CN107636100B - Bonding sheet - Google Patents

Abstract

The present invention relates to a kind of bonding sheet (10), it is used when being sealed to the semiconductor element on bonding sheet, which includes substrate (11), the adhesive phase (12) comprising adhesive and the oligomer sealant (13) being set between substrate (11) and adhesive phase (12).

Description

Bonding sheet

Technical field

The present invention relates to bonding sheets.

Background technique

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

For example, describing a kind of residual paste for inhibiting adhesive in patent document 1, for steadily producing QFN (square flat It is flat without lead, Quad Flat Non-lead) semiconductor packages mask sheet.The following contents is described in patent document 1: logical Cross using specific heat-resistant film and silicone adhesive category and make mask sheet, chip paste (ダ イ ア タ ッ チ) process and The environment of 150 DEG C~180 DEG C, 1 hour~6 hours is resistant in resin seal process.

Existing technical literature

Patent document

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

Summary of the invention

Problems to be solved by the invention

In recent years, even also being used in the process for being applied with 180 DEG C or more and 200 DEG C or less 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.) as in the case where substrate, after process from adherend When bonding sheet is peeled, the surface of adherend can be contaminated.The reason of as such pollution, it is believed that be due to as substrate Low molecular weight compositions contained in the resin film used (oligomer) are precipitated on the surface of adherend.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, there are semiconductor elements The surface of part is contaminated and generates the possibility of unfavorable condition in semiconductor devices.

The purpose of the present invention is to provide a kind of bonding sheets, even if the bonding sheet have passed through the process for applying hot conditions Later, it is also possible to prevent the surface contamination of adherend.

Solution to the problem

A mode according to the invention, provides a kind of bonding sheet, is carried out to the semiconductor element on bonding sheet It is used when sealing, which includes substrate, the adhesive phase comprising adhesive and be set to the substrate and described Oligomer sealant between adhesive phase.

In the bonding sheet involved in one embodiment of the present invention, the preferably described oligomer sealant is to seal oligomer Layer solidifies envelope made of being solidified with composition, and the oligomer sealant includes with composition: epoxide, polyester chemical combination Object and multifunctional amino-compound.

In the bonding sheet involved in one embodiment of the present invention, the preferably described oligomer sealant includes with composition: (A) 50 mass % or more and 80 mass % bisphenol A type epoxy compound below, (B) 5 mass % or more and 30 mass % or less Petchem and (C) 10 mass % or more and 40 mass % multifunctional amino-compound below.

In the bonding sheet involved in one embodiment of the present invention, storage modulus of the preferably described substrate at 100 DEG C is 1 ×10⁷Pa or more.

In the bonding sheet involved in one embodiment of the present invention, preferably described adhesive layer has acrylic adhesives Composition or silicone adhesive category composition.

In the bonding sheet involved in one embodiment of the present invention, the preferably described acrylic pressure-sensitive adhesive compositions include with Acrylic copolymer of the 2-EHA as principal monomer.

In the bonding sheet involved in one embodiment of the present invention, the preferably described silicone adhesive category composition includes to add Poly- type organic siliconresin.

In the bonding sheet involved in one embodiment of the present invention, preferably there is the oligomer on the two sides of the substrate Sealant.

In the bonding sheet involved in one embodiment of the present invention, the preferably described substrate includes polyester resin.

According to the present invention it is possible to provide even if 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.

Detailed description of the invention

[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

10,10A ... bonding sheet

11 ... substrates

12 ... adhesive phases

13,14 ... oligomer sealants

Specific embodiment

(first embodiment)

(bonding sheet)

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

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

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

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

(substrate)

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

As substrate 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, ethylene-(methyl) acrylic copolymer film, ethylene-(methyl) Acrylate copolymer film, polystyrene film, polycarbonate membrane and polyimide film etc..In addition, can also be lifted as substrate 11 Their cross linking membrane and stack membrane etc. out.

Substrate 11 preferably comprises polyester resin, is more preferably formed by the material using polyester resin as principal component.In In this specification, the so-called material using polyester resin as principal component refers to that the quality of polyester resin is constituting substrate Material gross mass in shared ratio be 50 mass % or more.

As polyester resin, such as it is preferably selected from pet resin, poly terephthalic acid fourth Terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin and these resins copolymer resins In arbitrary resin, more preferable pet resin.

