CN1922011A

CN1922011A - Multilayer body

Info

Publication number: CN1922011A
Application number: CN 200480038297
Authority: CN
Inventors: 石渡丰明; 佐胁透; 吉富孝; 中村勤
Original assignee: Teijin Ltd
Current assignee: Teijin Ltd
Priority date: 2003-12-24
Filing date: 2004-12-22
Publication date: 2007-02-28

Abstract

Disclosed is a multilayer body which is suitably used as an insulating layer for electronic mounting or an adhesive film for securing semiconductor wafers in semiconductor devices. Also disclosed are various laminates using such a multilayer body and a method for producing such a multilayer body. Specifically disclosed is a multilayer body (I) comprising a base layer (A) and an adhesive layer (B) wherein the layer (B) is formed on either or both sides of the layer (A). The layer (A) is a film composed of (A-1) a specific fully aromatic polyimide (PI<A-1>) or (A-2) a specific fully aromatic polyamide (PA<A-2>). The layer (B) is composed of (B-1) a specific fully aromatic polyimide (PI<B-1>), (B-2) a specific fully aromatic polyamide (PA<B-2>) or (B-3) a resin composition (RC<B-3>) composed of a specific fully aromatic polyimide (PI<B-3>) and a specific fully aromatic polyamide (PA<B-3>).

Description

Laminates

Technical field

The present invention relates to the laminates of cohesive and excellent heat resistance.In more detail, the laminates that the present invention relates to laminated adhesive layer on the substrate layer of making by full aromatic polyimide or Wholly aromatic polyamide and form.The present invention relates to the manufacture method of this laminates as the laminates such as semiconductor substrate of adhesive sheet.

Background technology

In recent years, along with electronic device constantly develops towards high function, high-performance, miniaturization, further miniaturization, light-weighted requirement have been proposed the electronic unit that is adopted.Thus, for semiconductor component package, wiring material and distribution component, also require to possess more high density, high function and high-performance.The material that need can be used as the hear resistance of the printed substrate material of package semiconductor, COL packing, LOC packing and MCM high density fabricated materials such as (multi-chip modules) and multi-layer FPC, electric reliability, cohesive excellence.

Particularly prevail and be used for the multi-layer FPC field of miniaturized electronic devices such as mobile phone in recent years, the material of the prepreg (pre-preg) of conventional epoxies dipping as an alternative, polyimides is, aromatic polyamides is that these have the concern that fusible thin-film material is subjected to market, and this can be with reference to " the up-to-date trend II of polyimides development " (living ベテ Network ノリサ-チ Co., Ltd. distribution) and " up-to-date polyimides-basis and application-" (エヌテイ of Co., Ltd.-エス distribution).The TPI of solubility and the blend of epoxy resin, silicone-modified (with reference to TOHKEMY 2000-109645 communique and TOHKEMY 2003-292778 communiques) such as polyimides are for example arranged.

Yet, owing to, need thinner film in recent years to the strong expectation of electronic unit miniaturization, and require when thickness reduces, to possess high rigidity.And in recent years for the consideration to environment, the solder flux that uses in the electronic assemblies purposes need use unleaded solder, and reflux temperature constantly rises, and the requirement that film is possessed hear resistance and dimensional stability improves.

Along with the miniaturization of semiconductor devices, slimming etc., the jointing material that uses in semiconductor devices manufacturing process is also needed to improve.

Operation and back operation before the manufacturing process of semiconductor device such as silicon, GaAs is divided into, preceding operation forms element etc. with the semiconductor wafer state in big footpath, and back operation becomes wafer-separate element fritter (chip) and is processed into end article.

In the preceding operation, as the method that makes semiconductor chip miniaturization, slimming, for example after the semiconductor wafer state with big footpath forms element, implement grinding back surface (back grinding) and handle, cut down the back side of semiconductor wafer, realize the slimming of chip integral body thus.When cutting down back surface of semiconductor wafer, the surface of semiconductor wafer need be adhesively fixed with supporter.

At this moment, as with semiconductor wafer surface and the bonding method of supporter, the someone proposes following proposal: go up heating coating wax at pad (supporter), fit with semiconductor wafer surface.But, after the slimming, semiconductor wafer need be carried out various processing such as metal evaporation, calcining under the state that supporter is adhesively fixed.When using the method for wax, the hear resistance of wax existing problems are being used under the bonding state of wax and supporter, and semiconductor wafer can not carry out processing such as metal evaporation, calcining, and this is the shortcoming of this method.

Therefore, wish to develop to have for example stable on heating adhesive sheet more than 400 ℃.

Then in the operation, at first, semiconductor wafer cut off separate (pelletizing) and become each chip, carry out then joining the chip small pieces on the lead frame chip join operation.During this, semiconductor wafer is carried out pelletizing, washing, drying with the state that is attached at adhesive sheet in advance, and then carry out the stretching (pressure shaping) of adhesive sheet, peel off each operation of chip (selecting (pickup)) from adhesive sheet.

To drying process, need adhesive sheet to keep sufficient adhesive from the pelletizing operation to chip.And when arrangement requires the good fissility with degree as not having bonding composition on the chip again.

For satisfying these requirements, people have proposed the scheme of various adhesive sheets.The scheme that the stickup crossed belt of sticking thermal adhesive layer and substrate layer formation is for example arranged, wherein sticking thermal adhesive layer forms (with reference to Japanese kokai publication hei 2-32181 communique) with the composition that contains (methyl) acrylate copolymer, epoxy resin, optical polymerism low molecular compound, hot active form potentiality epoxy curing agent and Photoepolymerizationinitiater initiater.

Also has such motion: have the support membrane on the surface that does not have peel ply in fact and the pelletizing film that conductive adhesive constitutes (with reference to the special fair 3-34853 communique of Japan).

As the stripping means of semiconductor substrate and supporting substrate, the someone has proposed to make the method (reference example such as TOHKEMY 2001-77304 communique, TOHKEMY 2002-237515 communique, TOHKEMY 2002-203821 communique and TOHKEMY 2002-192394 communique) of water etc.On adhesive surface, adhere to the swellability particle in addition, water swelling then, thereby the method (reference example such as TOHKEMY 2002-270553 communique) of utilizing volumetric expansion to peel off.But these methods are peeled off to be needed for a long time, so productivity is low, unrealistic.Particularly need to carry out the heat treated situation more than 350 ℃, exist adhesive surface to be reinforced, so that the problem that can't peel off.

Like this, as the stripping means under the heat treatment situation of carrying out more than 350 ℃, people have proposed more following schemes: add liquid swellability inorganic particles such as synthetic montmorillonite attritive powder on adhesive layer, the method for utilizing the liquid swelling to peel off; Make the organic protection layer swelling or make its dissolving etc., the method that it is peeled off (reference example such as TOHKEMY 2002-270553 communique and TOHKEMY 2002-343751 communique) thus with solvent etc.Yet swellability inorganic matter or solubility/swellability organic protection layer might be polluted because of metal ingredient, the pyrolysate of semiconductor article, need to use the more excellent jointing material of hear resistance, and the stripping means that can effectively peel off in the short time.

As battery case, the someone has proposed to have hear resistance, corrosion resistance and insulating properties, can with the film (with reference to TOHKEMY 2003-340960 communique and TOHKEMY 2002-56823 communique) of metal good bond.But, need further to improve hear resistance.

Consider from viewpoints such as hear resistance, light weight miniaturization, chemical stabilities, in various fields such as aviation purposes, automobile component purposes, food applications, all wish to develop the thin-film material that has with the stable cohesive of the various materials headed by the metal and hear resistance, chemical stability, excellent rigidity.

Summary of the invention

First purpose of the present invention be to provide hear resistance, rigidity and with all excellent laminates (I) of the cohesive of other material.

Second purpose of the present invention is to provide: on the surface of the adhesive layer (B) of described laminates (I) good bond bonded layer (C), hear resistance and all excellent laminates (II) of rigidity.

The 3rd purpose of the present invention is to provide: the laminates (III) that has formed organic protection layer (D) and object being treated layer (E) on the surface of the substrate layer (A) of described laminates (II).

The 4th purpose of the present invention is to provide: the object being treated layer (E) to described laminates (III) is handled, and makes the method for the laminates (V) that is made of organic protection layer (D) and treated layer (E ') thus.

Solve the method for problem

The present invention relates to laminates (I), this laminates (I) is made of substrate layer (A) and adhesive layer (B), is formed with the B layer on the single face or the two sides of A layer, wherein

The A layer be by

(A-1) glass transition temperature is the full aromatic polyimide (PI more than 350 ℃ ^A-1) or (A-2) glass transition temperature be Wholly aromatic polyamide (PA more than 350 ℃ ^A-2) film that forms,

The B layer by

(B-1) glass transition temperature is more than 180 ℃ but is lower than 350 ℃ full aromatic polyimide (PI ^B-1),

(B-2) vitrifying alternating temperature degree is more than 180 ℃ but is lower than 350 ℃ Wholly aromatic polyamide (PA ^B-2) or

(B-3) contain full aromatic polyimide (PI ^B-3) with glass transition temperature be more than 180 ℃ but low

Wholly aromatic polyamide (PA in 350 ℃ ^B-3) resin combination (RC ^B-3) form.

The present invention relates on the single face of A layer, be formed with the B layer, and on the B layer, be formed with the laminates (II) of bonded layer (C).

The invention still further relates to laminates (III); this laminates is made of substrate layer (A), adhesive layer (B), bonded layer (C), organic protection layer (D) and object being treated layer (E); on the one side of A layer, be formed with B layer and C layer in regular turn, on the another side of A layer, be formed with D layer and E layer in regular turn.

The invention further relates to the method for making laminates (V) by laminates (III), wherein laminates (V) by the D layer and the E layer after handling (E ') constitute, this method comprises the steps:

(1) the E layer outer surface of laminates (III) handled, made it become E ' layer, thereby obtain the surface treatment step of laminates (III ');

(2) laminates (III ') is remained on the heat treatment step of the temperature more than 350 ℃;

(3) peel off the C layer from laminates (III '), obtain the 1st strip step of the laminates (IV) that constitutes by B layer, A layer, D layer and E ' layer; And

(4) laminates (IV) is peeled off from the interface of A layer and D layer, obtained the 2nd strip step by the laminates (V) of D layer and E ' layer formation.

In this specification, (A) is called the A layer with substrate layer, and (B) is called the B layer with adhesive layer, and bonded layer (C) is called the C layer, and (D) is called the D layer with organic protection layer, and (E) is called the E layer with the object being treated layer, and the E layer after handling (E ') is called E ' layer.

The invention effect

Laminates of the present invention (I) hear resistance, rigidity, dimensional stability and aspect the cohesive of other material performance excellent.Therefore, can be adapted at using as adhesive sheet in the various fields such as process components material that electronic material such as fabricated material, semiconductor make, battery case, aerospace parts, automobile component, food.Particularly can be suitable for using as insulating materials with excellent in dimension stability in field of electronic materials.Laminates (I) has superior stiffness, therefore can realize than the thinner thickness of traditional used insulating materials, operability excellence.

Hear resistance, the excellent in dimensional stability of laminates of the present invention (II) are with the cohesive excellence of bonded layer (C).Therefore, even use the low material of thermal coefficient of expansions such as silicon, 42 alloys as bonded layer (C), situation such as can not take place that also bonded layer (C) is peeled off.

The hear resistance of laminates of the present invention (III), dimensional stability, cohesive excellence can be as the intermediate materials of semiconductor manufacturing process.

The manufacture method of the laminates according to the present invention (V) uses the laminates (I) with specific adhesive layer (B) as adhesive sheet, and by heat treatment, bonded layer (C) can easily be peeled off with adhesive layer (B).And organic protection layer (D) also can easily be peeled off with the interface of substrate layer (A).Thereby,, can under the situation of the pollution that does not have pyrolysate etc. to cause, be manufactured on the thin paper semiconductor device of heat-treating under the high temperature more than 350 ℃ effectively by the inventive method.

The best mode that carries out an invention

Below the present invention is described in detail.

＜laminates (I) 〉

Laminates of the present invention (I) is made of substrate layer (A) and the adhesive layer (B) that forms on the single face of substrate layer (A) or two sides.

The A layer is to be full aromatic polyimide (PI more than 350 ℃ by (A-1) glass transition temperature ^A-1) or (A-2) glass transition temperature be Wholly aromatic polyamide (PA more than 350 ℃ ^A-2) film that forms.

The B layer is more than 180 ℃ by (B-1) glass transition temperature but is lower than 350 ℃ full aromatic polyimide (PI ^B-1), (B-2) glass transition temperature is more than 180 ℃ but is lower than 350 ℃ Wholly aromatic polyamide (PB ^B-2) or (B-3) contain full aromatic polyimide (PI ^B-3) be more than 180 ℃ but be lower than 350 ℃ Wholly aromatic polyamide (PA with glass transition temperature ^B-3) resin combination (RC ^B-3) form.

Exist Young's modulus to surpass the both direction of the quadrature of 3GPa in the face of preferred laminates of the present invention (I).When being 3GPa when following, its rigidity is insufficient, may appear at the situation of the treatment process trafficability characteristic difference of various uses.Laminates is thin more, and this tendency is obvious more.The Young's modulus of the both direction of the quadrature that exists in the face is more preferably more than the 5GPa, more preferably more than the 7GPa.

The shape of laminates (I) can be made all shapes such as band shape, label-like.Laminates (I) can have following structure.

(1) the A layer is by PI ^A-1Form, the B layer is by PI ^B-1The structure that forms.

(2) the A layer is by PI ^A-1Form, the B layer is by PA ^B-2The structure that forms.

(3) the A layer is by PI ^A-1Form, the B layer is by containing PI ^B-3And PA ^B-3Resin combination (RC ^B-3) structure that forms.

(4) the A layer is by PA ^A-2Form, the B layer is by PI ^B-1The structure that forms.

(5) the A layer is by PA ^A-2Form, the B layer is by PA ^B-2The structure that forms.

(6) the A layer is by PA ^A-2Form, the B layer is by containing PI ^B-3And PA ^B-3Resin combination (RC ^B-3) structure that forms.

＜A layer 〉

When glass transition temperature was lower than 350 ℃, hear resistance and dimensional stability were not enough, can the generation problem in each operation such as reflow soldering operation of the heat treated of for example semiconductor fabrication process or assembling purposes.Glass transition temperature is preferably more than 355 ℃, more preferably 355-600 ℃.The dynamic storage modulus E ', the dynamic loss modulus E that obtain with Measurement of Dynamic Viscoelasticity " calculate the value of dynamic loss tangent tan δ, calculate glass transition temperature by this value.

Preferred A layer is to exist Young's modulus to surpass the film of both direction of the quadrature of 10GPa in the face.Young's modulus is 10GPa when following, can not obtain enough rigidity, and operability is poor.This tendency is that 25 μ m are remarkable especially when following at the A layer thickness.The Young's modulus of the both direction of quadrature more preferably more than the 12GPa, is preferably more than the 14GPa especially.

The thermal linear expansion coefficient of A layer is preferably-12ppm/ ℃～12ppm/ ℃.The thermal linear expansion coefficient of A layer more preferably-10ppm/ ℃～10ppm/ ℃.Can use by preferred especially insulating materials thus as excellent in dimensional stability in the electronic material purposes.

The average thickness of preferred A layer is below the 50 μ m.When thickness surpassed 50 μ m, the thickness of laminates integral body increased along with the increase of base material thickness, thereby can not satisfy various requirements for miniaturization, filming sometimes.Based on such requirement, the thickness of A layer more preferably below the 30 μ m, more preferably below the 20 μ m, is preferably below the 15 μ m especially.Lower limit is not particularly limited, considers the usability of film, be actually about 0.1 μ m.

＜full aromatic polyimide (PI ^A-1)

(A-1) glass transition temperature that constitutes the A layer is the full aromatic polyimide (PI more than 350 ℃ ^A-1), be the full aromatic polyimide that has from the construction unit of aromatic acid's composition and aromatic diamine composition.

