22 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd.) 4-22 parts by mass (amine equivalent: 665), and the mixture was stirred at 45 ° C for 1 hour under a nitrogen stream to carry out a reaction, followed by the addition of 3,3'-diamino-4,4'- 5.4 parts by mass of dihydroxydiphenyl hydrazine (hereinafter referred to as DABS) was stirred at 45 ° C for 2 hours to carry out a reaction. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water did not flow out, the temperature was raised again, and the mixture was stirred at 200 ° C for 1 hour. Then, the mixture was cooled and finished, and a varnish containing 55 wt% of a polyamidimide resin (B5) having no phenol group and HFA group was produced. At this time, the content of the siloxane structure in the resin was 66.2% by weight, and the OH equivalent was 1722 g/mol.

將所得之聚醯亞胺樹脂清漆塗佈於銅板上，由75℃~120℃以12分鐘昇溫，再以180℃加熱90分鐘使其乾燥。對於此塗膜，藉由反射法測定紅外線吸光光譜時，未發現基於顯示有未反應之官能基之聚醯胺酸的吸收，在1780cm-1 及1720cm-1 確認基於醯亞胺基的吸收，在3300~3500cm-1 確認源自酚性羥基的吸收。此外，秤取所得之聚醯亞胺樹脂清漆36mg與溶解有溴化鋰0.4重量%的N-甲基吡咯烷酮混合，調製成全體成為5g。使用此調製溶液進行GPC測定，測得Mn=16631、Mw=30691。The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. When the infrared absorption spectrum was measured by the reflection method, the absorption of the polyaminic acid based on the unreacted functional group was not observed, and the absorption based on the quinone imine group was confirmed at 1780 cm -1 and 1720 cm -1 . The absorption from the phenolic hydroxyl group was confirmed at 3,300 to 3,500 cm -1 . Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was adjusted to 5 g. GPC measurement was carried out using this preparation solution, and it was found that Mn was 66.31 and Mw was 30,691.

[合成例11][Synthesis Example 11]

在具備連結回流冷卻器之水分定量受器、氮導入管、攪拌器之500mL的可分離燒瓶中投入BTDA 20質量份、γ丁內酯76.5質量份、甲苯7質量份、二胺基矽氧烷X-22-9409(信越化學工業(股)製)72.9質量份(胺當量655)，氮氣流下以45℃攪拌1小時進行反應，接著添加HFA-NAP 2.7質量份，以45℃攪拌2小時進行反應。接著，使此反應溶液昇溫，在保持約160℃的狀態，氮氣流下，將縮合水與甲苯一同共沸除去。確認水分定量受器蓄積所定量的水及未見水流出時，再昇溫，以200℃攪拌14小時。然後進行冷卻、結束，製作含有具有HFA基之聚醯亞胺樹脂(A6)55重量%的清漆。此時，樹脂中的矽氧烷結構含量為78.0重量%，HFA基當量為8392g/mol。20 parts by mass of BTDA, 76.5 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, and diamine sulfoxane were placed in a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a stirrer connected to a reflux condenser. 72.9 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.), and stirred at 45 ° C for 1 hour under a nitrogen stream to carry out a reaction, followed by addition of HFA-NAP 2.7 parts by mass, and stirring at 45 ° C for 2 hours. reaction. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulates the amount of water accumulated and the water did not flow out, the temperature was raised again, and the mixture was stirred at 200 ° C for 14 hours. Then, the mixture was cooled and finished, and a varnish containing 55 wt% of the polyimine resin (A6) having an HFA group was prepared. At this time, the content of the decane structure in the resin was 78.0% by weight, and the HFA group equivalent was 8392 g/mol.

將所得之聚醯亞胺樹脂清漆塗佈於銅板上，由75℃~120℃以12分鐘昇溫，再以180℃加熱90分鐘使其乾燥。對於此塗膜，藉由反射法測定紅外線吸光光譜時，未發現基於顯示有未反應之官能基之聚醯胺酸的吸收，在1780cm-1 及1720cm-1 確認基於醯亞胺基的吸收，在3300~3500cm-1 確認源自酚性羥基的吸收。此外，秤取所得之聚醯亞胺樹脂清漆36mg與溶解有溴化鋰0.4重量%的N-甲基吡咯烷酮混合，調製成全體成為5g。使用此調製溶液進行GPC測定，測得Mn=19275、Mw=24410。The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. When the infrared absorption spectrum was measured by the reflection method, the absorption of the polyaminic acid based on the unreacted functional group was not observed, and the absorption based on the quinone imine group was confirmed at 1780 cm -1 and 1720 cm -1 . The absorption from the phenolic hydroxyl group was confirmed at 3,300 to 3,500 cm -1 . Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was adjusted to 5 g. GPC measurement was carried out using this preparation solution, and Mn = 19,275 and Mw = 24,410 were measured.

