CN107636100A

CN107636100A - Bonding sheet

Info

Publication number: CN107636100A
Application number: CN201680030959.7A
Authority: CN
Inventors: 高野健; 菊池和浩; 杉野贵志
Original assignee: Lintec Corp
Current assignee: Lintec Corp
Priority date: 2015-09-01
Filing date: 2016-09-01
Publication date: 2018-01-26
Anticipated expiration: 2036-09-01
Also published as: KR101930197B1; JP6148805B1; KR20170136644A; KR102612643B1; TWI621684B; JP2017197749A; KR20180133949A; TW201821570A; CN110628349A; CN107636100B; TW201723119A; WO2017038917A1; JPWO2017038917A1; JP6853731B2; TWI734893B

Abstract

The present invention relates to a kind of bonding sheet (10), and it is used when the semiconductor element on to bonding sheet seals, and the bonding sheet (10) has：Base material (11), the adhesive phase (12) comprising adhesive and the oligomer sealant (13) being arranged between base material (11) and adhesive phase (12).

Description

Bonding sheet

Technical field

The present invention relates to bonding sheet.

Background technology

For the various characteristics of bonding sheet requirement used in the manufacturing process of semiconductor device.In recent years, for bonding Piece, it is desirable to will not also pollute the device used in manufacturing process, component even across the process for applying hot conditions and be attached The property of thing.Furthermore it is required that after the process of hot conditions, when bonding sheet is peeled off at room temperature adhesive residue in being glued Unfavorable condition as addendum etc. (so-called residual paste) is few, and peeling force is small.

A kind of the residual paste of adhesive is inhibited for example, having been recorded in patent document 1, for stably producing QFN (square flats It is flat without lead, Quad Flat Non-lead) semiconductor packages mask sheet.Herein below has been recorded in patent document 1：It is logical Cross using specific heat-resistant film and silicone adhesive category to make mask sheet, chip paste (ダイアタッチ) process and 150 DEG C~180 DEG C, the environment of 1 hour~6 hours are resistant in resin seal process.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2002-275435 publications

The content of the invention

Problems to be solved by the invention

In recent years, even being applied with more than 180 DEG C and also being used in the process of less than 200 DEG C such hot conditions Bonding sheet.It is known in the process of such high temperature, such as used the heat resistance compared with polyimide film etc. low and cheap Film (such as film of polyethylene terephthalate etc.) be used as base material in the case of, after process terminates from adherend When bonding sheet is peeled, the surface of adherend can be contaminated.The reason for as such pollution, it is believed that be due to as base material Contained low molecular weight compositions (oligomer) separate out on the surface of adherend in the resin film used.For example, to being pasted on When semiconductor element on the adhesive phase of bonding sheet carries out applying hot conditions in the process of resin seal, semiconductor element be present The surface of part is contaminated and produces the possibility of unfavorable condition in semiconductor devices.

It is an object of the invention to provide a kind of bonding sheet, the bonding sheet is even in the process that have passed through application hot conditions Afterwards, it is also possible to prevent the surface contamination of adherend.

The method solved the problems, such as

According to the mode of the present invention, there is provided a kind of bonding sheet, it is the semiconductor element progress on to bonding sheet Used during sealing, the bonding sheet has：Base material, the adhesive phase comprising adhesive and it is arranged at the base material and described Oligomer sealant between adhesive phase.

In the bonding sheet involved by a mode in the present invention, preferably described oligomer sealant is to seal oligomer The solidification envelope that the solidification of layer composition forms, the oligomer sealant are included with composition：Epoxide, polyester chemical combination Thing and multifunctional amino-compound.

In the bonding sheet involved by a mode in the present invention, preferably described oligomer sealant is included with composition： (A) more than 50 mass % and below 80 mass % bisphenol A type epoxy compound, more than (B) 5 mass % and below 30 mass % Petchem and more than (C) 10 mass % and below 40 mass % multifunctional amino-compound.

In the bonding sheet involved by a mode in the present invention, storage modulus of the preferably described base material at 100 DEG C is 1 ×10⁷More than Pa.

In the bonding sheet involved by a mode in the present invention, preferably described adhesive layer has acrylic adhesives Composition or silicone adhesive category composition.

The present invention a mode involved by bonding sheet in, preferably described acrylic pressure-sensitive adhesive compositions include with Acrylic copolymer of the 2-EHA as principal monomer.

In the bonding sheet involved by a mode in the present invention, preferably described silicone adhesive category composition, which includes, to be added Poly- type organic siliconresin.

In the bonding sheet involved by a mode in the present invention, preferably there is the oligomer on the two sides of the base material Sealant.

In the bonding sheet involved by a mode in the present invention, preferably described base material includes polyester resin.

According to the present invention it is possible to provide after it have passed through the process for applying hot conditions, can also prevent from being glued The bonding sheet of the surface contamination of addendum.

Brief description of the drawings

[Fig. 1] is the diagrammatic cross-section of the bonding sheet of first embodiment.

[Fig. 2A] is the figure of the part manufacturing process of the semiconductor device for the bonding sheet that explanation has used first embodiment.

[Fig. 2 B] is the figure of the part manufacturing process of the semiconductor device for the bonding sheet that explanation has used first embodiment.

[Fig. 2 C] is the figure of the part manufacturing process of the semiconductor device for the bonding sheet that explanation has used first embodiment.

[Fig. 2 D] is the figure of the part manufacturing process of the semiconductor device for the bonding sheet that explanation has used first embodiment.

[Fig. 2 E] is the figure of the part manufacturing process of the semiconductor device for the bonding sheet that explanation has used first embodiment.

[Fig. 3] is the diagrammatic cross-section of the bonding sheet of second embodiment.

Symbol description

10th, 10A ... bonding sheets

11 ... base materials

12 ... adhesive phases

13rd, 14 ... oligomer sealants

Embodiment

(first embodiment)

(bonding sheet)

Fig. 1 shows the diagrammatic cross-section of the bonding sheet 10 of present embodiment.

Bonding sheet 10 has base material 11, adhesive phase 12 and oligomer sealant 13.

Base material 11 has：The first base material face 11a and the second substrate surface 11b of side opposite with the first base material face 11a. Oligomer sealant 13 is provided between base material 11 and adhesive phase 12.In bonding sheet 10, preferably oligomer sealant 13 is folded Layer is on the 11a of the first base material face, and the first base material face 11a is covered by oligomer sealant 13.

The shape of bonding sheet 10 can take all shapes such as sheet, banding, label-like.

(base material)

Base material 11 is the component for supporting adhesive phase 12 and oligomer sealant 13.

As base material 11, sheet material such as synthetic resin film etc. can be used.As synthetic resin film, example can be enumerated Such as：Polyethylene film, polypropylene screen, polybutene film, polybutadiene film, polymethylpentene film, polychloroethylene film, vinyl chloride copolymer Film, polyethylene terephthalate film, poly (ethylene naphthalate) film, polybutylene terephthalate (PBT) film, polyurethane Film, vinyl-vinyl acetate copolymer film, ionomer resin film, ethene-(methyl) acrylic copolymer film, ethene-(methyl) Acrylate copolymer film, polystyrene film, polycarbonate membrane and polyimide film etc..In addition, as base material 11, can also lift Go out their cross linking membrane and stack membrane etc..

Base material 11 preferably comprises polyester resin, is more preferably formed by the material using polyester resin as principal component. In this specification, the so-called material using polyester resin as principal component, refer to that the quality of polyester resin is forming base material Material gross mass in shared ratio be more than 50 mass %.

As polyester resin, such as it is preferably selected from pet resin, poly terephthalic acid fourth Terephthalate resin, PEN resin, the copolymer resins of PBN resin and these resins In arbitrary resin, more preferably pet resin.

It is more preferably poly- as base material 11, preferably polyethylene terephthalate film or poly (ethylene naphthalate) film Ethylene glycol terephthalate film.As oligomer contained in polyester film, from polyester formative monomer, dimer and Trimer etc..

From the viewpoint of dimensional stability during processing, the lower limit of storage modulus of the base material 11 at 100 DEG C is preferably 1 ×10⁷More than Pa, more preferably 1 × 10⁸More than Pa.From the viewpoint of flexibility (adaptability) of operation, energy storage of the base material 11 at 100 DEG C The upper limit of modulus is preferably 1 × 10¹²Below Pa.It should be noted that in this manual, storage modulus is to use Dynamic Viscoelastic Property measure device, the value that is measured by torsional shear method under frequency 1Hz.Base material to be determined is cut into wide 5mm, long 20mm, Surveyed using determination of viscoelasticity instrument (TA Instruments companies manufacture, DMAQ800), under frequency 1Hz by stretch mode Fixed 100 DEG C storage modulus.

In order to improve the adaptation with oligomer sealant 13, primary coat processing, corona can be implemented to the first base material face 11a At least any of surface treatment in processing and corona treatment etc..It can also be applied on the first base material face 11a of base material 11 Cloth adhesive implements adhesion process.As the adhesive of the adhesion process for base material, for example, acrylic compounds, rubber The adhesive of glue class, organic silicon and carbamates etc..

The thickness of base material 11 is preferably more than 10 μm and less than 500 μm, more preferably more than 15 μm and less than 300 μm, entered One step is preferably more than 20 μm and less than 250 μm.

(adhesive phase)

The adhesive phase 12 of present embodiment includes adhesive composition.As the bonding contained by the adhesive composition Agent, it is not particularly limited, various adhesives can be applied to adhesive phase 12.As the adhesive contained by adhesive phase 12, For example, rubber-like, acrylic compounds, organic silicon, polyesters and carbamates.It should be noted that it is contemplated that Species of purposes and the adherend being stuck etc. selects the species of adhesive.Adhesive phase 12 preferably comprises acrylic compounds and glued Mixture composite or silicone adhesive category composition.

Acrylic pressure-sensitive adhesive compositions

In the case that adhesive phase 12 includes acrylic pressure-sensitive adhesive compositions, preferred acrylic pressure-sensitive adhesive compositions bag Containing the acrylic copolymer using 2-EHA as principal monomer.

In addition, in the case that adhesive phase 12 includes acrylic pressure-sensitive adhesive compositions, acrylic copolymer is preferably comprised Thing and bonding agent.Acrylic copolymer is preferably the copolymer using 2-EHA as principal monomer.Bonding Auxiliary agent preferably comprises the rubber type of material with reactive group as principal component.

