JP2007050576A - Liquid crystal thermoplastic polyester film laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate excellent in low water absorption properties and interlayer adhesion properties and to provide a wiring board excellent in reliability of electric characteristics by using the laminate as a cover lay. <P>SOLUTION: The laminate has an adhesive layer obtained from a thermosetting resin composition containing a compound (A) selected from a polyvalent carboxylic acid (a<SB>1</SB>), a carboxylic anhydride (a<SB>2</SB>), a phenol novolac resin having alkyl substituents (a<SB>3</SB>), and a phenol adduct of an aliphatic compound having a double bond (a<SB>4</SB>) and an epoxy group-containing copolymer (B) obtained by polymerizing ethylene and/or propylene (b<SB>1</SB>) and a monomer expressed by formula (1) (b<SB>2</SB>) (R is a 2-18C hydrocarbon group having a double bond; and X is a single bond or a carbonyl group) and an organic insulating film layer containing a liquid crystal thermoplastic polyester. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a laminate suitable for a flexible wiring board. More specifically, the present invention relates to a laminate suitable as a coverlay that is a protective film of a flexible wiring board.

Conventionally, as a coverlay for protecting circuit boards in the electronics field, a polyimide film having a high heat resistance, a substantially high flow temperature, and a non-thermoplastic polyimide film is used as a base material, and a thermoplastic polyimide is used as an adhesive layer on the surface. A material provided with a thermoplastic resin layer is used. Such a coverlay using polyimide has an advantage of high adhesion to a copper foil which is a conductor pattern of a flexible wiring board (FPC). However, since the polyimide film itself has high water absorption, the yield may decrease in a high-temperature process such as a solder reflow process in the FPC manufacturing process, and a low water-absorbing organic film instead of polyimide has been demanded.

As an alternative to polyimide, there is an example in which a low-water-absorbing thermoplastic liquid crystal polyester film is used as a coverlay. An example of such a coverlay is an example of thermocompression bonding on a circuit board using the thermoplasticity of the liquid crystal polyester itself. However, this cover lay needs to be fusion-pressed at a temperature higher than the melting point of the thermoplastic liquid crystal polyester film used in order to obtain a strong adhesive force, and the circuit board is exposed to high heat. There was a problem that the circuit board itself was thermally deteriorated. As another example of suppressing such thermal deterioration of the circuit board, there is an attempt (Patent Document 1) to use a low molecular weight liquid crystal polyester having a low melting point as a protective film on the circuit board. Since film formation is difficult, it was difficult to use as a coverlay.

JP-A-8-97565

  The objective of this invention is providing the laminated body using the thermoplastic liquid-crystal polyester film which can express practical adhesiveness at low temperature rather than a prior art. Moreover, it is providing the wiring board excellent in the reliability of an electrical property by using the laminated body of this invention as a coverlay.

The present inventors have found that a laminate comprising an adhesive layer obtained from a specific thermosetting resin can achieve the above-mentioned problem in an organic insulating layer made of thermoplastic liquid crystal polyester. The present invention has been completed by finding that it can be used as a coverlay which is a protective film of a circuit board.

That is, this invention provides the laminated body provided with the organic insulating film layer containing the contact bonding layer obtained from the thermosetting resin composition containing following (A) and following (B), and thermoplastic liquid crystal polyester. It is.
(A): Compound (a ₁ ) selected from the following (a ₁ ), (a ₂ ), (a ₃ ), (a ₄ ), and (a ₅ ) having two or more —COOH groups in the molecule Polyhydric carboxylic acid (a ₂ ) containing phenol novolak resin (a ₄ ) double bond having carboxylic anhydride (a ₃ ) alkyl substituent having at least one —CO—O—CO— group in the molecule Phenol adduct of aliphatic compound (a ₅ ) Phenol adduct of alicyclic compound containing double bond (B): Epoxy obtained by polymerizing monomers containing the following (b ₁ ) and (b ₂ ) Group-containing copolymer (b ₁ ): ethylene and / or propylene (b ₂ ): monomer represented by the following formula (1)

(In the formula, R represents a C 2-18 hydrocarbon group having one or more double bonds, and the hydrogen atom of the hydrocarbon group may have a halogen atom, a hydroxyl group or a carboxyl group. X Represents a single bond or a carbonyl group.)

  The laminate obtained in this way is suitable for use in adhesiveness of the adhesive layer itself, coverlay, etc., without problems related to water absorption of the base material itself at the time of producing the laminate mentioned in the prior art. Can do.

As a preferred form of the thermosetting resin composition used in the present invention, (A) is an aliphatic polyvalent carboxylic acid having two or more —COOH groups in the molecule in (a ₁ ). A thermosetting resin composition is mentioned.

As another preferred embodiment of the thermosetting resin composition used in the present invention, (A) includes, in (a ₂ ), one —CO—O—CO— group in the molecule. The thermosetting resin composition which is the aliphatic carboxylic anhydride which has the above is mentioned.

In particular, as the most preferred form of the thermosetting resin composition used in the present invention, (A) includes (a ₃ ) or (a ₄ ). (A ₃ ) or (a ₄ ) has good compatibility with (B), and the adhesive layer obtained from the thermosetting resin containing (a ₃ ) or (a ₄ ) is the laminate of the present invention. In, it is more excellent in adhesion between layers.

The content of the structural unit derived from (b ₂ ) and the content of the structural unit derived from (b ₁ ) with respect to 100 parts by weight of the epoxy group-containing copolymer in the epoxy group-containing copolymer of (B). 1 to 30 parts by weight and 30 to 99 parts by weight, respectively. In such a range of structural units, it is possible to form an adhesive layer that is more excellent in adhesion and mechanical strength.

Moreover, this invention provides the laminated body which manufactures an adhesive film previously by extruding the thermosetting composition containing said (A) and (B), and equips it with it as an adhesive layer. It is.

Moreover, with respect to (A) and (B) of the present invention, an adhesive film is produced in advance using an adhesive obtained by further blending (D) an organic solvent and / or water, and this is provided as an adhesive layer. A laminated body is provided.

Furthermore, the present invention includes, as an adhesive layer, a modified adhesive film obtained by irradiating the adhesive film obtained by the above-described extrusion molding or the adhesive film obtained by using the adhesive with an electron beam. A laminated body is provided. Irradiation with an electron beam is preferable because elution of unreacted monomers remaining in the adhesive film from the adhesive film can be suppressed.

Further, the present invention reacts with a thermoplastic liquid crystal polyester containing a structural unit represented by the following formulas (E ′), (F ′), and (G ′) in the resin chain or a different aromatic hydroxycarboxylic acid. The present invention provides a laminate including an organic insulating film made of the obtained thermoplastic liquid crystal polyester.
(E ′) — O—Ar ¹ —CO—
(F ′) — CO—Ar ² —CO—
(G ′) — X—Ar ³ —Y—
(Wherein Ar ¹ represents phenylene, naphthylene, or biphenylene, Ar ² represents phenylene, naphthylene, biphenylene, or a plurality of aromatic groups condensed, and Ar ³ represents phenylene or a plurality of aromatic groups. And X and Y represent —O— or —NH—.)

Moreover, this invention provides use of the laminated body obtained in any of the above as a coverlay.

The laminate of the present invention can exhibit high adhesion at low temperatures, and when used as an FPC coverlay, has excellent water vapor barrier properties. Therefore, it is used in the industry as a protective film for circuit boards of electrical and electronic equipment. It can be used widely.

Hereinafter, preferred embodiments of the present invention will be described.
The laminate of the present invention is a laminate comprising an adhesive layer obtained from the thermosetting resin composition containing the above (A) and (B), and an organic insulating layer made of a thermoplastic liquid crystal polyester. A) is at least one compound selected from the above (a ₁ ), (a ₂ ), (a ₃ ), (a ₄ ), and (a ₅ ).

A preferable form of (A) includes those selected from the polyvalent carboxylic acids of (a ₁ ). The polyvalent carboxylic acid may be either an aliphatic polyvalent carboxylic acid or an aromatic polyvalent carboxylic acid.
Here, as the aliphatic polyvalent carboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, itaconic acid, maleic acid, citraconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid And cyclopentanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, oxalic acid, citric acid, tartaric acid and the like.
Examples of the aromatic polycarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, and benzophenone tetracarboxylic acid. Among these, an aliphatic polyvalent carboxylic acid and an aromatic polyvalent carboxylic acid having an alkyl group having 2 or more carbon atoms are preferable because of good compatibility with the above (B). preferable.

