CN1311039C - Adhesive sheet and layered product - Google Patents

Abstract

An adhesive sheet which comprises a base (A) comprising a wholly aromatic polyimide film having a glass transition temperature of 200 DEG C or higher and a thermal-adhesion layer (C) comprising a wholly aromatic polyamide having a glass transition temperature of 200 to 500 DEG C and which has a specific peel strength or shearing peel strength; a layered product including the adhesive sheet; and a process for producing the layered product. Also provided is a method for obtaining a layered product including a desired treated layer, which comprises subjecting a layered product including the adhesive sheet to a treatment and then removing the sheet.

Description

Adhesive sheet and laminate

Technical field

The present invention relates to adhesive sheet, laminate and manufacture method thereof.

Background technology

The manufacturing process of semiconductor device such as silicon, gallium arsenide be divided into state with large-diameter semiconductor wafer carry out element formation etc. preceding step and wafer is divided into element small pieces (chip), make the back step of the finished product.

In the preceding step, make semi-conductor chip realize that method small-sized, slimming is: for example after the state with large-diameter semiconductor wafer carries out element formation etc., handle by the grinding back surface of implementing grinding semiconductor chip etc., make the attenuation of semiconductor wafer own, realize the slimming of entire chip.During above-mentioned grinding semiconductor chip, need an opposite side with the abrasive surface of semiconductor wafer be adhesively fixed on support by adhesive sheet.And, after above-mentioned slimming step, also need implement the processing in the various manufacturing processes under the state that semiconductor wafer is kept being adhesively fixed on support, handle in order to carry out these, demand has for example 400 ℃ or above stable on heating adhesive sheet.

In addition, in the step of back, at first, semiconductor wafer is divided into each chip (stripping and slicing) by cutting, next is exactly the step of chip bonding on lead frame.

During this, in addition semiconductor wafer is carried out stripping and slicing, cleaning, drying with the state that is attached in advance on the adhesive sheet, then adhesive sheet is stretched (expansion), makes chip by each step of peeling off (stripping moves) on the adhesive sheet.

For from the stripping and slicing step of semiconductor wafer to the adhesive sheet that uses rapid process is moved one's steps in stripping, require it at the enough bounding forces that keep to the drying step process by the stripping and slicing step with chip, also wish when stripping moves, to have binding agent and be unlikely to attached to the good separability of degree like that on the chip.

In order to satisfy the requirement of above-mentioned back step, people have proposed the various adhesive sheets that are used to paste semiconductor wafer.

Sealing tape was for example proposed, it comprises adhesive layer and base material, and wherein said adhesive layer is to use (with reference to the Japanese kokai publication hei 2-32181 communique) of the composition formation that contains (methyl) acrylate copolymer, Resins, epoxy, optical polymerism low molecular compound, potentiality thermal activation type epoxy curing agent and Photoepolymerizationinitiater initiater; Stripping and slicing film, this film contain polymkeric substance supports film and conductive adhesive, and wherein said polymkeric substance support film has the surface (with reference to the special fair 3-34853 communique of Japan) that does not have peel ply in fact; And being arranged at the adhesive layer that is provided for chip adhesive on the heat foamable adhesive layer of supporting on the base material, by heating, the method (with reference to Japanese kokai publication hei 3-268345 communique) that this adhesive layer and heat foamable bonding coat are peeled off.

In recent years, owing to small-sized, the slimming of electronic machine requires high-density installation, this requirement is day by day surging.Therefore, semiconductor packages is changed pin insert type in the past, and the surface installing type that is fit to high-density installation is becoming main flow.These thin semiconductor encapsulation are installed by the heating of infrared rays Reflow Soldering or vapour phase Reflow Soldering, dipping soldering etc. in order directly to carry out soldering by surface mounting on printed base plate.Have hygroscopic moisture in the encapsulation, rapid heating can cause the moisture vaporization when then installing, thereby crack problem takes place.As such way to solve the problem, it is that Young's modulus under 1.5 volume % and 250 ℃ is 10MPa or following adhesive sheet (TOHKEMY 2002-256237 communique) that the someone has proposed rate of moisture absorption.

But adhesive sheet in the past has following problem.

With thin films of semiconductor wafers the time, the undercapacity of adhesive sheet in the past is with as support, in manufacturing process's processes such as the grinding of the semiconductor wafer that carries out in order to realize filming or carrying, semiconductor wafer breaks sometimes, and the yield rate of product has problem.

Therefore consider the laminated substrate material that contains inorganics on adhesive sheet, make adhesive sheet and semiconductor wafer after laminated bonding, be used for compensation intensity.At this moment, when keeping in the grinding steps that adhesive sheet need be implemented in the semiconductor wafer manufacturing, or show enough binding propertys in the carrying step, and requiring again before the stripping and slicing step of semiconductor wafer, adhesive sheet can not remain in semiconductor wafer one side and just can peel off.And consider from the angle that support utilizes again, wish finally easily to peel off from support.

Therefore to be exposed to 400 ℃ or above temperature in the manufacturing process, must satisfy and have 400 ℃ or above thermotolerance, withstand soldering, and can not discharge moisture in the high temperature, or can not decompose various requirement such as release lower-molecular substance.

Summary of the invention

The object of the present invention is to provide adhesive sheet and laminate, its have be suitable for the thermotolerance in semiconductor device manufacturing process, used and with the binding property of the appropriateness of bonded body, and realize separability after the purpose.Other purpose of the present invention is to provide the laminate that contains this adhesive sheet is implemented to peel off after the processing, and acquisition contains the method for the laminate of the processed layer of target thus.

Promptly, the present invention relates to adhesive sheet, it is characterized in that: this adhesive sheet contains base material (A) and thermal adhesive layer (C), wherein said base material (A) contains full aromatic polyimide film, and described thermal adhesive layer (C) contains and has the Wholly aromatic polyamide that second-order transition temperature is 200 ℃ of-500 ℃ of characteristics; During according to the sequential laminating of the bonded body that comprises silicon wafer, thermal adhesive layer (C) and base material (A), satisfy at least following condition (a) or (b) one of them:

(a) hot pressing is after 15 minutes under 300 ℃ and 5.0-6.0MPa, and thermal adhesive layer (C) is 0.1N/m-300N/m with the stripping strength at the interface of silicon wafer;

(b) hot pressing is after 2 minutes under 300 ℃ and 5.0-6.0MPa, and thermal adhesive layer (C) is 1N/cm with the shearing peel adhesion strength at the interface of silicon wafer ²-1000N/cm ²

The present invention relates to this adhesive sheet and inorganic materials adherent laminate (I).The invention still further relates to the laminate (II) of going up laminated organism protective layer (E) and object being treated layer (D) at laminate (I), and their manufacture method.

The invention still further relates to laminate (I '), it is characterized in that: this laminate (I ') contain base material (A) and inorganic materials (B), it is 200 ℃ or above full aromatic polyimide film that wherein said base material (A) contains second-order transition temperature; Base material (A) with comprise the bonded body of silicon wafer when laminated, base material (A)

(a ') hot pressing is after 15 minutes under 370 ℃ and 5.0-6.0MPa, and base material (A) is 0.1N/m-100N/m with the stripping strength at the interface of silicon wafer.

The present invention relates to laminate (I ') and go up laminated laminate that organism protective layer (E) and object being treated layer (D) arranged (II ') and manufacture method thereof.

The present invention relates to the manufacture method of laminate, it is characterized in that: after obtaining above-mentioned laminate, the face that exposes at the D layer carries out reduction processing, with this as D ' layer, after obtaining containing the laminate (III) of D ' layer, E layer, A layer, C layer and B layer, make the interface peel of E layer and A layer, obtain containing the laminate (IV) of D ' layer and E layer.

The best mode that carries out an invention

(adhesive sheet)

Adhesive sheet of the present invention can be enumerated following two kinds: a situation by the base material that contains full aromatic polyimide film (A) formation, and the situation that contains base material (A) and thermal adhesive layer (C), wherein said base material (A) contains full aromatic polyimide film, and described thermal adhesive layer (C) contains and has the Wholly aromatic polyamide that second-order transition temperature is 200 ℃ of-500 ℃ of characteristics.

The preferred Young's modulus of adhesive sheet of the present invention is in the scope of 1.0GPa-30GPa.Young's modulus is less than 1.0GPa, and then operability is poor; When higher than 30GPa, because thermal expansion difference, the residual stress that produces when being difficult to relax the hot pressing postcooling by adhesive sheet itself may make bounding force significantly reduce.The scope of preferred 2.0GPa-25GPa.Further preferred 3.0GPa-20GPa, the further scope of preferred 10.0GPa-20GPa.The following calculating of Young's modulus described here: the sample that uses 50mm * 10mm, draw speed with 5mm/ minute is measured, according to the initial gradient of the elongation-intensity curve of gained data, the intensity when being scaled elongation 100% is Young's modulus with this value.

The preferred thermal linear expansion coefficient of adhesive sheet is-10ppm/ ℃-+scope of 45ppm/ ℃.In the preferred version of the present invention, the thermal linear expansion coefficient of the inorganic materials of using as bonded body is-5ppm/ ℃-+scope of 35ppm/ ℃.Find out thus: the thermal linear expansion coefficient of adhesive sheet is preferably the approaching value of thermal linear expansion coefficient appropriateness with the bonded body that is made of inorganic materials.The thermal linear expansion coefficient of adhesive sheet is during than the value of-10ppm/ ℃ little value or ratio+35ppm/ ℃ high, and the bounding force of hot pressing postcooling to for example room temperature etc. may be not enough.Be preferably-5ppm/ ℃-+scope of 35ppm/ ℃.Therefore, the absolute value of preferred adhesive sheet and the thermal linear expansion coefficient difference of the bonded body that is made of inorganic materials is in the scope of 0.01ppm/ ℃-30ppm/ ℃.When the value of absolute value than 30ppm/ ℃ of described adhesive sheet and the thermal linear expansion coefficient difference of bonded body was big, because of temperature head produces residual stress, bond strength descended.During for the value than 0.01ppm/ ℃ little, the separability after bonding reduces, and is difficult to peel off the finished product semiconductor device from support under a lot of situations after by semiconductor device manufacturing process.This phenomenon is particularly particularly remarkable when making thin semiconductor device.Because semiconductor film, the intensity of semi-conductor chip self reduces, and semi-conductor chip takes place damaged mostly easily when peeling off.The absolute value of further preferred adhesive sheet and the thermal linear expansion coefficient difference of the bonded body that is made of inorganic materials is in the scope of 1ppm/ ℃-20ppm/ ℃.The following calculating of thermal linear expansion coefficient described here: be warming up to 50 ℃-250 ℃ scope with 10 ℃/minute heat-up rates, cooling is by 100 ℃ to 200 ℃ sample length variable quantity calculating down.