In this manual, it is so-called to refer to using 2-EHA as principal monomer, from acrylic acid 2- The quality of the copolymer composition of ethylhexyl ratio shared in the gross mass of acrylic copolymer is more than 50 mass %. In the present embodiment, ratio of the copolymer composition in acrylic copolymer from 2-EHA is preferred For more than 50 mass % and below 95 mass %, more preferably more than 60 mass % and below 95 mass %, more preferably More than 80 mass % and below 95 mass %, it is still more preferably more than 85 mass % and below 93 mass %.If source It is more than 50 mass % in the ratio of the copolymer composition of 2-EHA, then bonding force will not become after heating It is high, it is easier to bonding sheet is peeled off from adherend, if more than 80 mass %, then is more prone to peel off.If source Be below 95 mass % in the ratio of the copolymer composition of 2-EHA, then can prevent initial stage closing force deficiency and Base material during heating is caused to deform, bonding sheet is peeled off from adherend due to its deformation.

The species and quantity of copolymer composition beyond 2-EHA in acrylic copolymer are without spy Do not limit.For example, as the second copolymer composition, preferably have reactive functional group contains monomer.As second The reactive functional groups of copolymer composition, after use in the case of the crosslinking agent of face narration, it is preferably capable and the crosslinking agent The functional group of reaction.As the reactive functional groups, such as it is preferably selected from carboxyl, hydroxyl, amino, substituted-amino and epoxy radicals In at least any of substituent, the more preferably at least any of substituent in carboxyl and hydroxyl, more preferably carboxyl.

As the monomer (carboxyl group-containing monomer) with carboxyl, for example,：Acrylic acid, methacrylic acid, crotonic acid, The ethylenically unsaturated carboxylic acids such as maleic acid, itaconic acid and citraconic acid.In carboxyl group-containing monomer, from the aspect of reactivity and copolymerizable, It is preferred that acrylic acid.Carboxyl group-containing monomer can be used alone, and can also combine two or more use.

As the monomer (hydroxyl monomer) with hydroxyl, for example,：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) third (methyl) hydroxyalkyl acrylates such as olefin(e) acid 3- hydroxybutyls and (methyl) acrylic acid 4- hydroxybutyls etc..Hydroxyl monomer In, from the aspect of the reactivity and copolymerizable of hydroxyl, preferred (methyl) acrylic acid 2- hydroxy methacrylates.Hydroxyl monomer can be single Solely use, two or more use can also be combined.It should be noted that " (methyl) acrylic acid " in this specification is to represent Used form of presentation when both " acrylic acid " and " methacrylic acid ", other similar terms are similarly.

As the acrylate with epoxy radicals, for example,：Glycidyl acrylate and methacrylic acid contracting Water glyceride.

As other copolymer compositions in acrylic copolymer, the carbon number that can enumerate alkyl is 2~20 (methyl) alkyl acrylate.As (methyl) alkyl acrylate, for example,：(methyl) ethyl acrylate, (first Base) propyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, methyl-prop Olefin(e) acid 2- ethylhexyls, (methyl) Isooctyl acrylate monomer, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) acrylic acid dodecyl Ester, (methyl) myristyl ester, (methyl) acrylic acid palm ester and (methyl) stearyl acrylate ester etc..These (methyl) third In olefin(e) acid Arrcostab, from the viewpoint of further raising cohesive, preferably the carbon number of alkyl is 2~4 (methyl) third Olefin(e) acid ester, more preferably (methyl) n-butyl acrylate.(methyl) alkyl acrylate can be used alone, and can also combine 2 kinds It is used above.

As other copolymer compositions in acrylic copolymer, for example, from selected from containing alkoxy It is (methyl) acrylate of alkyl, (methyl) acrylate with cycloaliphatic ring, (methyl) acrylate with aromatic rings, non- In the acrylamide of bridging property, (methyl) acrylate with tertiary amino of non-crosslinked property, vinyl acetate and styrene The copolymer composition of at least any of monomer.

As (methyl) acrylate containing alkoxyalkyl, for example,：(methyl) methoxyethyl first Ester, (methyl) methoxyethyl acrylate, (methyl) ethioxy methyl esters and (methyl) ethoxyethyl acrylate.

As (methyl) acrylate with cycloaliphatic ring, for example, (methyl) cyclohexyl acrylate.

As (methyl) acrylate with aromatic rings, for example, (methyl) phenyl acrylate.

As the acrylamide of non-crosslinked property, for example, acrylamide and Methacrylamide.

As (methyl) acrylate with tertiary amino of non-crosslinked property, for example, (methyl) acrylic acid (N, N- dimethylaminos) ethyl ester and (methyl) acrylic acid (N, N- dimethylamino) propyl ester.

As other copolymer compositions in acrylic copolymer, from improving the polarity of adhesive, make adaptation and viscous From the viewpoint of improving with joint efforts, the copolymer composition of the monomer with the ring comprising nitrogen-atoms is further preferably derived from.

As the monomer with the ring comprising nitrogen-atoms, can enumerate：NVP, N- ethylene methacrylics Base pyrrolidones, N- vinylpiperidones, N- vinyl piperazine, N- vinylpyrazines, N- vinyl pyrroles, N- vinyl miaows Azoles, N- polyvinyl morpholinones, N- caprolactams and N- (methyl) acryloyl morpholine etc..As with including nitrogen-atoms The monomer of ring, preferably N- (methyl) acryloyl morpholine.

These monomers can be used alone, and can also combine two or more use.

In the present embodiment, as the second copolymer composition, preferably carboxyl group-containing monomer or hydroxyl monomer, more preferably third Olefin(e) acid.Acrylic copolymer includes and derives from the copolymer composition of 2-EHA and being total to from acrylic acid In the case of polymers composition, from acrylic acid copolymer composition quality in acrylic copolymer gross mass it is shared Ratio is preferably below 1 mass %, more preferably more than 0.1 mass % and below 0.5 mass %.If the ratio of acrylic acid is Below 1 mass %, then it can prevent from including the crosslinking of acrylic copolymer in the case of crosslinking agent in adhesive composition Carry out too quickly.

Acrylic copolymer can derive from the copolymer composition containing monomer comprising two or more.For example, propylene Acid copolymer can be 3 yuan of system copolymers.In the case that acrylic copolymer is 3 yuan of system copolymers, preferred propylene Sour 2- ethylhexyls, carboxyl group-containing monomer and acrylic copolymer obtained from hydroxyl monomer copolymerization, the carboxyl group-containing monomer are excellent Elect acrylic acid as, hydroxyl monomer is preferably acrylic acid 2- hydroxy methacrylates.It is preferred that derive from propylene in acrylic copolymer The ratio of the copolymer composition of sour 2- ethylhexyls is more than 80 mass % and below 95 mass %, from the copolymerization of acrylic acid The mass ratio of thing composition is below 1 mass %, and remainder is the copolymer composition from acrylic acid 2- hydroxy methacrylates.

The weight average molecular weight (Mw) of acrylic copolymer is preferably more than 300,000 and less than 2,000,000, more preferably 600,000 Above and less than 1,500,000, more preferably more than 800,000 and less than 1,200,000.If the Weight-average molecular of acrylic copolymer It is more than 300,000 to measure Mw, then can not peeled off in adherend residual adhesive residue.If acrylic copolymer The weight average molecular weight Mw of thing is less than 2,000,000, then effectively can be attached in adherend.

The weight average molecular weight Mw of acrylic copolymer is by gel permeation chromatography (Gel Permeation Chromatography；GPC) method determines and is converted into the value of polystyrene standard.

Acrylic copolymer can be manufactured using above-mentioned various starting monomers, according to known method.

The copolymerization form of acrylic copolymer is not particularly limited, and for block copolymer, random copolymer or can connect Any of graft copolymer.

In the present embodiment, the containing ratio of acrylic copolymer is preferably more than 40 mass % in adhesive composition And 90 below mass %, more preferably more than 50 mass % and below 90 mass %.

Bonding agent preferably comprises the rubber type of material with reactive group as principal component.Adhesive composition includes During reactive bonding auxiliary agent, it is possible to reduce residual paste.In adhesive composition the containing ratio of bonding agent be preferably 3 mass % with Upper and below 50 mass %, more preferably more than 5 mass % and below 30 mass %.If bonding agent in adhesive composition Containing ratio be more than 3 mass %, then can suppress the generation of residual paste, if below 50 mass %, then can suppress to bond Power reduces.

In this manual, the so-called rubber type of material with reactive group that includes refers to have anti-as principal component The quality of the rubber type of material of answering property group ratio shared in bonding agent gross mass is more than 50 mass %.In this embodiment party In formula, the ratio of the rubber type of material in bonding agent with reactive group is preferably greater than 50 mass %, and more preferably 80 More than quality %.Bonding agent is preferably substantially made up of the rubber type of material with reactive group.

As reactive group, hydroxyl, NCO, amino, Oxyranyle, anhydride group, alcoxyl are preferably selected from One or more of base, acryloyl group and methylacryloyl functional group, more preferably hydroxyl.It is anti-possessed by rubber type of material Answering property group can be one kind, or two or more.Rubber type of material with hydroxyl can be further with above-mentioned anti- Answering property group.In addition, in 1 molecule for forming rubber type of material, the quantity of reactive group can be 1, or 2 More than.

As rubber type of material, it is not particularly limited, preferably the hydrogenation of polybutadiene resinoid and polybutadiene resinoid The hydride of thing, more preferably polybutadiene resinoid.

As polybutadiene resinoid, the resin with Isosorbide-5-Nitrae-repeat unit can be enumerated, with 1,2- repeat units Resin and the resin with both 1,4- repeat units and 1,2- repeat units.The polybutadiene tree of present embodiment The hydride of fat also includes the hydride of the resin with these repeat units.

The hydride of polybutadiene resinoid and polybutadiene resinoid preferably has reactive base respectively in two ends Group.The reactive group of two ends can be the same or different.The reactive group of two ends is preferably selected from hydroxyl, isocyanide One or more of perester radical, amino, Oxyranyle, anhydride group, alkoxy, acryloyl group and methylacryloyl function Group, more preferably hydroxyl.In the hydride of polybutadiene resinoid and polybutadiene resinoid, more preferably two ends are hydroxyl Base.