Further, as another preferred embodiment of (A), include those selected from carboxylic acid anhydride of the (a _2).
Examples of the carboxylic acid anhydride include aromatic polyvalent carboxylic acid anhydrides and ester group-containing acid anhydrides, and any of them may be used. Here, as the aliphatic dicarboxylic acid anhydride, itaconic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, anhydrous Aliphatic carboxylic acid monoanhydrides such as methylhexahydrophthalic acid, endomethylenetetrahydrophthalic anhydride or methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, cyclopentanetetracarboxylic dianhydride, 1,2,3,4 -Aliphatic polycarboxylic dianhydrides such as butanetetracarboxylic dianhydride and maleated methylcyclohexene tetrabasic anhydride.
Examples of aromatic polycarboxylic anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, etc. Is mentioned. Examples of the ester group-containing acid anhydride include ethylene glycol bistrimellitate, glycerin tristrimitate, and the like. Among these, an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid having an alkyl group having 2 or more carbon atoms are preferable because of good compatibility with the (B), and an aliphatic carboxylic acid anhydride is particularly preferable.

As described above, since the compatibility with (B) is good, (A) of the present invention includes (a ₃ ) a phenol novolak having an alkyl substituent or (a ₄ ) an aliphatic containing a double bond. Most preferred is at least one compound selected from phenol adducts of compounds.

  Here, the phenol novolak having an alkyl substituent is a condensate of a phenol in which at least one hydrogen atom bonded to the phenol is substituted with an alkyl group having 2 to 20 carbon atoms and an aldehyde having 1 to 4 carbon atoms. Is preferred.

  Examples of the alkyl group include a linear alkyl group, a branched alkyl group, an alicyclic alkyl group, and the like, specifically, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Linear alkyl groups such as n-octyl group, n-nonyl group, n-decyl group, n-undecanyl group, n-octadecyl group and n-dodecyl group; isopropyl group, t-butyl group, ethylhexyl group, etc. Branched alkyl groups; alicyclic alkyl groups such as cyclopentyl group and cyclohexyl group.

  Among these, an alkyl group having 4 to 18 carbon atoms is preferable.

  Examples of the aldehyde having 1 to 4 carbon atoms include aldehydes such as formaldehyde, acetaldehyde, n-butyraldehyde, glyoxal, glutaraldehyde, glyoxylic acid, and paraformaldehyde. Among these, formaldehyde, acetaldehyde, and paraformaldehyde are preferable. Is preferred.

  As long as the resulting cured product shows compatibility, the phenol novolak having an alkyl substituent of the present invention may be copolymerized with an unsubstituted phenol, but substantially does not contain an unsubstituted phenol as a phenol novolak. It is preferable.

  The phenol novolak having an alkyl substituent of the present invention is particularly preferably one having as a main component a phenol novolak having about 2 to 5 phenols having an alkyl substituent in the resin chain.

  Examples of the phenol novolak having an alkyl substituent include “Hitanol 1501” (registered trademark, manufactured by Hitachi Chemical Co., Ltd.), “Tactrol 101” (registered trademark, manufactured by Taoka Chemical Co., Ltd.), “Tamanol 7508” (registered) Trademarks, manufactured by Arakawa Chemical Industries, Ltd.) are commercially available, and these commercially available products may be used.

  Examples of the phenol adduct of an aliphatic compound containing a double bond include an aliphatic compound containing a double bond such as a homopolymer of a conjugated diene compound such as polybutadiene or a copolymer of an α-olefin and a conjugated diene compound. Phenols such as phenol, cresol, resorcin, or phenol having the above alkyl substituent are reacted. Of these, hydroxybenzene is preferred as the phenol.

  As a phenol adduct of an aliphatic compound containing a double bond, for example, Nisseki special phenol resin “PP” series (registered trademark, manufactured by Nippon Petrochemical Co., Ltd.), Nisseki special phenol resin “DPP” series (registered trademark) , Nippon Petrochemical Co., Ltd.), Nisseki Special Phenolic Resin “DPA” series (registered trademark, manufactured by Nippon Petrochemical Co., Ltd.), etc. are commercially available.

(B) used in the present invention means (b ₁ ) ethylene and / or propylene, and the following general formula (1)

(In the formula, R represents a hydrocarbon group having 2 to 18 carbon atoms having a double bond, and the hydrocarbon group may be substituted with a halogen atom, a hydroxyl group or a carboxyl group. X is a single bond or Represents a carbonyl group.)
An epoxy group-containing copolymer obtained by polymerizing monomers containing (b ₂ ) represented by the formula:

Among these, ethylene is preferable as (b ₁ ).

Examples of R in the general formula (1) in (b ₂ ) include substituents such as the following formulas (2) to (8).

Specific examples of (b ₂ ) include unsaturated glycidyl ethers such as allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether, and glycidyl acrylate, glycidyl methacrylate, and itaconic acid glycidyl ester. Examples thereof include saturated glycidyl esters, and among them, glycidyl acrylate and glycidyl methacrylate are preferable.

The content of a structural unit derived from (B) in the epoxy group-containing copolymer (b _2), (B) relative to 100 parts by weight, preferably 1 to 30 parts by weight, more preferably 5 ~ 25 parts by weight. (B ₂ ) When the unit is 1 part by weight or more, the adhesiveness of the resulting adhesive film tends to be improved, and when it is 30 parts by weight or less, the mechanical strength of the adhesive film is improved. It is preferable because of its tendency.

The content of structural units derived from (b ₁₎ in the (B) epoxy group-containing copolymer, (B) relative to 100 parts by weight, preferably from 30 to 99 parts by weight, more 40-90 weight is preferable. When the (b ₁ ) unit is 30 parts by weight or more, the mechanical strength of the resulting adhesive film is preferably improved. On the other hand, when the unit is 99 parts by weight or less, the adhesiveness of the obtained adhesive film is It is preferable for improvement.

(B) is a monomer different from (b ₁ ) and (b ₂ ) in addition to (b ₁ ) and (b ₂ ), and is a functional group copolymerizable with ethylene such as a vinyl group or an alkylene group A monomer having the following (hereinafter referred to as (b ₃ )) may be polymerized. Note that (b ₃ ) must not contain a functional group capable of reacting with an epoxy group such as a carboxyl group (—COOH) or an acid anhydride group (—CO—O—CO—). It may be contained because it does not react with the epoxy group.

Specific examples of (b ₃ ) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, methacrylic acid. Α, β-unsaturated carboxylic acid alkyl having an alkyl group having about 3 to 8 carbon atoms such as ethyl, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate and isobutyl methacrylate Esters; vinyl esters having a carboxylic acid having about 2 to 12 carbon atoms such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl pivalate, vinyl laurate, vinyl isononanoate, vinyl versatate; 1-butene, isobutene, etc. Α-olefin having about 3 to 20 carbon atoms; pig Examples include diene compounds such as dienes, isoprene, and cyclopentadiene; vinyl compounds such as vinyl chloride, styrene, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.

Among them, vinyl acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are preferable as (b ₃ ).

The content of a structural unit derived from (B) in the epoxy group-containing copolymer (b _3), (B) relative to 100 parts by weight, usually from 0 to 70 parts by weight, inter alia, 5 to 60 Part by weight is preferred. It is preferable to carry out the copolymerization so that the content of the (b ₃ ) unit does not exceed 70 parts by weight, since (B) can be easily produced by the high-pressure radical method or the like.

(B) may be any of a block copolymer, a graft copolymer, a random copolymer, and an alternating copolymer. For example, the propylene / ethylene block copolymer described in Japanese Patent No. 2632980 is ( b ₂₎ copolymers obtained by graft-polymerization, Patent No. 2,600,248 No. of ethylene-epoxy group-containing monomer copolymers described in JP-alpha, and a copolymer of β- unsaturated carboxylic acid ester prepared by graft polymerizing .

As a production method of (B), for example, monomers containing (b ₁ ) and (b ₂ ) are added in the presence of a radical generator in the range of about 500 to 4000 atm, about 100 to 300 ° C., an appropriate solvent, A method of copolymerizing in the presence or absence of a chain transfer agent; a monomer obtained by polymerizing monomers containing (b ₁ ) and a monomer containing (b ₂ ) together with a radical generator and mixing in a extruder Examples thereof include a melt graft copolymerization method. Here, the resin obtained by polymerizing the monomer containing (b ₁ ) includes a homopolymer of (b ₁ ) or a copolymer composed of (b ₃ ) and (b ₁ ). .