The shape of adhesive sheet can adopt all shapes such as band shape, label-like.The scope of the preferred 1 μ m-2000 μ m of the thickness of this adhesive sheet.During less than 1 μ m, can't obtain the bonding precision with the bonded body that constitutes by inorganic materials, require to touch planarity, the smoothness precision height of sticking device contact surface,, produce bonding irregular mostly if planarity, smoothness precision are not enough.When being 2000 μ m or when above, be difficult to heat conduction with the bonded body that constitutes by inorganic materials when bonding, need spended time to transmit temperature, productivity may reduce.

(adhesive sheet that contains base material (A) and thermal adhesive layer (C))

The adhesive sheet that contains base material (A) and thermal adhesive layer (C) is described.

The present invention relates to adhesive sheet, it is characterized in that: this adhesive sheet contains base material (A) and thermal adhesive layer (C), wherein said base material (A) contains full aromatic polyimide film, and described thermal adhesive layer (C) contains and has the Wholly aromatic polyamide that second-order transition temperature is 200 ℃ of-500 ℃ of characteristics; During according to the sequential laminating of the bonded body that comprises silicon wafer, thermal adhesive layer (C) and base material (A), satisfy at least following condition (a) or (b) one of them:

(a) hot pressing is after 15 minutes under 300 ℃ and 5.0-6.0MPa, and thermal adhesive layer (C) is 0.1N/m-300N/m with the stripping strength at the interface of silicon wafer;

(b) hot pressing is after 2 minutes under 300 ℃ and 5.0-6.0MPa, and thermal adhesive layer (C) is 1N/cm with the shearing peel adhesion strength at the interface of silicon wafer ²-1000N/cm ²

Stripping strength can not obtain required enough bounding forces by semiconductor device manufacturing process during less than 0.1N/m, the situation that semi-conductor chip comes off from substrate might take place midway in operation.

But, consider according to stripping strength, with the binding property of bonded body be the value bigger than 300N/m, then adhesive sheet is difficult to peel off during the recycling silicon wafer, thereby not preferred.See that by above the stripping strength of preferred adhesive sheet of the present invention is 0.1N/m or above and for 300N/m or following; 5N/m or above and be 200N/m or following more preferably.

The following calculating of stripping strength described here: 25 ℃, be determined under 300 ℃ and the 5.0-6.0MPa the wide sheet adherend of 1cm of pressing with the bonded body heat that comprises silicon wafer 15 minutes with about 300mm/ minute draw speed, in the strip length scope of the length of 100mm at least outside removing initial 25mm, obtain average peeling force (N) by power-anchor clamps miles of relative movement curve, calculate the value (N/m) under every m width.As long as this moment, the silicon wafer surface roughness had the surface smoothing of the silicon wafer that uses in the common semi-conductor manufacturing.For example according to the practical measurement of laser microscope, the surfaceness of silicon wafer (Rt) is about 0.02 μ m.

Shear peel adhesion strength less than 1N/cm ²The time, can not obtain required enough bounding forces by semiconductor device manufacturing process, in operation the situation that semi-conductor chip comes off from substrate might take place midway.

But, consider according to shearing stripping strength, with the binding property of bonded body be than 1000N/cm ²Big value, then adhesive sheet is difficult to peel off during the recycling silicon wafer, thereby not preferred.See that by above the shearing stripping strength of preferred adhesive sheet of the present invention is 1N/cm ²Or it is above and be 1000N/cm ²Or below; 5N/cm more preferably ²Or it is above and be 500N/cm ²Or below.

The following calculating of shearing peel adhesion strength described here: be coated with binding agent on the face in exposing of laminate, stainless steel plate with two 25mm * 60mm * 1mm is bonding by sandwich, use method then based on JIS K6851, under the draw speed condition of 25 ℃, 10mm/ minute, stretch, obtain the maximum value (N) of peel stress, calculate every cm ²Under shearing peel adhesion strength (N/cm ²), wherein laminate is by pressing the sheet adherend of the 25mm * 25mm that obtained in 2 minutes to constitute with the bonded body heat that is made of silicon wafer under 300 ℃ and 5.0-6.0MPa.

The thermal adhesive layer (C) that contains Wholly aromatic polyamide by setting, the bonded body (B) that can make the base material (A) that contains full aromatic polyimide film and constitute by inorganic materials bonding firmly, in addition, for base material, can be the various formations of only using thermal adhesive layer etc., the bounding force of each interlayer is changed at single face.

By making the adhesive sheet that the thermal adhesive layer (C) that contains Wholly aromatic polyamide is set, make each layer hot pressing and when obtaining laminate, even the processing of short period of time also can obtain enough bounding forces, therefore hot pressed pressure hold time can be made as 0.1 second-1 hour short like this time.In addition,, therefore compare as the situation of adhesive sheet, can reduce hot pressed temperature condition with the base material (A) that only will contain full aromatic polyimide film even also can obtain enough bounding forces at 180-500 ℃.

In addition,, need not to implement the over-drastic hot-pressing processing, therefore obtain laminate, when after implementing various processing, peeling off required part, have and promptly carry out lift-off processing, the advantage of boosting productivity by hot pressing by thermal adhesive layer (C) is set.

(base material)

Constitute the film that base material of the present invention (A) contains full aromatic polyimide.

Full aromatic polyimide used in the present invention is the macromolecular compound that contains aromatic acid's composition and aromatic diamine composition.

Aromatic acid's composition for example has: pyromellitic acid, 1,2,3, the 4-benzene tertacarbonic acid, 2,3,5,6-pyridine tetracarboxylic acid, 2,3,4,5-thiophene tetracarboxylic acid, 2,2 ', 3,3 '-benzophenone tetracarboxylic acid, 2,3 ', 3,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 3,3 ', 4,4 '-p-terphenyl tetracarboxylic acid, 2,2 ', 3,3 '-p-terphenyl tetracarboxylic acid, 2,3,3 ', 4 '-p-terphenyl tetracarboxylic 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 tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 1,2,6, the luxuriant and rich with fragrance tetracarboxylic acid of 7-, 1,2,7, the luxuriant and rich with fragrance tetracarboxylic acid of 8-, 1,2,9, the luxuriant and rich with fragrance tetracarboxylic acid of 10-, 3,4,9, the 10-perylene tetracarboxylic acid, 2,6-dichloronaphtalene-1,4,5, the 8-tetracarboxylic acid, 2,7-dichloronaphtalene-1,4,5, the 8-tetracarboxylic acid, 2,3,6,7-Tetrachloronaphthalene-1,4,5, the 8-tetracarboxylic acid, 1,4,5,8-Tetrachloronaphthalene-2,3,6, the 7-tetracarboxylic 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, two (2, the 3-dicarboxyl phenyl) ethane of 1-, 1,1-two (3,4-dicarboxyl phenyl) ethane, 2, two (2, the 3-dicarboxyl phenyl) propane of 2-, 2, two (3, the 4-dicarboxyl phenyl) propane of 2-, 2,6-two (3, the 4-di carboxyl phenyloxy) pyridine, 1,1,1,3,3,3-hexafluoro-2, two (3, the 4-dicarboxyl phenyl) propane of 2-, two (3,4-dicarboxyl phenyl) dimethylsilane etc.2 kinds or above above-mentioned aromatic acid's composition can be used in combination simultaneously.

Wherein, preferred aromatic acid's composition for example has: only constitute by pyromellitic acid or contain pyromellitic acid with above-mentioned different aromatic acid's combination.More particularly, pyromellitic acid dianhydride is 50-100 mole % in preferred total tetracarboxylic acid composition.Details when pyromellitic acid dianhydride is 50 moles of % or when above, can improve the acylimino concentration in the full aromatic polyimide as described later, can make binding property good.Preferred pyromellitic acid dianhydride is 70-100 mole %, and more preferably 90-100 mole % especially preferably uses pyromellitic acid dianhydride separately.