The adhesive composition of present embodiment containing foregoing acrylic copolymer and bonding preferably except helping Beyond agent, cross-linking agent obtained from making the composition for being combined with crosslinking agent crosslinking is also included.In addition, the solid of adhesive composition Composition preferably substantially as mentioned earlier by foregoing acrylic copolymer, bonding agent and cross-linking agents and Obtained cross-linking agent is formed.It is mentioned here substantially to refer to, it is micro miscellaneous in adhesive except being inevitably mixed into Beyond matter, the solid constituent of adhesive composition only includes the cross-linking agent.

In the present embodiment, as crosslinking agent, for example,：Isocyanates crosslinking agent, epoxies crosslinking agent, Aziridines crosslinking agent, metal-chelating species crosslinking agent, amine cross-linking agent and amino resins class crosslinking agent.These crosslinking agents can To be used alone, two or more use can also be combined.

In the present embodiment, from the viewpoint of the heat resistance and bonding force for improving adhesive composition, in these friendships Join in agent, preferably comprise crosslinking agent (isocyanates crosslinking agent) of the compound with NCO as principal component.Make For isocyanates crosslinking agent, for example,：2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, 1,3- benzene Diformazan group diisocyanate, 1,4- xylylene diisocyanates, diphenyl methane -4,4 '-diisocyanate, diphenylmethyl Alkane -2,4 '-diisocyanate, 3- Dimethyl diphenylmethanes diisocyanate, hexamethylene diisocyanate, isophorone two are different Cyanate, dicyclohexyl methyl hydride -4,4 '-diisocyanate, dicyclohexyl methyl hydride -2,4 '-diisocyanate and lysine isocyanide The polyisocyanate compounds such as acid esters.

In addition, the trimethylolpropane adduct type that polyisocyanate compound can be foregoing compound is modified Biuret form modifier or the cyamelide ester type modifier with triple polyisocyanate annulus obtained from thing and water reaction.

In this manual, the so-called crosslinking agent using the compound with NCO as principal component refers to, tool Have the quality of the compound of NCO form ratio shared in the gross mass of composition of crosslinking agent for 50 mass % with On.

In the present embodiment, the content of crosslinking agent is as follows in adhesive composition：Relative to acrylic copolymer 100 Mass parts, preferably more than 0.1 mass parts and below 20 mass parts, more preferably more than 1 mass parts and below 15 mass parts, enter One step is preferably more than 5 mass parts and below 10 mass parts.If the content of crosslinking agent is such model in adhesive composition In enclosing, then it can improve bonding between the layer (adhesive phase) comprising adhesive composition and adherend (such as base material) Property, it is used to make the stabilized curing time of adhesion characteristic after bonding sheet manufacture so as to shorten.

In the present embodiment, from the viewpoint of the heat resistance of adhesive composition, isocyanates crosslinking agent is more excellent Elect the compound (cyamelide ester type modifier) with triple polyisocyanate annulus as.Preferably with respect to acrylic copolymer Hydroxyl equivalent to coordinate the compound with triple polyisocyanate annulus more than 0.7 equivalent and below 1.5 equivalents.If have The use level of the compound of triple polyisocyanate annulus is more than 0.7 equivalent, then bonding force will not become too high after heating, and easily will Bonding sheet is peeled off, so as to reduce residual paste.If the use level of the compound with triple polyisocyanate annulus be 1.5 equivalents with Under, then it can prevent Initial adhesion from becoming too low or can prevent adhesiveness from reducing.

In the case that adhesive composition in present embodiment includes crosslinking agent, adhesive composition preferably further wraps Containing crosslinking accelerator.Crosslinking accelerator suitably selects to use preferably according to species of crosslinking agent etc..For example, adhesive composition bag Containing polyisocyanate compound as crosslinking agent in the case of, preferably further comprising Organometallic compounds such as organo-tin compounds Species crosslinking accelerator.

Silicone adhesive category composition

In the case that adhesive phase 12 includes organic silicon adhesive composition, silicone adhesive category composition preferably wraps Organic siliconresin containing polyaddition type.In this manual, by the silicone adhesive category composition comprising polyaddition type organic siliconresin Referred to as addition reaction-type silicone adhesive category composition.

Addition reaction-type silicone adhesive category composition includes host and crosslinking agent.Addition reaction-type organic silicon bonds Agent composition has advantages below：Only it can be used by the one-step solidification of low temperature, without 2 solidifications at high temperature.That is, Solidify for 2 times at a high temperature of conventional peroxide curing type silicone class adhesive is needed more than 150 DEG C.

Therefore, by using addition reaction-type silicone adhesive category composition, can manufacture at relatively low temperatures Bonding sheet, energy saving is excellent, also, can also manufacture bonding sheet 10 than relatively low base material 11 using heat resistance.Further, since Accessory substance will not be produced in solidification as peroxide curing type silicone class adhesive, therefore foul smell and corruption is also not present The problems such as erosion.

Addition reaction-type silicone adhesive category composition generally comprises：By organic siliconresin composition and organic silicon rubber into Host, the crosslinking agent containing silicon hydrogen-based (SiH yls) and the curing catalysts used as needed that the mixture divided is formed.

Organic siliconresin composition is after organochlorosilanes or organoalkoxysilane are hydrolyzed, to pass through dehydrating condensation The organopolysiloxane of network structure obtained from reaction.

Organic silicon rubber composition is the diorganopolysiloxanecompositions for having linear chain structure.

As organic group, methyl, ethyl, propyl group, fourth are similarly with organic siliconresin composition and organic silicon rubber composition Base, phenyl etc..Above-mentioned organic group is partly substituted by vinyl, hexenyl, pi-allyl, cyclobutenyl, pentenyl, octene Base, (methyl) acryloyl group, (methyl) acryloyl methyl, (methyl) acryloyl propyl group and insatiable hunger as cyclohexenyl group And group.It is preferred that the organic group with vinyl being industrially readily available.In addition reaction-type silicone adhesive category In composition, it is crosslinked by the addition reaction of unsaturated group and silicon hydrogen-based, the webbed structure of shape, so as to show Cohesive.

For the quantity of unsaturated group as vinyl, relative to organic group 100, usually 0.05 Above and less than 3.0, be preferably more than 0.1 and less than 2.5.By making the unsaturation relative to organic group 100 The quantity of group is set to more than 0.05, can prevent from declining with the reactivity of silicon hydrogen-based and become to be difficult to solidify, so as to assign Give appropriate bonding force.By making the quantity relative to the unsaturated group of organic group 100 be less than 3.0, adhesive Crosslink density increase, bonding force and cohesiveness become big, can prevent from bringing harmful effect to being attached face.

As such organopolysiloxane noted earlier, specifically, there is what Shin-Etsu Chemial Co., Ltd manufactured KS-3703 (quantity of vinyl 100 relative to methyl is 0.6), Dow Corning Toray Co., Ltd. (Dow Corning Toray Co., Ltd) manufacture BY23-753 (quantity of vinyl is 0.1 relative to methyl 100) and BY24-162 (second The quantity of alkenyl 100 relative to methyl is 1.4) etc..Furthermore it is also possible to manufactured using Dow Corning Toray Co., Ltd. SD4560PSA, SD4570PSA, SD4580PSA, SD4584PSA, SD4585PSA, SD4587L and SD4592PSA etc..

As previously described, the organopolysiloxane as organic siliconresin composition is generally mixed with organic silicon rubber composition and made With as organic silicon rubber composition, the KS-3800 (quantity of vinyl of Shin-Etsu Chemial Co., Ltd's manufacture can be enumerated Be 7.6 relative to methyl 100), (quantity of vinyl is relative to first by the BY24-162 of Dow Corning Toray Co., Ltd.'s manufacture 100, base is 1.4), (quantity of vinyl is relative to methyl 100 by BY24-843 (not having unsaturated group) and SD-7292 Individual is 5.0) etc..

The concrete example of such addition reaction-type organosilicon noted earlier is documented in such as Japanese Unexamined Patent Publication 10-219229 In publication.

Crosslinking agent coordinates in such a way：Relative to the vinyl of organic siliconresin composition and organic silicon rubber composition this The unsaturated group of sample 1 so that the hydrogen atom being bonded on the silicon atoms is usually more than 0.5 and less than 10, is preferably 1 More than individual and less than 2.5, by making the hydrogen atom of bonding on the silicon atoms to prevent as vinyl for more than 0.5 The reaction of unsaturated group and silicon hydrogen-based completely without and cause to solidify it is bad, by making the hydrogen atom of bonding on the silicon atoms For less than 10, crosslinking agent unreacted can be prevented and left behind, so as to bring harmful effect to being attached face.

Addition reaction-type silicone adhesive category composition preferably containing foregoing addition reaction-type organosilicon into While dividing (host being made up of organic siliconresin composition and organic silicon rubber composition) and crosslinking agent, also containing solidification catalysis Agent.

The curing catalysts be in order to promote unsaturated group in organic siliconresin composition and organic silicon rubber composition with The silicon hydrogenation of Si-H bases in crosslinking agent and use.

As curing catalysts, platinum group catalyst, i.e. chloroplatinic acid, the alcoholic solution of chloroplatinic acid, chloroplatinic acid and alcohol can be enumerated The reactant of solution, the reactant of chloroplatinic acid and olefin(e) compound, chloroplatinic acid are anti-with the silicone compounds containing vinyl Answer thing, platinum-olefin complex, platinum-siloxanes complex containing vinyl and platinum-phosphorus complex etc..Before The concrete example of such curing catalysts described in face is documented in such as Japanese Unexamined Patent Publication 2006-28311 publications and Japanese Unexamined Patent Publication In 10-147758 publications.

More specifically, as commercially available product, SRX-212 and SHIN-ETSU HANTOTAI that Dow Corning Toray Co., Ltd. manufactures can be enumerated Learn PL-50T of Industrial Co., Ltd's manufacture etc..

Relative to the total amount of organic siliconresin composition and organic silicon rubber composition, the use level of curing catalysts is logical in terms of platinum Often it is more than 5 mass ppm and below 2000 mass ppm, preferably more than 10 mass ppm and below 500 mass ppm, by making The use level of curing catalysts is calculated as more than 5 mass ppm with platinum, can prevent curability from reducing and declining crosslink density, also It is to say, can prevents bonding force and cohesiveness (confining force) from declining, 2000 matter are calculated as with platinum by making the use level of curing catalysts Below ppm is measured, can prevent cost from improving and the stability of adhesive phase can be kept, and the solidification being excessively used can be prevented Catalyst brings harmful effect to being attached face.