The example of aromatic acid's composition has: PMA, 1,2,3, the 4-benzene tertacarbonic acid, 2,3,5,6-pyridine tetrabasic carboxylic acid, 2,3,4,5-thiophene tetrabasic carboxylic acid, 2,2 ', 3,3 '-benzophenone tetrabasic carboxylic acid, 2,3 ', 3,4 '-benzophenone tetrabasic carboxylic acid, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 3,3 ', 4,4 '-para-terpheny tetrabasic carboxylic acid, 2,2 ', 3,3 '-para-terpheny tetrabasic carboxylic acid, 2,3,3 ', 4 '-para-terpheny tetrabasic carboxylic acid, 1,2,4, the 5-naphthalene tetracarboxylic acid, 1,2,5, the 6-naphthalene tetracarboxylic acid, 1,2,6, the 7-naphthalene tetracarboxylic acid, 1,4,5, the 8-naphthalene tetracarboxylic acid, 2,3,6, the 7-naphthalene tetracarboxylic acid, 2,3,6,7-anthracene tetrabasic carboxylic acid, 1,2,5,6-anthracene tetrabasic carboxylic acid, 1,2,6, the luxuriant and rich with fragrance tetrabasic carboxylic acid of 7-, 1,2,7, the luxuriant and rich with fragrance tetrabasic carboxylic acid of 8-, 1,2,9, the luxuriant and rich with fragrance tetrabasic carboxylic acid of 10-, 3,4,9, the 10-perylene tetracarboxylic acid, 2,6-dichloronaphtalene-1,4,5, the 8-tetrabasic carboxylic acid, 2,7-dichloronaphtalene-1,4,5, the 8-tetrabasic carboxylic acid, 2,3,6,7-Tetrachloronaphthalene-1,4,5, the 8-tetrabasic carboxylic acid, 1,4,5,8-Tetrachloronaphthalene-2,3,6, the 7-tetrabasic carboxylic acid, two (2,3-dicarboxyl phenyl) ether, two (3,4-dicarboxyl phenyl) ether, two (2,3-dicarboxyl phenyl) methane, two (3,4-dicarboxyl phenyl) methane, two (2,3-dicarboxyl phenyl) sulfone, two (3,4-dicarboxyl phenyl) sulfone, 1,1-two (2,3-dicarboxyl phenyl) ethane, 1,1-two (3,4-dicarboxyl phenyl) ethane, 2,2-two (2,3-dicarboxyl phenyl) propane, 2,2-two (3,4-dicarboxyl phenyl) propane, 2,6-two (3, the 4-di carboxyl phenyloxy) pyridine, 1,1,1,3,3,3-hexafluoro-2,2-two (3,4-dicarboxyl phenyl) propane, two (3,4-dicarboxyl phenyl) dimethylsilane etc.These aromatic acid's compositions can two or morely be used in combination simultaneously.

Wherein, preferred aromatic acid's composition for example has the PMA of independent use; Perhaps PMA and the above-mentioned aromatic acid's different combination with it.

More particularly, be benchmark with whole tetrabasic carboxylic acid compositions, pyromellitic acid dianhydride is preferably the 50-100% mole.Making pyromellitic acid dianhydride is more than 50% mole, can improve the imide concentration in the full aromatic polyimide, can access the good material of cohesive.Preferred pyromellitic acid dianhydride is the 70-100% mole, more preferably the 90-100% mole.The preferred especially pyromellitic acid dianhydride that uses separately.

The example of aromatic diamine composition has: 1; the 4-phenylenediamine; 1; the 3-phenylenediamine; 1; the 4-diaminonaphthalene; 1; the 5-diaminonaphthalene; 1; the 8-diaminonaphthalene; 2; the 6-diaminonaphthalene; 2; the 7-diaminonaphthalene; 2, the 6-diaminoanthraquinone-; 2, the 7-diaminoanthraquinone-; 1; the 8-diaminoanthraquinone-; 2; the 4-diaminotoluene; 2,5-diaminourea meta-xylene; 2, the 5-diamino-pyridine; 2; the 6-diamino-pyridine; 3; the 5-diamino-pyridine; 2,4-diaminotoluene benzidine; 3,3 '-benzidine; 3; 3 '-dichloro-benzidine; 3; 3 '-dimethylbenzidine; 3,3 '-dimethoxy benzidine; 2,2 '-diaminobenzophenone; 4; 4 '-diaminobenzophenone; 3; 3 '-diaminodiphenyl ether; 4,4 '-diaminodiphenyl ether; 3,4 '-diaminodiphenyl ether; 3; 3 '-diaminodiphenyl-methane; 4; 4 '-diaminodiphenyl-methane; 3,4 '-diaminodiphenyl-methane; 3,4 '-DADPS; 4; 4 '-DADPS; 3; 3 '-diaminourea diphenyl sulfide; 3,4 '-diaminourea diphenyl sulfide; 4,4 '-diaminourea diphenyl sulfide; 4; 4 '-diamino-diphenyl thioether; 4; 4 '-diaminourea-3,3 ', 5; 5 '-tetramethyl diphenyl ether; 4; 4 '-diaminourea-3,3 ', 5; 5 '-tetraethyl diphenyl ether; 4; 4 '-diaminourea-3,3 ', 5; 5 '-tetramethyl diphenyl methane; 1; 3-two (3-amino-benzene oxygen) benzene; 1,3-two (4-amino-benzene oxygen) benzene; 1,4-two (3-amino-benzene oxygen) benzene; 1; 4-two (4-amino-benzene oxygen) benzene; 2; 6-two (3-amino-benzene oxygen) pyridine; 1,4-two (3-aminophenyl sulfonyl) benzene; 1,4-two (4-aminophenyl sulfonyl) benzene; 1; 4-two (3-aminophenyl-thioether) benzene; 1; 4-two (4-aminophenyl-thioether) benzene; 4,4 '-two (3-amino-benzene oxygen) diphenyl sulphone (DPS); 4,4 '-two (4-amino-benzene oxygen) diphenyl sulphone (DPS); two (4-aminophenyl) amine; two (4-aminophenyl)-N-methyl amine; two (4-aminophenyl)-N-phenyl amine; two (4-aminophenyl) phosphine oxide; 1; 1-two (3-aminophenyl) ethane; 1; 1-two (4-aminophenyl) ethane; 2,2-two (3-aminophenyl) propane; 2,2-two (4-aminophenyl) propane; 2; 2-two (4-amino-3; the 5-3,5-dimethylphenyl) propane; 4,4 '-two (4-amino-benzene oxygen) biphenyl; two [4-(3-amino-benzene oxygen) phenyl] sulfone; two [4-(4-amino-benzene oxygen) phenyl] sulfone; two [4-(4-amino-benzene oxygen) phenyl] ether; two [4-(4-amino-benzene oxygen) phenyl] methane; two [3-methyl-4-(4-amino-benzene oxygen) phenyl] methane; two [3-chloro-4-(4-amino-benzene oxygen) phenyl] methane; two [3,5-dimethyl-4-(4-amino-benzene oxygen) phenyl] methane; 1; 1-two [4-(4-amino-benzene oxygen) phenyl] ethane; 1; 1-two [3-methyl-4-(4-amino-benzene oxygen) phenyl] ethane; 1,1-two [3-chloro-4-(4-amino-benzene oxygen) phenyl] ethane; 1,1-two [3; 5-dimethyl-4-(4-amino-benzene oxygen) phenyl] ethane; 2; 2-two [4-(4-amino-benzene oxygen) phenyl] propane; 2,2-two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane; 2,2-two [3-chloro-4-(4-amino-benzene oxygen) phenyl] propane; 2; 2-two [3; 5-dimethyl-4-(4-amino-benzene oxygen) phenyl] propane; 2,2-two [4-(4-amino-benzene oxygen) phenyl] butane; 2,2-two [3-methyl-4-(4-amino-benzene oxygen) phenyl] butane; 2; 2-two [3; 5-dimethyl-4-(4-amino-benzene oxygen) phenyl] butane; 2,2-two [3,5-two bromo-4-(4-amino-benzene oxygen) phenyl] butane; 1; 1; 1,3,3; 3-hexafluoro-2; 2-two (4-aminophenyl) propane; 1,1,1; 3; 3,3-hexafluoro-2,2-two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane etc. and their virtue by halogen atom or alkyl replacement are examined substituent.Above-mentioned aromatic diamine composition can two or morely be used in combination simultaneously.

Preferred two amine components for example have 1,4-phenylenediamine, 1,3-phenylenediamine, 3,4 '-diaminodiphenyl ether and 1,3-two (3-amino-benzene oxygen) benzene, 4,4 '-diaminodiphenyl ether.With whole two amine components is benchmark, 1 in the further preferred aromatic diamine composition, and the 4-phenylenediamine is the 40-100% mole.As 1, other aromatic diamine composition beyond the 4-phenylenediamine, preferred 1,3-phenylenediamine, 3,4 '-diaminodiphenyl ether and 4,4 '-diaminodiphenyl ether, 1,3-two (3-amino-benzene oxygen) benzene.Wherein, preferred especially 3,4 '-diaminodiphenyl ether.

Thus, preferred full aromatic polyimide (PI ^A-1) the full aromatic polyimide that is made of construction unit shown in the following formula (I) for example arranged.

Ar in the following formula (I) ¹Be can contain non-reacted substituent 1, the 4-phenylene.

Non-reacted substituent example has: alkyl such as methyl, ethyl, propyl group, cyclohexyl; Aryl such as phenyl, naphthyl; Halogens such as chloro, fluorine-based, bromo; Alkoxyls such as methoxyl group, ethyoxyl, phenoxy group; Nitro etc.

Therefore, Ar ¹Example have: 2-chloro-1,4-phenylene, 2-bromo-1, the 4-phenylene, the 2-methyl isophthalic acid, the 4-phenylene, 2-ethyl-1, the 4-phenylene, 2-cyclohexyl-1, the 4-phenylene, 2-phenyl-1, the 4-phenylene, 2-nitro-1, the 4-phenylene, 2-methoxyl group-1, the 4-phenylene, 2,5-two chloro-1, the 4-phenylene, 2,6-two chloro-1, the 4-phenylene, 2,5-two bromo-1,4-phenylene, 2,6-two bromo-1, the 4-phenylene, 2-chloro-5-bromo-1, the 4-phenylene, 2-chloro-5-fluoro-1, the 4-phenylene, 2,5-dimethyl-1,4-phenylene, 2,6-dimethyl-1, the 4-phenylene, 2,5-dicyclohexyl-1, the 4-phenylene, 2,5-diphenyl-1,4-phenylene, 2,5-dinitro-1, the 4-phenylene, 2,5-dimethoxy-1, the 4-phenylene, 2,3,5-three chloro-1, the 4-phenylene, 2,3,5-three fluoro-1, the 4-phenylene, 2,3,5-trimethyl-1, the 4-phenylene, 2,3,5,6-tetrachloro-1, the 4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, 2,3,5,6-tetrabromo-1, the 4-phenylene, 2,3,5,6-tetramethyl-1, the 4-phenylene, 2,3,5,6-tetraethyl-1,4-phenylene etc.Wherein, preferred especially 1, the 4-phenylene.

Preferred full aromatic polyimide (PI ^A-1) for example have: by more than 40% mole but be lower than construction unit shown in 100% mole the following formula (I) and surpass 0% mole but be the full aromatic polyimide that construction unit constitutes shown in the following formula (IV) below 60% mole.

Ar in the following formula (IV) ^4aAnd Ar ^4bIndependent of separately containing the aryl of non-reacted substituent carbon number 6-20.

Non-reacted substituting group can exemplify with to the Ar in the following formula (I) ¹The same group of non-reacted substituting group that exemplifies when describing.The aryl of carbon number 6-20 for example has phenylene, naphthalene two bases.

Therefore, Ar ^4aAnd Ar ^4bExample have: 1, the 4-phenylene, 2-chloro-1, the 4-phenylene, 2-bromo-1, the 4-phenylene, the 2-methyl isophthalic acid, the 4-phenylene, 2-ethyl-1, the 4-phenylene, 2-cyclohexyl-1, the 4-phenylene, 2-phenyl-1, the 4-phenylene, 2-nitro-1, the 4-phenylene, 2-methoxyl group-1, the 4-phenylene, 2,5-two chloro-1,4-phenylene, 2,6-two chloro-1, the 4-phenylene, 2,5-two bromo-1, the 4-phenylene, 2,6-two bromo-1,4-phenylene, 2-chloro-5-bromo-1, the 4-phenylene, 2-chloro-5-fluoro-1, the 4-phenylene, 2,5-dimethyl-1, the 4-phenylene, 2,6-dimethyl-1,4-phenylene, 2,5-dicyclohexyl-1, the 4-phenylene, 2,5-diphenyl-1, the 4-phenylene, 2,5-dinitro-1,4-phenylene, 2,5-dimethoxy-1, the 4-phenylene, 2,3,5-three chloro-1, the 4-phenylene, 2,3,5-three fluoro-1, the 4-phenylene, 2,3,5-trimethyl-1, the 4-phenylene, 2,3,5,6-tetrachloro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, 2,3,5,6-tetrabromo-1,4-phenylene, 2,3,5,6-tetramethyl-1,4-phenylene, 2,3,5,6-tetraethyl-1,4-phenylene, 1, the 3-phenylene, 5-chloro-1, the 3-phenylene, 5-bromo-1, the 3-phenylene, the 5-methyl isophthalic acid, the 3-phenylene, 5-ethyl-1, the 3-phenylene, 5-cyclohexyl-1, the 3-phenylene, 5-phenyl-1, the 3-phenylene, 5-nitro-1, the 3-phenylene, 5-methoxyl group-1, the 3-phenylene, 2,5-two chloro-1, the 3-phenylene, 2,5-two bromo-1, the 3-phenylene, 2,5-two bromo-1, the 3-phenylene, 2-chloro-5-bromo-1, the 3-phenylene, 2-chloro-5-fluoro-1, the 3-phenylene, 2,5-dimethyl-1, the 3-phenylene, 2,5-dimethyl-1, the 3-phenylene, 2,5-dicyclohexyl-1, the 3-phenylene, 2,5-diphenyl-1, the 3-phenylene, 2,5-dinitro-1, the 3-phenylene, 2,5-dimethoxy-1, the 3-phenylene, 2,4,6-three chloro-1,3-phenylene, 2,4,6-three fluoro-1, the 3-phenylene, 2,4,6-trimethyl-1, the 3-phenylene, 1, the 6-biphenylene, 2,6-naphthylene etc.Wherein, preferred 1,4-phenylene, 1,3-phenylene.

N in the following formula (IV) is 1 or 2.N is 2 o'clock, then in fact has two Ar in the formula (VI) ^4a, these two Ar ^4aCan be different structures independently separately, also can be identical structure.Preferred especially n is 1.

The manufacturing of＜full aromatic polyimide film 〉

By full aromatic polyimide (PI ^A-1) film that forms can be by following method manufacturing.That is, make raw material aromatic acid composition and the polymerization in organic polar solvent of aromatic diamine composition, preparation contains the solution of precursor polyamic acid or polyamic acid derivative.Subsequently, this solution is carried out curtain coating on supporter etc., drying, heat treatment makes its imidizate, thereby makes object.

Raw material aromatic acid composition can be aromatic tetracarboxylic acid dianhydride for example.Part or all of aromatic acid's composition also can be dicarboxylic acids halide dicarboxylic acids alkyl derivative.Preferred use aromatic tetracarboxylic acid dianhydride.

Raw material aromatic diamine composition can be amic acid formation property derivative of for example aromatic diamine, aromatic diamine.The part or all of amino of aromatic diamine composition can be by trialkylsilklization.Perhaps can be with the such aliphatic acid of acetate with its amidatioon.Wherein, preferably use aromatic diamine.

The example of organic polar solvent has N-N-methyl-2-2-pyrrolidone N-, dimethylacetylamide and methylimidazole alkane ketone etc.Polymerization temperature is preferably in-30 ℃～120 ℃ scope.Dry temperature range is preferably 80～400 ℃.Heat treated temperature range is preferably 250-600 ℃.