It is more preferably poly- as substrate 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 when processing, the lower limit of storage modulus of the substrate 11 at 100 DEG C is preferably 1 ×10⁷Pa or more, more preferably 1 × 10⁸Pa or more.From the viewpoint of flexibility (adaptability) of operation, energy storage of the substrate 11 at 100 DEG C The upper limit of modulus is preferably 1 × 10¹²Pa or less.It should be noted that in the present specification, storage modulus is using Dynamic Viscoelastic It property measurement device, the value that is measured at frequency 1Hz by torsional shear method.Substrate to be determined is cut into wide 5mm, long 20mm, It is surveyed using determination of viscoelasticity instrument (manufacture of TA Instruments company, DMAQ800), at frequency 1Hz through stretch mode Fixed 100 DEG C of storage modulus.

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

The thickness of substrate 11 is preferably 10 μm or more and 500 μm or less, more preferably 15 μm or more and 300 μm or less, into One step is preferably 20 μm or more and 250 μm or less.

(adhesive phase)

The adhesive phase 12 of present embodiment includes adhesive composition.As bonding contained by the adhesive composition Agent is not particularly limited, and various adhesives can be applied to adhesive phase 12.As adhesive contained by adhesive phase 12, It can be cited for example that rubber, acrylic compounds, organic silicon, polyesters and carbamates.It should be noted that it is contemplated that Type of purposes and the adherend being stuck etc. selects the type of adhesive.It is viscous that adhesive phase 12 preferably comprises acrylic compounds 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 packet Containing the acrylic copolymer using 2-EHA as principal monomer.

In addition, preferably comprising acrylic copolymer in the case that adhesive phase 12 includes acrylic pressure-sensitive adhesive compositions Object 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 the present specification, so-called to refer to using 2-EHA as principal monomer, derive from acrylic acid 2- The quality of the copolymer composition of ethylhexyl ratio shared in the gross mass of acrylic copolymer is 50 mass % or more. In the present embodiment, preferred from ratio of the copolymer composition of 2-EHA in acrylic copolymer For 50 mass % or more and 95 mass % hereinafter, more preferably 60 mass % or more and 95 mass % are hereinafter, further preferably 80 mass % or more and 95 mass % are hereinafter, be still more preferably 85 mass % or more and 93 mass % or less.If source It is 50 mass % or more 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 be removed from adherend, if it is 80 mass % or more, be more easier to remove.If source In the ratio of the copolymer composition of 2-EHA be 95 mass % hereinafter, can then prevent initial stage closing force insufficient and Substrate when heating is caused to deform, remove bonding sheet from adherend due to its deformation.

The type and quantity of the copolymer composition other than 2-EHA in acrylic copolymer are without spy It does not limit.For example, preferably containing monomer with reactive functional group as the second copolymer composition.As second The reactive functional groups of copolymer composition are preferably capable and the crosslinking agent after use in the case where the crosslinking agent of face narration The functional group of reaction.As the reactive functional groups, such as it is preferably selected from carboxyl, hydroxyl, amino, substituted-amino and epoxy group In at least any one substituent group, more preferably at least any one substituent group in carboxyl and hydroxyl, further preferably carboxyl.

As the monomer (carboxyl group-containing monomer) with carboxyl, it can be cited for example that: 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 may be used alone or in combination of two or more kinds.

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

As the acrylate with epoxy group, it can be cited for example that: glycidyl acrylate and methacrylic acid contracting Water glyceride.

As other copolymer compositions in acrylic copolymer, the carbon atom number that can enumerate alkyl is 2~20 (methyl) alkyl acrylate.As (methyl) alkyl acrylate, it can be cited for example that: (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- ethylhexyl, (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 etc..These (methyl) third In olefin(e) acid Arrcostab, from the viewpoint of further increasing adhesiveness, (methyl) third that the carbon atom number of optimizing alkyl is 2~4 Olefin(e) acid ester, more preferable (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, it can be cited for example that containing alkoxy from being selected from 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 one monomer.

As (methyl) acrylate containing alkoxyalkyl, it can be cited for example that: (methyl) methoxyethyl first Ester, (methyl) methoxyethyl acrylate, (methyl) ethioxy methyl esters and (methyl) ethoxyethyl acrylate.

As (methyl) acrylate with cycloaliphatic ring, it can be cited for example that (methyl) cyclohexyl acrylate.

As (methyl) acrylate with aromatic rings, it can be cited for example that (methyl) phenyl acrylate.

As the acrylamide of non-crosslinked property, it can be cited for example that acrylamide and Methacrylamide.

As (methyl) acrylate with tertiary amino of non-crosslinked property, it can be cited for example that (methyl) acrylic acid (N, N- dimethylamino) 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 Copolymer composition from the viewpoint of resultant force improves, further preferably from the monomer with the ring comprising nitrogen-atoms.