[合成例12][Synthesis Example 12]

在具備連結回流冷卻器之水分定量受器、氮導入管、攪拌器之500mL的可分離燒瓶中投入BTDA 20質量份、γ丁內酯58.5質量份、甲苯7質量份、二胺基矽氧烷X-22-9409(信越化學工業(股)製)37.3質量份(胺當量655)，氮氣流下以45℃攪拌1小時進行反應，接著添加HFA-NAP 16.4質量份，以45℃攪拌2小時進行反應。接著，使此反應溶液昇溫，在保持約160℃的狀態，氮氣流下，將縮合水與甲苯一同共沸除去。確認水分定量受器蓄積所定量的水及未見水流出時，再昇溫，以200℃攪拌11小時。然後進行冷卻、結束，製作含有具有HFA基之聚醯亞胺樹脂(A7)55重量%的清漆。此時，樹脂中的矽氧烷結構含量為52.2重量%，HFA基當量為1069g/mol。20 parts by mass of BTDA, 58.5 parts by mass of γ-butyrolactone, 7 parts by mass of toluene, and diamine-based decane were placed in a 500 mL separable flask equipped with a moisture metering device, a nitrogen inlet tube, and a stirrer connected to a reflux condenser. 37.3 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd.), 37.3 parts by mass (amine equivalent: 655), and the mixture was stirred at 45 ° C for 1 hour under a nitrogen stream to carry out a reaction, followed by addition of 16.4 parts by mass of HFA-NAP, followed by stirring at 45 ° C for 2 hours. reaction. Next, the reaction solution was heated, and the condensed water was azeotropically removed together with toluene while maintaining a temperature of about 160 ° C under a nitrogen stream. When it was confirmed that the water quantitatively accumulating the amount of water accumulated and the amount of water not flowing out, the temperature was raised again, and the mixture was stirred at 200 ° C for 11 hours. Then, the mixture was cooled and finished to prepare a varnish containing 55 wt% of the polyimine resin (A7) having an HFA group. At this time, the content of the decane structure in the resin was 52.2% by weight, and the HFA group equivalent was 1069 g/mol.

將所得之聚醯亞胺樹脂清漆塗佈於銅板上，由75℃~120℃以12分鐘昇溫，再以180℃加熱90分鐘使其乾燥。對於此塗膜，藉由反射法測定紅外線吸光光譜時，未發現基於顯示有未反應之官能基之聚醯胺酸的吸收，在1780cm-1 及1720cm-1 確認基於醯亞胺基的吸收，在3300~3500cm-1 確認源自酚性羥基的吸收。此外，秤取所得之聚醯亞胺樹脂清漆36mg與溶解有溴化鋰0.4重量%的N-甲基吡咯烷酮混合，調製成全體成為5g。使用此調製溶液進行GPC測定，測得Mn=26629、Mw=37452。The obtained polyimine resin varnish was applied onto a copper plate, heated at 75 ° C to 120 ° C for 12 minutes, and further dried at 180 ° C for 90 minutes. When the infrared absorption spectrum was measured by the reflection method, the absorption of the polyaminic acid based on the unreacted functional group was not observed, and the absorption based on the quinone imine group was confirmed at 1780 cm -1 and 1720 cm -1 . The absorption from the phenolic hydroxyl group was confirmed at 3,300 to 3,500 cm -1 . Further, 36 mg of the obtained polyimide resin varnish was mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the total amount was adjusted to 5 g. GPC measurement was carried out using this preparation solution, and it was found that Mn = 26629 and Mw = 37452.

(樹脂組成物之調製)(modulation of resin composition)

將環氧樹脂、依據上述合成例1~12合成之含有矽氧烷之聚醯亞胺樹脂、必要時之硬化劑、硬化促進劑、無機填充材以表1及表2所示的調配量(以固形分之重量份表示)進行混合，使用離心脫泡混合機(商品名「脫泡練太郎」、(股)thinky製)進行攪拌混合，得到實施例1~8及比較例1~7之各樹脂組成物。此外，環氧樹脂為使用酚醛型環氧樹脂EP157(日本環氧樹脂(股)製)或雙酚A型與雙酚F型環氧樹脂的混合物的ZX1059(東都化成(股)製)。硬化劑為使用二環戊二烯變性酚樹脂DPP6115L(新日本石油(股)製)，硬化促進劑為使用咪唑系P200(日本環氧樹脂(股)製)，無機填充材為使用球狀氧化矽SC4050SX((股)admatechs製)。必要時混合溶劑使用。The amount of the epoxy resin, the polyfluorene-containing imide resin containing the alkoxysilane synthesized according to the above Synthesis Examples 1 to 12, the curing agent if necessary, the hardening accelerator, and the inorganic filler are shown in Tables 1 and 2 ( The mixture was mixed and mixed, and stirred and mixed using a centrifugal defoaming mixer (trade name "Defoaming Rantaro", manufactured by Thinky) to obtain Examples 1 to 8 and Comparative Examples 1 to 7. Each resin composition. Further, the epoxy resin is ZX1059 (manufactured by Tohto Kasei Co., Ltd.) which is a mixture of a phenolic epoxy resin EP157 (made by Nippon Epoxy Resin Co., Ltd.) or a bisphenol A type and a bisphenol F type epoxy resin. The hardener is a dicyclopentadiene-modified phenol resin DPP6115L (manufactured by Nippon Oil Co., Ltd.), the hardening accelerator is made of imidazole-based P200 (made by Nippon Epoxy Co., Ltd.), and the inorganic filler is spheroidized.矽SC4050SX (made by admatechs). Mix solvents if necessary.