In addition reaction-type silicone adhesive category composition, by coordinating foregoing each composition, even in normal Also bonding force is shown under temperature, from the aspect of the stability of bonding force, preferably by addition reaction-type silicone adhesive category group Compound is coated on base material 11 or stripping film described below, after base material 11 is bonded with stripping film, is heated or irradiates work Property energy line promotes organic siliconresin composition and cross-linking reaction of the organic silicon rubber composition in the presence of crosslinking agent.

Heating-up temperature during using heating to promote cross-linking reaction is usually more than 60 DEG C and less than 140 DEG C, is preferably 80 More than DEG C and less than 130 DEG C.By being heated more than 60 DEG C, can prevent organic siliconresin composition and organic silicon rubber into The crosslinking divided is insufficient and causes bonding force insufficient, by being heated below 140 DEG C, can prevent substrate sheets from producing heat and receiving Contracting fold, deterioration occurs, changes colour.

Irradiation active energy ray in the case of promoting cross-linking reaction, in electromagnetic wave or charged particle beam, can utilize Active energy ray with the quantum of energy, i.e. ultraviolet isoreactivity light or electron beam etc. can be utilized.Irradiating electron beam is crosslinked In the case of, it is not necessary to Photoepolymerizationinitiater initiater, but in the case where irradiation ultraviolet isoreactivity light is crosslinked, light preferably be present Polymerization initiator.

Photoepolymerizationinitiater initiater during as irradiation ultraviolet, is not particularly limited, can from it is conventional be generally used for it is ultraviolet Arbitrary Photoepolymerizationinitiater initiater is suitably selected to use in the Photoepolymerizationinitiater initiater of line gel-type resin.Trigger as the photopolymerization Agent, for example,：Benzoin class, benzophenone, acetophenones, Alpha-hydroxy ketone, alpha-amido ketone, α-diones, α-diketone dialkyl acetal (α-diketone dialkyl acetal) class, Anthraquinones, thioxanthene ketone class, other compounds etc..

These Photoepolymerizationinitiater initiaters may be used singly or in combination of two or more use.In addition, relative to as master The mass parts of total amount 100 of above-mentioned addition reaction-type silicone ingredients and crosslinking agent that agent uses, the usage amount of Photoepolymerizationinitiater initiater Scope choosing generally more than 0.01 mass parts and below 30 mass parts, preferably more than 0.05 mass parts and below 20 mass parts It is fixed.

It is crosslinked by heating or irradiating active energy ray, the bonding sheet with stable bonding force can be obtained.

The accelerating potential for irradiating electron beam when being crosslinked as the electron beam of one of active energy ray is usually 130kV Above and below 300kV, be preferably more than 150kV and below 250kV., can be to prevent by irradiating more than 130kV accelerating potential Only the crosslinking deficiency of organic siliconresin composition and organic silicon rubber composition and cause the insufficient situation of bonding force, by with Below 300kV accelerating potential irradiating electron beam, it can prevent adhesive phase and substrate sheets from deteriorating, changing colour.Electron beam current Preferred scope is more than 1mA and below 100mA.

The dosage of the electron beam of irradiation be preferably more than 1Mrad and below 70Mrad, more preferably more than 2Mrad and Below 20Mrad.By that with more than 1Mrad dose irradiation electron beam, can prevent adhesive phase and substrate sheets from deteriorating, discoloration, from And can prevent because of crosslinking deficiency and caused by the insufficient situation of cohesive.By with below 70Mrad dose irradiation electronics Beam, can prevent adhesive phase deterioration, change colour and caused cohesiveness declines, so as to prevent substrate sheets deterioration, shrink.

Exposure during as irradiation ultraviolet, can suitably be selected, light quantity 100mJ/cm²Above and 500mJ/cm²With Under, illumination 10mW/cm²Above and 500mW/cm²Below.

In order to prevent hindering to react due to oxygen, preferably heated under nitrogen atmosphere and the irradiation of active energy ray.

The thickness of adhesive phase 12 can suitably determine according to the purposes of bonding sheet 10.In the present embodiment, adhesive phase 12 thickness is preferably more than 5 μm and less than 60 μm, more preferably more than 10 μm and less than 50 μm.If the thickness of adhesive phase 12 Spend it is thin, worry adhesive phase 12 can not follow semiconductor chip circuit face bumps and produce gap.Such as layer insulation Material and sealing resin etc. enter its gap, and the wiring connecting electrode in chip circuit face is lined with and may be blocked.It is if viscous The thickness of mixture layer 12 is more than 5 μm, then adhesive phase 12 easily follows the bumps in chip circuit face, so as to prevent gap Generation.In addition, if the thickness of adhesive phase 12 is blocked up, semiconductor chip is sunk in adhesive phase, semiconductor chip portion Divide and be possible to produce difference of height with the resin portion of sealing semiconductor chips.If difference of height as producing, when connecting up again Wiring is possible to that broken string can be produced.If the thickness of adhesive phase 12 is less than 60 μm, difference of height is not likely to produce.

In the present embodiment, can contain in the range of effect of the present invention is not damaged, in adhesive composition other Composition.As the other compositions that can contain in adhesive composition, for example,：Organic solvent, fire retardant, thickening Agent, ultra-violet absorber, light stabilizer, antioxidant, antistatic agent, preservative, mould inhibitor, plasticizer, defoamer, colouring agent, Filler and Wetting-transition agent etc..

Dimethyl silicone polymer and polymethyl-benzene base silicon can be included in addition reaction-type silicone adhesive category composition Non-reacted polysiloxane is as additive as oxygen alkane.

(oligomer sealant)

Oligomer sealant 13 is to be used to prevent low molecular weight compositions (oligomer) to be immersed in the layer of adhesive phase 12.Bonding When piece 10 is exposed to hot conditions, it is believed that the oligomer included in base material 11 is separated out in the surface of base material 11, not in heating In the case that oligomer sealant 13 is set, immersed to adhesive phase 12, and then adhesive phase is reached through adhesive phase 12 12 surface.Oligomer sealant 13 is preferably prevented also from oligomeric under more than 180 DEG C and less than 200 DEG C of hot conditions Immersion of the thing to adhesive phase 12.

For the material of oligomer sealant 13, as long as oligomer can be prevented to be immersed in adhesive phase 12, It is not particularly limited.

For example, oligomer sealant 13 is preferably the solidification envelope for forming the solidification of oligomer sealant composition, institute State oligomer sealant composition and include (A) epoxide, (B) petchem and (C) multifunctional amino-compound. In order to promote curing reaction, oligomer sealant composition can further contain (D) acidic catalyst.

(A) epoxide

(A) epoxide is preferably bisphenol A type epoxy compound.As bisphenol A type epoxy compound, can enumerate double Phenol A glycidol ethers etc..The weight average molecular weight (Mw) of bisphenol A type epoxy compound is preferably 1 × 10⁴Above and 5 × 10⁴Below. If the weight average molecular weight (Mw) of bisphenol A type epoxy compound is 1 × 10⁴More than, then it can obtain as crosslinking necessary to film Density, easily prevent the precipitation of oligomer.If weight average molecular weight (Mw) is 5 × 10⁴Hereinafter, then it can prevent envelope from becoming Firmly.Weight average molecular weight Mw is to be determined by gel permeation chromatography (GPC) method and be converted into the value of polystyrene standard.

(B) petchem

As (B) petchem, it is not particularly limited, can the suitably selection use from known petchem. As petchem, specifically by resin obtained from the condensation reaction of polyalcohol and polyacid, can enumerate non-transformed Property petchem and convertibility petchem etc., the non-transformed property petchem is the condensation of binary acid and dihydric alcohol Thing or the compound obtained from non-drying oil aliphatic acid etc. is modified, the convertibility petchem is binary acid and three The condensation product of alcohol more than first.In the present embodiment, any compound in these petchems can be used.

As the polyalcohol of the raw material as (B) petchem, can enumerate more than dihydric alcohol, trihydroxylic alcohol and quaternary Polyalcohol.

As dihydric alcohol, for example,：Ethylene glycol, diethylene glycol, triethylene glycol, propane diols, trimethylene, Tetramethylene glycol and neopentyl glycol.

As trihydroxylic alcohol, for example,：Glycerine, trimethylolethane and trimethylolpropane.

As polyalcohol more than quaternary, for example,：Two glycerine, triglycerin, pentaerythrite, dipentaerythritol, Mannitol and sorbierite.

Polyalcohol may be used alone, can also be used in combination of two or more kinds.

As polyacid, for example,：Aromatic polyvalent acid, aliphatic saturated polybasic acid, aliphatic are unsaturated more First acid and the polyacid obtained from Diels-Alder reaction.

It is sour as aromatic polyvalent, for example,：Phthalic anhydride, terephthalic acid (TPA), M-phthalic acid and partially Benzenetricarboxylic anhydride.

As aliphatic saturated polybasic acid, for example,：Butanedioic acid, adipic acid and decanedioic acid.

As aliphatic unsaturation polyacid, for example,：Maleic acid, maleic anhydride, fumaric acid, itaconic acid and lemon Health acid anhydrides.

As the polyacid obtained from Diels-Alder reaction, for example,：Cyclopentadiene-maleic acid Acid anhydride addition product, terpenes-maleic anhydride adduct and rosin-maleic acid anhydride addition product.

Polyacid may be used alone, can also be used in combination of two or more kinds.

Non-drying oil aliphatic acid as modifying agent etc., for example,：Octanoic acid, laurate, palmitic acid, stearic acid, Oleic acid, linoleic acid, leukotrienes, eleostearic acid, ricinoleic acid, dehydrated castor alkyd or coconut oil, linseed oil, tung oil, castor-oil plant Oil, dehydrated castor oil, soybean oil, safflower oil and their aliphatic acid etc..These modifying agent can be used alone, and also may be used To combine two or more use.In addition, as petchem, may be used alone, can also be used in combination of two or more kinds.

(B) petchem preferably has the petchem of the active hydrogen group of the basic point as cross-linking reaction.As Active hydrogen group, for example, hydroxyl, carboxyl and amino.Petchem particularly preferably has the polyester chemical combination of hydroxyl Thing.The hydroxyl value of petchem is preferably more than 5mgKOH/g and below 500mgKOH/g, more preferably more than 10mgKOH/g and Below 300mgKOH/g.