  As (B) of the present invention, the MFR (melt flow rate) measured in accordance with JIS K7210 is usually about 30 to 1000 g / 10 min at 190 ° C. and a 2.16 kg load, especially 50 to 500 g / It is preferably about 10 minutes. When the MFR is 30 or more, the fluidity of the resulting thermosetting resin composition is improved, and even if there is an uneven portion on the surface of the adherend, it tends to be embedded easily. Moreover, in the case of 1000 or less, since the solder heat resistance of the thermosetting resin composition obtained tends to improve, it is preferable.

  (B) includes, for example, “Bond First” series (registered trademark, manufactured by Sumitomo Chemical Co., Ltd.), “Separjon G” series (registered trademark, manufactured by Sumitomo Seika Co., Ltd.), “Lex Pearl RA” series ( Commercial products such as a registered trademark, manufactured by Nippon Polyolefin Co., Ltd. can be used.

  The thermosetting resin composition in the present invention is obtained by mixing (A) and (B), and the thermosetting resin composition is generally compatible with (A) and (B). is doing.

  The weight ratio of (A) and (B) in the thermosetting resin composition is usually (A) / (B) = 4/96 to 50/50.

  Moreover, in order to accelerate the curing reaction of (A) and (B), the thermosetting resin composition may contain an epoxy resin curing accelerator such as amine compounds, imidazoles, and organic phosphorus compounds.

  The thermosetting resin composition in the present invention more preferably contains (C) an antioxidant in addition to the above (A) and (B). By containing (C), when the composition is made into a film, the generation of non-uniform foreign substances called “fish eyes” is suppressed, or the adhesive film obtained from the composition and the composition is used. It is preferable because the storage stability tends to be improved.

  Examples of (C) in the present invention include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and amine-based antioxidants. Two or more kinds of antioxidants may be used in combination as antioxidants, and in particular, any of phenolic antioxidants, phosphorus antioxidants and sulfur antioxidants from the viewpoint of gel prevention effect and coloring Is preferably used.

  Examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, and 2,6-dicyclohexyl-4-methylphenol. 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4 -Methyl-6-t-butylphenol, 2-t-butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl- 6-isopropylphenol, dl-α-tocopherol, t-butylhydroquinone, 2,2′-methylenebis (4-methyl-6-t-butyl) Enol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-) 6-t-butylphenol), 4,4′-methylenebis (2,6-di-t-butylphenol), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2 ′ -Ethylidenebis (4,6-di-tert-butylphenol),

2,2′-butylidenebis (2-t-butyl-4-methylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 1,1,3-tris (2-methyl-4- Hydroxy-5-t-butylphenyl) butane, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate Nate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, tris (2 , 6-Dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris [(3,5-di-t- Butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,

Tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2,2'-methylenebis (4-methyl-6-t- Butylphenol) terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl-2 -{Β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2, -Bis [4- (2- (3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)) ethoxyphenyl] propane, β- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionic acid stearyl ester and the like.

  Among these, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl ester, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl- 4-hydroxybenzyl) benzene, dl-α-tocopherol, tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, tris [(3,5-di-tert-butyl-4- Hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5) Methylphenyl) propionyloxy} ethyl] -2,4,8,10-spiro [5,5] undecane is preferred.

  Commercially available phenolic antioxidants may be used as the phenolic antioxidant, such as Irganox 1010 (registered trademark, manufactured by Ciba Specialty Chemicals), Irganox 1076 (registered trademark, Ciba Specialty). Chemicals), Irganox 1330 (registered trademark, manufactured by Ciba Specialty Chemicals), Irganox 3114 (registered trademark, manufactured by Ciba Specialty Chemicals), Irganox 3125 (registered trademark, Ciba Specialty Chemicals) ), Sumilizer BHT (registered trademark, manufactured by Sumitomo Chemical), Cyanox 1790 (registered trademark, manufactured by Cytec), Sumilizer GA-80 (registered trademark, manufactured by Sumitomo Chemical), Vitamin E (manufactured by Eisai) and the like.

  Two or more phenolic antioxidants may be used as the phenolic antioxidant.

  The blending amount of the phenolic antioxidant to the thermosetting resin composition in the present invention is usually about 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the component (A). The level is more preferably about 0.05 to 0.5 parts by weight.

Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl) diphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, triphenyl phosphite. Phyto, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-t-butyl-4 - hydroxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) -4,4'-butylidene bis (3-methyl-6 -T-butylphenol) diphosphite, tris (3,5- -t- butyl-4-hydroxyphenyl) phosphite, tris (mono-di mixed nonylphenyl) phosphite,

Hydrogenated-4,4′-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4′-butylidenebis (3-methyl-6-tert-butylphenol)]-1,6-hexanediol diphos Phyto, phenyl (4,4'-isopropylidene diphenol) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris [4,4'-isopropylidenebis (2-t-butylphenol)] phosphite, di (Isodecyl) phenyl phosphite, 4,4′-isopropylidenebis (2-tert-butylphenol) bis (nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10— Oxide, bis (2,4-di-tert-butyl-6-methyl) Ruphenyl) ethyl phosphite, 2-[{2,4,8,10-tetra-t-butyldibenz [d, f] [1.3.2] -dioxaphosphin-6-yl} oxy] -N , N-bis [2-[{2,4,8,10-tetra-t-butyldibenz [d, f] [1.3.2] -dioxaphosphin-6-yl} oxy] ethyl] ethanamine , 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1.3.2] -Dioxaphosphepine etc. are mentioned.

As bis (dialkylphenyl) pentaerythritol diphosphite ester, the following general formula (9)

(Wherein R ¹ , R ² , and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms).
Or the following general formula (10)

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having about 1 to 9 carbon atoms).
The cage type shown by is mentioned.

  As such a phosphite ester, a mixture of the general formulas (9) and (10) is usually used.

Here, when R < ¹ > -R < ⁶ > is an alkyl group, a branched alkyl group is preferable and a t-butyl group is especially preferable.

The substitution positions of R ^{1 to} R ⁶ in the phenyl group are preferably 2, 4, and 6.

  Specific examples of phosphite esters include bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite. Bis (nonylphenyl) pentaerythritol diphosphite and the like, and examples of the phosphonite having a structure in which carbon and phosphorus are directly bonded include tetrakis (2,4-di-t-butylphenyl) -4. , 4′-biphenylenediphosphonite and the like.

  Commercially available products may be used as the phosphorus-based antioxidant, such as Irgaphos 168 (registered trademark, manufactured by Ciba Specialty Chemicals), Irgaphos 12 (registered trademark, manufactured by Ciba Specialty Chemicals), Irgaphos 38 ( Registered trademark, manufactured by Ciba Specialty Chemicals), ADK STAB 329K (registered trademark, manufactured by Asahi Denka), ADK STAB PEP36 (registered trademark, manufactured by ASAHI DENKA), ADK STAB PEP-8 (registered trademark, manufactured by ASAHI DENKA), Sandstab P- EPQ (registered trademark, manufactured by Clariant), Weston 618 (registered trademark, manufactured by GE), Weston 619G (registered trademark, manufactured by GE), Ultranox 626 (registered trademark, manufactured by GE), Sumilyzer GP (registered trademark, manufactured by Sumitomo Chemical) Etc.

  Two or more phosphorus antioxidants may be used as the phosphorus antioxidant. The compounding amount of the phosphorus-based antioxidant to the thermosetting resin composition in the present invention is usually 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the component (A). More preferably, it is 0.05 to 0.5 parts by weight.

  Among phosphorus antioxidants, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphonite, Distearyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, 2-[{2,4,8,10-tetra-t-butyldibenz [d, f] [ 1.3.2] -Dioxaphosphin-6-yl} oxy] -N, N-bis [2-[{2,4,8,10-tetra-t-butyldibenz [d, f] [1 3.2] -Dioxaphosphin-6-yl} oxy] ethyl] ethanamine, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4 8,10-tetra- - butyldibenz [d, f] [1.3.2] - dioxaphosphepin are preferred.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl-, dimyristyl- and distearyl- and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl- and stearyl- (for example, glycerin). , Esters of trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythryltetrakis-3-laurylthiopropionate).

More specific examples include dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodibutyrate, and the like.
Of these, pentaerythryltetrakis-3-laurylthiopropionate is preferred.

  Examples of the sulfur-based antioxidant include, for example, Sumilizer TPS (registered trademark, manufactured by Sumitomo Chemical), Sumilizer TPL-R (registered trademark, manufactured by Sumitomo Chemical), Sumilizer TPM (registered trademark, manufactured by Sumitomo Chemical), and Sumilizer TP-D ( Registered trademark, manufactured by Sumitomo Chemical Co., Ltd.).

  Two or more types of sulfur-based antioxidants may be used as the sulfur-based antioxidant.