Can also be with the combination of organonitrogen compounds such as aliphatic anhydrides such as dicyclohexyl carbodiimide or acetic anhydride and pyridine, make its cyclodehydration that carries out chemistry reaction, obtain the swelling glued membrane, after this glued membrane at random stretched, carry out fixed length drying, heat treatment, can make object (TOHKEMY 2002-179810 communique) thus.This method particularly can be controlled thermal linear expansion coefficient and Young's modulus arbitrarily by its stretching condition, can be described as particularly preferred method for these purposes.

＜Wholly aromatic polyamide (PA ^A-2)

(A-2) glass transition temperature that constitutes the A layer is the Wholly aromatic polyamide (PA more than 350 ℃ ^A-2), be the Wholly aromatic polyamide that has from the construction unit of aromatic dicarboxylic acid composition and aromatic diamine composition.

The example of aromatic dicarboxylic acid composition has: terephthalic acid (TPA); M-phthalic acid; 1; 4-dicarboxyl naphthalene; 1; 5-dicarboxyl naphthalene; 1; 8-dicarboxyl naphthalene; 2; 6-dicarboxyl naphthalene; 2; 7-dicarboxyl naphthalene; 2; 6-dicarboxyl anthracene; 2; 7-dicarboxyl anthracene; 1; 8-dicarboxyl anthracene; 2; 4-dicarboxyl toluene; 2; 5-dicarboxyl meta-xylene; 3; 3 '-dicarboxylate biphenyl; 2; 2 '-benzophenonedicarboxylic acid; 4; 4 '-benzophenonedicarboxylic acid; 3; 3 '-dicarboxyl diphenyl ether; 4; 4 '-dicarboxyl diphenyl ether; 3; 4 '-dicarboxyl diphenyl ether; 3,3 '-dicarboxyl diphenyl methane; 4,4 '-dicarboxyl diphenyl methane; 3; 4 '-dicarboxyl diphenyl methane; 3; 4 '-Dicarboxy diphenylsulfone; 4,4 '-Dicarboxy diphenylsulfone; 3,3 '-dicarboxyl diphenyl sulfide; 3; 4 '-dicarboxyl diphenyl sulfide; 4; 4 '-dicarboxyl diphenyl sulfide; 4,4 '-dicarboxyl diphenylsulfide; 4,4 '-dicarboxyl-3; 3 '; 5,5 '-tetramethyl diphenyl ether; 4,4 '-dicarboxyl-3; 3 '; 5,5 '-tetraethyl diphenyl ether; 4,4 '-dicarboxyl-3; 3 '; 5,5 '-tetramethyl diphenyl methane; 1,3-two (3-carboxyl phenoxy group) benzene; 1; 3-two (4-carboxyl phenoxy group) benzene; 1; 4-two (3-carboxyl phenoxy group) benzene; 1,4-two (4-carboxyl phenoxy group) benzene; 2,6-two (3-carboxyl phenoxy group) pyridine; 1; 4-two (3-carboxyl phenyl sulfonyl) benzene; 1; 4-two (4-carboxyl phenyl sulfonyl) benzene; 1,4-two (3-carboxyl phenyl thioether) benzene; 1,4-two (4-carboxyl phenyl thioether) benzene; 4; 4 '-two (3-carboxyl phenoxy group) diphenyl sulphone (DPS); 4; 4 '-two (4-carboxyl phenoxy group) diphenyl sulphone (DPS); two (4-carboxyl phenyl) amine; two (4-carboxyl phenyl)-N-methyl amine; two (4-carboxyl phenyl)-N-phenyl amine; two (4-carboxyl phenyl) phosphine oxide; 1,1-two (3-carboxyl phenyl) ethane; 1,1-two (4-carboxyl phenyl) ethane; 2; 2-two (3-carboxyl phenyl) propane; 2; 2-two (4-carboxyl phenyl) propane; 2,2-two (4-carboxyl-3,5-3,5-dimethylphenyl) propane; 4; 4 '-two (4-carboxyl phenoxy group) biphenyl; two [4-(3-carboxyl phenoxy group) phenyl] sulfone; two [4-(4-carboxyl phenoxy group) phenyl] sulfone; two [4-(4-carboxyl phenoxy group) phenyl] ether; two [4-(4-carboxyl phenoxy group) phenyl] methane; two [3-methyl-4-(4-carboxyl phenoxy group) phenyl] methane; two [3-chloro-4-(4-carboxyl phenoxy group) phenyl] methane; two [3; 5-dimethyl-4-(4-carboxyl phenoxy group) phenyl] methane; 1,1-two [4-(4-carboxyl phenoxy group) phenyl] ethane; 1,1-two [3-methyl-4-(4-carboxyl phenoxy group) phenyl] ethane; 1; 1-two [3-chloro-4-(4-carboxyl phenoxy group) phenyl] ethane; 1; 1-two [3,5-dimethyl-4-(4-carboxyl phenoxy group) phenyl] ethane; 2,2-two [4-(4-carboxyl phenoxy group) phenyl] propane; 2; 2-two [3-methyl-4-(4-carboxyl phenoxy group) phenyl] propane; 2; 2-two [3-chloro-4-(4-carboxyl phenoxy group) phenyl] propane; 2,2-two [3,5-dimethyl-4-(4-carboxyl phenoxy group) phenyl] propane; 2; 2-two [4-(4-carboxyl phenoxy group) phenyl] butane; 2; 2-two [3-methyl-4-(4-carboxyl phenoxy group) phenyl] butane; 2,2-two [3,5-dimethyl-4-(4-carboxyl phenoxy group) phenyl] butane; 2; 2-two [3; 5-two bromo-4-(4-carboxyl phenoxy group) phenyl] butane; 1,1,1; 3; 3,3-hexafluoro-2,2-two (4-carboxyl phenyl) propane; 1; 1; 1,3,3; 3-hexafluoro-2,2-two [3-methyl-4-(4-carboxyl phenoxy group) phenyl] propane etc. and their virtue by halogen atom or alkyl replacement are examined substituent.Above-mentioned aromatic dicarboxylic acid composition can two or morely be used in combination simultaneously.

The preferred aromatic dicarboxylic acids composition is terephthalic acid (TPA), M-phthalic acid.Wherein from mechanical characteristic and stable on heating angle, preferred especially terephthalic acid (TPA).

The example of aromatic diamine composition has: 1; the 4-phenylenediamine; 1; the 3-phenylenediamine; 1; the 4-diaminonaphthalene; 1; the 5-diaminonaphthalene; 1; the 8-diaminonaphthalene; 2; the 6-diaminonaphthalene; 2; the 7-diaminonaphthalene; 2; the 6-diaminoanthraquinone-; 2; the 7-diaminoanthraquinone-; 1; the 8-diaminoanthraquinone-; 2, the 4-diaminotoluene; 2,5-diaminourea meta-xylene; 2; the 5-diamino-pyridine; 2; the 6-diamino-pyridine; 3, the 5-diamino-pyridine; 2,4-diaminotoluene benzidine; 3; 3 '-benzidine; 2; 2 '-diaminobenzophenone; 4,4 '-diaminobenzophenone; 3,3 '-diaminodiphenyl ether; 4; 4 '-diaminodiphenyl ether; 3; 4 '-diaminodiphenyl ether; 3,3 '-diaminodiphenyl-methane; 4,4 '-diaminodiphenyl-methane; 3; 4 '-diaminodiphenyl-methane; 3; 4 '-DADPS; 4,4 '-DADPS; 3,3 '-diaminourea diphenyl sulfide; 3; 4 '-diaminourea diphenyl sulfide; 4; 4 '-diaminourea diphenyl sulfide; 4,4 '-diamino-diphenyl thioether; 4,4 '-diaminourea-3; 3 '; 5,5 '-tetramethyl diphenyl ether; 4,4 '-diaminourea-3; 3 '; 5,5 '-tetraethyl diphenyl ether; 4,4 '-diaminourea-3; 3 '; 5,5 '-tetramethyl diphenyl methane; 1,3-two (3-amino-benzene oxygen) benzene; 1; 3-two (4-amino-benzene oxygen) benzene; 1; 4-two (3-amino-benzene oxygen) benzene; 1,4-two (4-amino-benzene oxygen) benzene; 2,6-two (3-amino-benzene oxygen) pyridine; 1; 4-two (3-aminophenyl sulfonyl) benzene; 1; 4-two (4-aminophenyl sulfonyl) benzene; 1,4-two (3-aminophenyl-thioether) benzene; 1,4-two (4-aminophenyl-thioether) benzene; 4; 4 '-two (3-amino-benzene oxygen) diphenyl sulphone (DPS); 4; 4 '-two (4-amino-benzene oxygen) diphenyl sulphone (DPS); two (4-aminophenyl) amine; two (4-aminophenyl)-N-methyl amine; two (4-aminophenyl)-N-phenyl amine; two (4-aminophenyl) phosphine oxide; 1,1-two (3-aminophenyl) ethane; 1,1-two (4-aminophenyl) ethane; 2; 2-two (3-aminophenyl) propane; 2; 2-two (4-aminophenyl) propane; 2,2-two (4-amino-3,5-3,5-dimethylphenyl) propane; 4; 4 '-two (4-amino-benzene oxygen) biphenyl; two [4-(3-amino-benzene oxygen) phenyl] sulfone; two [4-(4-amino-benzene oxygen) phenyl] sulfone; two [4-(4-amino-benzene oxygen) phenyl] ether; two [4-(4-amino-benzene oxygen) phenyl] methane; two [3-methyl-4-(4-amino-benzene oxygen) phenyl] methane; two [3-chloro-4-(4-amino-benzene oxygen) phenyl] methane; two [3; 5-dimethyl-4-(4-amino-benzene oxygen) phenyl] methane; 1,1-two [4-(4-amino-benzene oxygen) phenyl] ethane; 1,1-two [3-methyl-4-(4-amino-benzene oxygen) phenyl] ethane; 1; 1-two [3-chloro-4-(4-amino-benzene oxygen) phenyl] ethane; 1; 1-two [3,5-dimethyl-4-(4-amino-benzene oxygen) phenyl] ethane; 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane; 2; 2-two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane; 2; 2-two [3-chloro-4-(4-amino-benzene oxygen) phenyl] propane; 2,2-two [3,5-dimethyl-4-(4-amino-benzene oxygen) phenyl] propane; 2; 2-two [4-(4-amino-benzene oxygen) phenyl] butane; 2; 2-two [3-methyl-4-(4-amino-benzene oxygen) phenyl] butane; 2,2-two [3,5-dimethyl-4-(4-amino-benzene oxygen) phenyl] butane; 2; 2-two [3; 5-two bromo-4-(4-amino-benzene oxygen) phenyl] butane; 1,1,1; 3; 3,3-hexafluoro-2,2-two (4-aminophenyl) propane; 1; 1; 1,3,3; 3-hexafluoro-2,2-two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane etc. and their virtue by halogen atom or alkyl replacement are examined substituent.Above-mentioned aromatic diamine composition can two or morely be used in combination simultaneously.

Preferred two amine components for example have 1,4-phenylenediamine, 1,3-phenylenediamine, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether and 1,3-two (3-amino-benzene oxygen) benzene.Wherein, consider from mechanical property and hear resistance, preferred especially 1, the 4-phenylenediamine.

Thus, preferred Wholly aromatic polyamide (PA ^A-2) be specially the Wholly aromatic polyamide that constitutes by construction unit shown in the following formula (V).

Ar in the following formula (V) ^5aAnd Ar ^5bIndependent of separately having the aryl of non-reacted substituent carbon number 6-20.

The aryl of carbon number 6-20 for example has phenylene, naphthalene two bases, anthracene two bases, toluene two bases etc.

Non-reacted substituent example has: alkyl such as methyl, ethyl, propyl group, cyclohexyl; Aryl such as phenyl, naphthyl; Halogens such as chloro, fluorine-based, bromo; Nitro; Methoxyl group, ethyoxyl, phenoxy group etc.

Therefore, preferred especially Wholly aromatic polyamide (PA ^A-2) be the Wholly aromatic polyamide that constitutes by construction unit shown in the following formula (II).

The manufacturing of＜Wholly aromatic polyamide film 〉

Can prepare Wholly aromatic polyamide (PA by following method ^A-2).That is, make the chloride of above-mentioned aromatic dicarboxylic acid composition and aromatic diamine composition at N-N-methyl-2-2-pyrrolidone N-, N, N-dimethylacetylamide, N, reaction prepares in the organic polar solvents such as dinethylformamide.

Same raw material can also be carried out interfacial polymerization with lean solvents such as organic solvents such as oxolane, water prepares.At this moment, can be in interfacial polymerization with alkali such as sodium hydrate aqueous solutions as polymerization accelerant.

Film can be used gained Wholly aromatic polyamide solution, makes by wet method film forming, dry method film forming.Wholly aromatic polyamide solution after the polymerization directly former state uses.

After also Wholly aromatic polyamide can being separated for the time being, be dissolved in again in the solvent and use with the solution form.The preferred N-N-methyl-2-2-pyrrolidone N-of solvent, N, N-dimethylacetylamide, N, organic polar solvents such as dinethylformamide.For the low Wholly aromatic polyamide of dissolubility, preferably use strong acid such as the concentrated sulfuric acid, red fuming nitric acid (RFNA), polyphosphoric acid as solvent.

Can add inorganic salts as required in the Wholly aromatic polyamide solution, for example add calcium chloride, magnesium chloride, lithium chloride, lithium nitrate etc. as cosolvent.Wholly aromatic polyamide concentration in the solution is preferably 1-60% weight, more preferably 3-40% weight.

Can carry out various surface treatments such as sided corona treatment, plasma treatment, blasting treatment and carry out acid treatment the surface of the A layer that constitutes laminates (I) with nitric acid etc., carry out alkali treatment with potassium hydroxide etc., handle with various surface modifiers such as silane couplers, to realize the purposes such as stable bonding force of acquisition and B layer.

＜adhesive layer (B) 〉

The adhesive layer (B) that constitutes laminates of the present invention (I) is formed on the one or both sides of above-mentioned A layer.When forming the B layer on the two sides, can be according to its purpose, bonded layer (C), thickness, the one-tenth of setting each B layer in demonstration is enclosed down suitably, independently grade.Therefore, when constituting the B layer on the two sides, the laminate structures of thickness direction and formation can be symmetrical laminate structures, also can be asymmetric laminate structures.

The B layer is more than 180 ℃ by (B-1) glass transition temperature but is lower than 350 ℃ full aromatic polyimide (PI ^B-1), (B-2) glass transition temperature is more than 180 ℃ but is lower than 350 ℃ Wholly aromatic polyamide (PA ^B-2) or (B-3) contain full aromatic polyimide (PI ^B-3) be more than 180 ℃ but be lower than 350 ℃ Wholly aromatic polyamide (PA with glass transition temperature ^B-3) resin combination (RC ^B-3) form.

The B layer is by PI ^B-1Or PA ^B-2During formation, glass transition temperature is lower than 180 ℃, and then hear resistance becomes inadequately, and is higher than 350 ℃, then with the bonding high temperature that needs of bonded layer (C), has the situation of poor adhesion.Glass transition temperature is preferably 200-345 ℃, more preferably 220-340 ℃.

The thickness of B layer is preferably 0.1 μ m～50 μ m.When being lower than 0.1 μ m, can not obtain the bonding precision with bonded layer (C), the flatness of pressing device contact-making surface, the precision of flatness are all had requirement, fully control plane, flatness under a lot of situations, the result produces bonding irregular.And if greater than 50 μ m, then with itself and the bonded layer (c) that is formed by inorganic material when bonding, the difficulty of conducting heat needs spended time to transmit temperature, productivity decline.And the thickness thickening of laminates integral body sometimes, can not satisfy in the various uses requirement to miniaturization, filming.

Therefore, consider the preferred thickness of above-mentioned A layer, the whole thickness of preferred laminates (I) is essentially 1-150 μ m.1-100 μ m more preferably, more preferably 1-50 μ m is preferably 2-25 μ m especially.