As the monomer with the ring comprising nitrogen-atoms, can enumerate: n-vinyl-2-pyrrolidone, N- ethylene methacrylic Base pyrrolidones, N- vinylpiperidone, N- vinyl piperazine, N- vinylpyrazine, N- vinyl pyrrole, N- vinyl miaow Azoles, N- polyvinyl morpholinone, N- caprolactam and N- (methyl) acryloyl morpholine etc..Include nitrogen-atoms as having The monomer of ring, preferably N- (methyl) acryloyl morpholine.

These monomers may be used alone or in combination of two or more kinds.

In the present embodiment, as the second copolymer composition, preferably carboxyl group-containing monomer or hydroxyl monomer, more preferable third Olefin(e) acid.Acrylic copolymer includes to derive from the copolymer composition of 2-EHA and being total to from acrylic acid In the case where polymers ingredient, the quality from the copolymer composition of acrylic acid is shared in acrylic copolymer gross mass Ratio is preferably 1 mass % hereinafter, more preferably 0.1 mass % or more and 0.5 mass % or less.If the ratio of acrylic acid is 1 mass % is hereinafter, can then prevent in adhesive composition the crosslinking of acrylic copolymer in the case where comprising crosslinking agent It carries out too quickly.

Acrylic copolymer may include two or more from the copolymer composition containing monomer.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 Acrylic copolymer obtained from sour 2- ethylhexyl, carboxyl group-containing monomer and the copolymerization of hydroxyl monomer, the carboxyl group-containing monomer are excellent It is selected as acrylic acid, hydroxyl monomer is preferably acrylic acid 2- hydroxy methacrylate.It is preferred that deriving from propylene in acrylic copolymer The ratio of the copolymer composition of sour 2- ethylhexyl is 80 mass % or more and 95 mass % hereinafter, deriving from the copolymerization of acrylic acid The mass ratio of object ingredient is 1 mass % hereinafter, remainder is the copolymer composition from acrylic acid 2- hydroxy methacrylate.

The weight average molecular weight (Mw) of acrylic copolymer is preferably 300,000 or more and 2,000,000 hereinafter, more preferably 600,000 Above and 1,500,000 hereinafter, further preferably 800,000 or more and 1,200,000 or less.If the Weight-average molecular of acrylic copolymer Measuring Mw is 300,000 or more, then can not removed to residual adhesive residue in adherend.If acrylic copolymer The weight average molecular weight Mw of object is 2,000,000 hereinafter, then can effectively be attached in adherend.

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

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

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

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

Bonding agent preferably comprises the rubber type of material with reactive group as principal component.Adhesive composition includes When 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 50 mass % are hereinafter, more preferably 5 mass % or more and 30 mass % or less.If bonding agent in adhesive composition Containing ratio be 3 mass % or more, then can inhibit the generation of residual paste, if it is 50 mass % hereinafter, can then inhibit to bond Power reduces.

In the present specification, so-called to refer to comprising the rubber type of material with reactive group as principal component, have anti- 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, ratio of the rubber type of material in bonding agent with reactive group is preferably greater than 50 mass %, and more preferably 80 Quality % or more.Bonding agent is preferably substantially made of the rubber type of material with reactive group.

As reactive group, it is preferably selected from hydroxyl, isocyanate group, amino, Oxyranyle, anhydride group, alcoxyl 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, the quantity of reactive group can be 1, or 2 in 1 molecule for constituting rubber type of material More than.

It as rubber type of material, is not particularly limited, preferably the hydrogenation of polybutadiene resinoid and polybutadiene resinoid Object, the hydride of more preferable polybutadiene resinoid.

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

The hydride of polybutadiene resinoid and polybutadiene resinoid is preferably respectively provided with reactive base 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 preferable two ends are hydroxyl Base.

The adhesive composition of present embodiment containing mentioned-above acrylic copolymer and bonding preferably in addition to helping Other than agent, also comprising making cross-linking agent obtained from being combined with the composition crosslinking of crosslinking agent.In addition, the solid of adhesive composition Ingredient preferably substantially as mentioned earlier by mentioned-above acrylic copolymer, bonding agent and cross-linking agents and Obtained cross-linking agent is constituted.It is mentioned here substantially to refer to, it is micro miscellaneous in adhesive in addition to being inevitably mixed into Other than matter, the solid component of adhesive composition only includes the cross-linking agent.

In the present embodiment, as crosslinking agent, it can be cited for example that: 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 comprises crosslinking agent (isocyanates crosslinking agent) of the compound with isocyanate group as principal component.Make For isocyanates crosslinking agent, it can be cited for example that: 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI), 1,3- benzene Diformazan group diisocyanate, 1,4- xylylene diisocyanate, diphenyl methane -4,4 '-diisocyanate, diphenylmethyl Alkane -2,4 '-diisocyanate, 3- Dimethyl diphenylmethane 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 mentioned-above compound is modified Object, reacted with water obtained from biuret form modifier or the cyamelide ester type modifier with triple polyisocyanate annulus.