The aromatic diamine composition for example has: Ursol D; mphenylenediamine; 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-diamino m-xylene; 2, the 5-diamino-pyridine; 2; the 6-diamino-pyridine; 3; the 5-diamino-pyridine; 2,4 di amino toluene p-diaminodiphenyl; 3,3 '-benzidine; 3; 3 '-dichlorobenzidine; 3; 3 '-tolidine; 3,3 '-dimethoxy benzidine; 2,2 '-diaminobenzophenone; 4; 4 '-diaminobenzophenone; 3; 3 '-diaminodiphenyl oxide; 4,4 '-diaminodiphenyl oxide; 3,4 '-diaminodiphenyl oxide; 3; 3 '-diaminodiphenylmethane; 4; 4 '-diaminodiphenylmethane; 4,4 '-diaminodiphenylmethane; 3,4 '-diaminodiphenylsulfone(DDS); 4; 4 '-diaminodiphenylsulfone(DDS); 3; 3 '-diamino diphenyl sulfide; 3,4 '-diamino diphenyl sulfide; 4,4 '-diamino diphenyl sulfide; 4; 4 '-diamino-diphenyl thioether; 4; 4 '-diamino-3,3 ', 5; 5 '-tetramethyl-phenyl ether; 4; 4 '-diamino-3,3 ', 5; 5 '-tetraethyl-phenyl ether; 4; 4 '-diamino-3,3 ', 5; 5 '-tetramethyl-ditane; 1; two (3-amino-benzene oxygen) benzene of 3-; 1, two (4-amino-benzene oxygen) benzene of 3-; 1, two (3-amino-benzene oxygen) benzene of 4-; 1; two (4-amino-benzene oxygen) benzene of 4-; 2; two (3-amino-benzene oxygen) pyridines of 6-; 1, two (the 3-aminophenyl alkylsulfonyl) benzene of 4-; 1, two (the 4-aminophenyl alkylsulfonyl) benzene of 4-; 1; two (3-aminophenyl-thioether) benzene of 4-; 1; two (4-aminophenyl-thioether) benzene of 4-; 4,4 '-two (3-amino-benzene oxygen) sulfobenzide; 4,4 '-two (4-amino-benzene oxygen) sulfobenzide; two (4-aminophenyl) phosphine oxides of two (4-the aminophenyl)-N-phenyl amine of two (4-the aminophenyl)-N-methylamine of two (4-aminophenyl) amine; 1; two (3-aminophenyl) ethane of 1-; 1; two (4-aminophenyl) ethane of 1-; 2, two (3-aminophenyl) propane of 2-; 2, two (4-aminophenyl) propane of 2-; 2; two (the 4-amino-3 of 2-; 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; two [4-(4-amino-benzene oxygen) phenyl] ethane of 1-; 1; two [3-methyl-4-(4-amino-benzene oxygen) phenyl] ethane of 1-; 1, two [3-chloro-4-(4-amino-benzene oxygen) phenyl] ethane of 1-; 1,1-two [3; 5-dimethyl-4-(4-amino-benzene oxygen) phenyl] ethane; 2; two [4-(4-amino-benzene oxygen) phenyl] propane of 2-; 2, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane of 2-; 2, two [3-chloro-4-(4-amino-benzene oxygen) phenyl] propane of 2-; 2; 2-two [3; 5-dimethyl-4-(4-amino-benzene oxygen) phenyl] propane; 2, two [4-(4-amino-benzene oxygen) phenyl] butane of 2-; 2, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] butane of 2-; 2; 2-two [3; 5-dimethyl-4-(4-amino-benzene oxygen) phenyl] butane; 2, two [3,5-two bromo-4-(4-amino-benzene oxygen) phenyl] butane of 2-; 1; 1; 1,3,3; 3-hexafluoro-2; two (4-aminophenyl) propane of 2-; 1,1,1; 3; 3,3-hexafluoro-2, the virtue nuclear substituent that two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane of 2-etc. and their halogen atom or alkyl replace.2 kinds or above above-mentioned aromatic diamine composition can be used in combination simultaneously.Preferred aromatic diamine composition for example has: Ursol D, mphenylenediamine, 3,4 '-diaminodiphenyl oxide and 1, two (3-amino-benzene oxygen) benzene, 4 of 3-, 4 '-diaminodiphenyl oxide.Ursol D is 30-100 mole % in preferred whole two amine components of further preferred aromatic diamine composition.As described later, Ursol D be 40 moles of % or more than, then can improve the acylimino concentration in the full aromatic polyimide, can obtain the good adhesive sheet of binding property.In this case, other aromatic diamine composition beyond the Ursol D is preferred 3,4 '-diaminodiphenyl oxide and 4,4 '-diaminodiphenyl oxide, 1, two (3-amino-benzene oxygen) benzene of 3-.Wherein preferred especially 3,4 '-diaminodiphenyl oxide.

The complete preferred acylimino concentration of aromatic polyimide is 5.0 equivalents/kg-6.9 equivalent/kg.Acylimino concentration is the value of calculating by following formula (4).

Acylimino concentration (equivalent/kg)=the unitary molecular weight of the every formation of 2 * 1000/[] (4)

This acylimino concentration is during less than 5.0 equivalents/kg, and the concentration of the polar group in the full aromatic polyimide reduces, and therefore the bounding force with bonded body weakens, thereby not preferred.On chemical structure, the upper limit essence of acylimino concentration is about 6.9 equivalents/kg.Further preferred 5.5 equivalents/kg-6.9 equivalent/kg.

Therefore, the preferred full aromatic polyimide of essence can exemplify to contain and constitute unitary full aromatic polyimide shown in the following formula (1):

Ar ¹Non-reacted substituent 1 for containing, the 4-phenylene;

Perhaps contain to constitute shown in the 30-70 mole % following formula (1) and constitute the full aromatic polyimide of unitary copolymerization shown in unit and the 70-30 mole % following formula (2):

Ar ^2aAnd Ar ^2bIndependent separately, be 6 or above for containing non-reacted substituent carbonatoms to 20 or following aromatic group.

Only use the base material (A) that contains full aromatic polyimide film during, especially preferably enumerate the full aromatic polyimide of latter's copolymerization as adhesive sheet.

Ar in the following formula (1) ¹Non-reacted substituent 1 for containing, the 4-phenylene.Non-reacted substituting group described here for example has: alkyl such as methyl, ethyl, propyl group, cyclohexyl, aromatic groups such as phenyl, naphthyl; Halogen radicals such as chloro, fluorine-based, bromo; Alkoxyl groups such as methoxyl group, oxyethyl group, phenoxy group; Nitro etc.So 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-phenylbenzene-1,4-phenylene, 2,5-dinitrobenzene-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-trimethylammonium-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.Ar in the following formula (2) ^2aAnd Ar ^2bIndependent separately, be 6 or above 20 or following aromatic group for containing non-reacted substituent carbonatoms.Non-reacted substituting group described here can exemplify with following formula (1) in Ar ¹The illustrated identical group of non-reacted substituting group.So Ar ^2aAnd Ar ^2bCan be respectively: 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-phenylbenzene-1, the 4-phenylene, 2,5-dinitrobenzene-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-trimethylammonium-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-phenylbenzene-1, the 3-phenylene, 2,5-dinitrobenzene-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-trimethylammonium-1, the 3-phenylene, 1, the 6-biphenylene, 2,6-naphthyl etc.Wherein preferred example has 1,4-phenylene, 1,3-phenylene.

The second-order transition temperature of full aromatic polyimide of the present invention be 200 ℃ or more than.Second-order transition temperature is during less than 200 ℃, even the thermotolerance in the preferred version semiconductor device manufacturing process is also not enough, thereby not preferred.The upper limit is not particularly limited, even is included in 500 ℃ or the above polyimide of also not observing second-order transition temperature.The following calculating of second-order transition temperature: the dynamic energy storage elastic modulus E that obtains by mensuration ', dynamic loss elasticity modulus E " calculate dynamic loss tangent tan δ, calculate by this value.

In addition, the manufacture method of this full aromatic polyimide film is not particularly limited, can uses known in the past any manufacture method.For example the raw material of aromatic acid's composition can be aromatic tetracarboxylic acid dianhydride or aromatic acid's composition part or all be two carboxylic acid halides dicarboxylic acid alkyl derivatives.Preferred use aromatic tetracarboxylic acid dianhydride.The raw material of aromatic diamine composition can also be amido acid formation property derivative of aromatic diamine except that aromatic diamine.For example part or all of the amino of aromatic diamine composition can be by trialkylsilklization, also can be by the such fatty acid acyl amination of acetate.The preferred aromatic diamine of essence wherein.

The example of the manufacture method of full aromatic polyimide film has: for example N-N-methyl-2-2-pyrrolidone N-or N,N-DIMETHYLACETAMIDE, in the organic polar solvent of methylimidazole alkane ketone, for example under the temperature about-30 ℃ to 120 ℃, these raw materials are being carried out polyreaction, obtain as the polyamic acid of precursor or the organic polar solvent solution of polyamic acid derivative, with this solution casting in support etc., then for example dry about 80-400 ℃, further implement the thermal treatment of 250-600 ℃ of top temperature, carry out imidization reaction, obtain full aromatic polyimide film, perhaps use for example dicyclohexylcarbodiimide, or the combination of the aliphatic anhydride of diacetyl oxide etc. and organic nitrogen compound as pyridine, carry out the chemical dehydration cyclization, obtain the swell gel film, the fixed length drying is implemented in this gel film back that stretches arbitrarily, thermal treatment obtains by (the TOHKEMY 2002-179810 communiques) such as methods of full aromatic polyimide film.The method that particularly will be stretched by the gel film that chemical dehydration reaction obtains and make can be controlled thermal expansivity arbitrarily by its stretching condition, we can say in such use it is particularly preferred manufacture method.

(thermal adhesive layer that contains Wholly aromatic polyamide)

The Wholly aromatic polyamide that uses in the thermal adhesive layer of the present invention (C) contains the formation unit shown in the following formula (3):

Ar ^3aAnd Ar ^3bIndependent separately, be the aromatic group that can to have non-reacted substituent carbonatoms be 6-20;

Preferably contain the Ar that comprises in the following formula (3) ^3aThe aromatic dicarboxylic acid composition and comprise Ar in the following formula (3) ^3bThe Wholly aromatic polyamide of aromatic diamine composition.Ar in the following formula (3) ^3aAnd Ar ^3bIndependent separately, be the aromatic group that can to have non-reacted substituent carbonatoms be 6-20.Ar in the following formula (3) in addition ^3aAnd Ar ^3bThe non-reacted substituting group that can contain for example has alkyl such as methyl, ethyl, propyl group, cyclohexyl, aromatic groups such as phenyl, naphthyl; Halogen radicals such as chloro, fluorine-based, bromo; Nitro; Methoxyl group; Oxyethyl group; Phenoxy group etc.

Ar ^3aAs the aromatic dicarboxylic acid composition; for example have: terephthalic acid; 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 m-xylene; 3; 3 '-dicarboxylate biphenyl; 2; 2 '-benzophenonedicarboxylic acid; 4; 4 '-benzophenonedicarboxylic acid; 3; 3 '-dicarboxyl phenyl ether; 4,4 '-dicarboxyl phenyl ether; 3,4 '-dicarboxyl phenyl ether; 3; 3 '-dicarboxyl ditane; 4; 4 '-dicarboxyl ditane; 4,4 '-dicarboxyl ditane; 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-phenyl ether; 4; 4 '-dicarboxyl-3,3 ', 5; 5 '-tetraethyl-phenyl ether; 4; 4 '-dicarboxyl-3,3 ', 5; 5 '-tetramethyl-ditane; 1; two (the 3-carboxyl phenoxy group) benzene of 3-; 1, two (the 4-carboxyl phenoxy group) benzene of 3-; 1, two (the 3-carboxyl phenoxy group) benzene of 4-; 1; two (the 4-carboxyl phenoxy group) benzene of 4-; 2; two (the 3-carboxyl phenoxy group) pyridines of 6-; 1, two (the 3-carboxyl phenyl alkylsulfonyl) benzene of 4-; 1, two (the 4-carboxyl phenyl alkylsulfonyl) benzene of 4-; 1; two (the 3-carboxyl phenyl thioether) benzene of 4-; 1; two (the 4-carboxyl phenyl thioether) benzene of 4-; 4,4 '-two (3-carboxyl phenoxy group) sulfobenzide; 4,4 '-two (4-carboxyl phenoxy group) sulfobenzide; two (4-carboxyl phenyl) phosphine oxides of two (4-the carboxyl phenyl)-N-phenyl amine of two (4-the carboxyl phenyl)-N-methylamine of two (4-carboxyl phenyl) amine; 1; two (3-carboxyl phenyl) ethane of 1-; 1; two (4-carboxyl phenyl) ethane of 1-; 2, two (3-carboxyl phenyl) propane of 2-; 2, two (4-carboxyl phenyl) propane of 2-; 2; two (the 4-carboxyls-3 of 2-; the 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; two [4-(the 4-carboxyl phenoxy group) phenyl] ethane of 1-; 1; two [3-methyl-4-(the 4-carboxyl phenoxy group) phenyl] ethane of 1-; 1, two [3-chloro-4-(the 4-carboxyl phenoxy group) phenyl] ethane of 1-; 1,1-two [3; 5-dimethyl-4-(4-carboxyl phenoxy group) phenyl] ethane; 2; two [4-(the 4-carboxyl phenoxy group) phenyl] propane of 2-; 2, two [3-methyl-4-(the 4-carboxyl phenoxy group) phenyl] propane of 2-; 2, two [3-chloro-4-(the 4-carboxyl phenoxy group) phenyl] propane of 2-; 2; 2-two [3; 5-dimethyl-4-(4-carboxyl phenoxy group) phenyl] propane; 2, two [4-(the 4-carboxyl phenoxy group) phenyl] butane of 2-; 2, two [3-methyl-4-(the 4-carboxyl phenoxy group) phenyl] butane of 2-; 2; 2-two [3; 5-dimethyl-4-(4-carboxyl phenoxy group) phenyl] butane; 2, two [3,5-two bromo-4-(the 4-carboxyl phenoxy group) phenyl] butane of 2-; 1; 1; 1,3,3; 3-hexafluoro-2; two (4-carboxyl phenyl) propane of 2-; 1,1,1; 3; 3,3-hexafluoro-2, the virtue nuclear substituent that two [3-methyl-4-(4-carboxyl phenoxy group) phenyl] propane of 2-etc. and their halogen atom or alkyl replace.