According to the shape of laminates, shape, the application target of laminates, the method for bonded layer (C), the B layer can be got laminated arbitrarily form.Specifically, can make the B layer itself form fine and close filming.For the purpose of control bonding force, can under the prerequisite of not damaging primary characteristic, add for example inorganic salts such as glass, carbon, titanium oxide, talcum, foaminess particle, barium titanate, metal, glass equigranular thing, short fiber shape thing, whisker etc.For example can add with the amount below 40% volume.

In order to improve bonding precision, control bonding force, the B layer can be a porous matter.When being porous matter, porous can be continuous porous, also can be porous independently, can preferably adopt voidage for example to reach 80%.As the method for making porous matter B layer, can preferably adopt the preparation method of disclosed porous matter Wholly aromatic polyamide among the PCT/JP03/11729 for example.

And the B layer needn't necessarily be present on whole of A layer, but can get laminated arbitrarily form according to the shape of laminates, shape, the application target of laminates, the method for bonded layer (C).For example, the belt course component can only have the B layer at middle body, perhaps only at both ends the B layer is arranged, and perhaps the B layer exists with clathrate.Can get the peripheral part, central portion of disk shape laminates or with the radial form that partly has the B layer.Though be not particularly limited, but for example have the area of face,, then can both be suitable for to most applications if on the area more than 10%, have adhesive layer with respect to the adhesive of A layer.

As the full aromatic polyimide (PI that can be used as the B layer ^B-1) and Wholly aromatic polyamide (PA ^B-2) constituent, its example has and the identical constituent of material that can be used as substrate layer (A).Just,, need satisfy aforesaid glass transition temperature from the cohesive equal angles, in fact preferred full aromatic polyimide and Wholly aromatic polyamide, different at aspects such as the combination of constituent, ratio of components.

＜full aromatic polyimide (PI ^B-1)

(B-1) glass transition temperature that constitutes the B layer is more than 180 ℃ but is lower than 350 ℃ full aromatic polyimide (PI ^B-1), be the full aromatic polyimide that has from the construction unit of aromatic acid's composition and aromatic diamine composition.

The example of aromatic acid's composition can exemplify and above-mentioned full aromatic polyimide (PI ^A-1) the same example.

Consider PMA that preferred aromatic acid's composition be use separately or PMA and the above-mentioned aromatic acid's different combination with it from chemical stability, stable on heating angle.More particularly, be benchmark with whole tetrabasic carboxylic acid compositions, pyromellitic acid dianhydride is preferably the 50-100% mole.Making pyromellitic acid dianhydride is more than 50% mole, can improve the imide concentration in the full aromatic polyimide, can access the good material of cohesive.Preferred pyromellitic acid dianhydride is the 70-100% mole, and more preferably the 90-100% mole especially preferably uses pyromellitic acid dianhydride separately.

The aromatic diamine composition can exemplify and above-mentioned full aromatic polyimide (PI ^A-1) the same composition.

Preferred two amine components for example have 1,4-phenylenediamine, 1,3-phenylenediamine, 3,4 '-diaminodiphenyl ether and 1,3-two (3-amino-benzene oxygen) benzene, 4,4 '-diaminodiphenyl ether.Main preferably at least 3,4 '-diaminodiphenyl ether and 1,3-two (3-amino-benzene oxygen) benzene, 4,4 '-diaminodiphenyl ether.

As particularly preferred aromatic diamine composition, the 70-100% mole in preferred whole two amine components is at least aly to be selected from 3,4 '-diaminodiphenyl ether, 1,3-two (3-amino-benzene oxygen) benzene and 4, the composition of 4 '-diaminodiphenyl ether.As other aromatic diamine composition in addition, preferred 1,4-phenylenediamine, 1,3-phenylenediamine.Wherein, further preferably with 3,4 '-diaminodiphenyl ether and other aromatic diamine composition in addition are used in combination.Preferred especially use 3 separately, 4 '-diaminodiphenyl ether.

Thus, full aromatic polyimide (PI ^B-1) the full aromatic polyimide that is made of construction unit shown in the following formula (IV) for example arranged.

Ar in the following formula (IV) ^4aAnd Ar ^4bIndependent of separately containing the aryl of non-reacted substituent carbon number 6-20.N is 1 or 2.

The aryl of carbon number 6-20 for example has phenylene, naphthalene two bases etc.

Can exemplify by more than 70% mole but be lower than construction unit shown in 100% mole the following formula (IV) and surpass 0% mole but be the full aromatic polyimide that construction unit constitutes shown in the following formula (I) below 30% mole.

Ar in the formula (I) ¹Be can contain non-reacted substituent 1, the 4-phenylene.Non-reacted substituent example has: alkyl such as methyl, ethyl, propyl group, cyclohexyl; Aryl such as phenyl, naphthyl; Halogens such as chloro, fluorine-based, bromo; Alkoxyls such as methoxyl group, ethyoxyl, phenoxy group; Nitro etc.

＜by full aromatic polyimide (PI ^B-1) formation B layer

The B layer can be by with the organic polar solvent solution of the precursor-polyamic acid of full aromatic polyimide or polyamic acid derivative curtain coating and make its dry formation on the A layer.Can in drying, heat, make its hot-imide.At this moment can use two or more polyamic acids or polyamic acid derivative, form that Compatibilized blends by two or more polyimides forms layer.

As the imidizate auxiliary agent that is fit in this solution, can add organic alkali catalysts such as dehydrating agents such as using acetic anhydride or pyridine.

The preferred N-N-methyl-2-2-pyrrolidone N-of organic polar solvent, N, N-dimethylacetylamide, N, dinethylformamide etc.

The method of curtain coating for example has the die head extrusion molding, uses the method for spreader, uses the method for glue spreader etc.

The delay time temperature of this solution of convection current is not particularly limited, and preferably it is suitably selected, so that the viscosity of this solution is 30～20, between 000 pool.More preferably for example 50～2,000 moor.

After the curtain coating, make solvent evaporates by drying.Drying for example can be the drying of being undertaken by hot blast heating, heating in vacuum, infrared ray heating, heating using microwave, the preferably heat drying that is undertaken by hot blast.The baking temperature of this moment is 30 ℃～650 ℃, more preferably 40 ℃～600 ℃, and further preferred 70 ℃～550 ℃.

As other method, for example have by hot-rolling, hot press etc. the full aromatic polyimide film by the method manufacturing the same with above-mentioned A layer is in advance carried out laminated method.

＜Wholly aromatic polyamide (PA ^B-2)

(B-2) glass transition temperature that constitutes the B layer is more than 180 ℃ but is lower than 350 ℃ Wholly aromatic polyamide (PA ^B-2) be Wholly aromatic polyamide from aromatic dicarboxylic acid composition and aromatic diamine composition.

The example of aromatic dicarboxylic acid composition has terephthalic acid (TPA), M-phthalic acid.Wherein, consider, especially preferably ask phthalic acid from mechanical property and stable on heating angle.

The aromatic diamine composition for example has 1,4-phenylenediamine, 1,3-phenylenediamine, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether and 1,3-two (3-amino-benzene oxygen) benzene.Consider from mechanical property and stable on heating angle, more preferably 1,3-phenylenediamine, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether and 1,3-two (3-amino-benzene oxygen) benzene.Wherein preferred especially 1,3-phenylenediamine, 3,4 '-diaminodiphenyl ether.

Thus, as particularly preferred Wholly aromatic polyamide (PA ^B-2), its example has and comes from the aromatic dicarboxylic acid composition that is selected from terephthalic acid (TPA) and/or M-phthalic acid and be selected from 1,4-phenylenediamine, 1,3-phenylenediamine, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether and 1, the Wholly aromatic polyamide of at least a aromatic diamine composition of 3-two (3-amino-benzene oxygen) benzene.

Example has the Wholly aromatic polyamide that is made of construction unit shown in the following formula (V) more specifically.

Ar in the formula (V) ^5aAnd Ar ^5bIndependent of separately having the aryl of non-reacted substituent carbon number 6-20.

Preferred Wholly aromatic polyamide has Wholly aromatic polyamide shown in the following formula (III).

Also has Wholly aromatic polyamide shown in the following formula (VI).

Ar in the formula (VI) ^6aAnd Ar ^6bIndependent of separately containing the aryl of non-reacted substituent carbon number 6-20.

The aryl of carbon number 6-20 for example has phenylene, naphthalene two bases, anthracene two bases, toluene two bases etc.Preferred phenylene, particularly 1,4-phenylene, 1,3-phenylene.

N is 1 or 2.N is 2 o'clock, then in fact has two Ar in the formula (VI) ^6a, these two Ar ^6aCan be different structures independently separately, also can be identical structure.Preferred especially n is 1.

Also can exemplify the Wholly aromatic polyamide that constitutes by repetitive shown in repetitive shown in the formula (III) and the formula (VI).In the repetitive, the ratio of repetitive is 10～90% moles shown in the preferred formula (III), and repetitive is 90～10% moles shown in the formula (VI).

＜form the B layer by Wholly aromatic polyamide 〉

Can prepare Wholly aromatic polyamide (PA by following method ^B-2).That is, make the chloride of above-mentioned aromatic dicarboxylic acid composition and aromatic diamine composition at N-N-methyl-2-2-pyrrolidone N-, N, N-dimethylacetylamide, N, reaction prepares in the organic polar solvents such as dinethylformamide.

Can form the B layer thus with gained Wholly aromatic polyamide solution curtain coating and being dried on the A layer.Wholly aromatic polyamide solution after the polymerization directly former state uses.

The delay time temperature of this solution of convection current is not particularly limited, and preferably it is suitably selected, so that the viscosity of this solution is 30～20, between 000 pool.More preferably 50～2,000 moor.

After the curtain coating, make solvent evaporates by drying.Drying for example can be the drying of being undertaken by hot blast heating, heating in vacuum, infrared ray heating, heating using microwave, the preferably heat drying that is undertaken by hot blast.The baking temperature of this moment is 30 ℃～500 ℃, more preferably 40 ℃～450 ℃, and further preferred 70 ℃～400 ℃.

＜resin combination (RC ^B-3)

As the B layer, can use and contain full aromatic polyimide (PI ^B-3) be more than 180 ℃ but be lower than 350 ℃ Wholly aromatic polyamide (PA with glass transition temperature ^B-3) resin combination (RC ^B-3).

Wholly aromatic polyamide (PA ^B-3) glass transition temperature when being lower than 180 ℃, hear resistance is not enough.Be more than 350 ℃ the time, with bonding high temperature, high pressure, the poor adhesion sometimes of needing of adhesive piece (C).Wholly aromatic polyamide (PA ^B-3) glass transition temperature be preferably 200-345 ℃, more preferably 220-340 ℃.

Can select the B layer by the resin combination that uses such combination, this B layer is with respect to headed by semiconductor, the field of electronic materials, improve requirement in recent years gradually, need possess hear resistance and fusible various adhesive piece simultaneously, have required cohesive and hear resistance.

Preferred resin composition (RC ^B-3) contain the full aromatic polyimide (PI of 10～99% weight ^B-3) and the Wholly aromatic polyamide (PA of 1～90% weight ^B-3).More preferably RC ^B-3Full aromatic polyimide (the PI that contains 40～98% weight ^B-3) and the Wholly aromatic polyamide (PA of 2～60% weight ^B-3).

＜full aromatic polyimide (PI ^B-3)

Full aromatic polyimide (PI ^B-3) example have and full aromatic polyimide (PI ^A-1) have a material of identical constituent.

Therefore, preferred full aromatic polyimide (PI ^B-3) can exemplify the full aromatic polyimide that constitutes by construction unit shown in the following formula (I).

Ar in the following formula (I) ¹Non-reacted substituent 1 for containing, the 4-phenylene.Non-reacted substituent example has: alkyl such as methyl, ethyl, propyl group, cyclohexyl; Aryl such as phenyl, naphthyl; Halogens such as chloro, fluorine-based, bromo; Alkoxyls such as methoxyl group, ethyoxyl, phenoxy group; Nitro etc.

＜Wholly aromatic polyamide (PA ^B-3)

Wholly aromatic polyamide (PA ^B-3) example have with Wholly aromatic polyamide (PA ^B-2) material of identical constituent.Just, for Wholly aromatic polyamide, from the cohesive equal angles, need have the glass transition temperature of particular range as mentioned above, in fact preferred Wholly aromatic polyamide is different at aspects such as the combination of constituent, ratio of components.

Preferred Wholly aromatic polyamide (PA ^B-3) example Wholly aromatic polyamide shown in the following formula (III) is arranged.

Also can exemplify Wholly aromatic polyamide shown in the following formula (VI).

Ar in the following formula (VI) ^6aAnd Ar ^6bIndependent of separately containing the aryl of non-reacted substituent carbon number 6-20.

Also can exemplify the Wholly aromatic polyamide that constitutes by repetitive shown in repetitive shown in the formula (III) and the formula (VI).In the repetitive, the ratio of repetitive is 10～90% moles shown in the preferred formula (III), and repetitive is 90～1O% mole shown in the formula (VI)

＜by resin combination (RC ^B-3) formation B layer

The B layer can be by containing full aromatic polyimide (PI ^B-3) precursor and Wholly aromatic polyamide (PA ^B-3) and the solution of organic polar solvent curtain coating, drying and form on the A layer.Can in drying, heat, make its hot-imide.

This solution can pass through full aromatic polyimide (PI ^B-3) precursor-polyamic acid or polyamic acid derivative at Wholly aromatic polyamide (PA ^B-3) organic polar solvent in polymerization prepare.

This solution can also be prepared as follows: prepare full aromatic polyimide (PI respectively ^B-3) the organic polar solvent solution of precursor and the organic polar solvent solution of Wholly aromatic polyamide, with its suitably mix, dilution, make required solution thus.

Can add in this solution and use suitable imidizate auxiliary agent, for example organic alkali catalysts such as dehydrating agent such as acetic anhydride or pyridine.

The method of curtain coating for example has the die head extrusion molding, uses the method for spreader, uses the method for glue spreader etc.The delay time temperature of this solution of convection current is not particularly limited, and preferably it is suitably selected, so that the viscosity of this solution is 5～20, between 000 pool.More preferably 10～10,000 moor.

As other method, for example make the film that forms by the resin combination that contains full aromatic polyimide and Wholly aromatic polyamide in advance, by hot-rolling, hot press etc. it is carried out laminated method.

Wholly aromatic polyamide (PA ^B-3) can be by always known any means preparation such as polymerisation in solution, interfacial polymerization.Wholly aromatic polyamide solution after the polymerization directly former state uses, and also polymer can be separated for the time being, and then be dissolved in formation solution use in the solvent.The preferred N-N-methyl-2-2-pyrrolidone N-of solvent, N, N-dimethylacetylamide, N, organic polar solvents such as dinethylformamide, but also can use highly acid solvents such as the concentrated sulfuric acid, red fuming nitric acid (RFNA), polyphosphoric acid.Can add inorganic salts as required in the above-mentioned aromatic polyamides solution, for example add calcium chloride, magnesium chloride, lithium chloride, lithium nitrate etc. as cosolvent.Polymer concentration in the preferred solution is about 1-60% weight, more preferably 3-40% weight.

＜laminates (II) 〉

Present invention resides in the laminates (II) that has further formed bonded layer (C) on the B layer of laminates (I).The C layer can only form on the one side of laminates, also can distinguish bonding C layer on the two sides independently.That is, can exemplify the formation of A/B/C or the formation of C/B/A/B/C.This moment, the C layer of both sides can be identical, also can be different.Can also exemplify and for example on the one side of laminates, adopt metal forming, and adopt asymmetrical laminates on the thickness direction of full aromatic polyimide film as the C layer on the another side as the C layer.

＜bonded layer (C) 〉

The C layer can use organic material, inorganic material arbitrarily.Organic material can exemplify various macromolecular materials such as polyimides, polyester, nylon, polyarylate, PEI, Wholly aromatic polyamide, epoxy resin, phenolic resins, acrylic resin, polyether-ketone, polysulfones, polyphenylene oxide, BT resin, polybenzimidazoles.