(硬化薄膜之製作)(Production of hardened film)

其次，將所得之樹脂組成物塗佈於施予脫膜處理後的PET薄膜上，以75~120℃進行12分鐘加熱後，再以180℃加熱90分鐘，得到40μm厚的硬化薄膜。Next, the obtained resin composition was applied onto a PET film subjected to a release treatment, heated at 75 to 120 ° C for 12 minutes, and then heated at 180 ° C for 90 minutes to obtain a cured film having a thickness of 40 μm.

(耐溶劑性試驗)(solvent resistance test)

將硬化薄膜置於秤上，其表面使用含有丙酮之綿棒，使秤顯示10g的荷重，5此往返摩擦，觀察硬化薄膜的表面狀態。未觀察到硬化薄膜表面之顏色變化時，評價為○，產生顏色脫落時，評價為×。The hardened film was placed on a scale, and the surface of the hardened film was observed by using a cotton rod containing acetone to make the scale display a load of 10 g. When the color change of the surface of the cured film was not observed, it was evaluated as ○, and when color detachment occurred, it was evaluated as ×.

(耐熱性試驗)(heat resistance test)

對於合成例所得之聚醯亞胺樹脂，與上述同樣調製樹脂組成物，塗佈於銅箔光澤面使乾燥時的厚度成為40~100μm的範圍，以75~120℃加熱12分鐘後，接著以180℃加熱90分鐘得到硬化薄膜。將形成硬化薄膜的銅箔浸漬於氯化鐵溶液，蝕刻除去後，以100℃乾燥10分鐘製作銅箔被除去後的硬化薄膜。將銅箔被除去漏的硬化薄膜依據日本工業規格(JIS K7127)使用TENSILON萬能試驗機((股)A&D製)進行抗拉試驗測定熱處理前的彈性率。The polyimine resin obtained in the synthesis example was prepared in the same manner as described above, and applied to the shiny side of the copper foil so that the thickness during drying was 40 to 100 μm, and the mixture was heated at 75 to 120 ° C for 12 minutes, and then The hardened film was obtained by heating at 180 ° C for 90 minutes. The copper foil on which the cured film was formed was immersed in a ferric chloride solution, etched away, and dried at 100 ° C for 10 minutes to prepare a cured film obtained by removing the copper foil. The hardened film in which the copper foil was removed from the leak was subjected to a tensile test in accordance with Japanese Industrial Standards (JIS K7127) using a TENSILON universal testing machine (manufactured by A&D Co., Ltd.) to determine the modulus of elasticity before heat treatment.

另外，將藉由上述方法所得之附銅箔之硬化薄膜分別以、(1)空氣中220℃、30分鐘、(2)空氣中250℃、30分鐘、(3)空氣中270℃、30分鐘進行熱處理。將熱處理後之附銅箔之硬化薄膜浸漬於氯化鐵溶液，蝕刻除去後，以100℃乾燥10分鐘製作銅箔被除去後的硬化薄膜。將銅箔被除去漏的硬化薄膜依據日本工業規格(JIS K7127)使用TENSILON萬能試驗機((股)A&D製)進行抗拉試驗測定以各條件熱處理後之硬化薄膜的彈性率。「熱處理後之彈性率÷熱處理前之彈性率」當作彈性率的變化率。此外，空氣中270℃、30分鐘之熱處理後的彈性率與熱處理前之彈性率之差當作彈性率之變動寬度。In addition, the hardened film of the copper foil obtained by the above method is respectively (1) 220 ° C in air, 30 minutes, (2) 250 ° C in air, 30 minutes, (3) 270 ° C in air, 30 minutes. Heat treatment is performed. The cured film of the copper foil after the heat treatment was immersed in a ferric chloride solution, etched away, and dried at 100 ° C for 10 minutes to prepare a cured film obtained by removing the copper foil. The hardened film in which the copper foil was removed from the leak was subjected to a tensile test in accordance with Japanese Industrial Standards (JIS K7127) using a TENSILON universal testing machine (manufactured by A&D Co., Ltd.) to determine the elastic modulus of the cured film after heat treatment under various conditions. The "elasticity after heat treatment 弹性 the elastic modulus before heat treatment" is taken as the rate of change of the modulus of elasticity. Further, the difference between the elastic modulus after heat treatment at 270 ° C for 30 minutes in the air and the elastic modulus before heat treatment was taken as the variation width of the elastic modulus.