  The compounding amount of the sulfur-based antioxidant to the thermosetting resin composition in the present invention is about 0.005 to 2 parts by weight, preferably about 0.01 to 1 part by weight, more preferably 100 parts by weight of (A). The amount is preferably about 0.05 to 0.5 parts by weight.

  Examples of the amine antioxidant include a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N- ( 1,3-dimethylbutyl) -N′-phenyl-1,4-phenylenediamine, N-isopropyl-N′-phenyl-1,4-phenylenediamine and the like.

  The preparation method of the thermosetting resin composition is prepared by mixing (A) and (B) described above. Examples of the preparation method include (A) uniaxial or biaxial screw extrusion. Melting and kneading usually at about 120 ° C. to 200 ° C. with a machine, Banbury mixer, roll, various kneaders, etc., and mixing (B); (A) and (B) are dry blended to produce uniaxial or biaxial Examples thereof include a method of melt kneading usually at about 120 ° C. to 150 ° C. with a screw extruder, a Banbury mixer, a roll, various kneaders, and the like. Here, when (B) is in the form of a lump, it is preferable that the mixture is powdered with a pulverizer such as a feather mill, a Nara type pulverizer, or an air mill and then mixed to simplify the melt-kneading.

Moreover, it is preferable to melt-knead said (C) with (A).
Further, additives such as colorants, inorganic fillers, processing stabilizers, weathering agents, heat stabilizers, light stabilizers, nucleating agents, lubricants, mold release agents, flame retardants, antistatic agents, etc. are added to the thermosetting resin of the present invention. You may prepare by making it contain in a composition.

The manufacturing method of the laminated body of this invention is demonstrated concretely.
First, the laminated body which formed the contact bonding layer with the said thermosetting resin composition is formed on the surface of a thermoplastic liquid-crystal polyester film (it may abbreviate as a polyester film hereafter). As a manufacturing method of the laminate, a method of manufacturing an adhesive film directly on a polyester film, or an adhesive film is manufactured in advance on a substrate different from the polyester film (hereinafter referred to as a supporting substrate), A method of transferring an adhesive film on a supporting substrate to a polyester film is exemplified. In detail,
(I) A method of extruding a thermosetting resin composition into a film with a T-die extruder or the like, and laminating an adhesive film on the surface of the polyester film,
(II) An adhesive film in which a thermosetting resin composition is extruded into a film on a supporting substrate with a T-die extruder or the like, an adhesive film is produced on the supporting substrate, and is not laminated on the supporting substrate Examples include a method of peeling the support substrate after laminating the side to the polyester film.

  Moreover, as an adhesive layer of this invention, in addition to said (A) and (B), (D) the adhesive which mix | blended the organic solvent and / or water is manufactured, and a metal-clad laminated board is manufactured using it. You can also The adhesive may contain (C) described above.

Regarding a method for producing a metal-clad laminate using the adhesive, specifically, for example,
(III) A method of producing an adhesive layer on the surface of the polyester film by applying an adhesive to the polyester film like a paint, drying and removing (D),
(IV) Adhesive is applied onto a supporting substrate like a paint, dried and (D) is removed to produce an adhesive film on the supporting substrate. A method of peeling the support substrate after laminating the non-laminated adhesive film side to the polyester film,
Etc.

In the manufacturing method of the metal-clad laminate, the manufacturing methods (I) and (III) are preferable from the viewpoint of process simplification.

  Here, the production method of the film obtained by extrusion molding (for example, the production method of the above (I) and (II)) will be further described. The distance (air gap) between the T-die and the chill roll is usually about It is 10 cm or less, preferably about 8 cm or less, particularly preferably about 6 cm or less. An air gap of 10 cm or less is preferred because there is a tendency to suppress film breakage or a state in which the thickness of the film, commonly referred to as “single meat”, varies.

  The melt kneading temperature for obtaining the adhesive film is preferably not less than the melting temperature of the resin to be used and not more than about 120 ° C., and a melt kneading temperature of about 90 ° C. to 110 ° C. is particularly preferable. The melt-kneading temperature is preferably 120 ° C. or lower because “fish eyes” of the resulting adhesive film tend to be reduced.

  The thickness of the adhesive film obtained by extrusion molding is usually about 5 μm to 2 mm, preferably 8 μm to 1 mm.

  In addition, as a support base material used for this invention, for example, a polyolefin film such as a film made of 4-methyl-1-pentene copolymer, a cellulose acetate film, a silicon-based surface in contact with the thermosetting resin composition Examples include a release paper coated with a release agent or a fluorine-based release agent, and a release polyethylene terephthalate (PET) film.

  Next, the adhesive described in examples (III) and (IV) of the method for producing an adhesive film will be described.

  (D) used for manufacture of the adhesive is one or two or more mixed solvents selected from organic solvents and water. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, methanol, butanol, polyethylene glycol, partial Examples thereof include alcohols such as saponified polyvinyl alcohol and fully saponified polyvinyl alcohol, chlorinated hydrocarbons such as methylene chloride, and aliphatic hydrocarbons such as hexane, heptane and petroleum ether.

  When (D) is an organic solvent, aromatic hydrocarbons or ketones are preferably used.

  As (D), when using water, it can also be set as the adhesive agent which (A) and (B) were disperse | distributed. At that time, in order to improve the storage stability of the adhesive, it is preferable to use an emulsifying dispersant such as partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, or polyethylene glycol.

As a method for producing an adhesive, for example, (A) and (B) are each dissolved or dispersed in (D) and then mixed, and (A) and (B) are dissolved or dissolved in (D) all together. A method of dispersing, a method in which monomers containing (b ₁ ) and (b ₂ ) are polymerized by emulsion polymerization and (B) is produced as an aqueous emulsion, and then (A) is mixed, in the presence of (A) ( Examples thereof include a method of producing a mixture of (A) and (B) by subjecting monomers containing b ₁ ) and (b ₂ ) to emulsion polymerization.

  As the adhesive, in addition to the above (C), for example, inorganic fillers, pigments, processing stabilizers, weathering agents, heat stabilizers, light stabilizers, nucleating agents, lubricants, release agents, flame retardants, antistatic agents, etc. The additive may be contained. However, when the thermosetting resin composition contains an inorganic filler, the content of the inorganic filler is preferably 70 parts by weight or less with respect to a total of 100 parts by weight of (A) and (B).

  (A) and (B) used as adhesives, each molecular weight is not particularly limited, but usually when dissolved in the (D), it can be dissolved uniformly as an adhesive after dissolution, Moreover, it is preferable that the molecular weight give a viscosity capable of being applied.

  The thickness of the adhesive film obtained by applying the adhesive tends to be excellent in adhesiveness if it is about 3 μm or more, preferably about 3 to 100 μm, particularly preferably about 3 to 50 μm. .

  The total weight of (A) and (B) in the adhesive of the present invention is usually 10 to 150 parts by weight with respect to (D) 100 parts by weight. When the sum of (A) and (B) is 10 parts by weight or more, the coating property of the thermosetting resin composition of the present invention on the support substrate tends to be excellent, and the sum of (A) and (B). Is 150 parts by weight or less, the viscosity of the composition composed of (A), (B) and (D) decreases, and the coating property tends to be excellent when the adhesive is applied to a supporting substrate. Therefore, it is preferable.

  As a method for producing an adhesive film using an adhesive, for example, a reverse roll coater, a gravure coater, a micro bar coater, a kiss coater, a Meyer bar coater, a roll coater such as an air knife coater, a blade coater, etc. are applied, and then static And a method of drying in a heated air oven or the like.

  Among them, it is preferable to produce an adhesive film using a roll coater because the thickness of the film can be easily controlled from a thin film to a thick film.

  After the insulating film and the adhesive film are laminated by the above production methods (I) to (IV), they are bonded by heating and pressing. At that time, in order to prevent the resin component of the adhesive film from flowing out and tending to protrude from the insulating film, it is preferable to use an adhesive film that is further modified by irradiating the adhesive film with an electron beam. .

  The electron beam used in the present invention is a bundle of electrons accelerated by a voltage, a low energy type accelerated by a voltage of about 50 to 300 kV, a medium energy type accelerated by a voltage of about 300 to 5000 kV, 5000 Although classified into a high energy type accelerated by a voltage of about ˜10000 kV, the present invention normally uses a low energy type electron beam.

  Examples of the electron accelerator include a linear cathode type, a module cathode type, a thin plate cathode type, and a low energy scanning type.