Inorganic material for example has metals such as aluminium, iron, silicon, germanium; Alloys such as 42 alloys, iron/nickel alloy, stainless steel-like, brass; Nitride compounds such as barium titanate, potassium titanate, titanium nitride, aluminium nitride, boron nitride; The potteries such as セラジ Application (registration mark) that zirconia, aluminium oxide, aerochemistry Co., Ltd. of Mitsubishi make; Glass; Carbon etc.

Be preferably semiconductor alloys such as silicon, germanium, more preferably silicon wafer.Therefore, porous ceramic/epoxy compound of can exemplify carbon/epoxy compound of making by so-called prepreg, making by sintering etc.

The thermal linear expansion coefficient difference of preferred laminates (I) and C layer is in 30ppm/ ℃.More preferably the thermal linear expansion coefficient difference is 25ppm/ ℃, is preferably especially below 20ppm/ ℃.Thus, can be particularly suitable in field of electronic materials using as the insulating materials of excellent in dimensional stability.

Thickness to this C layer is not particularly limited, and can be the thickness corresponding to purposes, purpose, is preferably 1 μ m～5,000 μ m.If less than 1 μ m, then with laminates (I) when bonding, the precision of pressing device there is requirement, be difficult to sometimes fit adhesive surface equably and do not occur irregular.Can not obtain enough mechanical strengths in the time of can occurring overlaying, situation about being damaged when overlaying.If more than 5, the 000 μ m, the difficulty of conducting heat when then making itself and laminates (I) bonding needs spended time to transmit temperature, and productivity descends.

The manufacturing of＜laminates (II) 〉

The method of making laminates (II) is not particularly limited, can be at room temperature with laminates (I) and C layer, limit heating according to circumstances, add flanging and fit.The method of fitting has the pressure stickup of using hot press, vacuum press to close, and uses the applying of roller etc.

For example, for using hot press to press to paste the situation of closing, can be on the interface of the top board of hot press and laminates (I) and C layer, clamping thickness does not influence heat conducting fender, so that pressure is delivered on the whole adhesive surface.The example of fender has baffle, film and fiber etc.Baffle can use metals such as stainless steel, iron, titanium, aluminium, copper and their alloy etc.Film, fiber then can use the film that formed by heat resistant polymers such as full aromatic polyimide, Wholly aromatic polyamides, fiber etc.

Preferably suitably regulate bond conditions such as temperature, pressure, time according to the material or the combination of laminates (I) and C layer.Preferred temperature range is 20 ℃～600 ℃.Preferred scope is 50 ℃～550 ℃.Further preferred 100 ℃～500 ℃.Pressure is counted 0.001MPa～1 with the whole suffered average pressure of laminates (I) and C layer, 000MPa, preferred 0.01MPa～100MPa.Pressure can not be fully bonding during less than 0.001MPa, and be higher than 1, and during 000MPa, the C layer has breakage sometimes.

The preferred dwell time is considered pressure transmission method, heat conductivity etc. according to the shape of bonding mode, tack temperature, C layer etc., selects the optimum condition that is fit to.For example, for using the plane hot press to heat the situation of pressurized adhesion, preferred range is 0.1 second～48 hours.During less than 0.1 second, bonding force is not enough, is difficult to obtain the stable laminates of bonding force (II).And during greater than 48 hours; not only productivity reduces; and if be under the high-temperature and high-pressure conditions for a long time, when the laminates (II) and the organic protection layer (D) of other organic material formation are bonding, the situation that the bonding force of adhesive (II) and organic protection layer (D) can occur descending.That is the cohesive decline of the organic protection layer (D) on laminates (II) and the semiconductor chip, appears.Though its reason is indeterminate, think it to be that form (モロ Off オロジ-) that the chemical change that causes of the particularly lip-deep heat owing to laminates (II) or HTHP cause changes and causes.Dwell time when more preferably bonding is 1 second～24 hours.In addition, during bonding, temperature is risen, behind the pressure bonding official hour with regulation, at room temperature put cold certain hour, temperature is risen with pressurized state, pressure binding after the stipulated time with regulation is incubated certain hour under the state of pressure relief.

Make the two sides when having the laminates (II) of C layer, consider from viewpoints such as cost, bonding precision, bond locations precision, can the two sides simultaneously bonding according to purpose, also can be after bonding one side more bonding another side etc. carry out bonding successively.

＜laminates (III) 〉

Laminates (III) is made of A layer, B layer, C layer, organic protection layer (D layer) and object being treated layer (E layer), for be formed with B layer and C layer in regular turn on the one side of A layer, is formed with the laminates of D layer and E layer in regular turn on the another side of A layer.

＜organic protection layer (D) 〉

The D layer is to be organic film that purpose forms with protection E layer on the one side of E layer.The resin that constitutes the D layer for example has: polyimides, particularly full aromatic polyimide; Polyamide, particularly Wholly aromatic polyamide; PEI; Polyamidoimide; Polyether-ketone; Polyether-ether-ketone; Polybenzimidazoles; Polyvinyl alcohol; Triafol T; Poly--the 4-methylpentene; The ethylene/vinyl alcohol copolymer; Polymethyl methacrylate; The tetrafluoroethylene/fluoro alkyl vinyl ether co-polymer (PFA) of fluorine; Polyvinylidene fluoride (PVDF); Tetrafluoroethylene/hexafluoropropylene copolymer (FEP); Polychlorotrifluoroethylene (PCTFE); Chlorotrifluoroethylene/ethylene copolymer (E/CTFE) etc.

As the D layer, can exemplify when particularly making the thin paper semiconductor etc. and to be used for the protection in semiconductor loop, the organic protective film of insulation.Therefore, can use always known various organic insulating films.Wherein, can preferably use the material that has high-fire resistance as silicone modified polyimide, polyimides, polybenzimidazoles, polyamide etc.

The thickness of D layer is preferably 1nm～1,000 μ m.More preferably 10nm～500 μ m, more preferably 100nm～100 μ m.

The formation method of D layer can adopt always known any method, and the coating coating for example has surface aggregate method, sol-gel process etc.In more detail, the method for for example useful spinner coating varnish formation film.Heat cure if be thermosetting resin, then takes place if photocuring then takes place photosensitive resin in applied varnish, perhaps the solvent heat drying is formed film.Particularly, by exposure, can form protective layer as required with special specific pattern for the situation of photosensitive varnish.

＜object being treated layer (E) 〉

The E layer preferably adopts the multilayer structure of laminated various layers on the opposition side of treated exposure.The example of E layer has the electronic circuit that has used semiconductor substrate such as silicon wafer, gallium-arsenic wafer silicon carbide wafer or ceramic substrate.

The cambial structure of coating circuit parts on silicon wafer is for example arranged.Also can adopt the metal sputtering of aluminium etc. and use this metal to form circuit etc.

Thickness to the E layer is not particularly limited, preferred 5～2,000 μ m.More preferably 10～1,000 μ m, further preferred especially 10～500 μ m.

The formation method of E layer can adopt any method in the always known semiconductor making method.These methods are documented in for example " initial semiconductor technology " (preceding field and husband work, the census of manufacturing meeting), " semi-conductive all " (the positive allusion quotation of Kikuchi is shown, Japanese industry publishing house) etc.

The manufacture method of＜laminates (III) 〉

The method of making laminates (III) is not particularly limited, can adopts always known any method.For example there are the laminates that to constitute by above-mentioned C layer, E layer and D layer and laminates (I) to make the method for its applying via heating, pressurization.

Laminates (I) can use the laminates that has formed the B layer in advance on the A layer; Also can prepare A layer, the B layer of form of film respectively, in addition carry out bonding laminates then by crossing hot pressing etc.; Can also prepare A layer, the B layer of form of film respectively, the laminates that constitutes with the C layer or by E layer and D layer carries out laminated simultaneously then.

And then it is laminated to carry out the multistage by suitable any combination.Applying method for example has: the stickup of using hot press, vacuum press to be undertaken by pressurization, the stickup of being undertaken by roller etc.Just when fitting, A layer and the D layer that constitutes laminates (I) need be joined, with B layer and C layer join carry out laminated.Otherwise, the situation of enough bonding forces may appear obtaining, and the not enough situation of fissility after the heat treatment perhaps appears.

For example, use hot press to be undertaken to be set on the hot press with the layer of hot press top board lamination when bonding by pressurization.At this moment, can be between layer and top board that will be laminated, thickness is set does not influence heat conducting fender, so that pressure is delivered on the whole adhesive surface.Fender can preferably use for example metal and their baffles such as alloy such as stainless steel, iron, titanium, aluminium, copper; The film that forms by heat resistant polymers such as full aromatic polyimide and/or Wholly aromatic polyamides; The resin of fiber that forms by these heat resistant polymers etc.

When using semiconductor wafer such as silicon wafer, can use the mould that matches with its shape etc.Stickup condition to temperature, pressure, time etc. is not particularly limited, but can control arbitrarily by the material or the combination of used C layer, E layer, D layer and laminates (I).

Suitable temperature when bonding for example can be 150 ℃～600 ℃.Preferred 180 ℃～550 ℃.Further preferred 200 ℃～500 ℃.

Pressure when bonding is counted 0.01MPa～500MPa with C layer and the whole suffered average pressure of E layer.Average pressure can not be fully bonding during less than 0.01MPa, and when being higher than 500MPa, damaged situation can appear in C layer or E layer.Preferred 0.1MPa～100MPa.

Dwell time when bonding is preferably 0.1 second～and 24 hours.During less than 0.1 second, bonding force is not enough, is difficult to obtain the stable laminates of bonding force.And during greater than 24 hours, not only productivity reduces, and cost raises.Dwell time when more preferably bonding is 1 second～12 hours, further preferred 1 second～1 hour, and preferred especially 1 second～10 minutes.

When bonding, temperature is risen, behind the pressure binding official hour with regulation, at room temperature certain hour add press cold; Temperature is risen, behind the pressure binding official hour with regulation, under the state of pressure relief, be incubated certain hour; Can also make its cooling by pressures such as suitable air-supplies.

The manufacture method of＜laminates (V) 〉

The present invention relates to make the method for laminates (V) by laminates (III), wherein laminates (V) by the D layer and the E layer after handling (E ') constitute, this method comprises the steps:

(2) laminates (III ') is remained on the heat treatment step of the temperature more than at least 350 ℃;

The inventive method is characterised in that has found the following fact: the peel strength of C layer and B layer changes with heat treatment, by controlling this variation, can easily peel off.And D layer and A layer are peeled off and can be sheared the poor of peel strength (せん Duan Bao From Strong degree) and peel strength (ピ one Le Strong degree) by control, easily carry out mechanical stripping.

Peeling off preferably of C layer undertaken by ultrasonic irradiation.More preferably laminates (III ') is immersed in the water, to the laminates under the impregnation state (III ') irradiation ultrasonic wave more than 30 seconds.The outer surface of E layer is handled preferred thin paper processing.Preferred E layer is the semiconductor substrate that has formed circuit block.

＜surface treatment step 〉

Surface treatment step is to expose face by the E layer to laminates (III) to handle, obtain the having treated layer thus step of laminates (III ') of (E ').

To the E layer expose grinding that processing that face carries out is a wafer, thin paper steps such as polishing after grinding.It also is the surperficial pre-treatment that the wafer substrate back side is carried out with hydrofluoric acid (acid of boiling), nitric acid etc.Can also be for example to comprise that the metal evaporation of aluminium or gold etc. and 1 hour form with the metallic film on the wafer substrate back side of about 250 ℃ about interior～500 ℃ calcination processing etc. to handle etc.These processing can be carried out separately, also can multiple combination carry out.

The thin paper processing that wherein particularly preferably is grinding, carries out through grinding.The thickness of the E layer after the processing (E ') is preferably below the 400 μ m, more preferably below the 200 μ m, more preferably below the 100 μ m.Lower limit is not particularly limited, as long as can keep the intensity of E ' layer, but is preferably more than the 3 μ m, more preferably more than the 5 μ m.

Sometimes, also comprise following heat treatment step in this series of processes.For example, sometimes to the E layer expose that face grinds, the thin paper processing, implement then to import the heat treatment of handling as impurity.Perhaps, the surface being implemented make metal evaporation, this metal film is carried out the heat treatment of calcination processing sometimes as after the acid treatment of pre-treatment etc., perhaps by be etched in form the loop on the metal film after, this metal film is carried out the heat treatment of calcination processing.These heat treatment temperatures are more than 350 ℃ the time, promptly become heat treatment step.

＜heat treatment step 〉

Heat treatment step is the step that laminates (III ') is maintained the temperature more than 350 ℃.

Laminates of the present invention (III) is characterised in that: because use the laminates (I) that is made of A layer and B layer as adhesive sheet, even so carry out heat treatment more than 350 ℃, the bonding force of adhesive sheet is strengthened to more than the necessary degree, can keeps suitable cohesive and fissility.That is, under the situation of using the conventional adhesive sheet material, high-temperature heat treatment will make peels off the difficulty that becomes, and by adopting adhesive sheet of the present invention, even after the heat treatment more than 350 ℃, still can easily peel off.

Preferred heat treatment temperature is more than 375 ℃, and is further preferred more than 400 ℃, preferred especially more than 425 ℃.The upper limit to heat treatment temperature is not particularly limited, and is essentially about 700 ℃.Described heat treatment more than 350 ℃ can be carried out in air, also can carry out in inert gases such as nitrogen, but preferably carry out in inert gas.In addition, can under normal pressure, carry out, also can under vacuum, carry out, can also under reduced pressure carry out, preferably under normal pressure, carry out, but,, under reduced pressure carry out sometimes in order to carry out nitrogen replacement or to remove moisture by moisture absorption in the initial stage of handling.

Heat treatment period is preferably 1 second～in 48 hours.If be shorter than 1 second, fissility and cohesive can not reach proper state after the heat treatment sometimes, and heat treatment was longer than 48 hours, then will can not reach proper state because of heat ageing causes fissility and cohesive sometimes.More preferably more than 10 seconds in 24 hours, preferred especially more than 30 seconds in 12 hours.

According to the present invention, even carry out high-temperature heat treatment more than 350 ℃, phenomenons such as bonding reinforcement can not appear yet, can easily peel off, can make laminates (V) effectively.

＜the first strip step 〉

This is from having implemented that heat treated laminates (III ') is peeled off the C layer and the step that obtains laminates (IV).Originally, for obtaining laminates (V), can realize purpose, but because the bonding force at the interface of A layer and D layer is strong as long as on the interface of A layer and D layer, peel off, when existence resemble the C layer upright and outspoken like this layer time, be difficult to directly peel off.

Therefore, at first peel off the interface of B layer and C layer.Make the method for the interface peel of B layer and C layer that following method for example be arranged.

For example,, make its suction, then it contact with hot plate more than 200 ℃, heat suddenly and make moisture gasify the method for utilizing volumetric expansion to peel off thus laminates (III ') dipping about 1 second～12 hours in 0 ℃～100 ℃ water.Laminates after will absorbing water in addition (III ') cools off rapidly by dipping in liquid nitrogen etc., and water freezes, the method for utilizing volumetric expansion to peel off thus.Perhaps, the one side of laminates (III ') waited with ice be cooled to 0 ℃, and another side is contacted with the plate through heating more than 200 ℃, the method for utilizing the thermal expansion difference that causes by heating to peel off thus.Perhaps, dipping in liquid etc., irradiation ultrasonic wave, the method for peeling off thus.And in aqueous slkali etc. dipping dissolving and the method peeled off.

From easy and needn't worry to pollute or aging equal angles that chemical reagent etc. causes is considered, the especially preferred method that it is peeled off by the irradiation ultrasonic wave.Water is as solvent when more particularly, preferably shining ultrasonic wave.That is, preferably impregnated laminates in water (III ') is shone hyperacoustic method, preferably its irradiation time is more than 30 seconds.The upper limit to irradiation time is not particularly limited, and considers from the productivity equal angles, is essentially in 24 hours, in more preferably 5 hours, more preferably in 2 hours, is preferably especially in 1 hour.