2 kinds or above above-mentioned aromatic dicarboxylic acid composition can be used in combination simultaneously.The preferred aromatic dicarboxylic acids composition has terephthalic acid, m-phthalic acid.

Ar ^3bAs the aromatic diamine composition; its example has: Ursol D; mphenylenediamine; 1; the 4-diaminonaphthalene; 1; the 5-diaminonaphthalene; 1; the 8-diaminonaphthalene; 2; the 6-diaminonaphthalene; 2; the 7-amino naphthalenes; 2; the 6-diaminoanthraquinone-; 2; the 7-diaminoanthraquinone-; 1; the 8-diaminoanthraquinone-; 2; the 4-diaminotoluene; 2; 5-diamino m-xylene; 2, the 5-diamino-pyridine; 2, the 6-diamino-pyridine; 3; the 5-diamino-pyridine; 2; 4-diaminotoluene p-diaminodiphenyl; 3,3 '-benzidine; 2,2 '-diaminobenzophenone; 4; 4 '-diaminobenzophenone; 3; 3 '-diaminodiphenyl oxide; 4,4 '-diaminodiphenyl oxide; 3,4 '-diaminodiphenyl oxide; 3; 3 '-diaminodiphenylmethane; 4; 4 '-diaminodiphenylmethane; 4,4 '-diaminodiphenylmethane; 3,4 '-diaminodiphenylsulfone(DDS); 4; 4 '-diaminodiphenylsulfone(DDS); 3; 3 '-diamino diphenyl sulfide; 3,4 '-diamino diphenyl sulfide; 4,4 '-diamino diphenyl sulfide; 4; 4 '-diamino-diphenyl thioether; 4; 4 '-diamino-3,3 ', 5; 5 '-tetramethyl-phenyl ether; 4; 4 '-diamino-3,3 ', 5; 5 '-tetraethyl-phenyl ether; 4; 4 '-diamino-3,3 ', 5; 5 '-tetramethyl-ditane; 1; two (3-amino-benzene oxygen) benzene of 3-; 1, two (4-amino-benzene oxygen) benzene of 3-; 1, two (3-amino-benzene oxygen) benzene of 4-; 1; two (4-amino-benzene oxygen) benzene of 4-; 2; two (3-amino-benzene oxygen) pyridines of 6-; 1, two (the 3-aminophenyl alkylsulfonyl) benzene of 4-; 1, two (the 4-aminophenyl alkylsulfonyl) benzene of 4-; 1; two (3-aminophenyl-thioether) benzene of 4-; 1; two (4-aminophenyl-thioether) benzene of 4-; 4,4 '-two (3-amino-benzene oxygen) sulfobenzide; 4,4 '-two (4-amino-benzene oxygen) sulfobenzide; two (4-aminophenyl) phosphine oxides of two (4-the aminophenyl)-N-phenyl amine of two (4-the aminophenyl)-N-methylamine of two (4-aminophenyl) amine; 1; two (3-aminophenyl) ethane of 1-; 1; two (4-aminophenyl) ethane of 1-; 2, two (3-aminophenyl) propane of 2-; 2, two (4-aminophenyl) propane of 2-; 2; two (the 4-amino-3 of 2-; 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; two [4-(4-amino-benzene oxygen) phenyl] ethane of 1-; 1; two [3-methyl-4-(4-amino-benzene oxygen) phenyl] ethane of 1-; 1, two [3-chloro-4-(4-amino-benzene oxygen) phenyl] ethane of 1-; 1,1-two [3; 5-dimethyl-4-(4-amino-benzene oxygen) phenyl] ethane; 2; two [4-(4-amino-benzene oxygen) phenyl] propane of 2-; 2, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane of 2-; 2, two [3-chloro-4-(4-amino-benzene oxygen) phenyl] propane of 2-; 2; 2-two [3; 5-dimethyl-4-(4-amino-benzene oxygen) phenyl] propane; 2, two [4-(4-amino-benzene oxygen) phenyl] butane of 2-; 2, two [3-methyl-4-(4-amino-benzene oxygen) phenyl] butane of 2-; 2; 2-two [3; 5-dimethyl-4-(4-amino-benzene oxygen) phenyl] butane; 2, two [3,5-two bromo-4-(4-amino-benzene oxygen) phenyl] butane of 2-; 1; 1; 1,3,3; 3-hexafluoro-2; two (4-aminophenyl) propane of 2-; 1,1,1; 3; 3,3-hexafluoro-2, the virtue nuclear substituent that two [3-methyl-4-(4-amino-benzene oxygen) phenyl] propane of 2-etc. and their halogen atom or alkyl replace.2 kinds or above above-mentioned aromatic diamine composition can be used in combination simultaneously.

Preferred aromatic diamine composition has: Ursol D, mphenylenediamine, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide and 1, two (3-amino-benzene oxygen) benzene of 3-.The further preferred preferred mphenylenediamine of aromatic diamine composition.Be that preferred Wholly aromatic polyamide is that following formula (3) only is made of the formation unit shown in the following formula (3-1).

In addition, the manufacture method that the present invention is contained the thermal adhesive layer (C) of Wholly aromatic polyamide is not particularly limited, and can adopt known in the past manufacture method arbitrarily.For example make when containing the thermal adhesive layer (C) of Wholly aromatic polyamide, can directly use the polymers soln after the polymerization, also can earlier polymkeric substance be separated, and then be dissolved in solvent and use.The preferred N-N-methyl-2-2-pyrrolidone N-of solvent, N,N-dimethylacetamide, N, organic polar solvents such as dinethylformamide also can use strongly-acid solvents such as the vitriol oil, concentrated nitric acid, Tripyrophosphoric acid.Can add inorganic salt in the above-mentioned aromatic poly solution as required, for example calcium chloride, magnesium chloride, lithium chloride, lithium nitrate etc. as dissolution aids.About the preferred 1-60 weight of the polymer concentration in solution %, further preferred 3-40 weight %.

In the base material that contains full aromatic polyimide film (A) or comprise on the bonded body (B) of inorganic materials, solvent is flung to the polymers soln curtain coating of as above preparation by drying.

The method of curtain coating has: the method for the method that the through port mould is extruded, the method for using coater, use coating machine etc.The temperature of polymers soln is not particularly limited during for curtain coating, preferably selects temperature, and the viscosity that makes polymers soln is 30-20, between 000 pool.Preferred example has 50-2,000 pool.

The drying means that solvent is flung to has: the drying of being undertaken by hot blast heating, heating under vacuum, infrared heating, microwave heating, the preferably heat drying that is undertaken by hot blast.The drying temperature of this moment is 30 ℃-400 ℃, more preferably 40 ℃-350 ℃, and further preferred 70 ℃-300 ℃.

The present invention contains the scope of the preferred 0.1 μ m-1000 μ m of thickness of the thermal adhesive layer (C) of Wholly aromatic polyamide.During less than 0.1 μ m, can't obtain the bonding precision with the bonded body (B) that constitutes by inorganic materials, require to touch sticking high planarity, the smoothness precision of device contact surface,, produce bonding irregular mostly if planarity, smoothness control are not enough.When bigger than 2000 μ m, be difficult to heat conduction when bonding with the bonded body (B) that constitutes by inorganic materials, need spended time to transmit temperature, productivity may reduce.

Be not particularly limited for the surface roughness that contains the thermal adhesive layer (C) of Wholly aromatic polyamide of the present invention, preferred surface roughness (Rt) is in the scope of 0.01 μ m-100 μ m.During less than 0.01 μ m, when the impregnation solvent was peeled off, solvent can't permeate, and was difficult to peel off; Than 100 μ m when big, can't obtain the bonding precision with the bonded body (B) that constitutes by inorganic materials, bonding inequality mostly occurs greatly.

(the laminate I ' that contains adhesive sheet layer and inorganic materials)

When adhesive sheet only is made of the base material that contains full aromatic polyimide film (A), laminate of the present invention is laminate (I '), it is characterized in that: this laminate (I ') be the laminate that contains base material (A) and inorganic materials (B), it is 200 ℃ or above full aromatic polyimide film that wherein said base material (A) contains second-order transition temperature, base material (A) is with the bonded body that is made of silicon wafer when laminated, base material (A)

(a ') hot pressing is after 15 minutes under 370 ℃ and 5.0-6.0MPa, and base material (A) is 0.1N/m-100N/m with the stripping strength at the interface of silicon wafer.

Stripping strength can not obtain required enough bounding forces by semiconductor device manufacturing process during less than 0.1N/m, the situation that semi-conductor chip comes off from substrate might take place midway in operation.

