CN105711207A

CN105711207A - Three-layer film, method for producing three-layer film, laminated plate and printed circuit board

Info

Publication number: CN105711207A
Application number: CN201510940431.0A
Authority: CN
Inventors: 伊藤丰诚; 杉山贵之; 根津秀明
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2014-12-18
Filing date: 2015-12-16
Publication date: 2016-06-29
Also published as: JP2016117281A; TWI719955B; JP6644542B2; KR20160074407A; TW201643043A; KR102399755B1

Abstract

The invention relates to a three-layer film, a method for producing a three-layer film, a laminated plate, and a printed circuit board. The three-layer film includes a polyimide resin film and liquid crystal polymer layers taking hydroxy carboxylic acid as a liquid crystal raw group and laminated on both sides of the polyimide resin film. A thickness (T1) of the polyimide resin film and a thickness (T2) of the liquid crystal polymer layers taking the hydroxy carboxylic acid as the liquid crystal raw group satisfy the following relation formula (a) 20mum<= T1<=50mum; and (b) 0.3<=T2/T1<=1.5, wherein the two T2s are independent and may be the same or different.

Description

Trilamellar membrane, the manufacture method of trilamellar membrane, plywood and tellite

Technical field

The present invention relates to trilamellar membrane, the manufacture method of trilamellar membrane, plywood and tellite.

Background technology

The printed wiring board (printed base plate, tellite) installed in the electronic machines such as mobile phone, computer, digital household appliances uses the duplexer being provided with metal level on the insulating layer.As this duplexer, such as it is known that the duplexer (such as, patent documentation 1 ~ 2) that obtains of the layer stackup comprising polyimide resin film using the layer comprising the conductors such as metal forming with as insulating barrier.It addition, patent documentation 3 describes the duplexer using Copper Foil as metal level, being laminated with liquid-crystal polyester resin layer as insulating barrier.

It is poor that polyimide resin has water absorption, moisture-proof.Further, since be non-thermoplastic resin, therefore cannot direct laminated metal paper tinsel.It is thus possible, for instance patent documentation 4 ~ 5 describes the duplexer using liquid crystalline polymer film as insulating barrier with polyimide resin.As liquid crystalline polymer film, the film that patent documentation 6 ~ 9 is recorded can be listed.The water sorption of polyimide resin significantly affects the electrical characteristics of printed circuit board, and therefore the employing method of liquid crystalline polymer film is important for making the electrical characteristics of printed circuit board become well.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2006-008976 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2013-032532 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2007-106107 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2008-290424 publication

Patent documentation 5: Japanese Unexamined Patent Publication 2008-290425 publication

Patent documentation 6: Japanese Unexamined Patent Publication 2013-189535 publication

Patent documentation 7: Japanese Unexamined Patent Publication 2004-315678 publication

Patent documentation 8: Japanese Unexamined Patent Publication 2007-238915 publication

Patent documentation 9: Japanese Unexamined Patent Publication 2013-001902 publication.

Summary of the invention

The problem that invention is to be solved

But, the characteristic required for printed circuit board gradually steps up, and the duplexer used in printed circuit board still has the leeway of improvement.

The present invention is carried out in view of the foregoing, and its problem is, it is provided that dimensional stability when for printed circuit board duplexer and the excellent trilamellar membrane of electrical characteristics and the manufacture method of this trilamellar membrane.

Means for solving the above

The 1st aspect of the present invention is trilamellar membrane, wherein, the liquid crystalline polymer layer using hydroxy carboxylic acid as mesogen (mesogen) group it is laminated with on the two sides of polyimide resin film, the thickness (T2) of the thickness (T1) of aforementioned polyimide resin film and the aforementioned liquid crystalline polymer layer using hydroxy carboxylic acid as mesogenic group meets following relational expression (a) and (b) (wherein, two T2 are independent of one another, can be the same or different.).

(a) 20 μm≤T1≤50 μm

(b) 0.3≤T2/T1≤1.5.

In the 1st aspect of the present invention, it is preferred that contain using hydroxy carboxylic acid as the liquid crystalline polymer layer of mesogenic group and be derived from 2 hydroxybenzoic acid or the construction unit of 2-hydroxyl-6-naphthoic acid.

In the 1st aspect of the present invention, it is preferred that using hydroxy carboxylic acid as the liquid crystalline polymer layer of mesogenic group possibly together with following construction unit (1) and (2).

(1)-CO-Ar¹-CO-

(2)-X-Ar²-Y-

(in formula, Ar¹And Ar²Represent phenylene, naphthylene, biphenylene or the group shown in following formula (3) independently of one another.X and Y represents oxygen atom or imino group independently of one another.Ar¹Or Ar²The shown hydrogen atom in aforementioned group can be replaced by halogen atom, alkyl or aryl independently of one another.)

(3)-Ar³-Z-Ar⁴-

(Ar³And Ar⁴Represent phenylene or naphthylene independently of one another.Z represents oxygen atom, sulphur atom, carbonyl, sulfonyl or alkylidene.).

The 2nd aspect of the present invention is plywood, and wherein, the trilamellar membrane of aforementioned first method is used as insulating barrier, is formed with metal level at least one side of this insulating barrier.

In the 2nd aspect of the present invention, it is preferred that the maximum height (Rz) of aforementioned metal layer is formed as 0.5 ~ 2.5 μm.

In the 2nd aspect of the present invention, it is preferred that aforementioned metal layer comprises copper.

The 3rd aspect of the present invention is tellite, it uses the plywood of aforementioned 5th mode.

The 4th aspect of the present invention is the manufacture method of trilamellar membrane, it includes following operation: be coated on polyimide resin film by the liquid composition comprising solvent and liquid crystal polymer, covers the liquid composition painting process of aforementioned polyimide resin film with aforementioned liquid composition；Remove the solvent removing step of solvent in aforementioned liquid composition；And, heating treatment step, in the manufacture method of described trilamellar membrane, as foregoing liquid crystal polymer, containing being derived from 2 hydroxybenzoic acid or the construction unit of 2-hydroxyl-6-naphthoic acid and following construction unit (1) and (2).

(1)-CO-Ar¹-CO-

(2)-X-Ar²-Y-

(3)-Ar³-Z-Ar⁴-

The 5th aspect of the present invention is the manufacture method of trilamellar membrane, and it includes following operation: make polyimide resin film be impregnated in the liquid composition comprising solvent and liquid crystal polymer, covers the impregnation step of aforementioned polyimide resin film with aforementioned liquid composition；Remove the solvent removing step of solvent in aforementioned liquid composition；And, heating treatment step, in the manufacture method of described trilamellar membrane, as foregoing liquid crystal polymer, containing being derived from 2 hydroxybenzoic acid or the construction unit of 2-hydroxyl-6-naphthoic acid and following construction unit (1) and (2).

(1)-CO-Ar¹-CO-

(2)-X-Ar²-Y-

(3)-Ar³-Z-Ar⁴-

The 6th aspect of the present invention is the manufacture method of trilamellar membrane, and it includes following operation: prepare to comprise solvent and the liquid composition of liquid crystal polymer and the operation of the polyamic acid resin liquid composition as polyimide resin precursor；Aforementioned liquid composition, foregoing polyamides acid resin liquid composition, aforementioned liquid composition are coated into the operation of three layers by supporting mass successively；Remove the solvent removing step of solvent in the liquid composition of aforementioned three layers；And, trilamellar membrane formation process, in the manufacture method of described trilamellar membrane, as foregoing liquid crystal polymer, containing being derived from 2 hydroxybenzoic acid or the construction unit of 2-hydroxyl-6-naphthoic acid and following construction unit (1) and (2).

(1)-CO-Ar¹-CO-

(2)-X-Ar²-Y-

(3)-Ar³-Z-Ar⁴-

Invention effect

In accordance with the invention it is possible to provide the dimensional stability when for printed circuit board duplexer and the trilamellar membrane of electrical characteristics excellence and the manufacture method of this trilamellar membrane.

Accompanying drawing explanation

Fig. 1 is the ideograph for trilamellar membrane of the present invention is described.

Fig. 2 is the ideograph of the duplexer employing trilamellar membrane of the present invention for explanation.

Fig. 3 is the skeleton diagram of the manufacture method of the trilamellar membrane for the 3rd aspect of the present invention is described.

Detailed description of the invention

Trilamellar membrane

First, for the 1st aspect of the present invention i.e. trilamellar membrane, use Fig. 1 to illustrate.

Fig. 1 illustrates the trilamellar membrane 20 of the present invention.Trilamellar membrane 20 is laminated with liquid crystalline polymer layer 22a using hydroxy carboxylic acid as mesogenic group and 22b on the two sides of polyimide resin film 21.In other words, trilamellar membrane 20 comprises: using hydroxy carboxylic acid as liquid crystalline polymer layer 22a of mesogenic group and 22b and the polyimide resin film 21 being held in foregoing liquid crystal polymeric layer 22a and 22b.