表1及表2中表示該表中所記載之聚醯亞胺樹脂組成物之耐熱性試驗及耐溶劑性試驗的結果。Tables 1 and 2 show the results of the heat resistance test and the solvent resistance test of the polyimide composition of the polyimine resin described in the table.

以下說明表1及表2的結果。調配佈含有HFA基及酚基之含有矽氧烷結構的聚醯亞胺樹脂的組成物，如比較例1~3、6所示，結果耐溶劑性較差。此乃是聚醯亞胺樹脂與環氧樹脂之反應性較低的緣故。此外，調配具有酚基之含有矽氧烷結構的聚醯亞胺樹脂的組成物時，如表1及表2之比較例4、5、7所示，250℃、30分中之熱處理後之彈性率的變化率較大，而且彈性率之變動寬度變大。然而，調配具有HFA基之含有矽氧烷結構之聚醯亞胺樹脂的組成物之實施例1~3、5、6、8係250℃、30分鐘之熱處理後之彈性率的變化率較小，顯示優異的耐熱性，且耐溶劑性也優異。實施例4、7在250℃、30分鐘之熱處理後之彈性率的變化率較大，但是熱處理前之彈性率本身為60Mpa以下之非常小的數值，可知可充分維持柔軟性。實施例2、3、5，8的情形，可知具有HFA基之含有矽氧烷結構之聚醯亞胺樹脂的矽氧烷含量不會太大，特別是彈性率之變化率小，柔軟性維持效果優異。The results of Tables 1 and 2 will be described below. The composition of the polyimine resin containing a HFA group and a phenol group containing a decane structure was blended as shown in Comparative Examples 1 to 3 and 6, and as a result, solvent resistance was inferior. This is because the reactivity of the polyimide resin with the epoxy resin is low. Further, when a composition of a polyoxyimine resin having a phenol group-containing oxime structure was prepared, as shown in Comparative Examples 4, 5 and 7 of Tables 1 and 2, after heat treatment at 250 ° C for 30 minutes The rate of change of the modulus of elasticity is large, and the variation width of the modulus of elasticity becomes large. However, Examples 1 to 3, 5, 6, and 8 of the composition containing the HFA group-containing polyfluorene-containing polyoxyimine resin have a small change rate of the elastic modulus after heat treatment at 250 ° C for 30 minutes. It exhibits excellent heat resistance and is excellent in solvent resistance. In Examples 4 and 7, the rate of change of the modulus of elasticity after heat treatment at 250 ° C for 30 minutes was large, but the modulus of elasticity before heat treatment was itself a very small value of 60 MPa or less, and it was found that the flexibility can be sufficiently maintained. In the case of Examples 2, 3, 5, and 8, it is understood that the content of the decane having a HFA group-containing polyoxyalkylene resin is not too large, and in particular, the rate of change of the modulus of elasticity is small, and the flexibility is maintained. Excellent effect.

[實施例9][Embodiment 9] (黏著薄膜A1之製造)(Manufacture of adhesive film A1)

使用模塗佈機將實施例2之樹脂組成物塗佈於實施脫模處理後之厚度38μm之PET薄膜上，使乾燥後之厚度成為40μm。塗佈後，以75~120℃乾燥12分鐘，製作形成樹脂組成物層的黏著薄膜A1。其次，在樹脂組成物層之表面貼合厚度15μm之聚丙烯薄膜，同時捲繞成滾筒狀。The resin composition of Example 2 was applied onto a PET film having a thickness of 38 μm after the release treatment using a die coater to have a thickness of 40 μm after drying. After coating, it was dried at 75 to 120 ° C for 12 minutes to prepare an adhesive film A1 which forms a resin composition layer. Next, a polypropylene film having a thickness of 15 μm was bonded to the surface of the resin composition layer, and wound into a roll shape.

[實施例10][Embodiment 10] (黏著薄膜A2之製造)(Manufacture of adhesive film A2)

使用實施例5之樹脂組成物，使用與實施例9同樣的方法製作黏著薄膜A2。Using the resin composition of Example 5, an adhesive film A2 was produced in the same manner as in Example 9.

[實施例11][Example 11] (附樹脂之銅箔B1之製造)(Manufacture of copper foil B1 with resin)

使用模塗佈機將實施例2之樹脂組成物塗佈於厚度12μm之銅箔上，使乾燥後之厚度成為40μm。塗佈後，以75~120℃乾燥12分鐘，製作形成樹脂組成物層的附樹脂之銅箔B1。其次，在樹脂組成物層之表面貼合厚度15μm之聚丙烯薄膜，同時捲繞成滾筒狀。The resin composition of Example 2 was applied onto a copper foil having a thickness of 12 μm using a die coater to have a thickness of 40 μm after drying. After coating, it was dried at 75 to 120 ° C for 12 minutes to prepare a resin-attached copper foil B1 which forms a resin composition layer. Next, a polypropylene film having a thickness of 15 μm was bonded to the surface of the resin composition layer, and wound into a roll shape.