As mentioned above, by peeling off the interface of B layer and C layer, can obtain the laminates (IV) that constitutes by B layer, A layer, D layer and E ' layer.At this moment, being stripped from the C layer that gets off can reclaim, and is making laminates (II) and/or is utilizing (III) time again again.When utilizing the C layer again, can wash the surface of C layer as required, handle with alkalescence and/or acid solution, processing such as grind with diamond dust grinding agent etc.

＜the second strip step 〉

This is the interface of the A layer of peel ply component (IV) and D layer and obtain the step of laminates (V).That is, peel off the laminates (I) that constitutes by B layer and A layer, obtain step by the laminates (V) of D layer and E ' layer formation from the laminates (IV) that obtains as mentioned above by B layer, A layer, D layer and E ' layer formation.

Therefore as so-called peel strength peeling off (draw I and shell the Ga The) when measuring because laminates (I) is resilient laminates,, can peel off.This is because laminates (I) has the high shear peel strength, and peel strength is low simultaneously.Exfoliation temperature can be carried out suitable optimization according to the combination of the used composition of each layer, and it is not particularly limited.But, preferably for example carrying out below 300 ℃ more than 0 ℃.More preferably more than 0 ℃ below 200 ℃.

According to the inventive method, peel off by segmenting, can effectively obtain laminates (V).Just, when laminates (V) such as thin paper semiconductor are obviously very thin, produce application difficult because of the warpage of laminates (V) itself or distortion sometimes.Have in strip step and subsequent in using unwanted mechanical load affact laminates (V) and go up and make the impaired situation of laminates (V).In this case, before implementing strip step, preferably with the adhesive tape that is pasted on the dicing above the framework etc. etc. with the E ' layer of laminates (III ') to expose face fixing for the time being, directly carry out first, second strip step then, obtain to be the laminates (V) of the adhesive tape state that is pasted on dicing at last.

Through above-mentioned steps, can effectively obtain the laminates (V) that constitutes by E ' layer and D layer.Gained can be preferably used as semiconductor substrate or thin paper semiconductor substrate by the laminates (V) that E ' layer and D layer constitute.

Embodiment

Below, by embodiment the present invention is specifically described.The assay method of rerum natura, Evaluation on effect method are carried out according to following method among the present invention.

(1) cohesive

Trial is gone up at the laminates (I) that comprises A layer and B layer and is formed bonded layer (C), forms laminates (II) thus, estimates according to following benchmark during this period.

Fail bonding situation: *

Though can be bonding, when curved, bend is peeled off with record book in accordion form, the situation that firmly just laminates (I) can be stripped down from laminates (II) hardly with hand: △

Do not peel off with record book in accordion form is curved yet, try to peel off and the situation that is difficult on the adhesive interface peel off with hand: zero

(2) determination of viscoelasticity

Adopt the sample of 22mm * 10mm, make its temperature be elevated to 50 ℃～500 ℃ scope, under the frequency of 6.28rad/s, measure with rheometry instrument (Rheometrics) RSA II.With gained dynamic storage modulus E ', dynamic loss modulus E " calculate the value of dynamic loss tangent tan δ, calculate glass transition temperature by this value.

(3) film mechanical properties

Adopt the sample of 50mm * 10mm,, measure the Young's modulus and the strong percentage elongation of cohesive sheet material (laminates (I)) or substrate layer (A) by オリエ Application テ Star Network UCT-1T at 25 ℃ of draw speeds with 5mm/min.

(4) surface roughness measurement of silicon wafer

By the small surface configuration observation system of non-contact three-dimensional NT-2000 (WYKO), measure the middle body 1.2mm * 0.92mm of silicon wafer.

(5) swellbility

Weight (W with solvent swelling state _w) and the weight (W of drying regime _D), calculate by following formula (1).

Swellbility (wt/% weight)=(W _W/ W _D-1) * 100...... (1)

(6) thermal linear expansion coefficient

Adopt about 13mm (L ₀The sample of) * 4mm, by the hot Mechanics of Machinery analyzer of TA instrument TMA2940 (Thermomechanical Analyzer), programming rate with 10 ℃/min, in 50 ℃～250 ℃ scope, heat up, lower the temperature, measure the variation delta L of test portion length between 100 ℃ to 200 ℃, calculate by following formula (2).

Thermal linear expansion coefficient (ppm/ ℃)=10,000 * Δ L/L ₀... ... (2)

(7) viscosimetric analysis

, measure under 0 ℃ of aromatic polyamide acid composition concentration 0.05% weight, temperature as lysate with the lithium chloride/nmp solution of 1% weight, calculate inherent viscosity [η] (dl/g) by the gained measurement result.

Embodiment 1

(preparation of polyamic acid nmp solution (PAA solution))

Under nitrogen atmosphere, in the reaction vessel that thermometer, agitating device and raw material dog-house are housed, add 1920g dehydration NMP, add 26.52g 1 again, the 4-phenylenediamine dissolves it fully.Afterwards, cooling off in ice bath, is 3 ℃ with the adjustment of two amine aqueous solutions.In these cooled two amine aqueous solutions, add 53.46g PMA acid anhydride, make its reaction 1 hour.At this moment, the temperature of reaction solution is 5-20 ℃.This reaction solution was reacted 3 hours down in room temperature (23 ℃), add the 0.091g phthalic anhydride then, the end-blocking that its reaction was carried out the amine end in 1 hour obtains the 4% weight polyamide acid nmp solution (following PAA solution) into viscous solution.

(A layer (PI ^A-1))

Gained PAA solution scraper plate with thickness 1.5mm on glass plate is carried out curtain coating, dipping is 30 minutes in 30 ℃ of dehydrating condensations that contain 1050ml acetic anhydride, 450g pyridine and 1500ml NMP are bathed, make its acid imide/different imidizate, separate, obtain gel mould from the supporter glass plate.

With the gained gel mould in NMP under room temperature dipping 20 minutes, wash, then the two ends chuck of this gel mould is fixed, at room temperature, on two vertical direction of principal axis, carry out while diaxon stretching with 1.85 times, the speed of 10mm/ second respectively.The swellbility of gel mould is 1510% when stretching beginning.

With the gel mould frame fixation after stretching, by using the air drier of dry air, carry out multistage intensification from 160 ℃ to 300 ℃, implement drying and heat treatment thus.Then, adopt heated-air circulation oven, carry out multistage intensification, obtain full aromatic polyimide film (A layer) thus from 300 ℃ to 450 ℃.Therefore, the A layer is by only containing following formula (I-a)

Shown in the full aromatic polyimide of construction unit form.The thickness of gained A layer is 13 μ m, and the Young's modulus of portraitlandscape is respectively 17.2GPa, 18.5GPa.Carry out Measurement of Dynamic Viscoelasticity in 50 ℃～500 ℃ scope, the result does not observe glass transition point.Confirm that thus glass transition point is more than 500 ℃.The thermal linear expansion coefficient of A layer is-6ppm/ ℃.

(B layer (PA ^B-2))

The powder of the コ one ネ Star Network ス (registration mark) that Supreme Being people テ Network ノプロダ Network Star Co., Ltd. is made is scattered in N-N-methyl-2-2-pyrrolidone N-(being designated hereinafter simply as NMP) at 5 ℃, makes it 40 ℃ of dissolvings then, obtains 10% weight solution.With the scraping article spreader of thickness 28 μ m, pay curtain coating on the above-mentioned A layer that is fixed on the glass plate in subsides with this コ one ネ Star Network ス (registration mark) 10% weight solution.Then by air drier 160 ℃ of dryings 30 minutes, carry out multistage intensification afterwards, finally carry out 300 ℃/30 minutes drying and heat treatment, on the A layer, form adhesive layer (B) by Wholly aromatic polyamide thus.Therefore, the B layer is by following formula (III)

Shown in Wholly aromatic polyamide form.The laminates (I) that so just obtains on the one side of A layer, filming and formed the B layer.

The thickness of laminates is 16 μ m.Thereby the coating thickness of B layer is 3 μ m.The glass transition temperature of B layer is 285 ℃.The portraitlandscape Young's modulus of laminates is respectively 13.9GPa, 13.6GPa.Thermal linear expansion coefficient is-5ppm/ ℃.

Embodiment 2

(B/A/B)

Gained laminates (I) among the embodiment 1 paste paid be fixed on the glass plate, make on the A course.With the scraping article spreader of thickness 2g μ m, with コ one ネ Star Network ス (registration mark), 10% weight solution curtain coating on this laminates.Then by air drier 160 ℃ of dryings 30 minutes, carry out multistage intensification afterwards, finally carry out 300 ℃/30 minutes drying and heat treatment, form the B layer by Wholly aromatic polyamide thus.So just obtain on the two sides of A layer, all filming and formed the laminates of B layer.

The thickness of this laminates is 19 μ m.Promptly obtaining filming on the two sides of A layer has formed the laminates of B layer, and the thickness of wherein said A layer is 13 μ m, formed by full aromatic polyimide film, and the B layer thickness that forms of filming on the two sides of A layer is 3 μ m, is formed by Wholly aromatic polyamide.The glass transition temperature of B layer is the same with embodiment 1, is 285 ℃.

The portraitlandscape Young's modulus of laminates is respectively 11.2GPa, 10.7GPa.Thermal linear expansion coefficient is-4ppm/ ℃.

Embodiment 3

(A layer (PA ^A-2))

The Wholly aromatic polyamide film アラミカ (registration mark) that uses the manufacturing of Supreme Being people ア De バ Application スト Off イ Le system Co., Ltd. is as the A layer.Therefore, the A layer is by only containing following formula (II)

Shown in the Wholly aromatic polyamide film of construction unit form.The thickness of A layer is 12 μ m, and the Young's modulus of portraitlandscape is respectively 14.9GPa, 14.6GPa.The glass transition temperature of being calculated by Measurement of Dynamic Viscoelasticity is 355 ℃.The thermal linear expansion coefficient of A layer is 2ppm/ ℃.

(B layer (PA ^B-2))

Use the scraping article spreader of thickness 28 μ m again, pay curtain coating on the above-mentioned A layer that is fixed on the glass plate in subsides this コ one ネ Star Network ス (registration mark) 10% weight solution.Then by air drier 160 ℃ of dryings 30 minutes, carry out multistage intensification afterwards, finally carry out 300 ℃/30 minutes drying and heat treatment, obtain having the laminates (I) of B layer thus.Therefore,

The B layer is by following formula (III)

The thickness of this laminates is 15 μ m.Thereby the thickness of B layer is 3 μ m.The glass transition temperature of B layer is 285 ℃.The portraitlandscape Young's modulus of laminates is respectively 11.4GPa, 10.8GPa.Thermal linear expansion coefficient is 2ppm/ ℃.

Embodiment 4

(A layer (PI ^A-1))

Adopt with embodiment 1 in used identical full aromatic polyimide film as the A layer.

(B layer (PI ^B-1))

Under nitrogen atmosphere, in the reaction vessel that thermometer, agitating device and raw material dog-house are housed, add 1840g dehydration NMP, add 76.58g 3 again, 4 '-diaminodiphenyl ether dissolves it fully.Afterwards, cooling off in ice bath, is 3 ℃ with the adjustment of two amine aqueous solutions.In these cooled two amine aqueous solutions, add 83.42g PMA acid anhydride, make its reaction 1 hour.At this moment, the temperature of reaction solution is 5-20 ℃.Make this reaction solution 50 ℃ of reactions 3 hours again, obtain 8% weight polyamide acid nmp solution into viscous solution.With the scraping article spreader of thickness 28 μ m, pay curtain coating on the above-mentioned A layer that is fixed on the glass plate in subsides with this polyamic acid 8% weight nmp solution.Then by air drier 160 ℃ of dryings 30 minutes, carry out multistage intensification afterwards, the drying and the hot-imide that finally carried out 350 ℃/20 minutes are handled, and form the B layer by full aromatic polyimide thus on the A layer.Therefore, the B layer is by following formula (IV-a)

Shown in full aromatic polyimide form.The laminates (I) that so just obtains on the one side of A layer, filming and formed the B layer.

The thickness of this laminates is 16 μ m.Thereby the coating thickness of B layer is 3 μ m.The glass transition temperature of B layer is 330 ℃.The portraitlandscape Young's modulus of laminates is respectively 14.2GPa, 14.4GPa.Thermal linear expansion coefficient is-4ppm/ ℃.

Embodiment 5-18

(A/B/C)

Adopt the laminates (I) that as above makes, according to combination shown in the following table 1, to fit tightly above the B aspect of laminates (I) and the various bonded layers (C layers), use the metallic plate clamping then, and add that Kevlar system plain cloth is as fender, irregular to eliminate pressure, it is arranged in the hot press.After the surface temperature of actual contact face in the hot press is adjusted to 350 ℃,, obtain laminates (II) with 5.5MPa pressurization 2 minutes.Cohesive between the thickness of laminates (II), B layer and the C layer and laminates (I) are documented in the table 1 with the thermal linear expansion coefficient poor (Δ CTE) of bonded layer (C).

Table 1

Embodiment	Laminates (I)	Bonded layer (C layer)	Bonded layer (C layer) thickness (μ m)	Laminates (II) thickness (μ m)	Cohesive	ΔCTE (ppm/℃)
Embodiment	Laminates (I)	Bonded layer (C layer)	Bonded layer (C layer) thickness (μ m)	Laminates (II) thickness (μ m)	Cohesive	ΔCTE (ppm/℃)	5	Embodiment 1	Silicon wafer	625	640	○	9
6	Embodiment 1	SUS304	1,000	1016	○	22	5	Embodiment 1	Silicon wafer	625	640	○	9
6	Embodiment 1	SUS304	1,000	1016	○	22	7	Embodiment 1	The melanotype plate	500	515	○	Undetermined
8	Embodiment 1	Electrolytic copper foil	35	70	○	23	7	Embodiment 1	The melanotype plate	500	515	○	Undetermined
8	Embodiment 1	Electrolytic copper foil	35	70	○	23	9	Embodiment 1	42 alloys	18	34	○	11
10	Embodiment 1	カプトンH	25	41	○	30	9	Embodiment 1	42 alloys	18	34	○	11
10	Embodiment 1	カプトンH	25	41	○	30	11	Embodiment 3	Silicon wafer	625	639	○	2
12	Embodiment 3	SUS304	1,000	1014	○	15	11	Embodiment 3	Silicon wafer	625	639	○	2
12	Embodiment 3	SUS304	1,000	1014	○	15	13	Embodiment 3	The melanotype plate	500	515	○	Undetermined
14	Embodiment 3	42 alloys	18	31	○	16	13	Embodiment 3	The melanotype plate	500	515	○	Undetermined
14	Embodiment 3	42 alloys	18	31	○	16	15	Embodiment 3	Tinplate	500	513	○	Undetermined
16	Embodiment 4	Silicon wafer	625	641	○	8	15	Embodiment 3	Tinplate	500	513	○	Undetermined
16	Embodiment 4	Silicon wafer	625	641	○	8	17	Embodiment 4	Copper Foil	35	69	○	22
18	Embodiment 4	カプトンH	25	40	○	29	17	Embodiment 4	Copper Foil	35	69	○	22

Embodiment 19

(A/B/A/B/A/B/A/B/A)

With gained laminates (I) among 4 embodiment 1 make carry out on the B course superimposed, and then used identical base material (A layer) among superimposed thereon and the embodiment 1, use the metallic plate clamping afterwards, and add that Kevlar system plain cloth is as fender, irregular to eliminate pressure, it is arranged in the hot press.After the surface temperature of actual contact face in the hot press is adjusted to 350 ℃,, obtain the laminates that adhesive layer (B) alternately laminated that the substrate layer (A) that formed by 5 layers of full aromatic polyimide film and 4 layers of Wholly aromatic polyamide form forms with 5.5MPa pressurization 2 minutes.The thickness of this laminates is 71 μ m, and cohesive is evaluated as zero.