In trilamellar membrane 20, the thickness (T1) of polyimide resin film 21 with meet following relational expression (a) and (b) using hydroxy carboxylic acid as liquid crystalline polymer layer 22a of mesogenic group and 22b thickness (T2) each other, T2a and T2b in two T2(Fig. 1) independently of one another, can be the same or different.

(a) 20 μm≤T1≤50 μm

(b) 0.3≤T2/T1≤1.5.

[polyimide resin film]

Polyimide resin is as initiation material and to carry out polycondensation and the condensed type polyimides that obtains using Diamines and tetracarboxylic dianhydride.As Diamines, it is not particularly limited, it is possible to use normally used aromatic diamines, ester ring type Diamines, aliphatic diamine class etc. in the synthesis of polyimides.Diamines can be used alone, it is also possible to combines two or more and uses.

It addition, as tetracarboxylic dianhydride, it is possible to use aromatic tetracarboxylic acid's dianhydride, ester ring type tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride etc., it is not particularly limited.Tetracarboxylic dianhydride can be used alone, it is also possible to combines two or more and uses.

It addition, above-mentioned Diamines and tetracarboxylic dianhydride at least in any one, can have one or more at least one functional groups in fluorine-based, trifluoromethyl, hydroxyl, sulfo group, carbonyl, heterocycle, chain alkyl etc..

Among this polyimides, mechanical strength in time forming polyimide resin film 21, from the viewpoint of bendability, as tetracarboxylic dianhydride, aromatic tetracarboxylic acid dianhydride is preferably used.

About Diamines, can be used alone aromatic diamines, ester ring type Diamines, aliphatic diamine class, it is also possible to be applied in combination two or more.

It addition, mechanical strength in time forming polyimide resin film 21, from the viewpoint of bendability, as diamidogen, preferably aromatic diamine.

As polyimide resin film, commercially available polyimide resin (PI) film can be used, PI film (KAPTON), the PI film (IF30, IF70, LV300) of SKC KOLON PI, INC. manufacture that such as the PI film (U-pilex S, U-pilex R) of Ube Industries, Ltd's manufacture, レデュ Port Application manufacture can be listed.

In the present invention, the thickness (T1) of polyimide resin film meets following formula (a).

(a) 20 μm≤T1≤50 μm.

Herein, the value that the thickness of polyimide resin film represents in order to average mode when being and measure thickness with contact thickness gauge at any the 5 of polyimide resin film.It should be noted that, when measuring the thickness of polyimide resin film, when being difficult to directly apply contact thickness gauge, when overlapping with liquid crystalline polymer layer 22a and 22b etc. other layer, measure the thickness of entirety as described above, take the difference between its with the thickness of other overlapping layer (utilizing the thickness that method same as described above measures), thus can also calculate.

In the present invention, from the viewpoint of easily obtaining, the thickness of polyimide resin film is preferably 20 μm≤T1≤40 μm, more preferably 20 μm≤T1≤30 μm.

When the thickness of polyimide resin film is more than above-mentioned lower limit, it can be ensured that the insulation characterisitic of trilamellar membrane and posture keep function, for time below above-mentioned higher limit, it can be ensured that the flexibility of appropriateness.

[liquid crystal polymer]

The liquid crystal polymer used in the liquid crystalline polymer layer of the trilamellar membrane of the present invention is the liquid crystal polymer using hydroxy carboxylic acid as mesogenic group.As typical case, one or more aromatic hydroxy-carboxylics polymerization of sening as an envoy to can be enumerated and obtain polymer；Make the polymer that one or more aromatic hydroxy-carboxylics obtain with at least one compound polymerization (polycondensation) in aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyl amine and aromatic diamine；And, make the polyester such as polyethylene terephthalate be polymerized the polymer obtained with aromatic hydroxy-carboxylic.

The mesogenic group being derived from hydroxy carboxylic acid is not particularly limited, and preferably comprises and is derived from 2 hydroxybenzoic acid or the construction unit of 2-hydroxyl-6-naphthoic acid.Herein, mesogenic group refers to: the molecular shape comprised in liquid crystal molecule is bar-shaped or tabular and along the high strand of the long chain rigidity of molecule.Mesogenic group may reside in any one in the main chain of liquid crystal polymer or side chain or both, if pursuing high-fire resistance, be then preferably in main chain.

In the present invention, liquid crystal polymer preferably comprises and is derived from 2 hydroxybenzoic acid or the construction unit of 2-hydroxyl-6-naphthoic acid.

Liquid crystal polymer preferably has the repetitive shown in following (1) (hereinafter sometimes referred to " repetitive (1) ".), more preferably there is the repetitive shown in repetitive (1) and following formula (2) (hereinafter sometimes referred to " repetitive (2) ".).

(1)-CO-Ar¹-CO-

(2)-X-Ar²-Y-

(3)-Ar³-Z-Ar⁴-

As aforementioned halogen atoms, fluorine atom, chlorine atom, bromine atoms and atomic iodine can be listed.

As the example of aforesaid alkyl, can list methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-hexyl, 2-ethylhexyl, n-octyl and positive decyl, its carbon number is preferably 1 ~ 10.

As the example of aforesaid aryl, can list phenyl, o-tolyl, a tolyl, p-methylphenyl, 1-naphthyl and 2-naphthyl, its carbon number is preferably 6 ~ 20.

Ar¹~Ar⁴When the shown hydrogen atom in aforementioned group is replaced by these groups, its quantity is for each Ar¹~Ar⁴Separately it is preferably less than 2 for shown aforementioned group, more preferably 1.

As the example of aforementioned alkylidene, can list methylene, ethylidene, isopropylidene, sub-normal-butyl and 2-ethyl hexylen, its carbon number is preferably 1 ~ 10.

Repetitive (1) is derived from the repetitive of the aromatic dicarboxylic acid of regulation.As repetitive (1), it is preferred that Ar¹For to phenylene (being derived from the repetitive of p-phthalic acid), Ar¹For metaphenylene (being derived from the repetitive of M-phthalic acid), Ar¹For 2,6-naphthylene (being derived from the repetitive of 2,6 naphthalene dicarboxylic acid) and Ar¹The repetitive of '-diyl (be derived from diphenyl ether-4,4 '-dicarboxylic acids for diphenyl ether-4,4).

Repetitive (2) is derived from aromatic diol, aromatic hydroxyl amine or the repetitive of aromatic diamine of regulation.As repetitive (2), it is preferred that Ar²For to phenylene (being derived from the repetitive of hydroquinone, para-aminophenol or p-phenylenediamine) and Ar²It is 4,4 '-biphenylene (be derived from 4,4 '-dihydroxybiphenyl, 4-amino-4 '-xenol or the repetitive of 4,4 '-benzidine).

The content of repetitive (1) relative to the total amount of whole repetitives (by constituting the quality of each repetitive of liquid crystal polymer divided by the formula weight of each repetitive, obtain material amount a great deal of (mole) of each repetitive, and the value obtained by they adductions) it is preferably 40 moles of below %, more preferably 10 moles of more than % and 37.5 moles of below %, more preferably 20 moles of more than % and 37.5 moles of below %, is further preferably 25 moles of more than % and 37.5 moles of below %.

Similarly, the content of repetitive (2) is preferably 40 moles of below %, more preferably 10 moles of more than % and 37.5 moles of below %, more preferably 20 moles of more than % and 37.5 moles of below % relative to the total amount of whole repetitives, is further preferably 25 moles of more than % and 37.5 moles of below %.

The content of the mesogenic group being derived from hydroxy carboxylic acid is preferably 55 moles of below %, more preferably 20 moles of more than % and 50 moles of below %, more preferably 25 moles of more than % and 45 moles of below % relative to the total amount of all repetitives, is further preferably 30 moles of more than % and 45 moles of below %.In liquid crystal polymer, when the content of the mesogenic group being derived from hydroxy carboxylic acid is higher than 55 moles of %, there is gained liquid crystal polymer and be insoluble in the tendency of aftermentioned solvent, therefore there is the tendency being difficult to obtain liquid crystalline polymer layer.

When the ratio of the content of the content of repetitive (1) and repetitive (2) represents by [content of repetitive (1)]/[content of repetitive (2)] (moles/mole), preferably 0.9/1 ~ 1/0.9, more preferably 0.95/1 ~ 1/0.95, more preferably 0.98/1 ~ 1/0.98.