The following calculating of stripping strength described here: 25 ℃, be determined under 370 ℃ and the 5.0-6.0MPa the wide sheet adherend of 1cm of pressing with the bonded body heat that constitutes by silicon wafer 15 minutes with about 300mm/ minute draw speed, in the strip length scope of the length of 100mm at least outside removing initial 25mm, obtain average peeling force (N) by power-anchor clamps miles of relative movement curve, calculate the value (N/m) of every m under wide.

At this moment, this base material (A) is preferably to contain and constitutes unitary full aromatic polyimide shown in the following formula (1):

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

Wherein, this base material (A) preferably comprises and contains the unitary full aromatic polyimide of formation shown in formation unit shown in the 30-70 mole % following formula (1) and the 70-30 mole % following formula (2):

Ar ^2aAnd Ar ^2bIndependent separately, be 6 or above 20 or following aromatic group for containing non-reacted substituent carbonatoms.

Further preferred this base material (A) contains the acylimino concentration that with good grounds following formula (4) calculates, and (equivalent/kg) is the full aromatic polyimide of 5.5 equivalents/kg-6.9 equivalent/kg.

Acylimino concentration (equivalent/kg)=the unitary molecular weight of the every formation of 2 * 1000/[] (4)

Under the pressure of 180 ℃-600 ℃ temperature and 0.001MPa-1000MPa, will contain the base material (A) of full aromatic polyimide film and inorganic materials (B) hot pressing 0.1 second-48 hours, can obtain laminate (I ') thus.

Bond condition such as temperature or pressure, time can be controlled arbitrarily according to the material or the combination of used adhesive sheet and bonded body.Hot pressed temperature is 180 ℃-600 ℃ scope, preferred 180 ℃-550 ℃ scope, further preferred 180 ℃-500 ℃ scope.See that according to the overall each other suffered mean pressure of adhesive sheet and bonded body hot pressed pressure is in the 0.001MPa-1000MPa scope, preferred 0.01MPa-100MPa scope.Pressure can't be fully bonding during less than 0.001MPa, and pressure ratio 100MPa is when high, and bonded body may be damaged.

Pressure hold time was 0.1 second-48 hours scopes during hot pressing, and during less than 0.1 second, bounding force is not enough, is difficult to obtain the stable laminate of bounding force.When longer than 48 hours, productivity reduces.More preferably during hot pressing pressure hold time 1 second-24 hours scopes.

During hot pressing, temperature is risen,, then at room temperature, under the state of pressurization, place the cooling certain hour with the pressure binding specific time of regulation; Temperature is risen, behind the pressure binding specific time with regulation, under the state of pressure relief, be incubated certain hour.

(the laminate I that contains adhesive sheet layer and inorganic materials)

Adhesive sheet comprises the base material (A) that contains full aromatic polyimide film and contains and has second-order transition temperature when being the thermal adhesive layer (C) of Wholly aromatic polyamide of 200 ℃ of-500 ℃ of characteristics, the laminate (I) that laminate of the present invention is that the thermal adhesive layer (C) at adhesive sheet goes up is that further laminated inorganic materials (B) forms, form according to the sequential laminating of the base material that contains full aromatic polyimide film (A), thermal adhesive layer (C) and inorganic materials (B).

Has the thermal adhesive layer (C) that second-order transition temperature is the Wholly aromatic polyamide of 200 ℃ of-500 ℃ of characteristics via containing, under the pressure of 180 ℃-600 ℃ temperature and 0.001MPa-1000MPa, the base material (A) of full aromatic polyimide film and inorganic materials (B) hot pressing 0.1 second-1 hour will be contained, above-mentioned laminate (I) can be obtained thus.

Bond condition such as temperature or pressure, time can be controlled arbitrarily according to the material or the combination of used adhesive sheet and bonded body.Hot pressed temperature is 180 ℃-600 ℃ scope, preferred 180 ℃-550 ℃ scope, further preferred 180 ℃-500 ℃ scope.See that according to the overall each other suffered mean pressure of adhesive sheet and bonded body hot pressed pressure is in the 0.001MPa-1000MPa scope, preferred 0.01MPa-100MPa scope.Pressure can't be fully bonding during less than 0.001MPa, and pressure ratio 100MPa is when high, and bonded body may be damaged.

By thermal adhesive layer is set, be thermal bondable in the short period of time, the scope of pressure hold time is 0.1 second-1 hour during hot pressing, during less than 0.1 second, bounding force is not enough, is difficult to obtain the stable laminate of bounding force.More preferably during hot pressing pressure hold time 1 second-30 minutes scopes.

During hot pressing, temperature is risen,, then at room temperature, under the state of pressurization, place the cooling certain hour with the pressure binding specific time of regulation; Temperature is risen, behind the pressure binding specific time with regulation, under the state of pressure relief, be incubated certain hour.

(inorganic materials)

Inorganic materials of the present invention (B) is meant its 60 volume % or abovely is made of mineral compound.Mineral compound for example has metals such as aluminium, iron, silicon, germanium, carbon, nitrogen compounds such as barium titanate, potassium titanate, titanium nitride, aluminium nitride, boron nitride; The セ ラ ジ Application that zirconium white, aluminum oxide, the ガ ス of Mitsubishi chemistry are made ^On pottery; Glass, semiconductor alloys such as preferred silicon, germanium, more preferably silicon wafer.The form of these inorganic materials and the bonded body that is made of inorganic materials can be cross, netted, inorganic sintered thing, porous matter, tabular, sheet, film like etc., preferred porous matter, tabular, sheet.Therefore, mixture of porous ceramics of obtaining of plate that for example constitutes with the carbon/epoxy cpd by so-called prepreg manufacturing or sintering etc. and epoxy etc. etc. is also included within the bonded body that is made of inorganic materials.

Thickness for this bonded body inorganic materials is not particularly limited, mostly the scope of preferred 1 μ m-2000 μ m.During less than 1 μ m, require to touch the precision of sticking device when bonding with adhesive sheet, it is bonding irregular just bonding equably to be difficult to make adhesive face not have sometimes.In addition, can't obtain to touch sticking required enough physical strengths sometimes, touch and to destroy when sticking etc.When thickness is 2000 μ m or when above, be difficult to heat conduction with adhesive sheet when bonding, need spended time to transmit temperature, productivity may reduce.

(the laminate II, the II ' that further contain object being treated layer (D), organism protective layer (E))

The present invention relates to the laminate (II) that the sequential laminating according to object being treated layer (D), organism protective layer (E), the base material (A) that contains full aromatic polyimide film, thermal adhesive layer (C) and inorganic materials (B) forms.

The invention still further relates to according to object being treated layer (D), organism protective layer (E), contain the laminate that sequential laminating with the base material (A) of full aromatic polyimide film that second-order transition temperature is 200 ℃ or above characteristic and inorganic materials (B) forms (II ').

Object being treated layer (D) is not particularly limited this so long as can get final product with any method and following organism protective layer (E) adherent, and the preferred suitable example of the present invention is to have implemented to comprise that the circuit block that mixes impurity forms the semiconductor substrate of step.Inorganic materials this moment (B) is preferably supports to use substrate.

The purpose of using organism protective layer (E) is a protection object being treated layer (D).When object being treated layer (D) is when having implemented to comprise that the circuit block that mixes impurity forms the semiconductor substrate of step, preferred polyimide, fluorinated polyimide, poly-organic hydride silane, polysiloxane, polysiloxane-modified polyimide, polyphenylene, poly-benzylic ether, the polyarylethers etc. of using more preferably use polysiloxane-modified polyimide.

The laminating method of above-mentioned laminate is not particularly limited, can be at room temperature with above-mentioned adhesive sheet and adherend, and according to circumstances heating attaches while pressurize.The method that attaches has: use the sticking method of pressure of thermocompressor, vacuum press, by roller carry out bonding etc.

When for example using the sticking method of the pressure of thermocompressor; can be between the top board and above-mentioned adhesive sheet and bonded body of thermocompressor; not hinder the protecting sheet that heat conducting thickness accompanies metals such as stainless steel, iron, titanium, aluminium, copper or their alloy etc.; or contain the film of thermally stable polymers such as full aromatic polyimide and/or Wholly aromatic polyamide; and/or the resins such as fiber that contain these thermally stable polymers are as cushioning material, to transmit pressure along whole adhesive face.

Be not particularly limited for bond conditions such as temperature, pressure, times, it is bonding but can control arbitrarily according to the material of employed adhesive sheet and bonded body or combination.Preferred temperature for example can be enumerated 180 ℃-600 ℃ scope when bonding.Preferred 180 ℃-550 ℃ scope.Further preferred 180 ℃-500 ℃ scope.See that according to the overall each other suffered mean pressure of adhesive sheet and bonded body the pressure when bonding is in the 0.001MPa-1000MPa scope, preferred 0.01MPa-100MPa scope.Pressure can't be fully bonding during less than 0.001MPa, and pressure ratio 100MPa is when high, and bonded body may be damaged.

Preferred 0.1 second-48 hours scopes of pressure hold time when bonding.During less than 0.1 second, bounding force is not enough, is difficult to obtain the stable laminate of bounding force.When longer than 48 hours, productivity reduces.Pressure hold time was 1 second-24 hours scopes when more preferably bonding.When being provided with thermal adhesive layer, can carry out heat bonding at short notice.

When bonding, temperature is risen,, then at room temperature, under the state of pressurization, place the cooling certain hour with the pressure binding specific time of regulation; Temperature is risen, behind the pressure binding specific time with regulation, under the state of pressure relief, be incubated certain hour.

(manufacture method of laminate IV)

The bright preparation method who relates to laminate IV of this law; it is characterized in that: according to object being treated layer (D), organism protective layer (E), contain sequential layer and merge hot pressing with the base material (A) of full aromatic polyimide film that second-order transition temperature is 200 ℃ or above characteristic and inorganic materials (B) after; the face that exposes at the D layer carries out reduction processing; make D ' layer; after obtaining containing the laminate (III) of D ' layer, E layer, A layer and B layer; make the interface peel of E layer and A layer, obtain containing the laminate (IV) of D ' layer and E layer.