In the present specification, the so-called crosslinking agent using the compound with isocyanate group as principal component refers to, tool The ratio for having the quality of the compound of isocyanate group shared in the gross mass for constituting the ingredient of crosslinking agent be 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, more than preferably 0.1 mass parts and 20 below the mass, more than more preferably 1 mass parts and 15 below the mass, into One step be preferably 5 mass parts or more and 10 below the mass.If the content of crosslinking agent is such model in adhesive composition In enclosing, then it can be improved bonding between layer (adhesive phase) and adherend (such as substrate) comprising adhesive composition Property, so as to shorten after bonding sheet manufacture for making the stabilized curing time of adhesion characteristic.

In the present embodiment, from the viewpoint of the heat resistance of adhesive composition, isocyanates crosslinking agent is more excellent It is selected as the compound (cyamelide ester type modifier) with triple polyisocyanate annulus.Preferably with respect to acrylic copolymer Hydroxyl equivalent to cooperate the compound with triple polyisocyanate annulus more than 0.7 equivalent and below 1.5 equivalents.If had The use level of the compound of triple polyisocyanate annulus is 0.7 equivalent or more, then bonding force will not become excessively high after heating, and being easy will Bonding sheet removing, so as to reduce residual paste.If with triple polyisocyanate annulus compound use level 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 is preferably further wrapped Containing crosslinking accelerator.Crosslinking accelerator is preferably suitable for selecting to use according to type of crosslinking agent etc..For example, adhesive composition packet Containing polyisocyanate compound as crosslinking agent in the case where, preferably further comprising the Organometallic compounds such as organo-tin compound Species crosslinking accelerator.

Silicone adhesive category composition

In the case that adhesive phase 12 includes organic silicon adhesive composition, silicone adhesive category composition is preferably wrapped Organic siliconresin containing polyaddition type.In the present specification, 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 agent and crosslinking agent.The bonding of addition reaction-type organic silicon Agent composition has the advantage that and is only used by the one-step solidification of low temperature, without 2 solidifications at high temperature.That is, Previous peroxide curing type silicone class adhesive needs 2 solidifications at a high temperature of 150 DEG C or more.

Therefore, it 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 using the relatively low substrate 11 of heat resistance.In addition, due to By-product will not be generated 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 ingredient and organic silicon rubber at The host agent for the mixture composition divided, the crosslinking agent and curing catalysts used as needed for containing silicon hydrogen-based (SiH yl).

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

Organic silicon rubber ingredient is the diorganopolysiloxanecompositions with linear chain structure.

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

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

As such organopolysiloxane noted earlier, specifically, there is Shin-Etsu Chemial Co., Ltd to manufacture KS-3703 (quantity of vinyl is 0.6 relative to methyl 100), Dow Corning Toray Co., Ltd. (Dow Corning Toray Co., Ltd) manufacture BY23-753 (quantity of vinyl relative to methyl 100 be 0.1) and BY24-162 (second The quantity of alkenyl is 1.4 relative to methyl 100) 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, usually mixing with organic silicon rubber ingredient as the organopolysiloxane of organic siliconresin ingredient makes With the KS-3800 (quantity of vinyl of Shin-Etsu Chemial Co., Ltd's manufacture can be enumerated as organic silicon rubber ingredient Relative to methyl 100 be 7.6), Dow Corning Toray Co., Ltd. manufacture BY24-162 (quantity of vinyl is relative to first 100, base are 1.4), (quantity of vinyl is relative to methyl 100 by BY24-843 (do not have unsaturated group) and SD-7292 A 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 bulletin.

Crosslinking agent cooperates in the following way: relative to the vinyl of organic siliconresin ingredient and organic silicon rubber ingredient this The unsaturated group of sample 1, so that the hydrogen atom of bonding on the silicon atoms is usually 0.5 or more and 10 or less, preferably 1 More than a and 2.5 by making to be bonded hydrogen atom 0.5 or more on the silicon atoms hereinafter, can be prevented as vinyl The fully reacting of unsaturated group and silicon hydrogen-based without and cause to solidify bad, be bonded hydrogen atom on the silicon atoms by making For 10 hereinafter, crosslinking agent unreacted can be prevented and left behind, to bring adverse effect to the face of being attached.