It should be noted that liquid crystal polymer can have repetitive of more than two kinds (1) ~ (2) independently of one another.It addition, liquid crystal polymer can also have the repetitive outside repetitive (1) ~ (2), its content is relative to preferably more than 0 mole % of total amount of all repetitives and is 10 moles of below %, more preferably more than 0 mole of % and is 5 moles of below %.

Liquid crystal polymer has any one in X and Y or repetitive that both are imino group as repetitive (2), i.e. has the aromatic hydroxyl amine being derived from regulation repetitive and be derived from aromatic diamine repetitive in any one or both time, dissolubility in a solvent is excellent, so preferably, the most only there is any one in X and Y or repetitive that both are imino group as repetitive (2).

Liquid crystal polymer can be derived from the mesogenic group of hydroxy carboxylic acid and the polymer that repetitive (1) ~ (2) are randomly-bonded and obtain, if display liquid crystal liquid crystal property, then can also be block copolymer.

Liquid crystal polymer is preferably by making starting monomer corresponding with the repetitive constituting this polymer carry out melt polymerization, and makes resulting polymers (prepolymer) carry out the incompatible manufacture of solid polycondensation.Thereby, it is possible to the liquid crystal polymer of the high molecular that operability manufactures thermostability well, strength rigid is high.Melt polymerization can be carried out in the presence of a catalyst, as the example of this catalyst, can list the metallic compounds such as magnesium acetate, stannous acetate, butyl titanate, lead acetate, sodium acetate, potassium acetate, three stannum oxide；4-(dimethylamino) the nitrogenous heterocyclic compound such as pyridine, 1-Methylimidazole., nitrogenous heterocyclic compound is preferably used.

The flowing initial temperature of liquid crystal polymer is preferably more than 250 DEG C, more preferably more than 250 DEG C and less than 350 DEG C, more preferably more than 260 DEG C and less than 330 DEG C.Flowing initial temperature is the highest, then thermostability, strength rigid the most easily improve, and time too high, the easy step-down of dissolubility or solution viscosity in organic solvent easily uprise.

It should be noted that flowing initial temperature is also referred to as flow temperature or flowing temperature, it is to use capillary rheometer at 9.8MPa(100kgf/cm²) load-carrying under heat up with the speed of 4 DEG C/min, make liquid crystal polymer melted and when the nozzle of internal diameter 1mm and length 10mm is extruded simultaneously, display 4800Pas(48000 pool) the temperature of viscosity, become the index (with reference to little going out straight to compile, " liquid crystal polymer-synthesis shape apply-", Co., Ltd. シエ system シ, on June 5th, 1987, p.95) of the molecular weight of liquid crystal polymer.

In the present invention, liquid crystalline polymer layer can be formed by comprising the liquid composition of foregoing liquid crystal polymer and solvent.As solvent, it is preferably organic solvent, organic solvent can suitably select and use the solvent that can dissolve liquid crystal polymer used, specifically can dissolve the solvent of the concentration ([liquid crystal polymer]/[liquid crystal polymer+organic solvent]) of more than 1 mass % at 50 DEG C.

As the example of organic solvent, can list dichloromethane, chloroform, 1, the halogenated hydrocarbons such as 2-dichloroethanes, sym.-tetrachloroethane, o-dichlorohenzene；The halogenated phenols such as parachlorophenol, pentachlorophenol, Pentafluorophenol；The ethers such as diethyl ether, oxolane, 1,4-dioxane；The ketone such as acetone, Ketohexamethylene；The ester such as ethyl acetate, gamma-butyrolacton；The carbonic ester such as ethylene carbonate, propylene carbonate；The amine such as triethylamine；The nitrogen heterocyclic ring aromatic compounds such as pyridine；The nitrile such as acetonitrile, ethylene dicyanide；The amide series solvents such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, the N-Methyl pyrrolidone organic solvent of amido link (intramolecular have)；The carbamide compounds such as tetramethylurea；The nitro compound such as nitromethane, Nitrobenzol；The sulphur compound such as dimethyl sulfoxide, sulfolane；And, the phosphorus compound such as hexamethyl-phosphoramide, three normal-butyl phosphoric acid.It addition, among these organic solvents, organic solvent of more than two kinds can be applied in combination.

As organic solvent, owing to corrosivity is low, easily operate, be therefore preferably the solvent (non-protonic solvent) using aprotic compound as main constituent, particularly preferably using the aprotic compound solvent as main constituent without halogen atom.As this aprotic compound, due to easy lysate crystalline polymer, the amide series solvents such as DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone is therefore preferably used.It addition, the ratio that aprotic compound is shared by organic solvent entirety is preferably below more than below more than below more than 50 mass % and 100 mass %, more preferably 70 mass % and 100 mass %, more preferably 90 mass % and 100 mass %.

It addition, as organic solvent, due to easy lysate crystalline polymer, be therefore preferably using dipole moment be 3 ~ 5(unit: debye) compound as the solvent of main constituent, more preferably use and belong to above-mentioned aprotic compound and dipole moment is the compound of 3 ~ 5.

It addition, the ratio that the compound that dipole moment is 3 ~ 5 is shared by organic solvent entirety is preferably below more than below more than below more than 50 mass % and 100 mass %, more preferably 70 mass % and 100 mass %, more preferably 90 mass % and 100 mass %.

As belonging to aprotic compound and dipole moment is the compound of 3 ~ 5, dimethyl sulfoxide (dipole moment: 4.1 debye), N can be exemplified, N-dimethyl acetylamide (3.7 debye), DMF (3.9 debye), N-Methyl pyrrolidone (4.1 debye).

Additionally, as organic solvent, owing to easily removing, therefore it is preferably the solvent using the compound that boiling point is less than 220 DEG C under 1 atmospheric pressure as main constituent, more preferably uses and belong to the compound that boiling point is less than 220 DEG C under above-mentioned aprotic compound and 1 atmospheric pressure.It addition, the ratio that the compound that boiling point is less than 220 DEG C under 1 atmospheric pressure is shared by organic solvent entirety is preferably below more than below more than below more than 50 mass % and 100 mass %, more preferably 70 mass % and 100 mass %, more preferably 90 mass % and 100 mass %.

As the compound that boiling point is less than 220 DEG C belonged under aprotic compound and 1 atmospheric pressure, N can be exemplified, N-dimethyl acetylamide (boiling point: 160 DEG C), DMF (boiling point: 153 DEG C), N-Methyl pyrrolidone (boiling point: 202 DEG C).

(liquid composition)

The content of the liquid crystal polymer in liquid composition is preferably below more than below more than below more than 5 mass % and 60 mass %, more preferably 10 mass % and 50 mass %, more preferably 15 mass % and 45 mass % relative to the total amount of liquid crystal polymer and organic solvent, suitably adjusts in the way of can obtaining the liquid composition of desired viscosity.

It addition, liquid composition can comprise in the range of the effect not damaging trilamellar membrane of the present invention more than a kind packing material, additive, the composition such as resin outside liquid crystal polymer.

As the example of packing material, the inorganic filling materials such as silicon dioxide, aluminium oxide, titanium oxide, Barium metatitanate., strontium titanates, aluminium hydroxide, calcium carbonate can be listed；And, the organic filler material such as levelling agent, cured epoxy resin, crosslinking benzo melmac, crosslinked acrylic resin, its content is preferably below more than 0 mass parts and 100 mass parts relative to liquid crystal polymer 100 mass parts.

As the example of additive, can list levelling agent, defoamer, antioxidant, UV absorbent, fire retardant and coloring agent, its content is preferably below more than 0 mass parts and 5 mass parts relative to liquid crystal polymer 100 mass parts.

As the resin example beyond liquid crystal polymer, the thermoplastic resin beyond polypropylene, polyamide, polyester, polyphenylene sulfide, polyether-ketone, Merlon, polyether sulfone, polyphenylene oxide and the liquid crystal polymer such as modifier, Polyetherimide thereof can be listed；The elastomers such as the copolymer of glycidyl methacrylate and polyethylene；And the thermosetting resin such as phenol resin, epoxy resin, cyanate ester resin, its content is preferably below more than 0 mass parts and 20 mass parts relative to liquid crystal polymer 100 mass parts.

Liquid composition can be by mixing liquid crystal polymer, organic solvent and other composition used as desired or mix according to suitably order and prepare in the lump.When using packing material as other composition, it is preferred that after making liquid crystal polymer be dissolved in organic solvent and obtaining liquid composition, make packing material be dispersed in this liquid composition, thus prepare.

In the present invention, the thickness (T2) of liquid crystalline polymer layer, with the relation of the thickness (T1) of aforementioned polyimide resin film, meets following formula (b).

(b) 0.3≤T2/T1≤1.5.