[實施例12][Embodiment 12] (附樹脂之銅箔B2之製造)(Manufacture of copper foil B2 with resin)

使用實施例5之樹脂組成物，進行與實施例11同樣的作業製作附樹脂之銅箔B2。Using the resin composition of Example 5, a resin-attached copper foil B2 was produced in the same manner as in Example 11.

[實施例13][Example 13] (保護層薄膜之製造)(Manufacture of protective film)

使用模塗佈機將實施例2之樹脂組成物塗佈於厚度25μm之聚醯亞胺薄膜上，使乾燥後之厚度成為35μm。塗佈後，以75~120℃乾燥12分鐘，製作形成樹脂組成物層，製作保護層薄膜。其次，在樹脂組成物層之表面貼合厚度15μm之聚丙烯薄膜，同時捲繞成滾筒狀。The resin composition of Example 2 was applied onto a polyimide film having a thickness of 25 μm using a die coater to have a thickness of 35 μm after drying. After coating, it was dried at 75 to 120 ° C for 12 minutes to form a resin composition layer, thereby producing a protective layer film. Next, a polypropylene film having a thickness of 15 μm was bonded to the surface of the resin composition layer, and wound into a roll shape.

[實施例14][Embodiment 14] (阻焊劑油墨之製造)(Manufacture of solder resist ink)

調製實施例2之樹脂組成物時，預先將固形樹脂溶解於高沸點溶劑之卡必醇乙酸酯來使用，利用離心脫泡混合機(商品名「脫泡練太郎」、(股)thinky製)進行攪拌混合，製作阻焊劑油墨。When the resin composition of the second embodiment is prepared, the solid resin is dissolved in a high-boiling solvent, and the ketone alcohol acetate is used in advance, and a centrifugal defoaming mixer (trade name "defoaming ritaro" or "thin") is used. ) Stirring and mixing to prepare a solder resist ink.

[實施例15][Example 15] (軟質電路板P1之製造與折彎耐久性之評價)(Evaluation of manufacturing and bending durability of flexible circuit board P1)

首先，將實施例13製作之保護層薄膜之聚丙烯薄膜剝離。其次，使用由銅層(厚度12μm)與聚醯亞胺薄膜(厚度20μm)所構成之2層CCL(copper clad laminate)所得之軟質電路板之電路面與保護層薄膜之樹脂組成物面相對向，藉由真空層合機((股)名機製作所製)以溫度130℃、壓力7kgf/cm2 、氣壓5mmHg以下的條件進行層合。接著，依(1)120℃、30分鐘、(2)180℃、90分鐘的順序加熱硬化，製作單面電路基板P1。使保護層薄膜面為外側，進行折彎成180度的試驗，在保護層薄膜之折彎部未產生白化等，顯示良好的折彎性。First, the polypropylene film of the protective layer film produced in Example 13 was peeled off. Next, the circuit surface of the flexible circuit board obtained by using a copper clad laminate of a copper layer (thickness: 12 μm) and a polyimide film (thickness: 20 μm) is opposed to the resin composition of the protective layer film. The laminate was laminated under the conditions of a temperature of 130 ° C, a pressure of 7 kgf / cm 2 , and a gas pressure of 5 mmHg or less by a vacuum laminator (manufactured by Nihon Seiki Co., Ltd.). Subsequently, the film was heat-hardened in the order of (1) 120 ° C, 30 minutes, (2) 180 ° C, and 90 minutes to prepare a single-sided circuit board P1. When the protective layer film surface was made to the outside, the test was performed by bending to 180 degrees, and whitening or the like was not formed in the bent portion of the protective layer film, and good bending property was exhibited.

[實施例16][Example 16] (軟質電路板P2之製造與折彎耐久性之評價)(Evaluation of manufacturing and bending durability of flexible circuit board P2)

將實施例14所得之阻焊劑油墨使用200mesh版，網板印刷於使用由銅層(厚度12μm)與聚醯亞胺薄膜(厚度20μm)所構成之2層CCL所得之軟質電路板的電路面，以180℃、90分鐘硬化製作單面電路基板P2。製作後之單面電路基板P2之阻焊劑面為外側，進行折彎成180度的試驗，在保護層薄膜之折彎部未產生白化等，顯示良好的折彎性。The solder resist ink obtained in Example 14 was screen-printed on a circuit surface of a flexible circuit board obtained by using a two-layer CCL composed of a copper layer (thickness: 12 μm) and a polyimide film (thickness: 20 μm) using a 200-mesh plate. The single-sided circuit board P2 was produced by hardening at 180 ° C for 90 minutes. The solder resist surface of the single-sided circuit board P2 after the production was outside, and the test was performed by bending to 180 degrees, and whitening or the like was not formed in the bent portion of the protective layer film, and good bending property was exhibited.