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

The curing catalysts be in order to promote unsaturated group in organic siliconresin ingredient and organic silicon rubber ingredient with The silicon hydrogenation of Si-H base 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 the siloxanes complex of object, platinum-olefin complex, platinum-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 bulletin and Japanese Unexamined Patent Publication In 10-147758 bulletin.

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

Relative to the total amount of organic siliconresin ingredient and organic silicon rubber ingredient, the use level of curing catalysts is logical in terms of platinum Normal is 5 mass ppm or more and 2000 mass ppm or less, preferably 10 mass ppm or more and 500 mass ppm are hereinafter, by making The use level of curing catalysts is calculated as 5 mass ppm or more with platinum, can prevent curability from reducing and declining crosslink density, also It is to say, can prevents bonding force and cohesiveness (retentivity) from declining, by making the use level of curing catalysts be calculated as 2000 matter with platinum Amount ppm is hereinafter, can prevent cost from improving and can keep the stability of adhesive phase, and can prevent the solidification being excessively used Catalyst brings adverse effect to the face of being attached.

In addition reaction-type silicone adhesive category composition, by cooperating mentioned-above each ingredient, even if 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 It closes object to be coated on substrate 11 or stripping film described below, after substrate 11 is bonded with stripping film, is heated or irradiated work Property energy line promotes organic siliconresin ingredient and cross-linking reaction of organic silicon rubber ingredient under the action of crosslinking agent.

Promoting heating temperature when cross-linking reaction using heating is usually 60 DEG C or more and 140 DEG C or less, preferably 80 DEG C or more and 130 DEG C or less.By being heated at 60 DEG C or more, can prevent organic siliconresin ingredient and organic silicon rubber at The crosslinking divided is insufficient and causes bonding force insufficient, by being heated at 140 DEG C or less, can prevent substrate sheets from generating heat and receive Contracting fold occurs deterioration, changes colour.

Irradiation active energy ray in the case where promoting cross-linking reaction, in electromagnetic wave or charged particle beam, can use Active energy ray with the quantum of energy, that is, can use ultraviolet light isoreactivity light or electron beam etc..Irradiating electron beam is crosslinked In the case where, Photoepolymerizationinitiater initiater is not needed, but in the case where irradiation ultraviolet light isoreactivity light is crosslinked, preferably there is light Polymerization initiator.

Photoepolymerizationinitiater initiater when as irradiation ultraviolet light, is not particularly limited, can be from previous commonly used in ultraviolet It is suitable for that the arbitrary Photoepolymerizationinitiater initiater of selection uses in the Photoepolymerizationinitiater initiater of line gel-type resin.Cause as the photopolymerization Agent, it can be cited for example that: 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 100 mass parts of total amount of above-mentioned addition reaction-type silicone ingredients and crosslinking agent that agent uses, the usage amount of Photoepolymerizationinitiater initiater Usually more than 0.01 mass parts and 30 below the mass, preferably more than 0.05 mass parts and 20 range choosing below the mass It is fixed.

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

The acceleration voltage for irradiating electron beam when being crosslinked as the electron beam of one of active energy ray is usually 130kV Above and 300kV or less, preferably 150kV or more and 250kV or less.It, can be to prevent by irradiating the acceleration voltage of 130kV or more Only the crosslinking of organic siliconresin ingredient and organic silicon rubber ingredient is insufficient and the situation that causes bonding force insufficient, by with 300kV acceleration voltage irradiating electron beam below can prevent adhesive phase and substrate sheets from deteriorating, discoloration.Electron beam current Preferred scope is 1mA or more and 100mA or less.

The dosage of the electron beam of irradiation be preferably 1Mrad or more and 70Mrad or less, more preferably 2Mrad or more and 20Mrad or less.By that can prevent adhesive phase and substrate sheets from deteriorating, discoloration with the dosage irradiating electron beam of 1Mrad or more, from And the situation that the adhesiveness generated because being crosslinked deficiency can be prevented insufficient.By irradiating electronics with 70Mrad dosage below Beam, the cohesiveness decline that adhesive phase deterioration can be prevented, change colour and generate, so as to prevent substrate sheets deterioration, shrink.

Exposure when as irradiation ultraviolet light, can be suitable for selecting, light quantity 100mJ/cm²Above and 500mJ/cm²With Under, illumination 10mW/cm²Above and 500mW/cm²Below.

It hinders to react due to oxygen in order to prevent, preferably carries out heating and the irradiation of active energy ray under nitrogen atmosphere.