(B) number-average molecular weight (Mn) of petchem be preferably more than 500 and less than 10000, more preferably 1000 with It is upper and less than 5000.Above-mentioned number-average molecular weight is to be determined by gel permeation chromatography (GPC) method and be converted into polystyrene standard Value.

(B) glass transition temperature Tg of petchem is preferably more than 0 DEG C and less than 50 DEG C.

, can by using number-average molecular weight (Mn) and the petchem of glass transition temperature Tg with above range To assign the flexibility of appropriateness to the solidification envelope for forming oligomer sealant 13.Glass transition temperature Tg is according to JIS K 7121 standards, device, the temperature range measure extrapolation glass at -80 DEG C to 250 DEG C are determined using power back-off means of differential scanning calorimetry Glass transition start temperature, so as to obtain glass transition temperature Tg.

(C) multifunctional amino-compound

As (C) multifunctional amino-compound, such as melamine compound, urea compounds, benzene birds droppings can be used Amines and Diamines.

As melamine compound, for example, HMMM, methylated melamine Compound and butylated melamines compound.

As urea compounds, for example, methylated urea compound and butylated urea compound.

As benzene birds droppings amines, for example, benzene birds droppings amines and the butylation benzene birds droppings amination of methylating Compound.

As Diamines, for example, ethylenediamine, tetra-methylenedimine, hexamethylene diamine, N, N '-diphenyl second Diamines and terephthaldehyde's base diamines.

From the viewpoint of curability, as (C) multifunctional amino-compound, preferably HMMM.

(D) acidic catalyst

As acidic catalyst (D), for example, hydrochloric acid and p-methyl benzenesulfonic acid.

Solidify envelope

In the present embodiment, preferably oligomer sealant 13 be by following oligomer sealant composition solidification and Into solidification envelope, the oligomer sealant with composition include (A) bisphenol A type epoxy compound, (B) petchem and (C) multifunctional amino-compound, and their fit rate is respectively more than (A) 50 mass % and below 80 mass %, (B) 5 matter Measure more than % and below 30 mass % and more than (C) 10 mass % and below 40 mass %.In oligomer sealant composition In the case of middle cooperation (D) acidic catalyst, preferably the content of (D) composition is set to more than 1 mass % and below 5 mass %.

The solidification envelope formed using the oligomer sealant composition solidification for the fit rate for making above range, Ke Yili The effect for preventing that oligomer from immersing to adhesive phase 12 is effectively improved with oligomer sealant 13.

As the more specifically example of the oligomer sealant composition of present embodiment, for example, it is following this The example of the oligomer sealant composition of sample, but the present invention is not limited to such example.

As one of the oligomer sealant composition of present embodiment, can enumerate comprising (A) epoxide, (B) the oligomer sealant composition of petchem, (C) multifunctional amino-compound and (D) acidic catalyst, wherein, (A) epoxide is bisphenol A type epoxy compound, and (C) multifunctional amino-compound is melamine compound.

As one of the oligomer sealant composition of present embodiment, can enumerate comprising (A) epoxide, (B) the oligomer sealant composition of petchem, (C) multifunctional amino-compound and (D) acidic catalyst, wherein, (A) epoxide be bisphenol A type epoxy compound, (A) epoxide weight average molecular weight (Mw) be 1 × 10⁴Above and 5 ×10⁴Hereinafter, (C) multifunctional amino-compound is melamine compound.

As one of the oligomer sealant composition of present embodiment, can enumerate comprising (A) epoxide, (B) the oligomer sealant composition of petchem, (C) multifunctional amino-compound and (D) acidic catalyst, wherein, (A) epoxide is bisphenol A type epoxy compound, the number-average molecular weight (Mn) of (B) petchem for more than 500 and Less than 10000, the glass transition temperature Tg of (B) petchem is more than 0 DEG C and less than 50 DEG C, (C) multifunctional amination Compound is melamine compound.

As one of the oligomer sealant composition of present embodiment, can enumerate comprising (A) epoxide, (B) the oligomer sealant composition of petchem, (C) multifunctional amino-compound and (D) acidic catalyst, wherein, (A) epoxide be bisphenol A type epoxy compound, (A) epoxide weight average molecular weight (Mw) be 1 × 10⁴The above 5 × 10⁴Hereinafter, the number-average molecular weight (Mn) of (B) petchem is more than 500 and less than the 10000, glass of (B) petchem It is more than 0 DEG C and less than 50 DEG C to change transition temperature Tg, and (C) multifunctional amino-compound is melamine compound.

The thickness of oligomer sealant

The thickness of oligomer sealant 13 is preferably more than 50nm and below 500nm, more preferably more than 80nm and 300nm Below.If the thickness of oligomer sealant 13 is more than 50nm, it can effectively prevent oligomer to adhesive phase 12 Immerse.If the thickness of oligomer sealant 13 is below 500nm, by bonding sheet 10 with web-like on core when, Easily it is wound.As the material of core, for example, papery, plastics system and metal system.

The bonding sheet 10 of present embodiment preferably shows bonding force as described below after the heating.First, by bonding sheet 10 Adherend (copper foil or polyimide film) is pasted on, is heated under conditions of 100 DEG C and 30 minutes, then at 180 DEG C and 30 Heat under conditions of minute, further heated under conditions of 190 DEG C and 1 hour, the phase of adhesive phase 12 preferably so after heating It is respectively relative to the bonding force of polyimide film at room temperature for copper foil bonding force at room temperature and adhesive phase 12 More than 0.7N/25mm and below 2.0N/25mm.If it is more than 0.7N/25mm to have carried out the bonding force after such heating, Bonding sheet 10 is peeled off from adherend in the case of can preventing base material or adherend in heating there occurs deformation.Separately Outside, if the bonding force after heating is below 2.0N/25mm, peeling force will not become too high, easily by bonding sheet 10 from quilt Peeled off on bur.It should be noted that in this manual, room temperature refers to the temperature of more than 22 DEG C and less than 24 DEG C.At this In specification, bonding force is measured by 180 ° of stripping methods, under draw speed 300mm/ points, the width 25mm of bonding sheet Value.

As the more specifically example of the adhesive composition of present embodiment, for example, following such bonding The example of agent composition, but the present invention is not limited to such example.

As one of the adhesive composition of present embodiment, it can enumerate and be helped comprising acrylic copolymer, bonding Agent and the adhesive composition of crosslinking agent, wherein, the acrylic copolymer is at least by 2-EHA, containing carboxylic Acrylic copolymer obtained from base monomer and hydroxyl monomer copolymerization, the bonding agent, which includes, has reactive group Rubber type of material as principal component, the crosslinking agent is isocyanates crosslinking agent.

As one of the adhesive composition of present embodiment, it can enumerate and be helped comprising acrylic copolymer, bonding Agent and the adhesive composition of crosslinking agent, wherein, the acrylic copolymer is at least by 2-EHA, containing carboxylic Acrylic copolymer obtained from base monomer and hydroxyl monomer copolymerization, the bonding agent are the hydrogen that two ends are hydroxyl Change polybutadiene, the crosslinking agent is isocyanates crosslinking agent.

As one of the adhesive composition of present embodiment, it can enumerate and be helped comprising acrylic copolymer, bonding Agent and the adhesive composition of crosslinking agent, wherein, the acrylic copolymer is at least by 2-EHA, propylene Acrylic copolymer obtained from acid and the copolymerization of acrylic acid 2- hydroxy methacrylates, the bonding agent, which includes, has reactive base For the rubber type of material of group as principal component, the crosslinking agent is isocyanates crosslinking agent.

As one of the adhesive composition of present embodiment, it can enumerate and be helped comprising acrylic copolymer, bonding Agent and the adhesive composition of crosslinking agent, wherein, the acrylic copolymer is at least by 2-EHA, propylene Acrylic copolymer obtained from acid and the copolymerization of acrylic acid 2- hydroxy methacrylates, the bonding agent are the hydrogen that two ends are hydroxyl Change polybutadiene, the crosslinking agent is isocyanates crosslinking agent.

In these examples of the adhesive composition of present embodiment, preferably aforesaid propylene acid copolymer is at least will 2-EHA, carboxyl group-containing monomer, hydroxyl monomer and with nitrogen atom ring monomer copolymerization obtained from third Olefin(e) acid analog copolymer.

In these examples of the adhesive composition of present embodiment, preferably aforesaid propylene acid copolymer is at least will Third obtained from 2-EHA, acrylic acid, acrylic acid 2- hydroxy methacrylates and the copolymerization of N- (methyl) acryloyl morpholine Olefin(e) acid analog copolymer.

In these examples of the adhesive composition of present embodiment, the source preferably in aforesaid propylene acid copolymer In the copolymer composition of 2-EHA ratio for more than 80 mass % and below 95 mass %, from containing carboxyl The mass ratio of the copolymer composition of monomer is below 1 mass %, remainder is other copolymer compositions, as copolymer into Point, preferably comprise the copolymer composition from hydroxyl monomer.

(manufacture method of bonding sheet)

The manufacture method of bonding sheet 10 is not particularly limited.

For example, bonding sheet 10 can pass through following process to manufacture.

First, oligomer sealant composition is coated with the first base material face 11a of base material 11, forms film.Then, The film is heated and is solidified, form the solidification envelope as oligomer sealant 13.As the condition being heating and curing, it is, for example, Within more than 120 DEG C and less than 170 DEG C, more than 5 seconds and 5 minutes.

Then, the coating adhesive composition on oligomer sealant 13, film is formed.Then, the dried coating film, shape are made Composite adhesives layer 12.

It is coated with oligomer sealant composition and forms situation and the coating adhesive combination of oligomer sealant 13 Thing and in the case of forming adhesive phase 12, preferably with organic solvent to oligomer sealant composition and adhesive composition It is diluted, is used after coating liquid is made.

As organic solvent used in coating liquid is prepared, it is not particularly limited.As organic solvent, example can be enumerated Such as：Fragrant same clan's solvent, aliphatic category solvent, esters solvent, ketones solvent and alcohols solvent., can as fragrant same clan's solvent To enumerate such as benzene, toluene and dimethylbenzene.As aliphatic category solvent, for example, n-hexane and normal heptane.As ester Class solvent, for example, ethyl acetate and butyl acetate.As ketones solvent, for example, MEK, methyl are different Butyl ketone, cyclohexanone and cyclopentanone.As alcohols solvent, for example, isopropanol and methanol.