Further preferably between base material (A) and inorganic materials (B) thermal adhesive layer (C) is set, wherein said thermal adhesive layer (C) contains and has the Wholly aromatic polyamide that second-order transition temperature is 200 ℃ of-500 ℃ of characteristics.At this moment, the thermal adhesive layer (C) that contains Wholly aromatic polyamide preferably contains the formation unit shown in the following formula (3-1):

Base material (A) preferably contains the polymkeric substance that comprises full aromatic polyimide, and wherein said full aromatic polyimide contains and constitutes the unit shown in the following formula (1):

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

Base material (A) preferably contains the polymkeric substance that comprises full aromatic polyimide, and wherein said full aromatic polyimide contains shown in the 30-70 mole % following formula (1) to constitute and constitutes the unit shown in unit and the 70-30 mole % following formula (2):

Ar ^2aAnd Ar ^2bIndependent separately is 6 or above 20 or following aromatic group for containing non-reacted substituent carbonatoms.

Laminating method for above-mentioned laminate (III) is not particularly limited, can be by similarly obtaining with above-mentioned laminate (II), (II ') described method.

Object being treated layer (D) forms the semiconductor substrate of step for having implemented to comprise the circuit block that mixes impurity; and inorganic materials (B) is for supporting to use substrate; the processing treatment that face makes its attenuation of exposing through polishing D layer; the semiconductor substrate of formation attenuate (D ' layer); make the interface peel of organism protective layer (E) and base material (A) then; obtaining containing the semiconductor device laminate of semiconductor substrate (D ' layer) and organism protective layer (E), more than is one of the advantageous applications of the manufacture method of laminate of the present invention.Here, preferably will contain second-order transition temperature is that the thermal adhesive layer (C) of 200 ℃-500 ℃ Wholly aromatic polyamide is arranged between base material (A) and the inorganic materials (B).

(the interface peel method of E layer and A layer)

After obtaining laminate (III), make the interface peel of E layer and A layer, obtain containing the laminate (IV) of D ' layer and E layer, make the preferred stripping means of the interface peel of E layer and A layer that following four kinds of methods be arranged this moment.

Make the first method of the interface peel of E layer and A layer be: will contain D ' layer, E layer, A layer, (preferably also containing the C layer) and the laminate of B layer and impregnated in the liquid, make liquid infiltration enter the interface of E layer and A layer, be heated to rapidly then liquid boiling point or more than, make the method (method 1) of the vaporizing liquid that penetrates into the interface.The immersion condition of liquid be preferably 30 ℃ or more than.The boiling point of further preferred 40 ℃ or above, liquid or following.Temperature is lower than 30 ℃, and then liquid is difficult to penetrate into interlayer, peels off difficulty.

Preferred 1 minute of dipping time or more than.Further preferred 30 minutes or more than.1 minute weak point of time ratio, then infiltration can't make progress, and peels off difficulty, and is not preferred.

Can also be that laminate is exposed in the steam of this liquid, cooling makes the method for liquid in the interlayer dewfall then.

Heating condition behind the dipping be preferably boiling point of liquid or more than.Further preferably than the boiling point of liquid also high 50 ℃ or more than.Heat-up time preferably 5 minutes with interior rise to temperature required.Further preferred 30 seconds or in.5 minutes volumetric expansion effects long, that then being difficult to obtains to vaporize causes of time ratio are peeled off difficulty.

Liquid is so long as have the liquid of 30 ℃ or above boiling point and get final product under normal pressure, preferably have 40 ℃ or liquid above, 200 ℃ or following boiling point.These liquid specifically can use: water, methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, acetone, methyl ethyl ketone, diethyl ketone, pimelinketone, hexalin, 1,4-two  alkane, hexane, heptane, octane, nonane, decane, benzene, toluene, o-Xylol, m-xylene, p-Xylol, aniline, pyridine, ethyl acetate, chloroform, methylene dichloride, tetracol phenixin etc.It can also be their mixed solution.Preferably make water, methyl alcohol, ethanol, Virahol.Further preferably make water.

Make the second method of the interface peel of E layer and A layer be: will contain D ' layer, E layer, A layer, (preferably also containing the C layer) and the laminate of B layer and impregnated in the water, make water penetrate into the interface of E layer and A layer, be cooled to 0 ℃ or following then, and make the solid method of peeling off (method 2) of the water-setting that penetrates into the interface.The immersion condition of water be preferably 30 ℃ or more than.Further preferred 40 ℃ or above, 100 ℃ or following.Temperature is lower than 30 ℃, and then shipwreck is peeled off difficulty to penetrate into interlayer.

Preferred 1 minute of time or more than.Further preferred 5 minutes or more than.1 minute weak point of time ratio, then infiltration can't make progress, and peels off difficulty, and is not preferred.

Can also be that laminate is exposed in the water vapor, cooling makes the method for water in the interlayer dewfall then.

Cooling conditions behind the dipping is preferably 0 ℃ or following.Further preferred-5 ℃ or following.Cooling time is preferably extremely temperature required with internal cooling at 10 minutes.Further preferably 30 seconds or in.Time ratio 10 minutes is long, then is difficult to obtain to solidify the volumetric expansion effect that causes, and peels off difficulty.

Make the third method of the interface peel of E layer and A layer be: to produce 30-800 ℃ the temperature difference along the thickness direction of the laminate that contains D ' layer, E layer, A layer, (preferably also containing the C layer) and B layer, thereby make the method (method 3) of the interface peel of E layer and A layer.The method that produces the temperature difference is not particularly limited, and has laminate is transferred to the method for the condition of high temperature by low-temperature condition, or is transferred to the method for low-temperature condition by the condition of high temperature, perhaps produces the method for this temperature difference between inorganic layer B one side and object being treated layer D '.The state that laminate is transferred to the method for the condition of high temperature by low-temperature condition or is transferred to by the condition of high temperature in the method for low-temperature condition for example has: the room temperature state in the atmosphere or in the liquid; In addition hot blast heating, steam heating, heating under vacuum, infrared heating, microwave heating use the heated condition of the contact heating etc. of hot plate, hot-rolling, water-bath, oil bath, TEG bath, salt bath, weldering bath etc. in addition; The state of cooling of cold wind, dry ice, ice, cooling liqs etc.; In each state,, can be arbitrarily between the state so long as the generation temperature difference gets final product.

Produce the method for this temperature difference so long as produce above-mentioned state difference method for distinguishing at each face and get final product along the thickness direction of laminate, can use any means.Preferably from the method for the last side contacts dry ice that places the laminate on the hot plate, ice, cooling liqs.

The temperature difference is 30-800 ℃, preferred 100-600 ℃.

Make the 4th kind of method of the interface peel of E layer and A layer be: the laminate that will contain D ' layer, E layer, A layer, (preferably also containing the C layer) and B layer impregnated in the pH value in the alkaline solution of 8-14, make alkaline solution penetrate into the A layer, make the method (method 4) of the interface peel of E layer and A layer thus.The further preferred pH value of alkaline solution is 10-14, more preferably contains the aqueous solution of 0.1%-30% concentration ammonia.As long as the employed solvent of alkaline solution can make the solvent of this alkali dissolution, it is not particularly limited, be preferably water.As immersion condition, preferred-5 ℃ to 120 ℃ of temperature is lower than-5 ℃, and then the water in the aqueous solution freezes; Be 120 ℃ or more than, the then water in aqueous solution boiling, thereby not preferred.Dipping time preferred 1 second-36000 seconds is lower than 1 second, does not then fully penetrate in the film portion, peels off difficulty; It is 36000 seconds or when above, activity time increases, the productivity variation.

By using above-mentioned stripping means, but not only productive rate obtains to contain the laminate of D ' layer and E layer well, can also be easily with the A layer after peeling off, (preferably C layer) in addition and the recycling of B layer.

Embodiment

Below, further specifically describe the present invention in detail by embodiment.These embodiment not delimit the scope of the invention.The measuring method of rerum natura of the present invention, Evaluation on effect method are carried out in accordance with the following methods.

(1) mensuration of the Young's modulus of film

Use the sample of 50mm * 10mm, with 5mm/ minute draw speed, UCT-1T measured by オ リ エ Application テ Star Network.The initial gradient of the elongation-stress curve that obtains based on the data of measuring is that 100% o'clock stress (GPa) is obtained Young's modulus by elongation.

(2) mensuration of the thermal linear expansion coefficient of film

Use about 13mm (L ₀The sample of) * 4mm is warming up to 50 ℃-250 ℃ scope with 10 ℃/minute heat-up rates, and cooling is measured by TA イ Application ス Star Le メ Application ト TMA2940 thermodynamic analyzer.At this moment, the long variation delta L of sample when measuring by 100 ℃ to 200 ℃ is by following formula (5)

Thermal linear expansion coefficient (ppm/ ℃)=(1000000 * Δ L/L ₀)/100 ... (5)

Obtain the thermal linear expansion coefficient of film, calculate the mean value of 2 axial values that intersect vertically respectively.

(3) stripping strength is measured

In advance adherend is cut into the 10mm width, be 300 ℃ in embodiment 3, in embodiment 1,2,4 and embodiment 17, be 370 ℃ with bonded body then, and it is bonding with 5.0-6.0MPa hot pressing 15 minutes, it is gripped with anchor clamps, one end of adhesive sheet is gripped with another anchor clamps, and UCT-1T measures at 25 ℃ of draw speeds with 300mm/ minute with オ リ エ Application テ Star Network.In the strip length scope of the length of 100mm at least of removing initial 25mm, obtain average peeling force (N) by power-anchor clamps miles of relative movement curve, calculate the value (N/m) under every m width.

(4) shearing stripping strength measures

Adherend and bonded body are cut into the square of length of side 25mm in advance, laminated, at 300 ℃ and with 5.5MPa hot pressing 2 minutes, carry out bonding then.The face that exposes at this laminate is coated with binding agent, with the stainless steel plate of 2 25mm * 60mm * 1mm clamp from both sides carry out bonding, use method then, under 25 ℃, the condition of 10mm/ minute draw speed, measure with オ リ エ Application テ Star Network UCT-1T based on JIS K6851.Maximum value (N) by peel stress is calculated every cm ²Shearing peel adhesion strength (N/cm ²).

(5) determination of viscoelasticity

Use the sample of about 22mm * 10mm, be warming up to 50 ℃-500 ℃ scope, under the frequency of 6.28rad/s, measure with Rheometrics RSA II.The following calculating of second-order transition temperature: use the dynamic energy storage elastic modulus E that obtains by mensuration ', dynamic loss elasticity modulus E " calculate dynamic loss tangent tan δ, calculate by this value.

(6) surface roughness measurement of silicon wafer

With the three-dimensional microcosmic surface shape viewing system NT-2000 of noncontact (WYKO) the middle body 1.2mm * 0.92mm of used silicon wafer is measured.