The thickness of adhesive phase 12 can be suitable for determining according to the purposes of bonding sheet 10.In the present embodiment, adhesive phase 12 thickness is preferably 5 μm or more and 60 μm or less, more preferably 10 μm or more and 50 μm or less.If the thickness of adhesive phase 12 Spend it is thin, worry adhesive phase 12 can not follow semiconductor chip circuit face bumps and generate 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.If viscous Mixture layer 12 with a thickness of 5 μm or more, then adhesive phase 12 is easy to follow the bumps in chip circuit face, so as to prevent gap Generation.In addition, semiconductor chip is sunk in adhesive phase if the thickness of adhesive phase 12 is blocked up, semiconductor chip portion Divide and is possible to generate difference of height with the resin portion of sealing semiconductor chips.If such difference of height is generated, when being routed again Wiring is possible to that broken string can be generated.If adhesive phase 12 with a thickness of 60 μm hereinafter, if be not likely to produce difference of height.

In the present embodiment, within the scope of the effect of the invention, can contain in adhesive composition other Ingredient.As the other ingredients that can contain in adhesive composition, it can be cited for example that: organic solvent, fire retardant, thickening Agent, ultraviolet absorbing agent, light stabilizer, antioxidant, antistatic agent, preservative, mould inhibitor, plasticizer, defoaming agent, colorant, Filler and Wetting-transition agent etc..

It may include dimethyl silicone polymer and polymethyl-benzene base silicon in addition reaction-type silicone adhesive category composition Non-reacted polysiloxane is as additive as oxygen alkane.

(oligomer sealant)

Oligomer sealant 13 is the layer for preventing low molecular weight compositions (oligomer) to be immersed in adhesive phase 12.Bonding When piece 10 is exposed to hot conditions, it is believed that oligomer included in substrate 11 is precipitated when heated in 11 surface of substrate, not It in the case that oligomer sealant 13 is set, is immersed to adhesive phase 12, and then passes through adhesive phase 12 and reach adhesive phase 12 surface.Even if oligomer sealant 13 is preferably prevented also from oligomeric under 180 DEG C or more and 200 DEG C of hot conditions below Immersion of the object 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 solidifies envelope made of preferably solidifying oligomer sealant composition, institute Stating oligomer sealant composition includes (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 ether 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 is easy to prevent the precipitation of oligomer.If weight average molecular weight (Mw) is 5 × 10⁴Hereinafter, can then prevent envelope from becoming Firmly.Weight average molecular weight Mw is to be measured by gel permeation chromatography (GPC) method and be converted into the value of standard polystyren.

(B) petchem

It as (B) petchem, is not particularly limited, can be suitable for selecting to use from well known petchem. As petchem, resin obtained from the condensation reaction specifically by polyalcohol and polyacid can be enumerated non-transformed Property petchem and convertibility petchem etc., the non-transformed property petchem is the condensation of binary acid and dihydric alcohol Object or the compound obtained from non-drying oil fatty acid etc. is modified, the convertibility petchem is binary acid and three The condensation product of alcohol more than member.In the present embodiment, any compound in these petchems can be used.

As the polyalcohol for the raw material for being used as (B) petchem, dihydric alcohol, trihydroxylic alcohol and quaternary or more can be enumerated Polyalcohol.

As dihydric alcohol, it can be cited for example that: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene, Tetramethylene glycol and neopentyl glycol.

As trihydroxylic alcohol, it can be cited for example that: glycerol, trimethylolethane and trimethylolpropane.

As polyalcohol more than quaternary, it can be cited for example that: two glycerol, triglycerin, pentaerythrite, dipentaerythritol, Mannitol and sorbierite.

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

As polyacid, it can be cited for example that: aromatic polyvalent acid, aliphatic saturated polybasic acid, aliphatic are unsaturated more First acid and the polyacid obtained from Diels-Alder reaction.

As aromatic polyvalent acid, it can be cited for example that: phthalic anhydride, terephthalic acid (TPA), M-phthalic acid and partially Benzenetricarboxylic anhydride.

As aliphatic saturated polybasic acid, it can be cited for example that: succinic acid, adipic acid and decanedioic acid.

As aliphatic unsaturation polyacid, it can be cited for example that: maleic acid, maleic anhydride, fumaric acid, itaconic acid and lemon Health acid anhydrides.

As the polyacid obtained from Diels-Alder reaction, it can be cited for example that: 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 fatty acid etc. as modifying agent, it can be cited for example that: octanoic acid, lauric acid, palmitinic acid, stearic acid, Oleic acid, linoleic acid, linolenic acid, 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 fatty acid etc..These modifying agent can be used alone, can also To combine two or more use.In addition, may be used alone, can also be used in combination of two or more kinds as petchem.