As coating method, for example,：Spin-coating method, spraying process, stick coating method, scraper for coating method, roller knife rubbing method, Rolling method, scraper plate rubbing method, die coating method and gravure coating process etc..

In order to prevent organic solvent and low boiling point component from residuing in oligomer sealant 13 and adhesive phase 12, preferably exist Film is heated after coating liquid is coated on base material 11 and makes its drying.

In the case of coordinating crosslinking agent in adhesive composition, in order that cross-linking reaction carries out and improves cohesiveness, Preferred pair film is heated.

(use of bonding sheet)

Bonding sheet 10 uses when being sealed to semiconductor element.Bonding sheet 10 is preferably to being pasted on bonding sheet 10 The semiconductor element of state of the state without being mounted on metal ieadf iotaame use when being sealed.Specifically, glue Piece 10 is closed preferably to use when the semiconductor element of the state to being pasted on adhesive phase 12 seals, rather than to carrying Used when the semiconductor element of metal ieadf iotaame is sealed.Semiconductor element is entered as without using metal ieadf iotaame The form of row encapsulation, can enumerate Board level packaging (Panel Scale Package；) and wafer-level packaging (Wafer Level PSP Package；WLP).

Bonding sheet 10 is preferred for following technique, and the technique has following process：Make the frame structure formed with multiple opening portions Part is pasted on the process of bonding sheet 10, semiconductor chip is pasted on the adhesive exposed using the opening portion of above-mentioned frame component Process on layer 12, coat with sealing resin the process of above-mentioned semiconductor chip and make the work of above-mentioned sealing resin heat cure Sequence.

(manufacture method of semiconductor device)

The method that semiconductor device is manufactured for the bonding sheet 10 using present embodiment illustrates.

Fig. 2A~Fig. 2 E show the schematic diagram of the manufacture method of the semiconductor device for illustrating present embodiment.

Implement following process in the manufacture method of the semiconductor device of present embodiment：Make formed with multiple opening portions 21 Frame component 20, which is pasted on the process (bonding sheet adhering processes) of bonding sheet 10, is pasted on semiconductor chip CP utilizes frame component 20 Opening portion 21 and process (bonding (bonding) process) on the adhesive phase 12 that exposes, coated with sealing resin 30 and partly led Body chip CP process (sealing process), the process (heat curing processes) for making the heat cure of sealing resin 30 and after heat cure The process (stripping process) that bonding sheet 10 is peeled off.As needed, can also implement to make stiffener after heat curing processes 40 are pasted on the process (stiffener adhering processes) on the seal 50 sealed using sealing resin 30.Each operation is entered below Row explanation.

Bonding sheet adhering processes

Fig. 2A is illustrated that the schematic diagram of the process of the adhesive phase 12 for making frame component 20 be pasted on bonding sheet 10.

Frame component 20 in present embodiment is formed as clathrate, and has multiple opening portions 21.Frame component 20 preferably by Material with heat resistance is formed.As the material of frame component 20, for example,：The metal such as copper and stainless steel, Yi Jiju Heat-resistant resin such as imide resin and glass epoxy resin etc..

Opening portion 21 is the hole for the surface back side for penetrating frame component 20.For the shape of opening portion 21, as long as energy Enough shapes that semiconductor chip CP is accommodated in inframe, are not particularly limited.As long as the hole depth of opening portion 21 also can Semiconductor chip CP is stored, is not particularly limited.

Bond process

Fig. 2 B are illustrated that the schematic diagram of the process for illustrating to make semiconductor chip CP be pasted on adhesive phase 12.

After bonding sheet 10 is pasted on frame component 20, in each opening portion 21, adhesive phase 12 corresponds to opening portion 21 Shape and expose.Semiconductor chip CP is set to be pasted on the adhesive phase 12 of each opening portion 21.When pasting semiconductor chip CP, So that its circuit face is covered by adhesive phase 12.

For manufacture for semiconductor chip CP, manufactured by implementing for example following process：To formed with electricity The back of the body grinder sequence and the cutting action by semiconductor wafer singualtion that the back side of the semiconductor wafer on road is ground.Cutting Cut in process, semiconductor wafer is pasted on the bond layer of cutting sheet, use the shearing devices such as slicer (dicing saw) By semiconductor wafer singualtion, semiconductor chip CP (semiconductor element) is thus obtained.

Cutter device is not particularly limited, and can use known cutter device.In addition, do not have for the condition of cutting yet It is particularly limited to.It should be noted that it can also be cut using laser cutting method or stealthy patterning method etc. instead of using cutting knife The method cut.

After cutting action, it is possible to implement cutting sheet is stretched, so as to expand the interval between multiple semiconductor chip CP Spread sheet process.By implementing spread sheet process, semiconductor chip CP can be picked up using conveyers such as opening folders.In addition, By implementing spread sheet process, bonding force of the cutting sheet to bond layer can be reduced, make semiconductor chip CP become to easily pick up.

In the case of coordinating energy line polymerizable compound in the adhesive composite or bond layer of cutting sheet, from The substrate side of cutting sheet solidifies energy line polymerizable compound bond layer irradiation energy line.Make energy line polymerism After compound solidification, the cohesiveness of bond layer improves, and can make the bonding force of bond layer reduce.As energy line, Ke Yiju Go out such as ultraviolet (UV) and electron beam (EB), preferably ultraviolet.The irradiation of energy line can paste semiconductor wafer it Afterwards, any stage before the stripping (pickup) of semiconductor chip is carried out.For example, energy can be irradiated before being cut or after cutting Measure line, can also after spread sheet process irradiation energy line.

Sealing process and heat curing processes

Fig. 2 C are illustrated that close for illustrating to carry out the semiconductor chip CP and frame component 20 that are pasted onto on bonding sheet 10 The schematic diagram of the process of envelope.

The material of sealing resin 30 is heat-curing resin, and for example, epoxy resin etc..As sealing resin It can contain in 30 epoxy resin used such as phenolic resin, elastomer, inorganic filling material and curing accelerator.

The method that semiconductor chip CP and frame component 20 are coated with sealing resin 30 is not particularly limited.

In the present embodiment, enumerate exemplified by the mode for the sealing resin 30 for having used sheet to illustrate.Place piece The sealing resin 30 of shape simultaneously makes it cover semiconductor chip CP and frame component 20, sealing resin 30 is heating and curing and is formed sealing Resin bed 30A.So, semiconductor chip CP and frame component 20 are embedded in sealing resin layer 30A.Use the close of sheet In the case of sealing resin 30, preferably sealed by double of conductor chip CP of vacuum layer platen press and frame component 20.It is true by this Dead level platen press, it can prevent from producing space between semiconductor chip CP and frame component 20.Using the heating temperature of vacuum layer platen press It is, for example, more than 80 DEG C and less than 120 DEG C to spend condition and range.

In sealing process, the sealing resin 30 of sheet can be used by the resin sheet branch of polyethylene terephthalate etc. Support the laminated sheet formed.In this case, after placing laminated sheet in the way of covering semiconductor chip CP and frame component 20, will set Fat piece is peeled off from sealing resin 30, sealing resin 30 is heating and curing.As such laminated sheet, for example,：ABF Film (manufacture of Ajinomoto Fine-Techno companies).

As the method sealed to semiconductor chip CP and frame component 20, shifting formwork method (トラ Application ス Off ァ can be used ーモー Le De method).In this case, for example it is pasted onto semiconductor core on bonding sheet 10 in the mould inside storage of sealing device Piece CP and frame component 20.The resin material of mobility is injected to the inside of the mould, solidifies resin material.The situation of shifting formwork method Under, the condition of heating and pressure is not particularly limited.It is by more than 150 DEG C as one of the usual conditions in shifting formwork method The pressure of temperature, more than 4MPa and below 15MPa is kept for more than 30 seconds and less than 300 seconds.Then, pressurization is released, from sealing Solidfied material is taken out in device, is stood in an oven, keeps more than 150 DEG C of temperature more than 2 hours and less than 15 hours.Such one Come, semiconductor chip CP and frame component 20 are sealed.

In the case of using the sealing resin 30 of sheet in above-mentioned sealing process, the thermosetting of sealing resin 30 can be made Implement the first heating suppression process before the process (heat curing processes) of change.In the first heating suppression process, from two sides plate Shape component clamps the semiconductor chip CP covered by sealing resin 30 and the bonding sheet 10 with framed component 20, in given temperature Suppressed under conditions of degree, time and pressure.By implementing the first heating suppression process, sealing resin 30 is easily filled into In the space of semiconductor chip CP and frame component 20.In addition, by implementing to heat suppression process, can also be to by sealing resin 30 The sealing resin layer 30A of composition bumps are planarized.

If bonding sheet 10 is peeled off after heat curing processes, can obtain the semiconductor core sealed by sealing resin 30 Piece CP and frame component 20.Hereinafter, sometimes referred to as seal 50.

Stiffener adhering processes

Fig. 2 D are illustrated that the schematic diagram of the process for illustrating to make stiffener 40 be pasted on seal 50.

After bonding sheet 10 is peeled off, the circuit face of the semiconductor chip CP to exposing implements to be formed again the cloth again of wiring layer Line procedures and the process that projection (バ Application プ pays け) is set.In order to improve such cabling processes again and set in the process of projection Seal 50 operability, the process that can implement to make stiffener 40 be pasted on seal 50 as needed (strengthens structure Part adhering processes).In the case of implementing stiffener adhering processes, preferably implement before bonding sheet 10 is peeled off.Such as Fig. 2 D institutes Show, seal 50 is supported with the state clamped by bonding sheet 10 and stiffener 40.

In the present embodiment, stiffener 40 possesses the reinforcing plate 41 of heat resistance and the adhesive linkage 42 of heat resistance.As Reinforcing plate 41, for example, the tabular component for including the heat-resistant resins such as glass epoxy resin.Adhesive linkage 42 makes reinforcing plate 41 is be bonded with seal 50.As adhesive linkage 42, can suitably be selected according to reinforcing plate 41 and sealing resin layer 30A material.

In stiffener adhering processes, the second following heating suppression process is preferable to carry out：In the sealing of seal 50 Adhesive linkage 42 is sandwiched between resin bed 30A and reinforcing plate 41, then tabular component is used respectively from the side of reinforcing plate 41 and the side of bonding sheet 10 Clamping, suppressed under conditions of given temperature, time and pressure.By the second heating suppression process, by seal 50 Pre-fixed with stiffener 40.After the second heating suppression process, in order that adhesive linkage 42 solidifies, preferably will be close after fixation Envelope body 50 and stiffener 40 are heated under conditions of given temperature and time.The condition being heating and curing can be according to bonding The material of layer 42 is suitably set, for example, 185 DEG C, 80 minutes and 2.4MPa of condition.In the second heating suppression process, make For tabular component, such as the metallic plate of stainless steel etc. can be used.