As an electron beam irradiation method, for example, in an inert gas atmosphere such as nitrogen,
A method of directly irradiating the adhesive film obtained by the production method (I) or (III) with an electron beam;
A method of directly irradiating the adhesive film produced on the supporting substrate obtained by the production method (II) or (IV) with an electron beam;
The adhesive film produced on the support substrate obtained by the production method (II) or (IV) is irradiated with an electron beam from the side covered with the support substrate, and then the support substrate is peeled off. Method;
In the production method (II) or (IV), after transferring to an insulating film, the support substrate is peeled off, and one or both sides of the obtained laminate are irradiated with an electron beam;
Etc. are exemplified.
For example, when irradiating an electron beam of about 80 kGy or more, the appearance of the adhesive film after the electron beam irradiation is maintained, or the adhesive film is irradiated by the electron beam irradiation. In order to further increase the crosslink density, it is possible to irradiate an electron beam a plurality of times. When irradiating several times, twice are preferable.

  The total irradiation dose of the electron beam is usually about 10 to 300 kGy, preferably about 50 to 250 kGy. It is preferable that the irradiation dose is 10 kGy or more because the concealing effect of the adherend surface when the film is rolled at the time of heat bonding and thermosetting tends to be improved, and in the case of 300 kGy or less, The adhesive film is embedded in the unevenness, which is preferable because the adhesiveness tends to be improved.

  The laminate obtained by laminating at least one adhesive film obtained as described above and a polyester film is subjected to a heat treatment, whereby the adhesive film is thermoset and converted into an adhesive layer. Further, in the production method (II) or (IV) mentioned in the first step, a method of peeling the support substrate after performing the heat treatment with the support substrate attached may be used.

  The heat treatment conditions for thermosetting the adhesive film are usually about 100 to 350 ° C., preferably about 120 to 300 ° C., particularly preferably about 160 to 200 ° C., and heat treatment is performed for about 10 minutes to 3 hours. . A heat treatment temperature of 100 ° C. or higher is preferable because the heat curing time until solder heat resistance is obtained tends to be shortened, and a heat treatment temperature of 350 ° C. or lower is less likely to cause thermal deterioration of the adhesive layer of the present invention. preferable.

  Moreover, you may pressurize at 0-6 MPa using the press machine which can be heated when heat-processing.

Next, the thermoplastic liquid crystal polyester (hereinafter sometimes abbreviated as liquid crystal polyester) forming the organic insulating layer of the present invention will be described.
The liquid crystal polyester in the present invention is a polyester called a thermotropic liquid crystal polymer, and forms a melt exhibiting optical anisotropy at a temperature of 450 ° C. or lower.

The structural unit forming the liquid crystal polyester is not limited as long as the film made of the liquid crystal polyester exhibits thermotropic liquid crystal properties as described above, but particularly preferably, the thermoplastic liquid crystal polyester is: Having structural units derived from a compound selected from the group consisting of (E), (F) and (G).
(E) Aromatic hydroxycarboxylic acid (F) Aromatic dicarboxylic acid (G) At least one compound selected from the group consisting of aromatic diols, aromatic diamines and aromatic amines having phenolic hydroxyl groups.

Here, as the structural unit derived from (E) aromatic hydroxycarboxylic acid,

In the structural units (A ₁ ), (A ₂ ), (A ₃ ), (A ₄ ), and (A ₅ ), the aromatic ring is substituted with a halogen atom, an alkyl group, or an aryl group. There may also be mentioned structural units.

(F) As a structural unit derived from an aromatic dicarboxylic acid,

And a repeating structure represented by the above (B ₁ ), (B ₂ ), (B ₃ ), (B ₄ ), (B ₅ ), (B ₆ ), (B ₇ ), (B ₈ ) Examples of the unit include a structural unit in which an aromatic ring is substituted with a halogen atom, an alkyl group, or an aryl group.

Among (G), as a repeating structural unit derived from an aromatic amine having a phenolic hydroxyl group,

In the repeating structural unit represented by the above (C ₁ ), (C ₂ ), (C ₃ ), (C ₄ ), (C ₅ ), (C ₆ ), a halogen atom, alkyl on the aromatic ring Also included are repeating structural units substituted with groups or aryl groups.

In (G), as a structural unit derived from an aromatic diamine,

が挙げられ、上記の（D₁）、（D₂）、（D₃）、（D₄）、（D₅）、（D₆）、（D₇）、（D₈）、（D₉）、（D₁₀）、（D₁₁）で示される構造単位において、芳香環にハロゲン原子、アルキル基またはアリール基で置換されている構造単位も挙げられる。

(D ₁ ), (D ₂ ), (D ₃ ), (D ₄ ), (D ₅ ), (D ₆ ), (D ₇ ), (D ₈ ), (D ₉ ) , (D ₁₀ ) and (D ₁₁ ), structural units in which the aromatic ring is substituted with a halogen atom, an alkyl group or an aryl group are also included.

In (G), as the structural unit derived from the aromatic diol,

(E ₁ ), (E ₂ ), (E ₃ ), (E ₄ ), (E ₅ ), (E ₆ ), (E ₇ ), (E ₈ ), (E ₉ ) In the structural unit represented by (E ₁₀ ), a structural unit in which the aromatic ring is substituted with a halogen atom, an alkyl group or an aryl group is also included.

  In addition, as an alkyl group which may be substituted by the structural unit, for example, an alkyl group having 1 to 10 carbon atoms is usually used, and among them, a methyl group, an ethyl group, a propyl group, or a butyl group is preferable. As the aryl group which may be substituted on the structural unit, for example, an aryl group having 6 to 20 carbon atoms is usually used, and among them, a phenyl group is preferable.

  In addition, as a raw material monomer which guide | induces said structural unit, said (E) aromatic hydroxycarboxylic acid, (F) aromatic dicarboxylic acid, (G) aromatic diamine, aromatic amine which has phenolic hydroxyl group, and aromatic Not only diols can be mentioned, but also their ester-forming derivatives or amide-forming derivatives may be used instead.

Here, as the ester-forming derivative or amide-forming derivative of carboxylic acid, for example, a highly reactive derivative such as an acid chloride or acid anhydride whose carboxyl group promotes a polyester formation reaction or a polyamide formation reaction. And those in which the carboxyl group forms an ester or amide with an alcohol, ethylene glycol, amine or the like that forms a polyester or polyamide by an ester exchange reaction or an amide exchange reaction.

Examples of the ester-forming derivative of a phenolic hydroxyl group include those in which a phenolic hydroxyl group forms an ester with a carboxylic acid so that a polyester is produced by a transesterification reaction.

Furthermore, examples of amide-forming derivatives of amino groups include those in which amides are formed with carboxylic acids that form polyamides by amide exchange reaction.

In particular, as a preferable liquid crystal polyester, a thermoplastic liquid crystal polyester includes the following structural units (E ′), (F ′), and (G ′).
(E ′) — O—Ar ¹ —CO—
(F ′) — CO—Ar ² —CO—
(G ′) — X—Ar ³ —Y—
(In the formula, Ar ¹ represents phenylene, naphthalenediyl or biphenylylene, Ar ² represents phenylene, naphthalenediyl, biphenylylene, or a plurality of aromatic groups condensed, and Ar ³ represents phenylene or a plurality of aromatic groups. (Aromatic groups are condensed, and X and Y represent —O— or —NH—.)

As the liquid crystal polyester, for example,
(1) What is obtained by polymerizing an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and an aromatic amine having a phenolic hydroxyl group,
(2) those obtained by polymerizing aromatic dicarboxylic acids and aromatic amines having phenolic hydroxyl groups,
(3) What is obtained by polymerizing aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, and aromatic diamine,
(4) What is obtained by polymerizing an aromatic dicarboxylic acid and an aromatic diamine (note that the above (4) is generally referred to as polyamide, but in the present invention, it is also referred to as liquid crystal polyester. )
(5) Those obtained by polymerizing only different kinds of aromatic hydroxycarboxylic acids.

In order to improve the heat resistance and dimensional stability of the liquid crystal polyester film used in the present invention in a well-balanced manner, the liquid crystal polyester is preferably (A ₁ ) or (A ₃ ) among the aromatic hydroxycarboxylic acids, and the aromatic Among group dicarboxylic acids, it is preferable to include a structural unit represented by the formula (B ₁ ), (B ₂ ) or (B ₃ ). Those containing the structural unit represented by (A ₃ ) tend to be excellent in water vapor barrier properties, while those containing the structural unit represented by (A ₁ ) can obtain a thermoplastic liquid crystal polyester film at low cost. .