(B) petchem preferably has the petchem of the active hydrogen group of the basic point as cross-linking reaction.As Active hydrogen group, it can be cited for example that hydroxyl, carboxyl and amino.Petchem particularly preferably has the polyester chemical combination of hydroxyl Object.The hydroxyl value of petchem be preferably 5mgKOH/g or more and 500mgKOH/g hereinafter, more preferably 10mgKOH/g or more and 300mgKOH/g or less.

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

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

It, can by using the petchem of number-average molecular weight (Mn) and glass transition temperature Tg with above range To the flexibility for solidifying envelope and assigning appropriateness for forming oligomer sealant 13.Glass transition temperature Tg is according to JIS K 7121 standards measure extrapolation glass using power compensation differential scanning calorimetry measurement device, in -80 DEG C to 250 DEG C of temperature ranges Glass transition start temperature, so as to find out 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 Amine compounds and Diamines.

As melamine compound, it can be cited for example that hexamethoxymethyl melamine, methylated melamine Close object and butylated melamines compound.

As urea compounds, it can be cited for example that methylated urea compound and butylated urea compound.

As benzene birds droppings amine compounds, it can be cited for example that methylation benzene birds droppings amine compounds and butylation benzene birds droppings amination Close object.

As Diamines, it can be cited for example that 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 hexamethoxymethyl melamine.

(D) acidic catalyst

As acidic catalyst (D), it can be cited for example that hydrochloric acid and p-methyl benzenesulfonic acid.

Solidify envelope

In the present embodiment, preferably oligomer sealant 13 be by oligomer sealant composition below solidification and At 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 (A) 50 mass % or more and 80 mass % or less, (B) 5 matter Amount % or more and 30 mass % or less and (C) 10 mass % or more and 40 mass % or less.In oligomer sealant composition In the case where middle cooperation (D) acidic catalyst, the content of (D) ingredient is preferably set as 1 mass % or more and 5 mass % or less.

Solidify envelope, Ke Yili made of the oligomer sealant composition for the fit rate for making above range solidifies The effect for preventing oligomer from immersing to adhesive phase 12 is effectively improved with oligomer sealant 13.

The more specific example of oligomer sealant composition as present embodiment, it can be cited for example that it is following this The example of the oligomer sealant composition of sample, but the present invention is not limited to such examples.

An example of oligomer sealant composition as 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.

An example of oligomer sealant composition as 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.

An example of oligomer sealant composition as 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 be 500 or more and 10000 or less, the glass transition temperature Tg of (B) petchem is 0 DEG C or more and 50 DEG C hereinafter, (C) multifunctional amination Conjunction object is melamine compound.

An example of oligomer sealant composition as 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 5 × 10⁴Hereinafter, the number-average molecular weight (Mn) of (B) petchem is the glass of 500 or more and 10000 or less, (B) petchem Changing transition temperature Tg is 0 DEG C or more and 50 DEG C hereinafter, (C) multifunctional amino-compound is melamine compound.

The film thickness of oligomer sealant

The thickness of oligomer sealant 13 is preferably 50nm or more and 500nm or less, more preferably 80nm or more and 300nm Below.If oligomer sealant 13 with a thickness of 50nm or more, oligomer can be effectively prevented to adhesive phase 12 It immerses.If oligomer sealant 13 with a thickness of 500nm hereinafter, if by bonding sheet 10 with web-like on core material when, It is easy to be wound.As the material of core material, it can be cited for example that papery, plastics system and made of metal.

The bonding sheet 10 of present embodiment preferably shows bonding force as described below after the heating.Firstly, by bonding sheet 10 It is pasted on adherend (copper foil or polyimide film), is heated under conditions of 100 DEG C and 30 minutes, then at 180 DEG C and 30 It heats under conditions of minute, is further heated under conditions of 190 DEG C and 1 hour, preferably 12 phase of adhesive phase in this way 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 0.7N/25mm or more and 2.0N/25mm or less.If having carried out the bonding force after such heating is 0.7N/25mm or more, Bonding sheet 10 is removed from adherend in the case where can preventing substrate or adherend from deformation having occurred when heated.Separately Outside, if the bonding force after heating be 2.0N/25mm hereinafter, if peeling force will not become excessively high, be easy bonding sheet 10 from quilt It is removed on bur.It should be noted that in the present specification, room temperature refers to 22 DEG C or more and 24 DEG C of temperature below.At this In specification, bonding force be by 180 ° of stripping methods, tensile speed 300mm/ point, bonding sheet width 25mm under measure Value.

The more specific example of adhesive composition as present embodiment, it can be cited for example that following such bonding The example of agent composition, but the present invention is not limited to such examples.