[adhesive sheet Production Example 1]

Under nitrogen atmosphere, the 1920g NMP that dewaters is packed into and has in the reaction vessel of thermometer, whipping appts and raw material dog-house, add the 26.52g Ursol D again, it is dissolved fully.With the ice bath cooling, the temperature that makes two amine aqueous solutions is 3 ℃ then.In these refrigerative two amine aqueous solutions, add 53.46g pyromellitic acid acid anhydride, reacted 1 hour.This moment, the temperature of reaction soln was 5-20 ℃.Under room temperature (23 ℃), make this reaction solution reaction 3 hours again, then add the 0.091g Tetra hydro Phthalic anhydride, reacted 1 hour, carry out the amine end-capped, obtain polyamic acid nmp solution as viscous solution.

With the scraper of thickness 1.0mm with gained polyamic acid solution curtain coating on sheet glass, dipping is 30 minutes in 30 ℃ of dehydrating condensations that contain 250ml diacetyl oxide, 74g Triethylene Diamine and 2000mlNMP are bathed, carry out imide/different imidization, separate from sheet glass, obtain gel film as support.

At room temperature the gained gel film was flooded in NMP 20 minutes, washs, then the two ends of this gel film are fixed with anchor clamps, at room temperature with the speed of 10mm/ second along biaxial stretch-formed 1.05 times simultaneously of two direction of principal axis that intersect vertically.The swelling capacity of the gel film when stretching beginning is 1510%.(swelling capacity is calculated by the weight ratio of solvent swelling state and drying regime.The weight that is drying regime is W ¹, the weight during swelling is W ², swelling capacity=((W ²/ W ¹)-1) * 100).

Gel film after stretching is fixed with frame, carried out cascade raising temperature, be warming up to 300 ℃, enforcement drying and thermal treatment by 160 ℃ by the hot air dryer that uses dry air.Then, with heated air circulation type baking oven cascade raising temperature,, obtain containing the adhesive sheet of full aromatic polyimide film from 300 ℃ to 450 ℃.Therefore, this adhesive sheet is the adhesive sheet that contains full aromatic polyimide film, and wherein said full aromatic polyimide film only is made of the formation unit shown in the following formula (1-a).

Below, abbreviate the adhesive sheet that obtains like this as P-1.

The thickness of P-1, intensity, Young's modulus, second-order transition temperature, thermal linear expansion coefficient are as shown in table 1.

[adhesive sheet Production Example 2]

Under nitrogen atmosphere, the 2010g NMP that dewaters to be packed into and has thermometer, in the reaction vessel of whipping appts and raw material dog-house, adds 40.95g Ursol D and 91.77g 3 again, 4 '-diaminodiphenyl oxide dissolves it fully.With the ice bath cooling, the temperature that makes two amine aqueous solutions is 3 ℃ then.In these refrigerative two amine aqueous solutions, add 181.8g pyromellitic acid acid anhydride, reacted 1 hour.This moment, the temperature of reaction soln was 5-20 ℃.Under room temperature (23 ℃), make this reaction solution reaction 8 hours again, then add the 0.247g Tetra hydro Phthalic anhydride, reacted 1 hour, carry out the amine end-capped, obtain polyamic acid nmp solution as viscous solution.The concentration of gained polyamic acid NMP is 13 weight %.

With the scraper of thickness 1.0mm with gained 13 weight % polyamic acid nmp solutions curtain coating on sheet glass, dipping is 30 minutes in 30 ℃ of dehydrating condensations that contain 1050ml diacetyl oxide, 450ml pyridine and 1500mlNMP are bathed, carry out imide/different imidization, separate from sheet glass, obtain gel film as support.

At room temperature the gained gel film was flooded in NMP 20 minutes, washs, then the two ends of this gel film are fixed with anchor clamps, at room temperature with the speed of 10mm/ second along biaxial stretch-formed 3.10 times simultaneously of two direction of principal axis that intersect vertically.The swelling capacity of the gel film when stretching beginning is 394%.

Gel film after stretching is fixed with frame, carried out cascade raising temperature, be warming up to 300 ℃, enforcement drying and thermal treatment by 160 ℃ by the hot air dryer that uses dry air.Then, with heated air circulation type baking oven cascade raising temperature,, obtain full aromatic polyimide from 300 ℃ to 450 ℃.

Therefore, this adhesive sheet is the adhesive sheet that contains full aromatic polyimide film, and wherein said full aromatic polyimide film contains the formation unit shown in 50 moles of % following formulas (1-a):

With the formation unit shown in 50 moles of % following formulas (2-a).

Below, abbreviate the adhesive sheet that obtains like this as P-2.

The thickness of P-2, intensity, Young's modulus, second-order transition temperature, thermal linear expansion coefficient are as shown in table 1.

Table 1

Adhesive sheet	Thickness (μ m)	Second-order transition temperature (℃)	Young's modulus (GPa)	Thermal linear expansion coefficient (ppm/ ℃)
					P-1	12	＞500	16.2	-8.60
P-2	20	410	10.4	+5.75

Embodiment 1

Going up the full aromatic polyimide film P-1 that places as adhesive sheet as the silicon wafer of the bonded body that constitutes by inorganic materials (6 inches of diameters, thickness 600 μ m, the about 0.02 μ m of surfaceness (Rt), thermal linear expansion coefficient+4.15ppm/ ℃), make it tight contact, clamp with metal sheet then, be positioned in the thermocompressor.Making the surface temperature on actual contact surface by thermocompressor is 370 ℃, carries out bonding in 15 minutes with the 5.5MPa pressurization then.Cut off the heating of press, place and be cooled to 250 ℃, from press, take out.The stripping strength at gained full aromatic polyimide film P-1 and silicon wafer interface is 15.0N/m.The absolute value of the thermal linear expansion coefficient difference of full aromatic polyimide film P-1 and silicon wafer is 12.75ppm/ ℃.

Embodiment 2

Use adhesive sheet instead full aromatic polyimide film (P-2), in addition obtain laminate similarly to Example 1.As a result, the interface peel intensity of gained full aromatic polyimide film P-2 and silicon wafer is 32.5N/m.The absolute value of the thermal linear expansion coefficient difference of full aromatic polyimide film P-2 and silicon wafer is 1.60ppm/ ℃.

Embodiment 3

At 5 ℃, with the コ-ネ Star Network ス of Supreme Being people テ Network ノ プ ロ ダ Network ト Co., Ltd. manufacturing ^Powder is scattered in the N-N-methyl-2-2-pyrrolidone N-, then 40 ℃ of dissolvings, obtains 10 weight % solution.Coiling rod spreader with thickness 28 μ m makes this コ-ネ Star Network ス ^10 weight % solution are curtain coating on the full aromatic polyimide film P-1 that is attached on the sheet glass.Use hot air dryer with 160 ℃ of dryings 30 minutes then, cascade raising temperature to 280 ℃ carries out drying and thermal treatment then, obtain the having thermal adhesive layer thus adhesive sheet of (C), and wherein said thermal adhesive layer (C) contains the Wholly aromatic polyamide film.

Go up thermal adhesive layer (C) face of placing adhesive sheet at silicon wafer (6 inches of diameters, thickness 600 μ m, the about 0.02 μ m of surfaceness (Rt)) as the bonded body that constitutes by inorganic materials, make it tight contact, clamp with metal sheet then, be positioned in the thermocompressor.Making the surface temperature of actual contact face by thermocompressor is 300 ℃, carries out bonding in 2 minutes with the 5.5MPa pressurization then.From press, take out afterwards, place cooling.The interface peel intensity of thermal adhesive layer in the gained laminate (C) and silicon wafer is 200N/m, and the shearing peel adhesion strength is 170N/cm ²

Embodiment 4

Change full aromatic polyimide film P-1 into full aromatic polyimide film (eastern レ デ ユ Port Application system カ プ ト Application (registered trademark) 50H), the heat bonding temperature is 370 ℃, in addition all similarly to Example 3, obtain the having thermal adhesive layer adhesive sheet of (C), wherein said thermal adhesive layer (C) contains the Wholly aromatic polyamide film.

Go up thermal adhesive layer (C) face of placing adhesive sheet at silicon wafer (6 inches of diameters, thickness 600 μ m, the about 0.02 μ m of surfaceness (Rt)) as the bonded body that constitutes by inorganic materials, make it tight contact, clamp with metal sheet then, be positioned in the thermocompressor.Making the surface temperature of actual contact face by thermocompressor is 300 ℃, carries out bonding in 2 minutes with the 5.5MPa pressurization then.From press, take out afterwards, place cooling.The stripping strength at the interface of thermal adhesive layer in the gained laminate (C) and silicon wafer is 200N/m.

Embodiment 5

With the single face of the fit full aromatic polyimide film P-1 that constitutes of embodiment 3 identical layers on further stack be that 0.6mm, diameter are the silicon wafer of 150mm as the polyimide coating and the thickness of organism protective layer (E); it is positioned on the thermocompressor, with 5MPa, 300 ℃ the pressurization 2 minutes.That is, obtain according to silicon wafer (supporting to use substrate), コ-ネ Star Network ス ^The laminate of the sequential laminating of layer, full aromatic polyimide film P-1, organism protective layer (E) and silicon wafer (semiconductor substrate).

The silicon wafer (semiconductor substrate) of this laminate is exposed face be arranged on the polishing machine, at 160gf/cm ²Load under, use polishing paper with silicon-carbide particle, make the revolution rotation of polishing plate with 110rpm, the thickness that is polished to silicon wafer is 130 μ m.Polishing is carried out with the order of #150, #800, #2000 granularity.Do not observe peeling off of laminate during polishing.

The gained laminate was flooded 1 hour in 60 ℃ water, take out.Then on 200 ℃ hot plate, placed 30 seconds, return back to room temperature after the taking-up.

Laminate is peeled off at the interface easily polyimide coating and aromatic polyimide film P-1's.Silicon wafer (supporting to use substrate) and コ-ネ Star Network ス ^Does not peel off at each interface of layer and full aromatic polyimide film P-1.

Embodiment 6

Laminate after the polishing of making was similarly to Example 5 flooded 1 minute in 100 ℃ water.Then on 200 ℃ hot plate, placed 30 seconds, return back to room temperature after the taking-up.

Laminate is peeled off at the interface easily polyimide coating and aromatic polyimide film P-1's.Silicon wafer (how to hold and use substrate) and コ-ネ Star Network ス ^Does not peel off at each interface of layer and full aromatic polyimide film P-1.