Here, examples of a preferable combination of structural units including the structural unit include the following (a) to (d).
(A): one kind selected from the following structural unit combinations: a combination of the structural units (A ₁ ), (B ₂ ) and (C ₁ );
A combination of the structural units (A ₃ ), (B ₂ ) and (C ₁ ),
A combination of the structural units (A ₁ ), (B ₁ ), (B ₂ ) and (C ₁ ),
A combination of the structural units (A ₃ ), (B ₁ ), (B ₂ ) and (C ₁ ),
A combination of the structural units (A ₃ ), (B ₃ ) and (C ₁ ),
A combination of the structural units (B ₁ ), (B ₂ ) or (B ₃ ), and (C ₁ ), or
The combination of the structural units (A ₁₎ and (A ₃₎ (b): In each of the combination of said (a), by substituting a part or all of (C ₁₎ to (C ₂₎ combined.
(C): In each of the combination of said (a), by replacing part of (A ₁₎ to (A ₃₎ in combination.
(D): A combination in which (C ₁ ) is partially or entirely replaced with (D ₁ ) or (D ₅ ) in each of the combinations of (a).

The liquid crystalline polyester used in the present invention contains at least one structural unit selected from a structural unit derived from an aromatic diamine and a structural unit derived from an aromatic amine having a phenolic hydroxyl group, in an amount of 10 to 35 mol based on the total structural unit. %, A thermoplastic liquid crystal polyester composed only of structural units derived from two or more kinds of aromatic hydroxycarboxylic acids is preferred. That is, the following structural units (E ′), (F ′), and (G ″) are included, and the structural unit represented by (G ″) is 10 to 35 mol% with respect to the total structural units. The thermoplastic polyester is preferred.
(E ′) —O—Ar ¹ —CO—
(F ′) —CO—Ar ² —CO—
(G ″) — NH—Ar ³ —Y—
(In the formula, Ar ¹ , Ar ² , Ar ³ and Y have the same definitions as above.)

  More preferable combinations include 30 to 80 mol% of structural units derived from at least one compound selected from the group consisting of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, 4-hydroxyaniline and 4,4 10-35 mol% of structural units derived from at least one compound selected from the group consisting of '-diaminodiphenyl ether, 10-35 structural units derived from at least one compound selected from the group consisting of terephthalic acid and isophthalic acid More preferably, it consists of 30% by mole of structural units derived from 2-hydroxy-6-naphthoic acid, 10-35% by mole of structural units derived from 4-hydroxyaniline, and derived from isophthalic acid. It is particularly preferable that the structural unit consists of 10 to 35 mol%.

  The weight average molecular weight of the thermoplastic liquid crystal polyester is not particularly limited, but is usually about 100,000 to 500,000.

  The method for producing the liquid crystal polyester used in the present invention is not particularly limited. For example, an aromatic hydroxycarboxylic acid, an aromatic diol, an aromatic amine having a phenolic hydroxyl group, or an aromatic diamine is acylated with an excess amount of a fatty acid anhydride. An acylated product can be obtained by polymerization, and the resulting acylated product and an aromatic hydroxycarboxylic acid and / or aromatic dicarboxylic acid are polymerized by transesterification / amide exchange.

  In the acylation reaction, the amount of fatty acid anhydride added is preferably 1.0 to 1.2 times equivalent, more preferably 1.05 to 1.1 times equivalent to the total of phenolic hydroxyl groups and amino groups. is there. If the amount of fatty acid anhydride added is small, acylated products, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, etc., sublimate during polymerization by transesterification / amide exchange, and the reactor piping tends to be clogged. If the amount of fatty acid anhydride added is too large, the resulting liquid crystal polyester may be remarkably colored.

  The acylation reaction is preferably performed at 130 to 180 ° C. for 5 minutes to 10 hours, more preferably at 140 to 160 ° C. for 10 minutes to 3 hours.

  The fatty acid anhydride used in the acylation reaction is not particularly limited. For example, acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, monochloroacetic anhydride , Dichloroacetic anhydride, trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, β- Examples thereof include bromopropionic acid, and two or more of these may be used in combination. From the viewpoint of price and operability, acetic anhydride, propionic anhydride, butyric anhydride, or isobutyric anhydride is preferable, and acetic anhydride is more preferable.

  In the polymerization by transesterification / amide exchange, the acyl group of the acylated product is preferably 0.8 to 1.2 times equivalent to the carboxyl group. The polymerization temperature is preferably 400 ° C. or lower, more preferably 350 ° C. or lower. Moreover, it is preferable that the temperature increase rate at the time of temperature increase is 0.1-50 degreeC / min, More preferably, it is 0.3-5 degreeC / min. At this time, in order to move the equilibrium, it is preferable to distill out the by-product fatty acid and the unreacted fatty acid anhydride, for example, by evaporating.

  The polymerization by acylation reaction or transesterification / amide exchange may be performed in the presence of a catalyst. As the catalyst, those conventionally known as polyester polymerization catalysts can be used, such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide and the like. And organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole. The catalyst is usually present during the acylation reaction, and it is not always necessary to remove it after the acylation reaction. If the catalyst is not removed, the next treatment can be carried out as it is. Further, when the next treatment is performed, the above-described catalyst may be further added.

  Polymerization by transesterification / amide exchange is usually performed by melt polymerization, but melt polymerization and solid phase polymerization may be used in combination. The solid phase polymerization can be performed by a known solid phase polymerization method after the polymer is extracted from the melt polymerization step, solidified, pulverized into powder or flakes. Specifically, for example, a method of heat treatment in a solid state at 20 to 350 ° C. for 1 to 30 hours under an inert atmosphere such as nitrogen can be used. Solid phase polymerization may be carried out while stirring or in a state of standing without stirring. In addition, by providing an appropriate stirring mechanism, the melt polymerization tank and the solid phase polymerization tank can be made the same reaction tank. After the solid phase polymerization, the obtained thermoplastic liquid crystal polyester may be pelletized by a known method.

  Manufacture of liquid crystalline polyester can be performed using a batch apparatus, a continuous apparatus, etc., for example.

  In the present invention, a film can be formed using a liquid crystal polyester solution obtained by dissolving the liquid crystal polyester obtained by the above method in a solvent.

  The solvent contained in the liquid crystal polyester solution is not particularly limited as long as it dissolves the liquid crystal polyester. For example, N, N-dimethylacetamide, N-methyl-pyrrolidone, N-methylcaprolactam, N, N- Aprotic systems such as dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N-methylpropionamide, dimethyl sulfoxide, γ-butyllactone, dimethylimidazolidinone, tetramethylphosphoric amide and ethyl cellosolve acetate Examples include solvents and organic solvents such as halogenated phenols such as parachlorophenol. These solvents may be used as a mixture of two or more.

  In the liquid crystal polyester solution, the liquid crystal polyester is usually contained in an amount of 0.5 to 50% by weight, preferably 5 to 20% by weight, based on the organic solvent. Here, when the concentration of the liquid crystalline polyester is low, the film is overcoated many times to obtain a desired thickness, and thus production efficiency tends to decrease. When the concentration is high, the liquid crystalline polyester solution itself is high. There are cases where the viscosity becomes operability and the operability is poor, or dissolution itself becomes difficult.

  The liquid crystal polyester solution is preferably filtered with a filter or the like as necessary to remove fine foreign substances contained in the solution.

  The manufacturing method of the thermoplastic liquid crystal polyester film of the present invention will be described in detail. The liquid crystal polyester solution is cast on a support or the like to form a cast film containing an organic solvent. In this step, a general method is to cast the solution composition onto a support such as an endless band or a drum using a comma coater, a lip coater, a doctor blade coater, a bar coater, a roll coater, or the like. Although it does not specifically limit as this support body, It is preferable to use using metal, such as stainless steel which performed the mirror surface treatment, resin films, such as a polyethylene terephthalate, glass.

The thickness of the thermoplastic liquid crystal polyester film is usually 3 to 120 μm, preferably 4 to 70 μm, and more preferably 5 to 50 μm in terms of strength, water vapor barrier properties, flexibility, and the like. When the film thickness is less than 3 μm, there are cases where sufficient strength and water vapor barrier properties cannot be obtained. On the other hand, when the film thickness exceeds 120 μm, flexibility may be impaired, which is not preferable.

Examples of the method for removing the solvent used in the production of the liquid crystal polyester include a method of evaporating the solvent and drying. The evaporation of the solvent is preferably performed by heating in order to improve the evaporation efficiency. Although heating may be performed at a constant temperature, it is more preferable to change the heating temperature over several steps from the viewpoint of economy and smoothness of the film surface. In order to further reduce the amount of residual solvent, it is more preferable to heat under reduced pressure.