Embodiment 20

(A/B/A/B/A/B/A/B/A)

With gained laminates (I) among 4 embodiment 3 make carry out on the B course superimposed, and then used identical base material (A layer) アラミカ (registration mark) among superimposed thereon and the embodiment 3, use the metallic plate clamping afterwards, and add that Kevlar system plain cloth is as fender, irregular to eliminate pressure, it is arranged in the hot press.After the surface temperature of actual contact face in the hot press is adjusted to 350 ℃,, obtain the laminates that forms by adhesive layer (B) alternately laminated that 5 layers of film formed substrate layer of Wholly aromatic polyamide (A) and 4 layers of Wholly aromatic polyamide form with 5.5MPa pressurization 2 minutes.The thickness of this laminates is 69 μ m, and cohesive is evaluated as zero.

Embodiment 21

Adopt the A layer (PI of gained among the embodiment 1 ^A-1).

(B layer (PI ^B-3/ PA ^B-3=47/53))

The powder of the コ one ネ Star Network ス (registration mark) that Supreme Being people テ Network ノプロダ Network Star Co., Ltd. is made is scattered among the NMP at 5 ℃, makes it 60 ℃ of dissolvings then, obtains 4% weight solution.The glass transition temperature of コ one ネ Star Network ス is 285 ℃.

With PAA solution and 4% weight コ, one ネ Star Network ス nmp solution and NMP mediation, obtain containing the nmp solution of acid of 1.9% weight polyamide and 1.9% weight Wholly aromatic polyamide again.

(A/B)

Use the spiral spreader, pay curtain coating on the above-mentioned A layer that forms by full aromatic polyimide film that is fixed on the glass plate in subsides this nmp solution.Then by air drier 120 ℃ of dryings 30 minutes, then, carry out 350 ℃/30 minutes drying and heat treatment at last 280 ℃ of dryings 20 minutes, filming thus forms the B layer.Therefore, gained laminates (I) is the laminates that one side has the B layer, and described B layer is by full aromatic polyimide and 53% weight following formula (III) shown in the 47% weight following formula (I-a)

Shown in the resin combination that constitutes of Wholly aromatic polyamide form.

The thickness of this laminates is 16 μ m.Thereby the average thickness of filming of B layer is 3 μ m.The portraitlandscape Young's modulus of laminates is respectively 12.9GPa, 13.1GPa.

Embodiment 22

(B/A/B)

Gained laminates (I) among the embodiment 21 paste paid be fixed on the glass plate, make the A aspect upwards.With the scraping article spreader of thickness 28 μ m, with the dissolving of modulation among the embodiment 21 nmp solution curtain coating on this laminates of polyamic acid and Wholly aromatic polyamide.Then by air drier 120 ℃ of dryings 30 minutes, then 280 ℃ of dryings 20 minutes, carry out 300 ℃/30 minutes drying and heat treatment at last, form the B layer thus, this B layer is formed by the resin combination that Wholly aromatic polyamide constitutes shown in full aromatic polyimide and the 53% weight following formula (III) shown in the 47% weight following formula (I-a).The laminates (I) that so just obtains on the two sides of A layer, filming and formed the B layer.

The average thickness of this laminates is 19 μ m.Promptly obtain on the two sides of A layer, filming and formed the laminates of B layer, the average thickness of wherein said A layer is 13 μ m, form by full aromatic polyimide film, and the B layer average thickness that forms of filming on the two sides of A layer is 3 μ m, and the resin combination that is made of full aromatic polyimide and Wholly aromatic polyamide forms.The portraitlandscape Young's modulus of laminates is respectively 10.8GPa, 10.6GPa.

Embodiment 23

(A layer (PI ^A-1))

(B layer (PI ^B-3/ PA ^B-3=73/27))

Modulation PAA solution and 4% weight コ, one ネ Star Network ス nmp solution and NMP, use contains the nmp solution of acid of 2.77% weight polyamide and 0.93% weight Wholly aromatic polyamide, in addition, with embodiment 21 the same operations, obtaining filming on the one side of A layer has formed the laminates of B layer.Like this, just obtain the laminates (I) that one side has the B layer, described B layer is formed by the resin combination that Wholly aromatic polyamide constitutes shown in full aromatic polyimide and the 27% weight following formula (III) shown in the 73% weight following formula (I-a).

The average thickness of this laminates is 17 μ m.Thereby the average thickness of filming of B layer is 4 μ m.The portraitlandscape Young's modulus of laminates is respectively 13.4GPa, 11.8GPa.

Embodiment 24

(A layer (PI ^A-1))

(B layer (PI ^B-3/ PA ^B-3=83/17))

Modulation PAA solution and 4% weight コ, one ネ Star Network ス nmp solution and NMP use the nmp solution that contains acid of 2.97% weight polyamide and 0.53% weight Wholly aromatic polyamide, in addition, with embodiment 21 the same operations, form the B layer on the one side of A layer.Like this, just obtain the laminates (I) that one side has the B layer, described B layer is formed by the resin combination that Wholly aromatic polyamide constitutes shown in full aromatic polyimide and the 17% weight following formula (III) shown in the 83% weight following formula (I-a).

The average thickness of this laminates is 16 μ m.Thereby the average thickness of filming of B layer is 3 μ m.The portraitlandscape Young's modulus of laminates is respectively 12.1GPa, 13.4GPa.

Embodiment 25

(A layer (PI ^A-1))

(B layer (PI ^B-3/ PA ^B-3=91/9))

Modulation PAA solution and 4% weight コ, one ネ Star Network ス nmp solution and NMP use the nmp solution that contains acid of 3.04% weight polyamide and 0.26% weight Wholly aromatic polyamide, in addition, with embodiment 21 the same operations, form the B layer on the one side of A layer.Like this, just obtain the laminates (I) that one side has the B layer, described B layer is formed by the resin combination that Wholly aromatic polyamide constitutes shown in full aromatic polyimide and the 9% weight following formula (III) shown in the 91% weight following formula (I-a).

The average thickness of this laminates is 16 μ m.Thereby the average thickness of filming of B layer is 3 μ m.The portraitlandscape Young's modulus of laminates is respectively 13.3GPa, 13.1GPa.

Embodiment 26

(A layer (PI ^A-1))

(B layer (PI ^B-3/ PA ^B-3=96/4))

Modulation PAA solution and 4% weight コ, one ネ Star Network ス nmp solution and NMP use the nmp solution that contains acid of 2.88% weight polyamide and 0.12% weight Wholly aromatic polyamide, in addition, with embodiment 21 the same operations, form the B layer on the one side of A layer.Like this, just obtain the laminates (I) that one side has the B layer, described B layer is formed by the resin combination that Wholly aromatic polyamide constitutes shown in full aromatic polyimide and the 4% weight following formula (III) shown in the 96% weight following formula (I-a).

The average thickness of this laminates is 15 μ m.Thereby the average thickness of filming of B layer is 2 μ m.The portraitlandscape Young's modulus of laminates is respectively 12.6GPa, 13.9GPa.

Embodiment 27

(A layer (PA ^A-2))

The Wholly aromatic polyamide film アラミカ 090-RP (registration mark) that uses the manufacturing of Supreme Being people ア De バ Application スト Off イ Le system Co., Ltd. is as the A layer.Therefore, the A layer is formed by the Wholly aromatic polyamide film that only contains construction unit shown in the following formula (II).The average thickness of A layer is 9 μ m, and the Young's modulus of portraitlandscape is respectively 14.9GPa, 14.6GPa.The thermal linear expansion coefficient of アラミカ is 2ppm/ ℃, and the glass transition temperature of being calculated by Measurement of Dynamic Viscoelasticity is 355 ℃.

(B layer (PI ^B-3/ PA ^B-3=47/53))

Modulate PAA solution and 4% weight コ, one ネ Star Network ス nmp solution and NMP, obtain containing the nmp solution of acid of 1.9% weight polyamide and 1.9% weight Wholly aromatic polyamide.

(A/B)

Use the spiral spreader, with this nmp solution paste to pay be fixed in above-mentioned on the glass plate by Wholly aromatic polyamide curtain coating on the film formed A layer.Then by air drier 120 ℃ of dryings 30 minutes, then, carry out 300 ℃/30 minutes drying and heat treatment at last 280 ℃ of dryings 20 minutes, on the A layer, form the B layer thus.Thus, obtain the laminates (I) that one side has the B layer, described B layer is formed by the resin combination that Wholly aromatic polyamide constitutes shown in full aromatic polyimide and the 53% weight following formula (III) shown in the 47% weight following formula (I-a).

The average thickness of this laminates is 13 μ m.Thereby the average thickness of filming of B layer is 4 μ m.The portraitlandscape Young's modulus of laminates is respectively 9.2GPa, 9.5GPa.

Embodiment 28-42

(A/B/C)

Adopt the laminates that makes among the embodiment 21,23～27, according to combination shown in the following table 2, to fit tightly above adhesive layer (B) face of laminates and the various bonded layers (C), use the metallic plate clamping then, and add that Kevlar system plain cloth is as fender, irregular to eliminate pressure, it is arranged in the hot press.After the surface temperature of actual contact face in the hot press is adjusted to 350 ℃,, obtain laminates (II) with 2.7MPa pressurization 2 minutes.The average thickness of laminates and cohesive evaluation result are documented in the table 2.

As the bonded layer (C) shown in the following table 2,6 inches monitor boards (GKO-3516-A) that silicon wafer uses Shinetsu Handotai KK to make, with minute surface as adhesive surface.SUS304 uses the mirror board of thick 1mm.42 alloys use 42 invar of the thick 10 μ m of ニラコ manufacturing, are recited as 42 invar in the table 2.Electrolytic copper foil uses the GTS-MP of the thick 35 μ m of Furukawa サ one キ Star ト Off オイ Le Co., Ltd. manufacturing.The melanotype plate uses ASANUMA﹠amp; CO., glazing plate, standard sample, the stainless steel hard chrome 0.4mm of LTD. manufacturing.Kapton (the カプト Application) 100H that organic high molecular layer Shi Yong East レデユ Port Application Co., Ltd. makes is recited as kapton H in the table 2.

Embodiment 43

Except that moulding pressure is changed into the 0.5MPa, equally with embodiment 28 heat pressurization, obtain laminates.The average thickness of laminates and fusible evaluation result are as shown in table 2.

Embodiment 44

Except that moulding pressure is changed into the 7.0MPa, equally with embodiment 28 heat pressurization, obtain laminates.The average thickness of laminates and fusible evaluation result are as shown in table 2.

Embodiment 45

(C/B/A/B/C)

Use gained laminates among the embodiment 22, clamp this laminates with 2 silicon wafers and carry out overlappingly, make the B layer on this laminates two sides and the minute surface applying of silicon wafer, and then use the metallic plate clamping.Subsequently, add Kevlar system plain cloth as fender, the pressure when pressurizeing to eliminate is irregular, and it is arranged in the hot press.After the surface temperature of actual contact face in the hot press is adjusted to 350 ℃,, obtain laminates with 2.7MPa pressurization 2 minutes.The average thickness of laminates and fusible evaluation result are documented in the table 2.

As the C layer shown in the following table 2,6 inches monitor boards (GKO-3516-A) that silicon wafer uses Shinetsu Handotai KK to make, with minute surface as adhesive surface.

Table 2

Embodiment	Laminates (I)	Bonded layer (C layer)	Bonded layer (C layer) thickness (μ m)	Laminates (II) thickness (μ m)	Cohesive
Embodiment	Laminates (I)	Bonded layer (C layer)	Bonded layer (C layer) thickness (μ m)	Laminates (II) thickness (μ m)	Cohesive	28	Embodiment 21	Silicon wafer	625	639	○
29	Embodiment 21	SUS304	1,000	1,014	○	28	Embodiment 21	Silicon wafer	625	639	○
29	Embodiment 21	SUS304	1,000	1,014	○	30	Embodiment 21	The melanotype plate	500	515	○
31	Embodiment 21	Electrolytic copper foil	35	49	○	30	Embodiment 21	The melanotype plate	500	515	○
31	Embodiment 21	Electrolytic copper foil	35	49	○	32	Embodiment 21	42 invar	10	25	○
33	Embodiment 21	Kapton H	25	38	○	32	Embodiment 21	42 invar	10	25	○
33	Embodiment 21	Kapton H	25	38	○	34	Embodiment 23	Silicon wafer	625	641	○
35	Embodiment 24	Silicon wafer	625	641	○	34	Embodiment 23	Silicon wafer	625	641	○
35	Embodiment 24	Silicon wafer	625	641	○	36	Embodiment 25	Silicon wafer	625	640	○
37	Embodiment 26	Silicon wafer	625	638	○	36	Embodiment 25	Silicon wafer	625	640	○
37	Embodiment 26	Silicon wafer	625	638	○	38	Embodiment 27	Silicon wafer	625	636	○
39	Embodiment 27	Electrolytic copper foil	35	45	○	38	Embodiment 27	Silicon wafer	625	636	○
39	Embodiment 27	Electrolytic copper foil	35	45	○	40	Embodiment 27	The melanotype plate	500	512	○
41	Embodiment 27	42 invar	10	23	○	40	Embodiment 27	The melanotype plate	500	512	○
41	Embodiment 27	42 invar	10	23	○	42	Embodiment 27	Kapton H	25	38	○
43	Embodiment 21	Silicon wafer	625	640	○	42	Embodiment 27	Kapton H	25	38	○
43	Embodiment 21	Silicon wafer	625	640	○	44	Embodiment 21	Silicon wafer	625	638	○
45	Embodiment 22	Silicon wafer (two sides)	625	1,267	○	44	Embodiment 21	Silicon wafer	625	638	○

Embodiment 46

(A/B/A/B/A/B/A/B/A)

With gained laminates among 4 embodiment 21 make carry out on the B course closely superimposed, and then used identical A layer among closely superimposed thereon and the embodiment 21, use the metallic plate clamping afterwards, and add that Kevlar makes plain cloth as fender, irregular to eliminate pressure, it is arranged in the hot press.After the surface temperature of actual contact face in the hot press is adjusted to 350 ℃,, obtain the laminates that adhesive layer (B) alternately laminated that the substrate layer (A) that formed by 5 layers of full aromatic polyimide film and 4 layers of Wholly aromatic polyamide form forms with 2.7MPa pressurization 2 minutes.The average thickness of this laminates is 76 μ m, and cohesive is evaluated as zero.

Embodiment 47

(A/B/A/B/A/B/A/B/A)

With gained laminates among 4 embodiment 27 make carry out on the B course closely superimposed, and then the アラミカ 090RP (registration mark) of used identical base material (A layer)-Supreme Being people ア De バ Application スト Off イ Le system Co., Ltd. manufacturing among closely superimposed thereon and the embodiment 27, use the metallic plate clamping afterwards, and add that Kevlar system plain cloth is as fender, irregular to eliminate pressure, it is arranged in the hot press.After the surface temperature of actual contact face in the hot press is adjusted to 350 ℃,, obtain the laminates that forms by adhesive layer (B) alternately laminated that 5 layers of film formed substrate layer of Wholly aromatic polyamide (A) and 4 layers of Wholly aromatic polyamide form with 2.7MPa pressurization 2 minutes.The average thickness of this laminates is 59 μ m, and cohesive is evaluated as zero.

Embodiment 48

(E/D/A/B/C)

(bonded layer (C))

Prepare the silicon wafer (C) of thick 625 μ m, diameter 150mm, the supporting substrate of using as supporter.

(semiconductor substrate (D/E))

Mirrored sides at the silicon wafer (E) of thick 625 μ m, diameter 150mm, the 20% weight nmp solution of the commodity that spin coating New Japan Chem Co., Ltd makes リカコ one ト EN20 by name, to carry out drying in 120 ℃/30 minutes, 200 ℃/90 minutes, forming average thickness on wafer is the polyimide coating (D) of 20 μ m, with this wafer that has formed coating (D) as semiconductor substrate.

(adhesive sheet (A/B))

Gained laminates (A/B) is as adhesive sheet among the preparation embodiment 24.

Subsequently, bonded layer (C), adhesive sheet (A/B) and semiconductor substrate (D/E) is laminated.In addition, when laminated, B layer and C layer minute surface are joined, D layer and A layer join.Directly be arranged in the hot press with such state, with 2.7MPa, 300 ℃ the pressurization 2 minutes, obtain laminates (III).