[實施例17][Example 17] (多層軟質電路板MP1之製造與剝離強度之測定)(Measurement of manufacturing and peeling strength of multilayer flexible circuit board MP1)

首先，將實施例9製作之黏著薄膜A1之聚丙烯薄膜剝離。然後，使用由銅層(厚度12μm)與聚醯亞胺薄膜(厚度20μm)所構成之2層CCL所得之軟質電路板之電路面與黏著薄膜之樹脂組成物面相對向，藉由真空層合機((股)名機製作所製)以溫度130℃、壓力7kgf/cm2 、氣壓5mmHg以下的條件進行層合。然後，將層合後之黏著薄膜之脫模處理PET薄膜剝離，使樹脂組成物面與厚度18μm之銅箔的M面相對向，再藉由真空層合機((股)名機製作所製)在溫度130℃、壓力7kgf/cm2 、氣壓5mmHg以下的條件進行層合。再以120℃、30分鐘、180℃、90分鐘的順序進行熱處理，製造多層軟質電路板MP1。電路基板MP1上之導體層(相當於銅箔S面)與黏著薄膜之剝離強度係0.94kgf/cm，具有強固的黏著性。剝離強度測定係依據JIS C6481進行評價。First, the polypropylene film of the adhesive film A1 produced in Example 9 was peeled off. Then, the circuit surface of the flexible circuit board obtained by using a two-layer CCL composed of a copper layer (thickness 12 μm) and a polyimide film (thickness: 20 μm) is opposed to the resin composition surface of the adhesive film by vacuum lamination The machine (manufactured by Nihon Seiki Co., Ltd.) was laminated at a temperature of 130 ° C, a pressure of 7 kgf/cm 2 , and a gas pressure of 5 mmHg or less. Then, the release-treated PET film of the adhesive film after lamination was peeled off, and the resin composition surface was opposed to the M surface of the copper foil having a thickness of 18 μm, and was further laminated by a vacuum laminator (manufactured by Nippon Seiki Co., Ltd.). Lamination was carried out under the conditions of a temperature of 130 ° C, a pressure of 7 kgf/cm 2 , and a gas pressure of 5 mmHg or less. Further, heat treatment was performed in the order of 120 ° C, 30 minutes, 180 ° C, and 90 minutes to produce a multilayer flexible wiring board MP1. The peeling strength of the conductor layer (corresponding to the S surface of the copper foil) on the circuit board MP1 and the adhesive film is 0.94 kgf/cm, and has strong adhesiveness. The peel strength measurement was evaluated in accordance with JIS C6481.

[實施例18][Embodiment 18] (多層軟質電路板MP2之製造與剝離強度之測定)(Manufacture of multilayer flexible circuit board MP2 and determination of peel strength)

首先，將實施例10所得之黏著薄膜A2之聚丙烯薄膜剝離。然後，使用由銅層(厚度12μm)與聚醯亞胺薄膜(厚度20μm)所構成之2層CCL所得之軟質電路板之電路面與黏著薄膜之樹脂組成物面相對向，藉由真空層合機((股)名機製作所製)以溫度130℃、壓力7kgf/cm2 、氣壓5mmHg以下的條件進行層合。然後，將層合後之黏著薄膜之脫模處理PET薄膜剝離，使樹脂組成物面與厚度18μm之銅箔的M面相對向，再藉由真空層合機((股)名機製作所製)在溫度130℃、壓力7kgf/cm2 、氣壓5mmHg以下的條件進行層合。再以120℃、30分鐘、180℃、90分鐘的順序進行熱處理，製造多層軟質電路板MP2。電路基板MP2上之導體層(相當於銅箔S面)與黏著薄膜之剝離強度係1.05kgf/cm，具有強固的黏著性。剝離強度測定係依據JIS C6481進行評價。First, the polypropylene film of the adhesive film A2 obtained in Example 10 was peeled off. Then, the circuit surface of the flexible circuit board obtained by using a two-layer CCL composed of a copper layer (thickness 12 μm) and a polyimide film (thickness: 20 μm) is opposed to the resin composition surface of the adhesive film by vacuum lamination The machine (manufactured by Nihon Seiki Co., Ltd.) was laminated at a temperature of 130 ° C, a pressure of 7 kgf/cm 2 , and a gas pressure of 5 mmHg or less. Then, the release-treated PET film of the adhesive film after lamination was peeled off, and the resin composition surface was opposed to the M surface of the copper foil having a thickness of 18 μm, and was further laminated by a vacuum laminator (manufactured by Nippon Seiki Co., Ltd.). Lamination was carried out under the conditions of a temperature of 130 ° C, a pressure of 7 kgf/cm 2 , and a gas pressure of 5 mmHg or less. Further, heat treatment was performed in the order of 120 ° C, 30 minutes, 180 ° C, and 90 minutes to produce a multilayer flexible circuit board MP2. The peeling strength of the conductor layer (corresponding to the S surface of the copper foil) on the circuit board MP2 and the adhesive film is 1.05 kgf/cm, and has strong adhesiveness. The peel strength measurement was evaluated in accordance with JIS C6481.