The obtained liquid crystal polyester film may be used by bonding a plurality of sheets. Examples of the bonding method include adhesion by various methods. Examples of the bonding method include a method of bonding using a good solvent for the liquid crystal polyester film, a method of bonding using a pressure-sensitive adhesive or an adhesive, and the like.

  The laminate of the present invention is a laminate comprising at least one organic insulating layer made of the liquid crystal polyester film obtained as described above and at least one adhesive layer obtained from the thermosetting resin composition. And can be suitably provided as a coverlay for a flexible wiring board.

As said coverlay, 5-200 micrometers is preferable and, as for the thickness of the liquid crystalline polyester film to be used, 5-100 micrometers is especially preferable. In addition, the method exemplified above can be used for the adhesive layer of the coverlay. The thickness of the adhesive film is preferably 5 to 200 μm, particularly preferably 5 to 100 μm.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

  The components (A), (B) and (C) constituting the thermosetting resin were as follows. In addition, MFR (melt flow rate) showed the value measured on condition of 190 degreeC and a 2160g load based on JIS-K7210.

<Component (A)>
A-1: “PP-700-300” manufactured by Nippon Petrochemical Co., Ltd.
Phenol-modified product of liquid polybutadiene

<Component (B)>
B-1: Ethylene-glycidyl methacrylate manufactured by Sumitomo Chemical Co., Ltd.
Copolymer, glycidyl methacrylate content 18.0% by weight,
(MFR = 350g / 10min)
B-2: Ethylene-glycidyl methacrylate manufactured by Sumitomo Chemical Co., Ltd.
Copolymer, glycidyl methacrylate content 12.0% by weight,
(MFR = 3g / 10min)

<Ingredient (C)>
C-1: β- (3,5-di-t-butyl-4-hydroxyphenyl)
Propionic acid stearyl ester
(Phenolic antioxidants,
Ciba Specialty Chemicals Irganox 1076)
C-2: Tris (2,4-di-t-butylphenyl) phosphite (phosphorus antioxidant, manufactured by Ciba Specialty Chemicals)
Irgafos 168)
C-3: Pentaerythryltetrakis-3-laurylthiopropionate
(Sulfur antioxidant, Sumilizer TP-D manufactured by Sumitomo Chemical)

Production Example 1
[Production of polyester film PF1]
In a reactor equipped with a stirrer, a torque meter, a nitrogen inlet tube, a thermometer and a reflux condenser, 940.9 g (5.0 mol) of 2-hydroxy-6-naphthoic acid, 272.8 g of 2-aminophenol (2 0.5 mol), 415.3 g (2.5 mol) of isophthalic acid, and 1123 g (11 mol) of acetic anhydride. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen gas stream, and the temperature was maintained and refluxed for 3 hours.

  Thereafter, the temperature was raised to 320 ° C. over 170 minutes while distilling off the by-product acetic acid and unreacted acetic anhydride, and the time when an increase in torque was observed was regarded as the completion of the reaction, and the contents were taken out. The obtained resin was pulverized by a coarse pulverizer, and a part of the liquid crystal polyester powder was observed at a temperature of 10 ° C./min by observation with a polarizing microscope. The obtained coarsely pulverized liquid crystal polyester powder was held at 250 ° C. for 3 hours in a nitrogen atmosphere, and the polymerization reaction was advanced in a solid phase. Next, 8 g of the obtained liquid crystal polyester powder was added to 92 g of N-methyl-2-pyrrolidone, heated to 160 ° C. and completely dissolved to obtain a brown transparent solution. This solution was stirred and degassed to obtain a liquid crystal polyester solution.

  The liquid crystalline polyester solution obtained here was cast on a glass plate using a film applicator, and dried on a hot plate at 80 ° C. for 1 hour. A heat treatment was performed by heating from 30 ° C. to 300 ° C. in a hot air oven under a nitrogen atmosphere at a rate of temperature increase of 5 ° C./min and holding at that temperature for 1 hour. Next, a liquid crystal polyester film having a thickness of 31 μm was obtained by peeling from the glass plate. This liquid crystal polyester film is designated as PF1.

Production Example 2
[Production of polyester film PF2]
In a reactor equipped with a stirrer, a torque meter, a nitrogen inlet tube, a thermometer and a reflux condenser, 940.9 g (5.0 mol) of 2-hydroxy-6-naphthoic acid and 465.5 g of 4,4′-dihydroxybiphenyl were added. (2.5 mol), 415.3 g (2.5 mol) of isophthalic acid and 1123.0 g (11.0 mol) of acetic anhydride were charged. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen gas stream, and the temperature was maintained and refluxed for 3 hours.

  Thereafter, the temperature was raised to 320 ° C. over 170 minutes while distilling off the by-product acetic acid and unreacted acetic anhydride, and the time when an increase in torque was observed was regarded as the completion of the reaction, and the contents were taken out. The obtained resin was pulverized by a coarse pulverizer, and a part of the liquid crystal polyester powder was observed at a temperature of 10 ° C./min by observation with a polarizing microscope. The obtained coarsely pulverized liquid crystal polyester powder was held at 250 ° C. for 3 hours in a nitrogen atmosphere, and the polymerization reaction was advanced in a solid phase. Next, 8 g of the obtained liquid crystal polyester powder was added to 92 g of p-chlorophenol and heated to 160 ° C. to completely dissolve it, thereby obtaining a brown transparent solution. This solution was stirred and degassed to obtain a liquid crystal polyester solution.

  The liquid crystalline polyester solution obtained here was cast on a glass plate using a film applicator, and dried on a hot plate at 80 ° C. for 1 hour. A heat treatment was performed by heating from 30 ° C. to 300 ° C. in a hot air oven under a nitrogen atmosphere at a rate of temperature increase of 5 ° C./min and holding at that temperature for 1 hour. Next, a liquid crystal polyester film having a thickness of 28 μm was obtained by peeling from the glass plate. This liquid crystal polyester film is designated as PF2.

Production Example 3
[Production of polyester film PF3]
In a reactor equipped with a stirrer, a torque meter, a nitrogen inlet tube, a thermometer and a reflux condenser, 28.2 g (0.15 mol) of 2-hydroxy-6-naphthoic acid and 145.0 g of 4-hydroxybenzoic acid (1 0.05 mol), 98.2 g (0.9 mol) of 4-aminophenol, 149.5 g (0.9 mol) of isophthalic acid and 245.0 g (2.4 mol) of acetic anhydride. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen gas stream, and the temperature was maintained and refluxed for 3 hours.

  Thereafter, the temperature was raised to 320 ° C. over 170 minutes while distilling off the by-product acetic acid and unreacted acetic anhydride, and the time when an increase in torque was observed was regarded as the completion of the reaction, and the contents were taken out. The obtained resin was pulverized by a coarse pulverizer, and a part of the liquid crystal polyester powder was observed at a temperature of 10 ° C./min by observation with a polarizing microscope. The obtained coarsely pulverized liquid crystal polyester powder was held at 250 ° C. for 3 hours in a nitrogen atmosphere, and the polymerization reaction was advanced in a solid phase. Next, 16 g of the obtained liquid crystal polyester powder was added to 84 g of N, N-dimethylacetamide and heated to 140 ° C. to completely dissolve it to obtain a brown transparent solution. This solution was stirred and degassed to obtain a liquid crystal polyester solution.

  The liquid crystalline polyester solution obtained here was cast on a glass plate using a film applicator, and dried on a hot plate at 80 ° C. for 1 hour. A heat treatment was performed by heating from 30 ° C. to 280 ° C. in a hot air oven in a nitrogen atmosphere at a temperature rising rate of 5 ° C./min and holding at that temperature for 1 hour. Next, a liquid crystal polyester film having a thickness of 31 μm was obtained by peeling from the glass plate. The water vapor transmission rate of the obtained film was measured according to JIS Z0208 (cup method) under the conditions of a temperature of 40 ° C. and a relative humidity of 90%. This liquid crystal polyester film is designated as PF3.

Production Example 4
[Manufacture of adhesive film]
The cylinder temperature was set to 100 ° C. and the T-die temperature was set to 90 ° C. for an extruder equipped with a T-die having an air gap of 4 cm and φ40 mm. Subsequently, A-1 (5 parts by weight), B-1 (75 parts by weight), B-2 (25 parts by weight), C-1 (0.1 parts by weight), C-2 (0.1 parts by weight) ) And C-3 (0.05 parts by weight) at the blending ratio described above, fed to a Φ30 mm co-directional twin-screw extruder (L / D = 42), and a screw at 180 rpm under a temperature of 120 ° C. A thermosetting resin composition melt-kneaded at a rotational speed of 16 kg / hour is melt-kneaded with the extruder, and then a polyethylene terephthalate film (SC-38 manufactured by Unitika) coated with a silicon release agent is applied. And a layer obtained from the thermosetting resin composition having a thickness of about 30 μm and a polyethylene terephthalate film by extrusion molding the thermosetting resin composition on the surface coated with a release agent (hereinafter abbreviated as a release PET film). Adhesive film with a support substrate It was obtained Lum.