Embodiment 7

With the laminate after the polishing of making similarly to Example 5 at 3kgf/cm ²Water vapour in expose 1 minute.Then in 20 ℃ water, flooded 3 seconds immediately, take out.On 200 ℃ of hot plates, placed 30 seconds again, return back to room temperature after the taking-up.

Laminate is peeled off at the interface easily polyimide coating and aromatic polyimide film P-1's.Silicon wafer (supporting to use substrate) and コ-ネ Star Network ス ^Does not peel off at each interface of layer and full aromatic polyimide film P-1.

Embodiment 8

Laminate after the polishing of making was similarly to Example 5 flooded 1 hour in 30 ℃ methyl alcohol.Then on 200 ℃ hot plate, placed 30 seconds, return back to room temperature after the taking-up.

Laminate is peeled off at the interface easily polyimide coating and aromatic polyimide film P-1's.Silicon wafer (supporting to use substrate) and コ-ネ Star Network ス ^Does not peel off at each interface of layer and full aromatic polyimide film P-1.

Embodiment 9

Laminate after the polishing of making was similarly to Example 5 flooded 1 hour in 50 ℃ ethanol.Then on 200 ℃ hot plate, placed 30 seconds, return back to room temperature after the taking-up.

Laminate is peeled off at the interface easily polyimide coating and aromatic polyimide film P-1's.Silicon wafer (supporting to use substrate) and コ-ネ Star Network ス ^Does not peel off at each interface of layer and full aromatic polyimide film P-1.

Embodiment 10

Laminate after the polishing of making was similarly to Example 5 flooded 1 hour in 80 ℃ Virahol.Then on 200 ℃ hot plate, placed 30 seconds, return back to room temperature after the taking-up.

Laminate is peeled off at the interface easily polyimide coating and aromatic polyimide film P-1's.Silicon wafer (supporting to use substrate) and コ-ネ Star Network ス ^Does not peel off at each interface of layer and full aromatic polyimide film P-1.

Embodiment 11

Laminate after the polishing of making was similarly to Example 5 flooded 1 hour in 60 ℃ water, take out.Then in liquid nitrogen, placed 30 seconds, return back to room temperature after the taking-up.

Laminate is peeled off at the interface easily polyimide coating and aromatic polyimide film P-1's.Silicon wafer (supporting to use substrate) and コ-ネ Star Network ス ^Does not peel off at each interface of layer and full aromatic polyimide film P-1.

Embodiment 12

Laminate after the polishing of making was similarly to Example 5 flooded 1 hour in 100 ℃ water.Then in liquid nitrogen, placed 30 seconds, return back to room temperature after the taking-up.

Laminate is peeled off at the interface easily polyimide coating and aromatic polyimide film P-1's.Silicon wafer (supporting to use substrate) and コ-ネ Star Network ス ^Does not peel off at each interface of layer and full aromatic polyimide film P-1.

Embodiment 13

With the laminate after the polishing of making similarly to Example 5 at 3kgf/cm ²Water vapour in expose 1 minute.Then in 20 ℃ water, flooded 3 seconds immediately, take out.In liquid nitrogen, placed 30 seconds again, return back to room temperature after the taking-up.

Laminate is peeled off at the interface easily polyimide coating and aromatic polyimide film P-1's.Silicon wafer (supporting to use substrate) and コ-ネ Star Network ス ^Does not peel off at each interface of layer and full aromatic polyimide film P-1.

Embodiment 14

Laminate after the polishing of making similarly to Example 5 is placed on 300 ℃ the hot plate with the ventricumbent state of substrate supporting, on silicon wafer (semiconductor substrate) face, places to ice then and cool off.

Laminate is peeled off at the interface easily polyimide coating and aromatic polyimide film P-1's.Silicon wafer (supporting to use substrate) and コ-ネ Star Network ス ^Does not peel off at each interface of layer and full aromatic polyimide film P-1.

Embodiment 15

Laminate after the polishing of making similarly to Example 5 is placed on 400 ℃ the hot plate with the ventricumbent state of substrate supporting, crosses liquid nitrogen at silicon wafer (semiconductor substrate) surface current then and cool off.

Laminate is peeled off at the interface easily polyimide coating and aromatic polyimide film P-1's.Silicon wafer (supporting to use substrate) and コ-ネ Star Network ス ^Does not peel off at each interface of layer and full aromatic polyimide film P-1.

Embodiment 16

Laminate after the polishing of making similarly to Example 5 at room temperature be impregnated in 25% ammonia soln.The visible layer zoarium is peeled off after 3 hours, takes out.

Laminate is peeled off at the interface polyimide coating and aromatic polyimide film P-1's, and the aromatic polyimide film dissolves fully.In addition, support also to peel off with the interface of substrate and aromatic poly layer.

Embodiment 17

Sequential laminating according to the silicon wafer (semiconductor substrate) of silicon wafer (support use substrate), full aromatic polyimide film P-2, polyimide coating and thickness 0.6mm, diameter 150mm places on the thermocompressor, pressurizes 15 minutes with 5.5MPa, 370 ℃.Promptly obtain laminate according to the sequential laminating of silicon wafer (supporting to use substrate), full aromatic polyimide film P-2, polyimide coating and silicon wafer (semiconductor substrate).

The silicon wafer (semiconductor substrate) of this laminate is exposed face be arranged on the polishing machine, at 160gf/cm ²Load under, use polishing paper with silicon-carbide particle, make the revolution rotation of polishing plate with 110rpm, the thickness that is polished to silicon wafer is 130 μ m.Polishing is carried out with the order of #150, #800, #2000 granularity.Do not observe peeling off of laminate during polishing.

Laminate after the polishing at room temperature be impregnated in 25% ammonia soln.The visible layer zoarium is peeled off after 3 hours, takes out.

Aromatic polyimide film P-2 in the laminate dissolves fully, and polyimide coating and aromatic polyimide film P-2 are peeling off at the interface.

Claims (14)

1. adhesive sheet, it is characterized in that: this adhesive sheet contains base material (A) and thermal adhesive layer (C), it is 200 ℃ or above full aromatic polyimide film that wherein said base material (A) contains second-order transition temperature, and described thermal adhesive layer (C) contains and has the Wholly aromatic polyamide that second-order transition temperature is 200 ℃ of-500 ℃ of characteristics; During according to the sequential laminating of the bonded body that comprises silicon wafer, thermal adhesive layer (C) and base material (A), satisfy at least following condition (a) or (b) one of them:

(a) hot pressing is after 15 minutes under 300 ℃ and 5.0-6.0MPa, and thermal adhesive layer (C) is 0.1N/m-300N/m with the stripping strength at the interface of silicon wafer;

(b) hot pressing is after 2 minutes under 300 ℃ and 5.0-6.0MPa, and thermal adhesive layer (C) is 1N/cm with the shearing peel adhesion strength at the interface of silicon wafer ²-1000N/cm ²

2. the adhesive sheet of claim 1 is characterized in that: thermal linear expansion coefficient is-10ppm/ ℃ to+45ppm/ ℃ scope.

3. the adhesive sheet of claim 1, it is characterized in that: Young's modulus is in the scope of 1.0GPa-30GPa.

4. the adhesive sheet of claim 1, it is characterized in that: described base material (A) contains full aromatic polyimide, and described full aromatic polyimide contains the formation unit shown in the following formula (1):

Ar ¹Non-reacted substituent 1 for containing or not containing, the 4-phenylene.

5. the adhesive sheet of claim 1, it is characterized in that: described base material (A) contains full aromatic polyimide, and described full aromatic polyimide contains the formation unit shown in the 30-70 mole % following formula (1):

Ar ¹Non-reacted substituent 1 for containing or not containing, the 4-phenylene,

With the formation unit shown in the 70-30 mole % following formula (2):

Ar ^2aAnd Ar ^2bIndependent separately is 6 to 20 aromatic group for containing or do not contain non-reacted substituent carbonatoms.

6. the adhesive sheet of claim 1, it is characterized in that: this adhesive sheet contains full aromatic polyimide, and it calculates by following formula (4) and is 5.5 equivalents/kg-6.9 equivalent/kg with the acylimino concentration that equivalent/kg represents,

The unitary molecular weight of the every formation in acylimino concentration=2 * 1000/ (4).

7. the adhesive sheet of claim 1, it is characterized in that: thermal adhesive layer (C) contains Wholly aromatic polyamide, and wherein this Wholly aromatic polyamide contains the formation unit shown in the following formula (3):

Ar ^3aAnd Ar ^3bIndependent separately, be the aromatic group that to contain or do not contain non-reacted substituent carbonatoms be 6-20.

8. the adhesive sheet of claim 1, it is characterized in that: thermal adhesive layer (C) contains Wholly aromatic polyamide, and wherein this Wholly aromatic polyamide contains the formation unit shown in the following formula (3-1),

9. laminate (I), this laminate (I) is the laminate that forms in the last further laminated inorganic materials (B) of the thermal adhesive layer (C) of the adhesive sheet of claim 1, and its sequential laminating according to the base material that comprises full aromatic polyimide film (A), thermal adhesive layer (C) and inorganic materials (B) forms.

10. the laminate of claim 9 (I) is characterized in that: described inorganic materials (B) is silicon wafer.

11. the manufacture method of the laminate of claim 9 (I), it is characterized in that, has the thermal adhesive layer (C) that second-order transition temperature is the Wholly aromatic polyamide of 200 ℃ of-500 ℃ of characteristics by containing, under the pressure of 180 ℃-600 ℃ temperature and 0.001MPa-1000MPa, will contain the base material (A) of full aromatic polyimide film and inorganic materials (B) hot pressing 0.1 second-1 hour.

12. laminate (II); this laminate (II) is the laminate that last further laminated organism protective layer (E) of the base material (A) of the laminate (I) in claim 9 and object being treated layer (D) form, and its sequential laminating according to object being treated layer (D), organism protective layer (E), the base material (A) that contains full aromatic polyimide film, thermal adhesive layer (C) and inorganic materials (B) forms.

13. the laminate of claim 12 (II) is characterized in that: object being treated layer (D) is to have implemented to comprise that the circuit block that mixes impurity forms the semiconductor substrate of step, and inorganic materials (B) is for supporting to use substrate.

14. the manufacture method of the laminate of claim 12 (II); it is characterized in that: according to the sequential laminating of object being treated layer (D), organism protective layer (E), base material (A), thermal adhesive layer (C) and inorganic materials (B), hot pressing is 0.1 second-1 hour under the pressure of 180 ℃-600 ℃ temperature and 0.001MPa-1000MPa.