In the present invention, " thickness of liquid crystalline polymer layer " refers to the respective thickness of the liquid crystalline polymer layer of stacking on the two sides of polyimide resin film.Specifically, T2a and T2b in Fig. 1 meets above-mentioned formula (b) respectively.

Herein, the value that the thickness of liquid crystalline polymer layer represents in order to average mode when being and measure thickness with contact thickness gauge at any the 5 of liquid crystalline polymer layer.It should be noted that, when measuring the thickness of liquid crystalline polymer layer, when being difficult to directly apply contact thickness gauge, when overlapping with polyimide resin film etc. other layer, measure the thickness of entirety as described above, take the difference between its with the thickness of other overlapping layer (utilizing the thickness that method same as described above measures), thus can also calculate.

In the present invention, the thickness (T2) of liquid crystalline polymer layer is preferably the scope of 0.35≤T2/T1≤1.4 with the relation of the thickness (T1) of above-mentioned polyimide resin film, is particularly preferably the scope of 0.4≤T2/T1≤1.3.

In the trilamellar membrane of the present invention, during for example with the polyimide resin film that thickness is 25 μm, the thickness of liquid crystalline polymer layer is preferably 7.5 μm ~ 50 μm, more preferably 8 μm ~ 40 μm, particularly preferably 9 μm ~ 35 μm.

In the trilamellar membrane of the present invention, the thickness (T2a and T2b in Fig. 1) of liquid crystalline polymer layer is independent of one another, can be the same or different.In the present invention, preferred thickness is identical, as long as playing the effect of the present invention and then not producing in the range of warpage at trilamellar membrane, then and can suitable adjustment.

Such as, when polyimide resin film has the hardness of the degree that can prevent warpage, the thickness (T2a and T2b in Fig. 1) of liquid crystalline polymer layer can arrange difference.

When making the thickness (T2a and T2b in Fig. 1) of liquid crystalline polymer layer different, such as, within the difference of the thickness of T2a and the thickness of T2b is preferably ± 10%, within more preferably ± 5%, within particularly preferably ± 3%.

Liquid crystal polymer has the agent of low hygroscopicity of excellence, insulating properties, mechanical strength etc., therefore by liquid crystalline polymer layer is laminated in the two sides of polyimide resin film, it is possible to highly suppression has the hygroscopic effect of hygroscopic polyimide resin film.Therefore, even if the tellite etc. making metal stacking obtain in the trilamellar membrane of the present invention is placed on many wet environments, when impregnated in water, it is also possible to highly suppress the electrical characteristics deterioration caused by the hygroscopicity of polyimide resin film.

Additionally, the relation of thickness (T1) about thickness (T2) and the polyimide resin film of liquid crystalline polymer layer, by being set as below the higher limit of above-mentioned regulation, make metal stacking in the case of trilamellar membrane of the present invention, it is possible to make the dimensional stability of this metal laminate become good.

And then, about the relation of thickness (T1) of thickness (T2) and the polyimide resin film of liquid crystalline polymer layer, by being set as more than the lower limit of above-mentioned regulation, it is possible to highly suppress the hygroscopic effect of polyimide resin film.Therefore, make metal stacking in the case of trilamellar membrane of the present invention, it is possible to highly show this metal laminate of sening as an envoy to transmits the effect that loss reduces.About the trilamellar membrane of the present invention, when the two sides laminated metal layer of this trilamellar membrane, especially can show the dimensional stability of height and reduce the effect transmitting loss.Therefore, the trilamellar membrane of the present invention is preferred for the duplexer obtained at the two sides laminated metal layer of this trilamellar membrane.

As the duplexer of the trilamellar membrane that can compatibly use the present invention, the most as shown in Figure 2, two sides laminated metal layer 30a, 30b of trilamellar membrane 20 in the present invention can be listed and the duplexer that obtains.That is, duplexer comprises metal level 30a and 30b and is held on the trilamellar membrane 20 of metal level 30a and 30b.

As metal level, preferably copper, aluminum, silver or comprise the alloy of more than one metals in them.Wherein, from the viewpoint of there is more superior electrical conductivity, preferably copper or copper alloy.Further, easily operating from material, can easy be formed, from the viewpoint of economy also excellence, metal level is preferably formed by metal forming, is more preferably formed by Copper Foil.When metal level is arranged at the two sides of trilamellar membrane, the material of these metal levels can be identical, it is also possible to different.

The thickness of metal level is preferably 1 ~ 50 μm, more preferably 3 ~ 35 μm, more preferably 5 ~ 20 μm.

Herein, the value that the thickness of metal level represents in order to average mode when being and measure thickness with contact thickness gauge at any the 5 of metal level.It should be noted that, when measuring the thickness of metal level, when being difficult to directly apply contact thickness gauge, when overlapping with liquid crystalline polymer layer etc. other layer, measure the thickness of entirety as described above, take the difference between its with the thickness of other overlapping layer (utilizing the thickness that method same as described above measures), thus can also calculate.

The manufacture method 1 of trilamellar membrane

The 2nd aspect of the present invention is the manufacture method of the trilamellar membrane of the 1st aspect of the present invention, it includes following operation: be coated on polyimide resin film by the liquid composition comprising solvent and liquid crystal polymer, covers the liquid composition painting process of aforementioned polyimide resin film with aforementioned liquid composition；Remove the solvent removing step of solvent in aforementioned liquid composition；And, heating treatment step, in the manufacture method of the trilamellar membrane of the described 1st aspect of the present invention, as foregoing liquid crystal polymer, containing being derived from 2 hydroxybenzoic acid or the construction unit of 2-hydroxyl-6-naphthoic acid and following construction unit (1) ~ (2).

(1)-CO-Ar¹-CO-

(2)-X-Ar²-Y-

(3)-Ar³-Z-Ar⁴-

[liquid composition painting process]

The manufacture method of the trilamellar membrane of the present invention has and is coated on polyimide resin film by the liquid composition comprising solvent and liquid crystal polymer, covers the liquid composition painting process of aforementioned polyimide resin film with aforementioned liquid composition.

The related description comprising solvent and the liquid composition of liquid crystal polymer and polyimide resin film is identical with the explanation in the trilamellar membrane of the aforementioned present invention.

As the method being coated on polyimide resin film by aforementioned liquid composition, the various means such as such as rolling method, dip coating, spraying process, curtain coating, slot coated method, silk screen print method can be listed.Temperature during coating is preferably 10 ~ 40 DEG C.

In the present invention, by above-mentioned coating process, at the two sided coatings liquid composition of polyimide resin film.Now, in the way of liquid crystalline polymer layer reaches aforementioned specific thickness, adjust the coating weight of liquid composition.

[solvent removing step]

After aforementioned [liquid composition painting process], remove the solvent in aforementioned liquid composition.

Herein, the minimizing technology of solvent is not particularly limited, and the evaporation preferably by solvent is carried out.As the method making this solvent evaporate, can list heating, reduce pressure, the method such as ventilation, wherein, from the viewpoint of production efficiency, operability, preferably carry out heating and making it evaporate, more preferably carry out heating while ventilating and make it evaporate.

Heat treated in solvent removing step suitably can select by being applied to the solvent of liquid composite, with 60 ~ 200 DEG C of heat treated 60 ~ 600 seconds, and preferably 120 ~ 600 seconds.By being set to more than lower limit, solvent is sufficiently removed, and the adhesion of resulting three-layer film is suppressed.

It addition, without removing solvent completely in [solvent removing step], residual solvent can be removed in following [heating treatment step].From the viewpoint of the rough surface preventing liquid crystalline polymer layer, preferably by [solvent removing step] solvent should be removed in advance.

[heating treatment step]

After aforementioned [solvent removing step], carry out heat treated.Heat treated such as can use the method under not reactive gas atmosphere, trilamellar membrane being applied heat and heat.Heat treated condition suitably adjusts according to the liquid composition used, such as, carry out 1 minute ~ 4 hours with the scope of 250 DEG C ~ 400 DEG C.

In the manufacture method of the trilamellar membrane of the 2nd aspect of the present invention, first to the single spreading liquid composition of polyimide resin film, remove the solvent in aforementioned liquid composition.Then, another side is repeated this operation, finally carries out heat treated such that it is able to obtain the trilamellar membrane of the 1st aspect of the present invention.

The manufacture method 2 of trilamellar membrane

The 3rd aspect of the present invention is the manufacture method of the trilamellar membrane of the 1st aspect of the present invention, it includes following operation: make polyimide resin film be impregnated in the liquid composition comprising solvent and liquid crystal polymer, covers the impregnation step of aforementioned polyimide resin film with aforementioned liquid composition；Remove the solvent removing step of solvent in aforementioned liquid composition；And, heating treatment step, in described manufacture method, as foregoing liquid crystal polymer, containing being derived from 2 hydroxybenzoic acid or the construction unit of 2-hydroxyl-6-naphthoic acid and following construction unit.