  Subsequently, by using an electron beam irradiation apparatus having an acceleration voltage of 100 to 200 kV and an irradiation line width of 450 mm manufactured by Iwasaki Electric Co., Ltd., the adhesive film is irradiated with an electron beam of 160 kGy at an acceleration voltage of 150 kV. An adhesive film irradiated with rays was obtained.

Example 1
The adhesive film obtained in Production Example 4 is laminated on the liquid crystal polyester film PF1 or polyimide film obtained in Production Example 1 (Kapton H (registered trademark) manufactured by Toray DuPont), and a laminator (manufactured by Taisei Laminator Co., Ltd.). Using “First Laminator VA-700”), thermocompression bonding was performed under the conditions of an upper and lower roll temperature of 150 ° C., a linear pressure of 14.5 kg / cm, and a speed of 0.5 m / min. Subsequently, the release PET film on the surface of the laminate was peeled off to obtain a laminate comprising an organic insulating layer made of thermoplastic liquid crystal polyester and an adhesive layer. With respect to the obtained laminate, the following peel test was performed. The results are shown in Table-1.

Peel test method From the laminate obtained above, an electrolytic copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd. 3EC-VLP foil: thickness 35 μm, glossy surface roughness Ra = 0.10) on the adhesive film side of the laminate. 4 [mu] m) is bonded, and using a vacuum press ("VH1-1765" manufactured by Kitagawa Seiki Co., Ltd.), thermosetting is performed by heating at a temperature of 150 [deg.] C. for 120 minutes under a pressure of 1 MPa, and a thermoplastic liquid crystal A test piece composed of a polyester film, an adhesive layer and a copper foil was obtained. The obtained test piece was cut out for a 10 mm width peeling test, and the results of 90 ° peeling at a peeling speed of 50 mm / min are shown in Table 1.

Examples 2-3
A laminated body was obtained by the same method as in Example 1 except that the liquid crystal polyester film PF1 in Example 1 was replaced with PF2 and PF3, which were liquid crystal polyester films obtained in Production Examples 2 and 3. A body peel test was performed. The results are shown in Table-1.

Comparative Example 1
A laminated body was obtained by the same method as in Example 1 except that the liquid crystal polyester film PF1 in Example 1 was replaced with a commercially available polyimide film (Kapton H (registered trademark) manufactured by Toray DuPont). A peel test was performed. The results are shown in Table-1.

The laminate of the present invention can be laminated at a low temperature of about 150 ° C., which is impossible with a laminate using a liquid crystal polyester disclosed so far, in the step of laminating a copper foil. The peel strength was 30 N / cm or more, and it was possible to obtain a laminate having higher adhesion than a laminate using polyimide generally used so far.

Claims (17)

A laminate comprising an adhesive layer obtained from a thermosetting resin composition containing the following (A) and (B) and an organic insulating layer comprising a thermoplastic liquid crystal polyester.
(A): At least one compound selected from the following (a ₁ ), (a ₂ ), (a ₃ ), (a ₄ ), and (a ₅ ).
(A ₁ ) polyvalent carboxylic acid having two or more —COOH groups in the molecule (a ₂ ) carboxylic acid anhydride (a ₃ ) alkyl substituent having one or more —CO—O—CO— groups in the molecule phenol novolak resin having (a ₄₎ phenol adducts of aliphatic compounds containing a double bond (a ₅₎ phenol adducts of alicyclic compounds containing double bonds (B): the following (b ₁₎ and ( An epoxy group-containing copolymer obtained by polymerizing monomers containing b ₂ ).
(B ₁ ): ethylene and / or propylene (b ₂ ): monomer represented by the following formula (1)

(In the formula, R represents a C 2-18 hydrocarbon group having one or more double bonds, and the hydrogen atom of the hydrocarbon group may have a halogen atom, a hydroxyl group or a carboxyl group. X Represents a single bond or a carbonyl group.) The adhesive layer obtained from the thermosetting resin composition which (A) is 1 type (s) or 2 or more types chosen from the aliphatic polyhydric carboxylic acid which has two or more -COOH groups in a molecule | numerator is provided. The laminated body of description. An adhesive layer obtained from a thermosetting resin composition in which (A) is one or more selected from aliphatic carboxylic acid anhydrides having one or more —CO—O—CO— groups in the molecule; The laminated body of Claim 1 provided. (A) is, (a ₃₎ or laminate according to claim 1, further comprising one or adhesive layer obtained from the thermosetting resin composition is 2 kinds selected from the group shown in (a _4). The content of (b ₂₎ a structural unit derived from a monomer in (B) is provided with an adhesive layer obtained from the thermosetting resin composition is 1 to 30 parts by weight per 100 parts by weight (B) The laminated body in any one of Claims 1-4. The content of structural units derived from at (b ₁₎ (B) is, claim comprising an adhesive layer obtained from (B) thermosetting resin composition is 30 to 99 parts by weight per 100 parts by weight The laminated body in any one of 1-5. Any of Claims 1-6 provided with the contact bonding layer obtained from the thermosetting resin composition whose weight ratio of (A) and (B) is (A) / (B) = 4 / 96-50 / 50. The laminated body of crab.   The laminated body in any one of Claims 1-7 provided with the contact bonding layer obtained from the adhesive film formed by extrusion-molding the thermosetting resin composition containing (A) and (B). The laminated board in any one of Claims 1-7 provided with the contact bonding layer obtained from the adhesive film formed by apply | coating the adhesive agent containing the following (D) in addition to (A) and (B).
(D): Organic solvent and / or water   The total weight of (A) and (B) is provided with the adhesive layer obtained from the adhesive film formed by apply | coating the adhesive agent which is 10-150 weight part with respect to 100 weight part of said (D). 9. The laminated board according to 9.   The laminated board of Claim 9 or 10 provided with the contact bonding layer obtained from the adhesive film which apply | coated the adhesive agent containing said (A), (B) and (D) to a support base material, and was dried.   The laminated board according to any one of claims 8 to 11, wherein the adhesive film is provided with an adhesive film that has been subjected to electron beam irradiation treatment and modified as a bonding layer. The laminated body in any one of Claims 1-12 provided with the organic insulating layer which consists of thermoplastic liquid crystal polyester which has a structural unit derived from following (E), (F), (G).
(E) Aromatic hydroxycarboxylic acid (F) Aromatic dicarboxylic acid (G) At least one compound selected from the group consisting of aromatic diols, aromatic diamines and aromatic amines having phenolic hydroxyl groups. The laminated body in any one of Claims 1-13 provided with the organic insulating layer which consists of thermoplastic liquid crystal polyester which has a structural unit of the following (E '), (F'), (G ').
(E ′) — O—Ar ¹ —CO—
(F ′) — CO—Ar ² —CO—
(G ′) — X—Ar ³ —Y—
(In the formula, Ar ¹ represents a phenylene group, a naphthalenediyl group or a biphenyldiyl group, and Ar ² represents a group in which a phenylene group, a naphthalenediyl group, a biphenyldiyl group or a plurality of aromatic groups are condensed). Ar ³ represents a phenylene group or a group in which a plurality of aromatic groups are condensed, and X and Y represent —O— or —NH—.) The following structural units (E ′), (F ′), and (G ″) are included, and the structural unit represented by (G ″) is 10 to 35 mol% with respect to the total structural units. The laminated body in any one of Claims 1-14 provided with the organic insulating layer which consists of thermoplastic liquid-crystal polyester.
(E ′) —O—Ar ¹ —CO—
(F ′) —CO—Ar ² —CO—
(G ″) —NH—Ar ³ —Y—
(In the formula, Ar ¹ , Ar ² , Ar ³ and Y have the same definitions as above.)   The structural unit having the structural units (E ′), (F ′), and (G ″) and represented by (G ″) is 10 to 35 mol% with respect to the total structural units. 16. An organic insulating layer comprising a thermoplastic liquid crystal polyester film formed into a film by casting using a solution obtained by dissolving a thermoplastic liquid crystal polyester in an aprotic solvent and / or a halogenated phenol. The laminated body as described in. Use of the laminate according to any one of claims 1 to 16 as a coverlay film.