Stripping process

Fig. 2 E are illustrated that the schematic diagram of the process for illustrating to peel off bonding sheet 10.

In the present embodiment, in the case that the base material 11 of bonding sheet 10 can be bent, can make bonding sheet 10 bend and Easily peeled off from frame component 20, semiconductor chip CP and sealing resin layer 30A.Peel angle θ is not particularly limited, preferably Bonding sheet 10 is peeled off with more than 90 degree of peel angle θ.If peel angle θ is more than 90 degree, will easily can glue Piece 10 is closed to peel off from frame component 20, semiconductor chip CP and sealing resin layer 30A.Peel angle θ be preferably more than 90 degree and Below 180 degree, it is more preferably below more than 135 degree and 180 degree.By making the bending of bonding sheet 10 in this wise while being shelled From, the load to frame component 20, semiconductor chip CP and sealing resin layer 30A application can be reduced to peel off, so as to With suppress because of the stripping of bonding sheet 10 and caused by semiconductor chip CP and sealing resin layer 30A damage.Bonding sheet 10 is shelled From rear, process for implementing above-mentioned cabling processes again and setting projection etc..After the stripping of bonding sheet 10, implement cabling processes again and set Before process for putting projection etc., above-mentioned stiffener adhering processes can also be implemented as needed.

In the case of pasting stiffener 40, after cabling processes again and the process for setting projection etc. are implemented, not The stage of the support of stiffener 40 is needed to peel off stiffener 40 from seal 50.

Then, seal 50 is subjected to singualtion (singualtion operation) in the form of semiconductor chip CP units.Make sealing The method of the singualtion of body 50 is not particularly limited.For example, can be by with above describing when being cut to semiconductor wafer The same method of used method carries out singualtion.Make the process of the singualtion of seal 50 can also be pasted by seal 50 Implement in the state of cutting sheet etc..By carrying out singualtion to seal 50, partly leading for semiconductor chip CP units can be manufactured Body encapsulates, and the semiconductor package is mounted in installation procedure and is installed in printed circuit board etc..

In the embodiment, can be provided in have passed through implement hot conditions process after be also possible to prevent to be attached The bonding sheet 10 of the surface contamination of thing.

The adherend contacted as adhesive phase 12, for example, semiconductor chip CP and frame component 20.Semiconductor core Piece CP and frame component 20 are exposed under hot conditions with the state being in contact with adhesive phase 12.Bonding sheet 10 is due in base material Oligomer sealant 13 is included between 11 and adhesive phase 12, therefore, even if bonding sheet 10 is exposed under hot conditions, can also be prevented Only immersion of the oligomer in base material 11 to adhesive phase 12.Therefore, using bonding sheet 10, can prevent semiconductor chip CP and The surface contamination of frame component 20.

(second embodiment)

The difference of second embodiment and first embodiment is have oligomer close on the base material two sides of bonding sheet Sealing.Second embodiment is identical with first embodiment in other side, therefore its explanation is omitted or simplified.

Fig. 3 is illustrated that the bonding sheet 10A of second embodiment constructed profile.

Bonding sheet 10A has base material 11, adhesive phase 12, oligomer sealant 13 (the first oligomer sealant) and oligomeric Thing sealant 14 (the second oligomer sealant).

Bonding sheet 10A has oligomer close respectively at the two sides of base material 11 (the first base material face 11a and the second substrate surface 11b) Sealing 13,14.In bonding sheet 10A, oligomer sealant 13 is stacked on the first base material face 11a, the quilt of oligomer sealant 14 It is stacked on the second substrate surface 11b.It is preferred that the first base material face 11a is covered by oligomer sealant 13, the second substrate surface 11b is oligomeric Thing sealant 14 covers.In the same manner as first embodiment, oligomer sealant is provided between base material 11 and adhesive phase 12 13.Bonding sheet 10A shape can also take all shapes such as sheet, banding, label-like.

Oligomer sealant 13 (the first oligomer sealant) is same with first embodiment.

Oligomer sealant 14 (the second oligomer sealant) is to separate out second in base material 11 for preventing from being heated Substrate surface 11b oligomer adheres to and pollutes the layer of other components.Oligomer sealant 14 preferably by with oligomer sealant 13 Same material is formed.

The thickness of oligomer sealant 14 is not particularly limited, preferably close with the oligomer illustrated by first embodiment The thickness of 13 same scope of sealing.The thickness of oligomer sealant increases, and the effect of oligomer sealing improves, such as When from the viewpoint of the productivity and cost of bonding sheet, the thickness of oligomer sealant 13 and oligomer sealant 14 is More than 100nm and below 200nm, can be 150nm or so.

Bonding sheet 10A manufacture method is also not particularly limited.

For example, the process under bonding sheet 10A may travel to manufactures.First, applied on the first base material face 11a of base material 11 Cloth oligomer sealant composition, film is formed, then, the film is heated and is solidified, form oligomer sealant 13.So Afterwards, oligomer sealant composition is coated with the second substrate surface 11b of base material 11, film is formed, then, adds the film Heat and solidification, form oligomer sealant 14.Then, the coating adhesive composition on oligomer sealant 13, film is formed, Then, make the dried coating film, form adhesive phase 12.

Bonding sheet 10A can also apply the application method same with the bonding sheet 10 of first embodiment, can be with bonding Piece 10 similarly uses in the manufacture method of semiconductor device.

Using bonding sheet 10A, bonding sheet 10 similarly, can also prevent after it have passed through the process for applying hot conditions The surface contamination of adherend.

In addition, using bonding sheet 10A, due to being also formed with oligomer sealant 14 on the second substrate surface 11b, therefore, It can prevent from separating out and pollute the component beyond adherend and device in the oligomer attachment on the second substrate surface 11b.For example, In the manufacture method of semiconductor device, can prevent in suppression process is heated with the bonding sheet 10A tabular components contacted Pollution.

(deformation of embodiment)

The present invention is not limited to above-mentioned embodiment, deformation and improvement in the range of it can realize the object of the invention Etc. being also included in the present invention.It should be noted that in the following description, as long as the component illustrated by with above-mentioned embodiment Etc. identical, just imparting identical symbol, and its explanation is omitted or simplified.

In addition, bonding sheet can be provided with the state of monolithic, can also provided with the state of multiple bonding sheet laminations.The feelings Under condition, for example, adhesive phase can also be treated the base material covering of other bonding sheets of lamination.

In addition, bonding sheet can be provided in the form of the piece of strip, can also provided with the state being rolled into a roll.Rolled up Into web-like bonding sheet can be extracted out from volume after be cut into the rear use such as desired size.

The adhesive phase of bonding sheet can be stripped piece covering.As stripping film, it is not particularly limited.For example, from operation From the viewpoint of easiness, stripping film is preferably provided with peeling base and the stripping for being coated with remover in peeling base and being formed From oxidant layer.In addition, stripping film only can have peeling agent layer in the one side of peeling base, can also be in two masks of peeling base There is peeling agent layer.As peeling base, for example,：Paper base material, the thermoplasticity such as laminated polyethylene on the paper base material Laminated paper and plastic foil that resin forms etc..As paper base material, glassine paper, coating paper and cast-coated paper (cast can be enumerated Coated paper) etc..As plastic foil, polyethylene terephthalate, polybutylene terephthalate (PBT) can be enumerated And polyolefin film such as the polyester film such as PEN and polypropylene and polyethylene etc..As remover, Ke Yiju Go out for example：Olefine kind resin, heat-resistant powder filler (such as butadiene type resin, isoprene resinoid etc.), chain alkyl class Resin, alkyd based resin, fluorine-containing resinoid and organic silicon resin.

The thickness of stripping film is not particularly limited, and the thickness of stripping film is usually more than 20 μm and less than 200 μm, is preferably More than 25 μm and less than 150 μm.

The thickness of peeling agent layer is not particularly limited, and the situation of peeling agent layer is formed in solution of the coating comprising remover Under, the thickness of peeling agent layer is preferably more than 0.01 μm and less than 2.0 μm, more preferably more than 0.03 μm and less than 1.0 μm.

In the case of using plastic foil as peeling base, the thickness of the plastic foil is preferably more than 3 μm and less than 50 μm, More preferably more than 5 μm and less than 40 μm.

Bonding sheet with stripping film for example manufactures by following process.First, the coating adhesive group on stripping film Compound, film is formed, then, make dried coating film, form adhesive phase 12.In addition, as illustrated by above-mentioned embodiment, Oligomer sealant 13 is formd on the first base material face 11a of base material 11.Make the adhesive phase 12 and base material 11 on stripping film On oligomer sealant 13 be bonded.In the case of mode with oligomer sealant 14, formd on the two sides of base material 11 After oligomer sealant 13,14, adhesive phase 12 is bonded with oligomer sealant 13.

For above-mentioned embodiment, list sealing resin 30 material be heat-curing resin in case of enter Explanation is gone, but the present invention is not limited to such mode.For example, sealing resin 30 can also utilize the energy such as ultraviolet The energy ray-curable resin of line solidification.

For above-mentioned embodiment, in the explanation of the manufacture method of semiconductor device, enumerating makes frame component 20 viscous It is affixed on exemplified by the mode of bonding sheet 10 and is illustrated, but the present invention is not limited to such mode.Bonding sheet 10 can also Used in the manufacture method of the semiconductor device sealed without using frame component to semiconductor element.

Embodiment

Hereinafter, enumerate embodiment the present invention will be described in more detail, but the present invention is not appointed by these embodiments What is limited.

(evaluation method)

The evaluation of bonding sheet is carried out according to method as shown below.

[confirmation of residue]

Semiconductor chip is pasted on to the adhesive phase of bonding sheet, has obtained the bonding sheet with semiconductor chip.

The bonding sheet with semiconductor chip is heated under conditions of 190 DEG C and 1 hour., will after heating Bonding sheet is peeled off.Utilize digit microscope (manufacture of KEYENCE companies, digit microscope；VHX-1000) to partly leading after stripping Observed in the face that is attached of body chip, it is thus identified that whether there is residue, observation multiplying power is set to 500 times.By the residue unconfirmed of arriving Situation is determined as " A ", will confirm that the situation of residue is determined as " B ".