[實施例19][Embodiment 19] (多層軟質電路板MP3之製造)(Manufacture of multilayer flexible circuit board MP3)

首先，將實施例11所得之附樹脂之銅箔B1的聚丙烯薄膜剝離。然後，使用由銅層(厚度12μm)與聚醯亞胺薄膜(厚度20μm)所構成之2層CCL所得之軟質電路板之電路面與附樹脂之銅箔B1的樹脂組成物面相對向，藉由真空層合機((股)名機製作所製)以溫度130℃、壓力7kgf/cm2 、氣壓5mmHg以下的條件進行層合。然後以120℃、30分鐘、180℃、90分鐘的順序進行熱處理，製造多層軟質電路板MP3。First, the polypropylene film of the resin-attached copper foil B1 obtained in Example 11 was peeled off. Then, a circuit surface of a flexible circuit board obtained by using a two-layer CCL composed of a copper layer (thickness: 12 μm) and a polyimide film (thickness: 20 μm) is opposed to the resin composition surface of the resin-attached copper foil B1. Lamination was carried out under the conditions of a temperature of 130 ° C, a pressure of 7 kgf/cm 2 , and a gas pressure of 5 mmHg or less, by a vacuum laminator (manufactured by Nihon Seiki Co., Ltd.). Then, heat treatment was performed in the order of 120 ° C, 30 minutes, 180 ° C, and 90 minutes to produce a multilayer flexible circuit board MP3.

[實施例20][Example 20] (多層軟質電路板MP4之製造)(Manufacture of multilayer flexible circuit board MP4)

首先，將實施例12所得之附樹脂之銅箔B2的聚丙烯薄膜剝離。然後，使用由銅層(厚度12μm)與聚醯亞胺薄膜(厚度20μm)所構成之2層CCL所得之軟質電路板之電路面與附樹脂之銅箔B2的樹脂組成物面相對向，藉由真空層合機((股)名機製作所製)以溫度130℃、壓力7kgf/cm2 、氣壓5mmHg以下的條件進行層合。然後以120℃、30分鐘、180℃、90分鐘的順序進行熱處理，製造多層軟質電路板MP4。First, the polypropylene film of the resin-attached copper foil B2 obtained in Example 12 was peeled off. Then, the circuit surface of the flexible circuit board obtained by using the two-layer CCL composed of the copper layer (thickness: 12 μm) and the polyimide film (thickness: 20 μm) is opposed to the resin composition surface of the resin-attached copper foil B2. Lamination was carried out under the conditions of a temperature of 130 ° C, a pressure of 7 kgf/cm 2 , and a gas pressure of 5 mmHg or less, by a vacuum laminator (manufactured by Nihon Seiki Co., Ltd.). Then, heat treatment was performed in the order of 120 ° C, 30 minutes, 180 ° C, and 90 minutes to produce a multilayer flexible wiring board MP4.

本申請案係以於日本申請的特願2008-288152為基礎，其內容全部包含於本說明書中。The present application is based on Japanese Patent Application No. 2008-288152, the entire contents of which are incorporated herein.

Claims (21)