(1)-CO-Ar¹-CO-

(2)-X-Ar²-Y-

(3)-Ar³-Z-Ar⁴-

[impregnation step]

In impregnation step, polyimide resin film is made to be impregnated in the liquid composition comprising solvent and liquid crystal polymer.The infiltration time is preferably 30 seconds ~ 5 minutes.Temperature during infiltration is preferably 10 ~ 40 DEG C.

Comprise solvent identical with the explanation in the trilamellar membrane of the aforementioned present invention with the related description of polyimide resin film with the liquid composition of liquid crystal polymer.

After impregnation step, make the polyimide resin film infiltrating liquid composition through the narrow pair of rolls of its thickness of gap-ratio.By this operation, it is possible to remove excess and be attached to the liquid composition on polyimide resin film surface.

Fig. 3 is for illustrating that the polyimide resin film of use strip carries out impregnation step and the roller skeleton diagram through the method for operation continuously.Wherein, illustrated herein are an example, the impregnation step in the present invention is not limited to example shown herein.

Polyimide resin film 10 is by deflector roll 4 and deflector roll G₁Induce and move to the direction of arrow, maceration tank 3 impregnated in liquid composition W, then, just infiltrated the polyimide resin film 11 after liquid composition and be raised from maceration tank 3, and be transferred to the squeezing roller 5 possessing pair of rolls 5A and 5B.Pair of rolls 5A and 5B are oppositely disposed in the way of clamping aforementioned polyimide resin film 11, and the mode at least narrow than the thickness of aforementioned polyimide resin film 11 (include polyimide resin film 10 and the gross thickness being infiltrated in including its liquid composition W) according to their interval is adjusted.Aforementioned polyimide resin film 11 is by through such pair of rolls 5A and 5B thus by mud jacking, and unnecessary liquid composition is removed, and becomes liquid composition simultaneously and is fully infiltrated in the liquid composition infiltration polyimide resin film 12 of inside.

Pair of rolls 5A and 5B can be with autorotation (rotations), it is also possible to rotate along with the traveling of the polyimide resin film 11 after just infiltrating liquid composition.Pair of rolls 5A and 5B carry out time rotational, the adhesion amount of the liquid composition can being easily adjusted in liquid composition infiltration polyimide resin film 12, it addition, also be able to be adequately formed the liquid composition as target to infiltrate the surface of polyimide resin film, the flatness on surface improves.

About the thickness of liquid crystalline polymer layer, by adjusting speed, the interval between pair of rolls 5A and 5B squeezing roller 5 mentioned from maceration tank 3 such that it is able to be adjusted the trilamellar membrane to regulation thickness.

[solvent removing step] in the 3rd aspect of the present invention is identical with the explanation in the aforementioned 2nd aspect of the present invention with the related description of [heating process].

Specifically, as [solvent removing step], by the aforementioned liquid composition infiltration polyimide resin film that have passed through between roller 5A and 5B with 60 ~ 200 DEG C of heat treated 60 ~ 600 seconds, preferably 120 ~ 600 seconds.

By this heat treated, it is infiltrated in the solvent evaporation of the liquid composition in liquid composition infiltration polyimide resin film and is removed such that it is able to obtain the trilamellar membrane as target.

Further, as [heating process], such as, the heat treated of 1 minute ~ 4 hours is carried out with the scope of 250 DEG C ~ 400 DEG C.By setting the temperature and time of heat treated in this wise, it is possible to stably obtain the trilamellar membrane that emptying aperture (ボイ De) is minimized.

The manufacture method 3 of trilamellar membrane

The 4th aspect of the present invention is the manufacture method of the trilamellar membrane of the 1st aspect of the present invention, and it includes following operation: prepare to comprise solvent and the liquid composition of liquid crystal polymer and the operation of the polyamic acid resin liquid composition as polyimide resin precursor；Aforementioned liquid composition, foregoing polyamides acid resin liquid composition, aforementioned liquid composition are coated into the operation of three layers by supporting mass successively；Remove the solvent removing step of solvent in the liquid composition of aforementioned three layers；And, heating treatment step, in described manufacture method, as foregoing liquid crystal polymer, containing being derived from 2 hydroxybenzoic acid or the construction unit of 2-hydroxyl-6-naphthoic acid and following construction unit.

(1)-CO-Ar¹-CO-

(2)-X-Ar²-Y-

(3)-Ar³-Z-Ar⁴-

[polyamic acid resin liquid composition]

Polyimide resin can be obtained by the precursor of polyimides, i.e. by being obtained by the dehydration conversion reaction of polyamic acid.As the method carrying out this conversion reaction, it is known to the thermal curing method carried out merely with heat and the chemical curing method the two method of use chemical dehydrator.

Polyamic acid such as, as patent documentation 1 is recorded, can be polymerized in raw material by making tetracarboxylic dianhydride and diamidogen, thus obtain.By the heating (thermal curing method) or chemistry closed loop agent utilizing more than 200 DEG C, polyamic acid is processed (chemical curing method) such that it is able to advance cyclodehydration reaction to obtain polyimide resin.

[on supporting mass by comprise the solvent liquid composition with liquid crystal polymer, polyamic acid resin liquid composition, comprise solvent be coated with successively with the liquid composition of liquid crystal polymer walk into the operation of three layers]

In this operation, as supporting mass, glass etc. generally can be used, it is possible to use conductor.As described conductor, metallic plate or the metal formings such as gold, silver, copper, aluminum, nickel, rustless steel can be listed.

As comprising liquid composition and the polyamic acid resin liquid composition curtain coating method on supporting mass of solvent and liquid crystal polymer, solvent and the liquid composition of liquid crystal polymer is comprised or polyamic acid resin liquid composition filters with filter etc. as required by aforementioned, remove after comprising the foreign body comprised in solvent and the liquid composition of liquid crystal polymer and polyamic acid resin liquid composition, supporting mass utilizes rolling method, dip coating, spraying process, spin-coating method, curtain coating, slot coated method, the various means such as silk screen print method carry out surface and smooth and be cast equably, thereafter solvent is removed, it is hereby achieved that.

By comprising the liquid composition of solvent and liquid crystal polymer on supporting mass, polyamic acid resin liquid composition, the liquid composition that comprises solvent and liquid crystal polymer are coated into three layers successively.Now, in the way of liquid crystalline polymer layer reaches aforementioned specific thickness, adjust the coating weight of the liquid composition comprising solvent and liquid crystal polymer.

The related description of [solvent removing step] in the 4th aspect of the present invention is identical with the explanation in the aforementioned 2nd aspect of the present invention.

[trilamellar membrane formation process]

Then carry out heat treated, peel off supporting mass and trilamellar membrane can be obtained.Herein, replace carrying out heat treated, it is also possible to utilize chemistry closed loop agent to process.As chemical closed loop agent now, it is possible to use the chemical closed loop agent used for being obtained polyimides by polyamic acid, it is possible to use such as pyridine, acetic anhydride, benzoic acid etc..When carrying out heat treated, the temperature range of 250 ~ 400 DEG C can be made in a nitrogen atmosphere.

In the manufacture method of the trilamellar membrane of the 4th aspect of the present invention, on supporting mass, first coating comprises the liquid composition of solvent and liquid crystal polymer, removes the solvent in aforementioned liquid composition.Then, it is coated with polyamic acid resin liquid composition, removes the solvent of foregoing polyamides acid resin liquid composition.And then, coating comprises the liquid composition of solvent and liquid crystal polymer, removes the solvent in aforementioned liquid composition.Process finally by heat treated or chemistry closed loop agent, peel off from supporting mass such that it is able to obtain trilamellar membrane.

Additionally, in the manufacture method of the trilamellar membrane of the 4th aspect of the present invention, supporting mass is coated with successively by comprising the liquid composition of solvent and liquid crystal polymer, polyamic acid resin liquid composition and the liquid composition comprising solvent and liquid crystal polymer, removes the solvent in aforementioned liquid composition.Finally utilize heat treated or chemistry closed loop agent to process, peel off from supporting mass, such that it is able to obtain trilamellar membrane.

Plywood

The 5th aspect of the present invention is plywood, and wherein, the trilamellar membrane utilizing aforementioned the second ~ tetra-mode to obtain is used as insulating barrier, and at least one side of this insulating barrier is formed with metal level.

About the plywood of the present invention, at least one side at aforementioned trilamellar membrane is formed with metal level, is preferably laminated with metal level on two sides.That is, plywood preferably includes: the 1st metal level and the 2nd metal level and be held on the 1st metal level and the trilamellar membrane of the 2nd metal level.Be laminated with the plywood of metal level as the two sides at aforementioned trilamellar membrane, more specifically, be the duplexer shown in Fig. 2, be 30a and 30b in Fig. 2 be the plywood of metal level.