It should be noted that whether residue is that the confirmation of oligomer from base material is entered according to method as shown below OK.Using the spectrum of Raman spectrum analysis method measure residue, being consistent by spectrum with the feature of the base material of bonding sheet, it is residual to confirm Slag thing is derived from the oligomer of base material.

(making of bonding sheet)

(embodiment 1)

(1) preparation of coating oligomer sealant solution

Coordinate following (A) bisphenol A type epoxy compounds, (B) petchem, (C) multifunctional amino-compound and (D) acid Property catalyst and be sufficiently carried out stirring, being prepared for the coating of embodiment 1, (oligomer sealant is used with oligomer sealant solution Composition).

(A) bisphenol A type epoxy compound

" EPICLON H-360 " (trade name), the solid component concentration of DIC companies manufacture：40 mass %, Weight-average molecular Amount：25000

(B) petchem

" VYLON GK680 " (trade name), the number-average molecular weight of Toyo Boseki K.K's manufacture：6000th, vitrifying turns Temperature：10℃

(C) multifunctional amino-compound

HMMM, the " (business of CYMEL 303 " of NIHON CYTEC INDUSTRIES INC. manufactures The name of an article)

(D) acidic catalyst

The methanol solution of p-methyl benzenesulfonic acid (solid component concentration is 50 mass %)

Specifically, the first of above-mentioned (B) petchem is added in the above-mentioned mass parts of (A) bisphenol A type epoxy compound 100 Benzene dilute solution (solid component concentration：30%) 14.29 mass parts and the above-mentioned matter of (C) HMMM 11.4 Measure part, the mass % of the mass % of again with toluene/MEK=50/50 mixed solvent is diluted so that solid constituent is 3 matter % is measured, and is stirred.The methanol solution of (D) p-methyl benzenesulfonic acid is added in solution after agitation, and (solid component concentration is 50 mass %) 2.9 mass parts (relative to the mass parts of (A) bisphenol A type epoxy compound 100), it is close to have obtained coating oligomer Seal agent solution.

(2) making of oligomer sealant

The coating being prepared is uniformly coated on biaxial tension with oligomer sealant solution using Le rod coating method advanced in years Polyethylene terephthalate film (" DIAFOIL T-100 " (trade name), the μ of thickness 50 of Mitsubishi Plastics Inc's manufacture M, the storage modulus at 100 DEG C is 3.2 × 10⁹Pa one side), and make it that dried thickness is 150nm.After making coating Film is in the inside of baking oven by making film be heating and curing, having obtained oligomer sealant.Bar is blown out as the hot blast in baking oven Part, temperature is set to 150 DEG C, wind speed is set to 8m/min, as process velocity in an oven, be adjusted to the film after coating with Pass through oven interior within 20 seconds.

(3) making of adhesive composition

Coordinate following material (polymer, bonding agent, crosslinking agent and retarder thinner) and be sufficiently stirred, is prepared for The coating of embodiment 1 is with binder solution (adhesive composition).

Polymer：Acrylate copolymer, 40 mass parts (solid constituent)

By the mass % of 2-EHA 92.8, the mass % of acrylic acid 2- hydroxy methacrylates 7.0 and the matter of acrylic acid 0.2 Amount % is copolymerized and is prepared for acrylate copolymer.

Bonding agent：Two ends are hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan's manufacture of hydroxyl；GI-1000〕、5 Mass parts (solid constituent)

Crosslinking agent：Aliphatic category isocyanates (hexamethylene diisocyanate with hexamethylene diisocyanate Cyamelide ester type modifier) (Nippon Polyurethane Industry Co., Ltd. manufacture；Coronate HX), 3.5 mass parts (Gu Body composition)

Retarder thinner：Using MEK, coating is adjusted to 30 mass % with the solid component concentration of adhesive liquid.

(4) making of adhesive phase

Prepared coating is coated on provided with organic with binder solution using comma coater (registration mark) (Lindeke Co., Ltd manufactures the transparent polyethylene terephthalate film stripping film of 38 μm of silicon class peel ply；SP- PET382150) stripping aspect side, and make it that dried thickness is 50 μm, the heating of 90 seconds carried out at 90 DEG C, is connect The heating carried out at 115 DEG C 90 seconds, makes dried coating film.

(5) making of bonding sheet

Adhesive phase made on stripping film surface is bonded with oligomer sealant made on substrate surface, obtained The bonding sheet of embodiment 1 is arrived.

(embodiment 2)

For the bonding sheet of embodiment 2, in addition to the polymer contained by adhesive phase and the difference of embodiment 1, with Embodiment 1 is similarly made.

The polymer used in embodiment 2 is by the mass % of 2-EHA 80.8, acrylic acid 2- hydroxy methacrylates 7 What the mass % of quality %, the 4- acryloyl morpholine 12 and mass % of acrylic acid 0.2 was copolymerized and prepared.

(comparative example 1)

For the bonding sheet of comparative example 1, except bonding agent contained in adhesive phase is different from embodiment 1, base Material it is different from embodiment 1 and without oligomer sealant beyond, made similarly to Example 1.

The bonding agent used in comparative example 1 is tributyl 2-acetylcitrate (Taoka Chemical Industries Co. Ltd.'s manufacture). It should be noted that tributyl 2-acetylcitrate does not have above-mentioned reactive group.

The base material used in comparative example 1 is that (Mitsubishi Plastics Inc manufactures polyethylene terephthalate film； PET50T-100,50 μm of thickness, the storage modulus at 100 DEG C are 3.2 × 10⁹Pa〕.The bonding that will be made on stripping film surface Oxidant layer is bonded with base material, has obtained the bonding sheet of comparative example 1.

(comparative example 2)

For the bonding sheet of comparative example 2, except bonding agent contained in adhesive phase it is different from comparative example 1 with Outside, made in the same manner as comparative example 1.

The bonding agent used in comparative example 2 is the hydrogenated butadiene polymer (Tso Tat Co., Ltd., Japan that two ends are hydroxyl Manufacture；GI-1000〕.

(comparative example 3)

For the bonding sheet of comparative example 3, except adhesive contained in adhesive phase is different from embodiment 1, bonding The thickness of oxidant layer is different from embodiment 1, base material and embodiment 1 it is different and without oligomer sealant beyond, with embodiment 1 is similarly made.

Silicone adhesive category has been used in comparative example 3.

In comparative example 3, coordinate following component：

The mass parts (solid constituent) of silicone adhesive category Ad1 (SD4580PSA) 18,

The mass parts (solid constituent) of silicone adhesive category Ad2 (SD4587L) 40,

The mass parts (solid constituent) of catalyst Cat1 (NC-25CAT) 0.3,

The mass parts (solid constituent) of catalyst Cat2 (CAT-SRX-212) 0.65 and

The mass parts (solid constituent) of subbing (BY24-712) 5, are sufficiently stirred, are prepared for coating adhesive liquid (adhesive composition).Material used in the adhesive composition of comparative example 3 is Dow Corning Toray Co., Ltd.'s manufacture.

The coating of comparative example 3 is coated on the stripping aspect side of stripping film with adhesive liquid and is dried so that be dry Thickness after dry is 30 μm, has made adhesive phase.Drying condition is 130 DEG C and 2 minutes.The base material used in comparative example 3 makes It is that (Mitsubishi Plastics Inc manufactures polyethylene terephthalate film；DIAFOIL PET50T-100, the μ of thickness 50 M, the storage modulus at 100 DEG C is 3.2 × 10⁹Pa〕.The adhesive phase made on stripping film surface is bonded with base material, obtained The bonding sheet of comparative example 3 is arrived.

The evaluation result of the bonding sheet of embodiment 1, embodiment 2 and comparative example 1~3 is shown in table 1.

[table 1]

	Adhesive	The thickness of adhesive phase	Oligomer sealant	Residue confirms result
					Embodiment 1	Crylic acid resin	50μm	Have	A
Embodiment 2	Crylic acid resin	50μm	Have	A
					Comparative example 1	Crylic acid resin	50μm	Nothing	B
Comparative example 2	Crylic acid resin	50μm	Nothing	B
					Comparative example 3	Organic siliconresin class	30μm	Nothing	B

The bonding sheet due to comparative example 1~3 is thought due to not having oligomer sealant between adhesive phase and base material, Therefore residue is being separated out on adherend (semiconductor chip) surface under 190 DEG C of hot conditions.

On the other hand, it is believed that the bonding sheet of embodiment 1 and embodiment 2 is oligomeric due to having between adhesive phase and base material Thing sealant, thus it is residual if exposed to also not separated out on adherend (semiconductor chip) surface under 190 DEG C of hot conditions Slag thing.

Claims

1. a kind of bonding sheet, it is used when the semiconductor element on to bonding sheet seals, and the bonding sheet has：

Base material,

Adhesive phase comprising adhesive and

The oligomer sealant being arranged between the base material and described adhesive layer.

2. bonding sheet according to claim 1, wherein,

The oligomer sealant is the solidification envelope for forming the solidification of oligomer sealant composition,

The oligomer sealant is included with composition：Epoxide, petchem and multifunctional amino-compound.

3. bonding sheet according to claim 2, wherein, the oligomer sealant is included with composition：

(A) it is more than 50 mass % and below 80 mass % bisphenol A type epoxy compound,

(B) it is more than 5 mass % and below 30 mass % petchem and

(C) it is more than 10 mass % and below 40 mass % multifunctional amino-compound.

4. according to bonding sheet according to any one of claims 1 to 3, wherein, storage modulus of the base material at 100 DEG C is 1×10⁷More than Pa.

5. according to bonding sheet according to any one of claims 1 to 4, wherein, described adhesive layer contains acrylic adhesive Agent composition or silicone adhesive category composition.

6. bonding sheet according to claim 5, wherein, the acrylic pressure-sensitive adhesive compositions are included with acrylic acid 2- second Acrylic copolymer of the own ester of base as principal monomer.

7. bonding sheet according to claim 5, wherein, the silicone adhesive category composition includes polyaddition type organosilicon Resin.

8. according to bonding sheet according to any one of claims 1 to 7, wherein, have on the two sides of the base material described oligomeric Thing sealant.

9. according to bonding sheet according to any one of claims 1 to 8, wherein, the base material includes polyester resin.