一種印刷電路板用樹脂組成物，其特徵係含有(A)具有六氟異丙醇基及矽氧烷結構的聚醯亞胺樹脂及(B)熱硬化性樹脂。 A resin composition for a printed circuit board, comprising: (A) a polyimide resin having a hexafluoroisopropanol group and a decane structure; and (B) a thermosetting resin. 如申請專利範圍第1項之印刷電路板用樹脂組成物，其係更含有(C)無機填充材。 The resin composition for a printed circuit board according to the first aspect of the invention, further comprising (C) an inorganic filler. 如申請專利範圍第1項之印刷電路板用樹脂組成物，其中熱硬化性樹脂為環氧樹脂。 The resin composition for a printed circuit board according to the first aspect of the invention, wherein the thermosetting resin is an epoxy resin. 如申請專利範圍第1~3項中任一項之印刷電路板用樹脂組成物，其中聚醯亞胺樹脂具有下式(1)及(2)表示的重複單位的聚醯亞胺樹脂，該聚醯亞胺樹脂中之式(1)之重複單位之一分子中之重複數M係1以上100以下(1≦M≦100)的整數，式(2)之重複單位之一分子中之重複數N係1以上100以下(1≦N≦100)的整數， (式中，R1係表示4價之有機基，R2係表示具有六氟異丙醇基之2價之二胺殘基，R3係表示2價之矽氧烷二胺殘基)。The resin composition for a printed circuit board according to any one of claims 1 to 3, wherein the polyimine resin has a repeating unit polyimine resin represented by the following formulas (1) and (2), In the polyimine resin, one of the repeating units of the formula (1), the number of repeats in the molecule M is an integer of 1 or more and 100 or less (1≦M≦100), and the repeating unit of the formula (2) repeats in the molecule. The number N is an integer of 1 or more and 100 or less (1≦N≦100), (wherein R1 represents a tetravalent organic group, R2 represents a divalent diamine residue having a hexafluoroisopropanol group, and R3 represents a divalent acroxane diamine residue). 如申請專利範圍第1~3項中任一項之印刷電路板用樹脂組成物，其中(A)具有六氟異丙醇基及矽氧烷結構之聚醯亞胺樹脂之六氟異丙醇基的官能基當量為 1000~10000g/mol。 The resin composition for a printed circuit board according to any one of claims 1 to 3, wherein (A) hexafluoroisopropanol having a polyfluoroimine resin having a hexafluoroisopropanol group and a decane structure The functional group equivalent of the base is 1000~10000g/mol. 如申請專利範圍第1~3項中任一項之印刷電路板用樹脂組成物，其中(A)具有六氟異丙醇基及矽氧烷結構之聚醯亞胺樹脂的矽氧烷含量為50~80重量%。 The resin composition for a printed circuit board according to any one of claims 1 to 3, wherein (A) the polyoxyimide resin having a hexafluoroisopropanol group and a decane structure has a decane content of 50 to 80% by weight. 一種阻焊劑油墨，其特徵係含有申請專利範圍第1~6項中任一項之印刷電路板用樹脂組成物。 A solder resist ink comprising the resin composition for a printed circuit board according to any one of claims 1 to 6. 一種黏著薄膜，其特徵係在支持體上形成申請專利範圍第1~6項中任一項之印刷電路板用樹脂組成物層所成。 An adhesive film formed by forming a resin composition layer for a printed circuit board according to any one of claims 1 to 6 on a support. 一種附金屬箔之黏著薄膜，其特徵係在金屬箔上形成申請專利範圍第1~6項中任一項之印刷電路板用樹脂組成物層所成。 An adhesive film with a metal foil, which is formed by forming a resin composition layer for a printed circuit board according to any one of claims 1 to 6 on a metal foil. 一種預浸體，其特徵係申請專利範圍第1~6項中任一項之印刷電路板用樹脂組成物含浸於薄片狀纖維基材所成。 A prepreg characterized in that the resin composition for a printed circuit board according to any one of claims 1 to 6 is impregnated into a sheet-like fibrous base material. 一種附金屬箔之預浸體，其特徵係金屬箔被層合於申請專利範圍第10項之預浸體所成。 A metal foil prepreg characterized in that the metal foil is laminated to the prepreg of claim 10 of the patent application. 一種保護層薄膜，其特徵係在耐熱薄膜上形成申請專利範圍第1~6項中任一項之印刷電路板用樹脂組成物層所成。 A protective layer film which is formed by forming a resin composition layer for a printed circuit board according to any one of claims 1 to 6 on a heat-resistant film. 一種印刷電路板，其特徵係絕緣層含有申請專利範圍第1~6項中任一項之印刷電路板用樹脂組成物。 A printed circuit board comprising the resin composition for a printed circuit board according to any one of claims 1 to 6. 如申請專利範圍第13項之印刷電路板，其中前述絕緣層含有阻焊劑層、層間絕緣層及保護層。 The printed circuit board of claim 13, wherein the insulating layer comprises a solder resist layer, an interlayer insulating layer, and a protective layer. 一種印刷電路板，其特徵係藉由申請專利範圍第7項之阻焊劑油墨形成阻焊劑層。 A printed circuit board characterized in that a solder resist layer is formed by the solder resist ink of claim 7 of the patent application. 一種印刷電路板，其特徵係藉由申請專利範圍第8項之黏著薄膜形成阻焊劑層。 A printed circuit board characterized in that a solder resist layer is formed by the adhesive film of claim 8 of the patent application. 一種印刷電路板，其特徵係藉由申請專利範圍第8項之黏著薄膜形成層間絕緣層。 A printed circuit board characterized in that an interlayer insulating layer is formed by an adhesive film of claim 8 of the patent application. 一種印刷電路板，其特徵係藉由申請專利範圍第9項之附金屬箔之黏著薄膜形成層間絕緣層及/或導體層。 A printed circuit board characterized in that an interlayer insulating layer and/or a conductor layer is formed by an adhesive film attached to a metal foil of claim 9. 一種印刷電路板，其特徵係藉由申請專利範圍第10項之預浸體形成層間絕緣層。 A printed circuit board characterized by forming an interlayer insulating layer by a prepreg according to claim 10 of the patent application. 一種印刷電路板，其特徵係藉由申請專利範圍第11項之附金屬箔之預浸體形成層間絕緣層及/或導體層。 A printed circuit board characterized by forming an interlayer insulating layer and/or a conductor layer by a metal foil prepreg according to claim 11 of the patent application. 一種印刷電路板，其特徵係藉由申請專利範圍第12項之保護層薄膜形成保護層。 A printed circuit board characterized in that a protective layer is formed by a protective layer film of claim 12 of the patent application.
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