Illustrate for the metal level being laminated in above-mentioned trilamellar membrane.

Metal level in the plywood of the present invention be with 300 DEG C carry out the tensile modulus of elasticity after heat treatment as 60GPa below, breakaway poing stress as 150MPa below Copper Foil.As the lower limit of this tensile modulus of elasticity, it is more than 10GPa, preferably more than 20GPa in usage range.As the lower limit of this breakaway poing stress, in usage range, it is preferably more than 20MPa, particularly preferably more than 30MPa.As the kind of metal level used in the present invention, can be any one in the layer formed by electrolysis, the layer that formed by rolling, as an example of the metal level of above-mentioned characteristic, in order to obtain Copper Foil, can be by High well known in the art Temperature Elongation(high temperature high elongation rate Copper Foil, hereinafter referred to as " HTE Copper Foil "), in commercially available as rolled copper foil Copper Foil, obtain tensile modulus of elasticity and breakaway poing stress according to the method for JIS C2151 defined, and select.

Thickness preferably greater than 5 μm of the metal level used in the plywood of the present invention and be the scope of below 35 μm.Particularly preferably it is in the scope of 9 ~ 28 μm.When the thickness of metal level is above-mentioned scope, being easily adjusted the tension force of metal level when manufacturing plywood, the bendability of resultant layer lamination improves further, so preferably.

Herein, the value that the thickness of metal level represents in order to average mode when being and measure thickness with contact thickness gauge at any the 5 of metal level.It should be noted that, when measuring the thickness of metal level, when being difficult to directly apply contact thickness gauge, when overlapping with trilamellar membrane etc. other layer, measure the thickness of entirety as described above, take the difference between its with the thickness of other overlapping layer (utilizing the thickness that method same as described above measures), thus can also calculate.

It addition, the maximum height (Rz) of the metal level in plywood is preferably in the range of 0.5 ~ 2.5 μm, more preferably in the range of 0.6 ~ 2.4 μm, particularly preferably in the range of 0.6 ~ 2.2 μm.

nullConcrete example be shown as in the present invention application metal level and preferably example time，It is preferably Copper Foil，Wherein，As HTE Copper Foil，Such as SQ-HTE Copper Foil (Mitsu Mining & Smelting Co., Ltd's system) can be listed、3EC-M3S-HTE Copper Foil (Mitsu Mining & Smelting Co., Ltd's system)、NS-HTE Copper Foil (Mitsu Mining & Smelting Co., Ltd's system)、3EC-HTE Copper Foil (Mitsu Mining & Smelting Co., Ltd's system)、F2-WS Copper Foil (Furukawa Co., Ltd. system)、HLB(Nippon Denkai, Ltd. system)、Bo Fen Co., Ltd. of CF-T4X-DS-SVR(FUKUDA METAL system) etc.，As rolled copper foil，Bo Fen Co., Ltd. of such as RCF-T5B-HPC(FUKUDA METAL system can be listed)、BHY-22B-T(JX Kuang Shi metal Co., Ltd. system)、BHY-22B-HA(JX Kuang Shi metal Co., Ltd. system)、BHYA-T(JX Kuang Shi metal Co., Ltd. system)、BHYA-HA(JX Kuang Shi metal Co., Ltd. system) etc..These Copper Foils can obtain the most from the market.

By using the Copper Foil with above-mentioned characteristic in the plywood of the present invention, it is possible to realize the plywood that metal level is the best with the adaptation of resin bed also excellent, flexibility and folding resistance.

Carry out integrated method as by aforementioned trilamellar membrane with metal level, can compatibly apply the method that metal level and trilamellar membrane are carried out hot pressing.Can list and such as use conventional pressuring machine to keep 10 minutes ~ 60 minutes with the pressure of 200 ~ 350 DEG C, 3 ~ 10MPa, thus the method carrying out hot pressing.

So operation and liquid crystal polymer plywood of the present invention of obtaining from the excellent characteristic such as dimensional stability, agent of low hygroscopicity, the semiconductor packages obtained by lamination method etc. that can be applied suitably to receive much concern in recent years, motherboard multilayer printed board, flexible printing wiring substrate, tape automated bonds film etc..

The 6th aspect of the present invention is that aforementioned trilamellar membrane is used as the tellite of insulating barrier.The tellite of the present invention, in addition to using aforementioned trilamellar membrane as insulating barrier, can present identical composition with known tellite, it is possible to use identical method manufactures.That is, tellite includes: the insulating barrier that comprises trilamellar membrane and be positioned at the circuit pattern on aforementioned trilamellar membrane.In other words, tellite includes: comprise the circuit pattern formed in the insulating barrier of at least one trilamellar membrane and the one at least the 1st and the 2nd of insulating barrier.Insulating barrier can be formed by a trilamellar membrane, it is also possible to is laminated with multiple trilamellar membrane.Circuit pattern can be only located at the 1st, it is also possible to there is the 1st circuit pattern on the 1st, there is the 2nd circuit pattern on the 2nd.

The tellite of the present invention can manufacture as follows: be such as produced on the insulating barrier formed by a piece of aforementioned trilamellar membrane or be laminated with the aforementioned trilamellar membrane of multi-disc insulating barrier, one or two sides be provided with the duplexer of metal level, the metal level of described duplexer is waited by etching and forms the circuit pattern of regulation, will be formed with more than the direct stacking of duplexer of this circuit pattern or stacking two panels as required, thus manufacture.The tellite of the present invention is preferably laminated with metal level on the two sides of trilamellar membrane.In other words, tellite preferably includes: trilamellar membrane, is positioned at the 1st circuit pattern of the 1st of trilamellar membrane and is positioned at the 2nd circuit pattern of the 2nd of trilamellar membrane.

When being laminated with the insulating barrier of the aforementioned trilamellar membrane of multi-disc, these multi-disc trilamellar membranes can be the most identical, it is also possible to only part is identical, it is also possible to all different.As long as being just not particularly limited it addition, its sheet number is more than 2.Such insulation layers, as multi-disc trilamellar membrane can be made overlapping along its thickness direction, carries out adding hot pressing and making it mutually merge, carries out integration and make.

The material of metal level preferably copper, aluminum, silver or comprise the alloy of more than one metals in them.Wherein, from the viewpoint of there is more excellent electric conductivity, preferably copper or copper alloy.Further, easily operating from material, can be simply forming, from the viewpoint of economy also excellence, metal level is preferably formed by metal forming, is more preferably formed by Copper Foil.When metal level is arranged at the two sides of insulating barrier, the material of these metal levels can be identical, it is also possible to different.

As the method arranging metal level, can exemplify: make metal forming be fused to the method for surface of insulating layer, make with bonding agent metal forming be adhered to the method for surface of insulating layer, the method for plating surface of insulating layer, the method that utilizes silk screen print method or sputtering method metal powder or metallic particles to carry out covering.

When insulating barrier is laminated with multi-disc aforementioned trilamellar membrane, these trilamellar membranes are overlapped along its thickness direction, at the surface being positioned at one or two trilamellar membrane outermost further overlapped metal paper tinsel, these metal formings and multi-disc trilamellar membrane are added hot pressing, thus metal level can be set in the one or two sides of insulating barrier when forming insulating barrier simultaneously.

By metal level is carried out pattern formation, thus form circuit pattern.As the method forming circuit pattern, etching etc. can be exemplified.It is briefly described for etching (processing).First, sheltering of this metal level is carried out in the way of this metal level forms the circuit pattern of regulation, for masked metal layer part and the most masked metal layer part, metal layer part damp process (agent treated) this etching and processing of the latter is removed such that it is able to implement described etching.As the reagent used in this etching and processing, such as ferric chloride in aqueous solution can be listed.It addition, shelter as this, it is possible to use commercially available etching resist, dry film.

Then, with acetone, sodium hydrate aqueous solution, etching resist, dry film are removed from masked metal layer part.So operate and metal level is carried out pattern formation such that it is able to form the circuit pattern (wiring) of regulation.

Embodiment

Hereinafter, use embodiment to further illustrate the present invention, but the present invention is not limited to embodiment.

In the reactor possessing agitating device, torquemeter, nitrogen ingress pipe, thermometer and reflux condenser, (set forth below is " HNA " to put into 2-hydroxyl-6-naphthoic acid.) 677.4g(3.6 mole), (set forth below be " APAP " to 4-hydroxyacetanilide.) 332.6g(2.2 mole), (set forth below be " IPA " to phthalic acid.) 99.7g(0.6 mole), diphenyl ether-4,4 ' (set forth below be " DEDA " to-dioctyl phthalate.) 413.2g(1.6 mole) and acetic anhydride 673.8g(6.6 mole).