(surface treatment step)

The E layer of the semiconductor substrate of this laminates (III) is exposed side be arranged on the grinder, by with pouncing paper, at 160gf/cm with silicon-carbide particle ²Load under, make abrasive sheet with 110rpm revolution revolution, the E layer is ground, obtain having the laminates (III ') of the E ' layer of thick 130 μ m.Grinding is with granularity #150, #800, #2, and 000 order is carried out.Do not observe peeling off of laminates during grinding.

(heat treatment step)

Gained laminates (III ') is arranged at the high-speed and high-temperature stove, and (MOTOYAMA makes, SBA-2045), under the blanket of nitrogen of flow 1.5L/min, carry out intensification during 300 ℃～450 ℃ with 10 ℃/min, carry out intensification during 450 ℃～500 ℃ with 5 ℃/min, carry out heat treatment in 1 hour at 450 ℃, put then and be chilled to room temperature.

(first strip step)

Subsequently, laminates (III ') is flooded in the water of sonic washing machine, at room temperature shine 30 minutes ultrasonic waves.At this moment, begin in 10 minutes from ultrasonic irradiation, peel off naturally at the interface of C layer minute surface and B interlayer.Like this, obtain by B layer, A layer, D layer and E ' layer of laminates (IV) that constitutes.During this, do not see especially aging etc. on the C layer that strips down, can be as required wait and utilize again after handling through washing.

(second strip step)

After wiping moisture etc., the adhesive sheet (A/B) that is present in gained laminates (IV) surface by tear-off is peeled off, and makes the interface peel of A layer and D layer.As a result, obtain by E ' layer and the laminates (V) of D layer formation through thin paperization.At this moment, the D laminar surface of laminates (V) does not almost have A component residual layer by layer, and the surface is very clean.

As from the foregoing, laminates of the present invention can be adapted in the semiconductor fabrication processes, as the adhesive sheet in the semiconductor substrate thin paper step.

Embodiment 49

(A/B/C)

(A layer (PI ^A-1))

The full aromatic polyimide film of gained is as the A layer among the preparation embodiment 1.

That is, the A layer is the full aromatic polyimide film that is only formed by construction unit shown in the following formula (I-a).

(B layer (PI ^B-3/ PA ^B-3=50/50))

Then, under blanket of nitrogen, in the reaction vessel that thermometer, agitating device and raw material dog-house are housed, add 1500g dehydration NMP, NMP is cooled to 3 ℃ in ice bath.Then, add 49.99g in advance 120 ℃ of dryings the powder of Wholly aromatic polyamide-コ one ネ Star Network ス (registration mark) of making of Supreme Being people テ Network ノプロダ Network Star Co., Ltd. of 6 hours, slowly heat up,, make the Wholly aromatic polyamide nmp solution of 3.2% weight finally 60 ℃ of dissolvings.

This Wholly aromatic polyamide nmp solution as solvent, is also dissolved fully to wherein adding 18.62g (0.1722mol) p-phenylenediamine (PPD).Afterwards, in ice bath, cool off.With the adjustment of aromatic diamine solution is 3 ℃.In these cooled two amine aqueous solutions, add 37.74g (0.1730mol) PMA acid anhydride, make its reaction 1 hour.At this moment the temperature of reaction solution is 5～20 ℃.Make this reactant liquor 60 ℃ of reactions 2 hours again, obtain containing the composition solution of thickness polyamic acid and Wholly aromatic polyamide.Said composition solution is the nmp solution that contains acid of 3.5% weight polyamide and 3.1% weight Wholly aromatic polyamide.The inherent viscosity of aromatic polyamides acid composition is 11.2dl/g.

Gained resin combination nmp solution is further diluted with NMP, formation contains the nmp solution of acid of 1.8% weight polyamide and 1.6% weight Wholly aromatic polyamide, use the spiral spreader then, pay curtain coating on the above-mentioned A layer that forms by full aromatic polyimide film that is fixed on the glass plate in subsides.Then by air drier 120 ℃ of dryings 30 minutes, then, carry out 350 ℃/30 minutes drying and heat treatment at last 280 ℃ of dryings 20 minutes, filming thus forms the B layer.Thus, obtain the adhesive sheet that one side has adhesive layer (B), described adhesive layer (B) is formed by the resin combination that Wholly aromatic polyamide constitutes shown in full aromatic polyimide and the 50% weight following formula (III) shown in the 50% weight following formula (I-a).

The average thickness of this laminates is 15 μ m.Thereby the average thickness of filming of B layer is 2 μ m.The portraitlandscape Young's modulus of laminates is respectively 13.4GPa, 11.3GPa.Thermal linear expansion coefficient is 1ppm/ ℃.

Except that using the laminates make as mentioned above, the same with embodiment 28, carry out silicon wafer bonding of thick 625 μ m.The thick 638 μ m of gained laminates (II) can not peel off with record book in accordion form is curved under the tacky state yet, and are very good, are evaluated as zero.

Embodiment 50

(E/D/A/B/C)

(bonded layer (C))

Prepare the silicon wafer (C) of thick 625 μ m, diameter 150mm, as bonded layer (C).

(semiconductor substrate (D/E))

In the mirrored sides of the silicon wafer (E) of thick 625 μ m, diameter 150mm, form polyimide film (D) by spin coating, with this wafer that has formed film (D) as semiconductor substrate.

(adhesive sheet (A/B))

Will be by PMA acid anhydride and the synthetic condensation product cyclodehydration of p-phenylenediamine (PPD), obtain thick 12.5 μ m, glass transition temperature is the aromatic polyimide film (A) that (does not all observe peeling off transition point until 500 ℃ in the mensuration) more than 500 ℃, with this as adhesive sheet.Coating is by m-phthaloyl chloride and synthetic aromatic polyamides (the Supreme Being people テ Network ノプロダ Network Star Co., Ltd. manufacturing of m-phenylene diamine (MPD) on its one side, registration mark コ one ネ Star Network ス) 15%N-N-methyl-2-2-pyrrolidone N-solution, drying forms the B layer of thick 3 μ m.

Subsequently, bonded layer (C), adhesive sheet (A/B) and semiconductor substrate (D/E) is laminated.In addition, when laminated, B layer and C layer minute surface are joined, D layer and A layer join.Directly be arranged in the hot press with such state, with 5MPa, 300 ℃ the pressurization 2 minutes, obtain laminates (III).

(surface treatment step)

The E layer of this laminates (III) is exposed side be arranged on the grinder, by with pouncing paper, at 160gf/cm with silicon-carbide particle ²Load under, make abrasive sheet with the revolution of the revolution of 110rpm, the E layer is ground, obtain having the laminates (III ') of the E ' layer of thick 130 μ m.Grinding is with granularity #150, #800, #2, and 000 order is carried out.Do not observe peeling off of laminates during grinding.

(heat treatment step)

Gained laminates (III ') is arranged at the high-speed and high-temperature stove, and (MOTOYAMA makes, SBA-2045) in, under the blanket of nitrogen of flow 1.5L/min, carry out intensification during 300 ℃～450 ℃ with 10 ℃/min, carry out intensification during 450 ℃～500 ℃ with 5 ℃/min, carry out heat treatment in 1 hour at 500 ℃, put then and be chilled to room temperature.

(first strip step)

Subsequently, laminates (III ') is flooded in the water of sonic washing machine, at room temperature shine 30 minutes ultrasonic waves.At this moment, begin in 10 minutes from ultrasonic irradiation, peel off naturally at the interface of C layer and B interlayer.Like this, obtain by B layer, A layer, D layer and E ' layer of laminates (IV) that constitutes.During this, do not see especially aging etc. on the C layer that strips down, can be as required wait and utilize again after handling through washing.

(second strip step)

After wiping moisture etc., tear-off is present in the adhesive sheet on gained laminates (IV) surface and peels off, and obtains the laminates (V) that is made of D layer and E ' layer.At this moment, the D laminar surface of laminates (V) does not almost have the residual of A layer, and the surface is very clean.

Embodiment 51

(bonded layer (C))

The silicon wafer of preparing thick 625 μ m, diameter 150mm is as bonded layer (C).

(semiconductor substrate (D/E))

(adhesive sheet (A/B))

Will be by PMA acid anhydride and the synthetic condensation product cyclodehydration of p-phenylenediamine (PPD), obtaining glass transition temperature is aromatic polyimide film (the A layer: thick 12.5 μ m) that (does not all observe peeling off transition point until 500 ℃ in the mensuration) more than 500 ℃.Coating is by m-phthaloyl chloride and synthetic aromatic polyamides (the Supreme Being people テ Network ノプロダ Network Star Co., Ltd. manufacturing of m-phenylene diamine (MPD) on its one side, registration mark コ one ネ Star Network ス) 15%N-N-methyl-2-2-pyrrolidone N-solution, drying forms the B layer of thick 3 μ m, obtains adhesive sheet (A/B).

Subsequently, bonded layer (C), adhesive sheet (A/B) and semiconductor substrate (D/E) is laminated.In addition, when laminated, B layer and C layer are joined, D layer and A layer join.Directly be arranged in the hot press with such state, with 2MPa, 300 ℃ the pressurization 2 minutes, obtain laminates (III).

(surface treatment step)

The E layer of this laminates (III) is exposed side be arranged on the grinder, by with pouncing paper, at 160gf/cm with silicon-carbide particle ²Load under, make abrasive sheet with the revolution of the revolution of 110rpm, the E layer is ground, obtain having the laminates (III ') of the E ' layer of thick 130 μ m.Grinding is carried out with the order of granularity #150, #800, #2000.Do not observe peeling off of laminates during grinding.

(heat treatment step)

Gained laminates (III ') is arranged at the high-speed and high-temperature stove, and (MOTOYAMA makes, SBA-2045) in, under the blanket of nitrogen of flow 1.5L/min, carry out intensification during 300 ℃～400 ℃ with 10 ℃/min, carry out intensification during 400 ℃～450 ℃ with 5 ℃/min, carry out heat treatment in 1 hour at 450 ℃, put then and be chilled to room temperature.

(first strip step)

Subsequently, laminates (III ') is flooded in the water of sonic washing machine, at room temperature shine 30 minutes ultrasonic waves.At this moment, begin in 10 minutes from ultrasonic irradiation, bonded layer (C) is peeled off naturally with the interface of B interlayer.Like this, obtain by B layer, A layer, D layer and E ' layer of laminates (IV) that constitutes.During this, do not see especially aging etc. on the C layer that strips down, can be as required wait and utilize again after handling through washing.

(second strip step)

Industrial applicability

Laminates of the present invention can be suitable as the cohesive sheet material in the various fields such as section's material, battery case, aerospace parts, automobile component, food of electronic material, the semiconductor device manufacturing process of mounting material etc.

The inventive method can be used for making the thin paper semiconductor device.

Claims

1. laminates (I), this laminates (I) is made of substrate layer (A) and adhesive layer (B), is formed with the B layer on the single face or the two sides of A layer, wherein

The A layer be by

(A-1) glass transition temperature is the full aromatic polyimide (PI more than 350 ℃ ^A-1) or

(A-2) glass transition temperature is the Wholly aromatic polyamide (PA more than 350 ℃ ^A-2) film that forms,

The B layer by

(B-2) glass transition temperature is more than 180 ℃ but is lower than 350 ℃ Wholly aromatic polyamide (PA ^B-2) or

(B-3) contain full aromatic polyimide (PI ^B-3) be more than 180 ℃ but be lower than 350 ℃ Wholly aromatic polyamide (PA with glass transition temperature ^B-3) resin combination (RC ^B-3) form.

2. the laminates of claim 1 exists Young's modulus to surpass the both direction of the quadrature of 3GPa in its face.

3. the laminates of claim 1, wherein the A layer is to exist Young's modulus to surpass the film of both direction of the quadrature of 10GPa in the face.

4. the laminates of claim 1, wherein the A layer is that thermal linear expansion coefficient is-film of 12ppm/ ℃～12ppm/ ℃.

5. the laminates of claim 1, wherein the average thickness of A layer is below the 50 μ m.

6. the laminates of claim 1, wherein (A-1) glass transition temperature of A layer is the full aromatic polyimide (PI more than 350 ℃ ^A-1) contain construction unit shown in the following formula (I),

In the formula, Ar ¹Non-reacted substituent 1 for containing, the 4-phenylene.

7. the laminates of claim 1, wherein (A-2) glass transition temperature of A layer is the Wholly aromatic polyamide (PA more than 350 ℃ ^A-2) contain following formula (II):

Shown in construction unit.

8. the laminates of claim 1, wherein (B-1) glass transition temperature of B layer is more than 180 ℃ but is lower than 350 ℃ full aromatic polyimide (PI ^B-1) contain construction unit shown in the following formula (IV),

In the formula, Ar ^4aAnd Ar ^4bIndependent of separately containing the aryl of non-reacted substituent carbon number 6-20, n is 1 or 2.

9. the laminates of claim 1, wherein (B-2) glass transition temperature of B layer is more than 180 ℃ but is lower than 350 ℃ Wholly aromatic polyamide (PA ^B-2) contain following formula (III):

Shown in construction unit.

10. the laminates of claim 1, wherein resin combination (RC ^B-3) for containing the full aromatic polyimide (PI of 10-99% weight ^B-3) and 1-90% weight glass transition temperature be more than 180 ℃ but be lower than 350 ℃ Wholly aromatic polyamide (PA ^B-3) resin combination.

11. the laminates of claim 10 wherein constitutes resin combination (RC ^B-3) full aromatic polyimide (PI ^B-3) contain construction unit shown in the following formula (I),

In the formula, Ar ¹Non-reacted substituent 1 for containing, the 4-phenylene.

12. the laminates of claim 10 wherein constitutes resin combination (RC ^B-3) Wholly aromatic polyamide (PA ^B-3) contain following formula (III):

Shown in construction unit.

13. the laminates of claim 1, wherein the A layer is by PI ^A-1Form, the B layer is by PI ^B-1Form.

14. the laminates of claim 1, wherein the A layer is by PI ^A-1Form, the B layer is by PA ^B-2Form.

15. the laminates of claim 1, wherein the A layer is by PI ^A-1Form, the B layer is by containing PI ^B-3And PA ^B-3Resin combination (RC ^B-3) form.

16. the laminates of claim 1, wherein the A layer is by PA ^A-2Form, the B layer is by PI ^B-1Form.

17. the laminates of claim 1, wherein the A layer is by PA ^A-2Form, the B layer is by PA ^B-2Form.

18. the laminates of claim 1, wherein the A layer is by PA ^A-2Form, the B layer is by containing PI ^B-3And PA ^B-3Resin combination (RC ^B-3) form.

19. laminates (II), this laminates are the laminates that is formed with the claim 1 of B layer on the single face of A layer, and are formed with bonded layer (C) on the B layer.

20. the laminates of claim 19, wherein the C layer is formed by inorganic material.

21. the laminates of claim 19, wherein the C layer is formed by silicon wafer or metal.

22. laminates (III); this laminates is the laminates by the claim 1 of substrate layer (A), adhesive layer (B), bonded layer (C), organic protection layer (D) and object being treated layer (E) formation; and the order according to B, C is formed with B layer and C layer on the one side of A layer, and the order by D, E on the another side of A layer is formed with D layer and E layer.

23. the laminates of claim 22, wherein the D layer is formed by polyimides.

24. the laminates of claim 22, wherein the E layer is formed by silicon wafer.

25. make the method for laminates (V) by the laminates (III) of claim 22, wherein laminates (V) is made of D layer and treated E layer (E '), this method comprises the steps:

(4) laminates (IV) is peeled off on the interface of A layer and D layer, obtained the 2nd strip step by the laminates (V) of D layer and E ' layer formation.

26. the manufacture method of claim 25 is wherein carried out peeling off of C layer by the irradiation ultrasonic wave.

27. the manufacture method of claim 25 wherein more than 30 seconds, is peeled off the C layer to the laminates that flooded water (III ') irradiation ultrasonic wave.

28. the manufacture method of claim 25 wherein is treated to the thin paper processing to E layer outer surface.

29. the manufacture method of claim 25, wherein the E layer is the semiconductor substrate that is formed with circuit block.