After fully replacing with nitrogen in reactor, within time-consuming 15 minutes under stream of nitrogen gas, it is warming up to 150 DEG C, keeps temperature and reflux 3 hours.

Thereafter, the by-product acetic acid and unreacted acetic anhydride distillated is removed in distillation, within the most time-consuming 170 minutes, is warming up to 320 DEG C, will confirm that the moment that moment of torsion rises regards as reaction and terminates, and takes out content.Gained solid constituent is cooled to room temperature, after pulverizing with Roughpulverizer, uses polarizing microscope (NIKON company ECLIPSE LV100POV) to observe, thus confirms and show liquid crystalline phase distinctive schlieren pattern at 230 DEG C.And then, the liquid crystal polymer of powder is kept 3 hours with 250 DEG C in a nitrogen atmosphere, solid phase advances polyreaction.Gained liquid crystalline polymer powders 100g is added to METHYLPYRROLIDONE 900g, is heated to 120 DEG C and makes it be completely dissolved, obtain the liquid crystal polymer liquid composite (1) that brown is transparent.

In the reactor possessing agitating device, torquemeter, nitrogen ingress pipe, thermometer and reflux condenser, (set forth below is " APAP " to put into 4-hydroxyacetanilide.) 332.6g(2.2 mole), (set forth below be " IPA " to phthalic acid.) 99.7g(0.6 mole), diphenyl ether-4,4 ' (set forth below be " DEDA " to-dioctyl phthalate.) 413.2g(1.6 mole) and acetic anhydride 269.5(2.6 mole).After fully replacing with nitrogen in reactor, within time-consuming 15 minutes under stream of nitrogen gas, it is warming up to 150 DEG C, keeps temperature and reflux 3 hours.

Thereafter, the by-product acetic acid and unreacted acetic anhydride distillated is removed in distillation, within the most time-consuming 170 minutes, is warming up to 320 DEG C, will confirm that the moment that moment of torsion rises regards as reaction and terminates, and takes out content.Gained solid constituent is cooled to room temperature, after pulverizing with Roughpulverizer, while room temperature to 400 DEG C, implements polarized light microscope observing, but cannot observe liquid crystalline phase distinctive schlieren pattern.

[embodiment 1]

KAPTON H(レデュ Port Application system in thickness 25 μm as commercial polyimide resin molding) on, use film applicator (coating thickness is 100 μm) at its single spreading liquid crystal polymer liquid composite (1), solvent is removed so that 100 DEG C carry out heating with air drier, repeat this operation on the other surface, by high temperature air drying machine heat treated to 300 DEG C, thus obtain trilamellar membrane (liquid crystal polymer/polyimides/μm/10, μm/25, liquid crystal polymer=10 μm).

Using trilamellar membrane obtained above as insulating barrier, its two sides laminated copper foil (" BHY-22B-T " (thickness is 18 μm, Rz=0.7 μm) of JX Nippon Mining & Metals Co., Ltd.).Utilize high-temperature vacuum pressuring machine (" KVHC-PRESS " of Kitagawaseiki Co., Ltd., long 300mm, wide 300mm), under conditions of temperature 340 DEG C, pressure 5MPa, within time-consuming 20 minutes, carry out hot pressing and make its integration, thus obtain two sides copper-clad laminated board.

For two sides obtained above copper-clad laminated board, carrying out TDR mensuration, make tellite in the way of reaching 50 Ω, result defines has sealant (grand And wiring width is 110 μm, the circuit pattern of a length of 100mm layer).

For being formed with the printed circuit pattern of circuit pattern, use Agilent The mensuration probe " E8363B " of Technologies, measures loss (S21 parameter).Before and after impregnating 48 hours in water with 23 DEG C, measure the loss under frequency 5GHz, 10GHz, 20GHz, 40GHz.

The loss under 5GHz, 10GHz, 20GHz, 40GHz before impregnating in water is shown in table 3,4.It addition, the rate of change of the loss (frequency is as 5GHz) before and after impregnating 48 hours with 23 DEG C is shown in table 3,4.

Use ferric chloride solution (Mu Tian Co., Ltd. system, 40 ° of Baumes), whole Copper Foil is removed from the copper-clad laminated board of two sides, according to JIS C6481 " printed wiring board-use copper-clad laminated board test method ", use thermo-mechanical analysis device (Co., Ltd. system " Thermo plus of science TMA8310 "), the load-carrying to test film (insulating barrier) the applying 2.5g of 20mm × 50mm, measure the face thermal expansion coefficient (temperature range is 50 ~ 250 DEG C: scanning for the first time) when being warming up to 250 DEG C with 5 DEG C/min under stream of nitrogen gas simultaneously.The results are shown in table 1 and 2.

[embodiment 2]

In embodiment 1, the coating thickness of film applicator is changed to 200 μm, obtains trilamellar membrane (liquid crystal polymer/polyimides/μm/20, μm/25, liquid crystal polymer=20 μm), in addition, carry out identical operation, make copper-clad laminated board.For gained copper-clad laminated board, carrying out TDR mensuration, make tellite in the way of reaching 50 Ω, its wiring width of result reaches 142 μm, length reaches 100mm.

[embodiment 3]

In embodiment 1, use the Upilex S(Ube Industries, Ltd system of thickness 25 μm as commercial polyimide resin molding), in addition, carry out identical operation, make copper-clad laminated board.For gained copper-clad laminated board, carrying out TDR mensuration, make tellite in the way of reaching 50 Ω, its wiring width of result is 110 μm, a length of 100mm.

[embodiment 4]

In embodiment 1, laminated copper foil (" F2-WS " (thickness is 18 μm, Rz=2.1 μm) of Furukawa Co., Ltd.), in addition, carry out identical operation, make copper-clad laminated board.For gained copper-clad laminated board, carrying out TDR mensuration, make tellite in the way of reaching 50 Ω, its wiring width of result reaches 110 μm, length reaches 100mm.

[embodiment 5]

In embodiment 1, the coating thickness of film applicator is changed to 250 μm, obtains trilamellar membrane (liquid crystal polymer/polyimides/μm/25, μm/25, liquid crystal polymer=25 μm), in addition, carry out identical operation, make copper-clad laminated board.

[embodiment 6]

In embodiment 1, the coating thickness of film applicator is changed to 335 μm, obtains trilamellar membrane (liquid crystal polymer/polyimides/μm/33.5, μm/25, liquid crystal polymer=33.5 μm), in addition, carry out identical operation, make copper-clad laminated board.

[comparative example 1]

In embodiment 1, the coating thickness of film applicator is changed to 50 μm, obtains trilamellar membrane (liquid crystal polymer/polyimides/μm/5, μm/25, liquid crystal polymer=5 μm), in addition, carry out identical operation, make copper-clad laminated board.For gained copper-clad laminated board, carrying out TDR mensuration, make tellite in the way of reaching 50 Ω, its wiring width of result reaches 95 μm, length reaches 100mm.Understand in water the change of loss before and after dipping greatly to 23%.

[comparative example 2]

Using ESPANEX-MB(Nippon Steel & Sumitomo Metal Corporation system, polyimides thickness is 50 μm), carry out TDR mensuration, tellite is made in the way of reaching 50 Ω, its wiring width of result reaches 110 μm, length reaches 100mm, and described ESPANEX-MB is the use of the copper-clad laminated board of commercial polyimide resin molding.

Then, for model sample, use the mensuration probe " E8363B " of Agilent Technologies Co., Ltd., measure the loss (S21 parameter) of tellite.

Understand in water the change of loss before and after dipping greatly to 35%.

[comparative example 3]

On Copper Foil (" BHY-22B-T " (thickness is 18 μm, Rz=0.7 μm) of JX Nippon Mining & Metals Co., Ltd.), use film applicator (coating thickness is 500 μm) at its single spreading liquid crystal polymer liquid composite (1), air drier is used to remove solvent so that 100 DEG C carry out heating, by high temperature air drying machine heat treated to 300 DEG C, thus obtain one side copper-clad laminated board (50 μm).

Further laminated copper foil (" BHY-22B-T " (thickness is 18 μm, Rz=0.7 μm) of JX Nippon Mining & Metals Co., Ltd.) in the liquid crystal polymer of one side copper-clad laminated board obtained above, utilize high-temperature vacuum pressuring machine (" KVHC-PRESS " of Kitagawaseiki Co., Ltd., long 300mm, wide 300mm), under conditions of temperature 340 DEG C, pressure 5MPa, within time-consuming 20 minutes, carry out hot pressing and make its integration, thus obtain two sides copper-clad laminated board.

Use ferric chloride solution (Mu Tian Co., Ltd. system, 40 ° of Baumes), whole Copper Foil is removed from the copper-clad laminated board of two sides, according to JIS C6481 " printed wiring board-use copper-clad laminated board test method ", use thermo-mechanical analysis device (Co., Ltd.'s system " Thermo plus TMA8310 " of science), test film (insulating barrier) to 20mm × 50mm applies the load-carrying of 2.5g, measures the face thermal expansion coefficient (temperature range is 50 ~ 250 DEG C: scanning for the first time) when being warming up to 250 DEG C with 5 DEG C/min under stream of nitrogen gas simultaneously.Understand: compared with trilamellar membrane, significantly expand, change in size big.

[comparative example 4]

Using commercially available liquid crystalline polymer film (ベ Network スタ 50 μm of KURARAY company) as insulating barrier, its two sides laminated copper foil (" BHY-22B-T " (thickness is 18 μm, Rz=0.7 μm) of JX Nippon Mining & Metals Co., Ltd.).Used high-temperature vacuum pressuring machine (" KVHC-PRESS " of Kitagawaseiki Co., Ltd., long 300mm, wide 300mm), under conditions of temperature 340 DEG C, pressure 5MPa, within time-consuming 20 minutes, carry out hot pressing and make its integration, thus obtain two sides copper-clad laminated board.

Use ferric chloride solution (Mu Tian Co., Ltd. system, 40 ° of Baumes), whole Copper Foil is removed from the copper-clad laminated board of two sides, according to JIS C6481 " printed wiring board-use copper-clad laminated board test method ", use thermo-mechanical analysis device (Co., Ltd. system " Thermo plus of science TMA8310 "), the load-carrying to test film (insulating barrier) the applying 2.5g of 20mm × 50mm, measure the face thermal expansion coefficient (temperature range is 50 ~ 250 DEG C: scanning for the first time) when being warming up to 250 DEG C with 5 DEG C/min under stream of nitrogen gas simultaneously.Understand: compared with trilamellar membrane, significantly shrink, change in size big.

[table 1]

[table 2]

[table 3]

[table 4]

As shown in the above results, compared with the two sides copper-clad laminated board of comparative example 1, the rate of change employing the two sides copper-clad laminated board of embodiment 1 ~ 4 of trilamellar membrane of the present invention loss before and after water retting is low, and then dimensional stability is the best.

It addition, as embodiment 5 ~ 6, even if in the case of thickening liquid crystalline polymer layer, dimensional stability is the best.The liquid crystalline polymer layer of the trilamellar membrane of embodiment 5 ~ 6 is thicker, therefore when the trilamellar membrane using embodiment 5 ~ 6 makes tellite, it is possible to the rate of change of the loss playing this tellite fully is reduced to equal with embodiment 1 ~ 4 or equal above effect.

It should be noted that compared with the trilamellar membrane of the present invention, the change in size of comparative example 3 ~ 4 is big, therefore it is not transmitted the mensuration of loss.

As it has been described above, in the embodiment of this specification, by being coated on polyimide resin film by the liquid composition comprising solvent and liquid crystal polymer, thus manufacture trilamellar membrane.About trilamellar membrane, in addition to the method, following<method manufacturing trilamellar membrane based on infiltration>or<based on being coated with the method manufacturing trilamellar membrane successively>can also be utilized to manufacture, utilize the trilamellar membrane of the method manufacture can play identical effect with the trilamellar membrane of manufacture in above-described embodiment.

Using the KAPTON 200H(レデュ Port Application system as commercial polyimide resin molding；50 μm) mention after 1 minute with room temperature immersion in liquid crystal polymer liquid composite (1), after passing through between pair of rolls to excess be attached to the liquid crystal polymer removal on surface, solvent is made to evaporate with air drier, and then use high temperature air drying machine to carry out heat treated such that it is able to make trilamellar membrane.

Now, by adjusting pull rate, it is also possible to adjust the thickness of liquid crystal polymer.

As supporting mass, liquid crystal polymer liquid composite (1), polyamic acid resin liquid composition, liquid crystal polymer liquid composite (1) are coated with by SUS paper tinsel successively, air drier is used to remove solvent so that 100 DEG C carry out heating, then heat treated is to 330 DEG C, peel off from supporting mass such that it is able to manufacture trilamellar membrane.

Industrial usability

Description of reference numerals

20 ... trilamellar membrane；21 ... polyimide resin film；22a, 22b ... liquid crystalline polymer layer；30a, 30b ... metal level；3 ... maceration tank；4 ... deflector roll；5 ... squeezing roller；5A, 5B ... roller；10 ... polyimide resin film；11 ... the just polyimide resin film after infiltration liquid composition；12 ... liquid composition infiltration polyimide resin film；W ... liquid composition；G₁... deflector roll.

Claims

1. trilamellar membrane, wherein, the two sides of polyimide resin film is laminated with the liquid crystalline polymer layer using hydroxy carboxylic acid as mesogenic group, the thickness (T1) of described polyimide resin film meets following relational expression (a) and (b) with the thickness (T2) of the described liquid crystalline polymer layer using hydroxy carboxylic acid as mesogenic group, wherein, two T2 are independent of one another, can be the same or different

(a) 20 μm≤T1≤50 μm

(b) 0.3≤T2/T1≤1.5.

Trilamellar membrane the most according to claim 1, wherein, the described liquid crystalline polymer layer using hydroxy carboxylic acid as mesogenic group contains and is derived from 2 hydroxybenzoic acid or the construction unit of 2-hydroxyl-6-naphthoic acid.

Trilamellar membrane the most according to claim 1 and 2, wherein, the described liquid crystalline polymer layer using hydroxy carboxylic acid as mesogenic group is possibly together with following construction unit (1) and (2):

(1)-CO-Ar¹-CO-

(2)-X-Ar²-Y-

In formula, Ar¹And Ar²Represent phenylene, naphthylene, biphenylene or the group shown in following formula (3) independently of one another；X and Y represents oxygen atom or imino group independently of one another；Ar¹Or Ar²The shown hydrogen atom in described group can be replaced by halogen atom, alkyl or aryl independently of one another,

(3)-Ar³-Z-Ar⁴-

Ar³And Ar⁴Represent phenylene or naphthylene independently of one another；Z represents oxygen atom, sulphur atom, carbonyl, sulfonyl or alkylidene.

4. plywood, wherein, the trilamellar membrane described in claim 1 or 2 is used as insulating barrier, is formed with metal level at least one side of this insulating barrier.

Plywood the most according to claim 4, wherein, maximum height Rz of described metal level is 0.5 ~ 2.5 μm.

Plywood the most according to claim 4, wherein, described metal level comprises copper.

Plywood the most according to claim 5, wherein, described metal level comprises copper.

8. tellite, it uses the plywood described in claim 4.

9. tellite, it uses the plywood described in claim 5.

10. tellite, it uses the plywood described in claim 6.

11. tellites, it use the plywood described in claim 7.

The manufacture method of 12. trilamellar membranes, it includes following operation:

The liquid composition comprising solvent and liquid crystal polymer is coated on polyimide resin film, covers the liquid composition painting process of described polyimide resin film with described liquid composition；

Remove the solvent removing step of solvent in described liquid composition；And

Heating treatment step,

In the manufacture method of described trilamellar membrane, as described liquid crystal polymer, containing being derived from 2 hydroxybenzoic acid or the construction unit of 2-hydroxyl-6-naphthoic acid and following construction unit:

(1)-CO-Ar¹-CO-

(2)-X-Ar²-Y-

(3)-Ar³-Z-Ar⁴-

The manufacture method of 13. trilamellar membranes, it includes following operation:

Make polyimide resin film be impregnated in the liquid composition comprising solvent and liquid crystal polymer, cover the impregnation step of described polyimide resin film with described liquid composition；

Heating treatment step,

In the manufacture method of described trilamellar membrane, as described liquid crystal polymer, containing being derived from 2 hydroxybenzoic acid or the construction unit of 2-hydroxyl-6-naphthoic acid and following construction unit (1) and (2):

(1)-CO-Ar¹-CO-

(2)-X-Ar²-Y-

(3)-Ar³-Z-Ar⁴-

The manufacture method of 14. trilamellar membranes, it includes following operation:

Prepare to comprise solvent and the liquid composition of liquid crystal polymer and the operation of the polyamic acid resin liquid composition as polyimide resin precursor；

Described liquid composition, described polyamic acid resin liquid composition, described liquid composition are coated into the operation of three layers by supporting mass successively；

Remove the solvent removing step of solvent in the liquid composition of described three layers；And

Trilamellar membrane formation process,

(1)-CO-Ar¹-CO-

(2)-X-Ar²-Y-

(3)-Ar³-Z-Ar⁴-