An example of adhesive composition as present embodiment can be enumerated and be helped comprising acrylic copolymer, bonding The adhesive composition of agent and crosslinking agent, wherein the acrylic copolymer is at least by 2-EHA, containing carboxylic Acrylic copolymer obtained from base monomer and the copolymerization of hydroxyl monomer, the bonding agent include to have reactive group Rubber type of material as principal component, the crosslinking agent is isocyanates crosslinking agent.

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

An example of adhesive composition as present embodiment can be enumerated and be helped comprising acrylic copolymer, bonding The adhesive composition of agent and 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 methacrylate, the bonding agent include to have reactive base For the rubber type of material of group as principal component, the crosslinking agent is isocyanates crosslinking agent.

An example of adhesive composition as present embodiment can be enumerated and be helped comprising acrylic copolymer, bonding The adhesive composition of agent and 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 methacrylate, 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 above-mentioned acrylic copolymer is at least will 2-EHA, carboxyl group-containing monomer, hydroxyl monomer and the ring with nitrogen atom monomer copolymerization obtained from third Olefin(e) acid analog copolymer.

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

Source in these examples of the adhesive composition of present embodiment, in preferably above-mentioned acrylic copolymer In the ratio of the copolymer composition of 2-EHA be 80 mass % or more and 95 mass % or less, from containing carboxyl The mass ratio of the copolymer composition of monomer is 1 mass % or less, remainder is other copolymer compositions, as copolymer at Point, preferably comprise the copolymer composition from hydroxyl monomer.

(manufacturing method of bonding sheet)

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

For example, bonding sheet 10 can be manufactured by following process.

Firstly, being coated with oligomer sealant composition on the first base material face 11a of substrate 11, film is formed.Then, So that the film is heated and is solidified, forms the solidification envelope as oligomer sealant 13.As the condition being heating and curing, for example, 120 DEG C or more and 170 DEG C or less, 5 seconds or more and within 5 minutes.

Then, the coating adhesive composition on oligomer sealant 13 forms film.Then, make the dried coating film, shape Composite adhesives layer 12.

The case where being coated with oligomer sealant composition and forming oligomer sealant 13 and coating adhesive combination Object and in the case where 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: aromatic solvent, aliphatic category solvent, esters solvent, ketones solvent and alcohols solvent.It, can as aromatic solvent To enumerate such as benzene, toluene and dimethylbenzene.As aliphatic category solvent, it can be cited for example that n-hexane and normal heptane.As ester Class solvent, it can be cited for example that ethyl acetate and butyl acetate.As ketones solvent, it can be cited for example that methyl ethyl ketone, methyl are different Butyl ketone, cyclohexanone and cyclopentanone.As alcohols solvent, it can be cited for example that isopropanol and methanol.

As coating method, it can be cited for example that: spin-coating method, spray coating method, stick coating method, scraper for coating method, roller knife rubbing method, Rolling method, scraper coating method, die coating method and gravure coating process etc..

Organic solvent and low boiling point component remain on oligomer sealant 13 and adhesive phase 12 in order to prevent, preferably exist Film is heated after coating liquid is coated on substrate 11 and is made it dry.

In the case where cooperating crosslinking agent in adhesive composition, cohesiveness is improved in order to carry out cross-linking reaction, It is preferred that being heated to film.

(use of bonding sheet)

The use when being sealed to semiconductor element of bonding sheet 10.Bonding sheet 10 is preferably to being pasted on bonding sheet 10 Use when being sealed of the semiconductor element of state of the state without being mounted on made of metal lead frame.Specifically, it glues The preferably use when the semiconductor element to the state for being pasted on adhesive phase 12 is sealed of piece 10 is closed, rather than to carrying The use when semiconductor element of metal ieadf iotaame is sealed.As without using double of conductor element of metal ieadf iotaame into 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 is with the following process: making the frame structure for being formed with multiple opening portions Part is pasted on the process of bonding sheet 10, semiconductor chip is made to be pasted on the adhesive exposed using the opening portion of above-mentioned frame component Layer 12 on process, coat the process of above-mentioned semiconductor chip with sealing resin and make the work of above-mentioned sealing resin heat cure Sequence.

(manufacturing method of semiconductor device)

The method for using the bonding sheet 10 of present embodiment to manufacture semiconductor device is illustrated.

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

Implement following process in the manufacturing method of the semiconductor device of present embodiment: making to be 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, partly led with the cladding of sealing resin 30 The process (sealing process) of body chip CP, the process (heat curing processes) for making 30 heat cure of sealing resin and after heat cure The process (stripping process) that bonding sheet 10 is removed.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.Below to each process into Row explanation.

Bonding sheet adhering processes

Fig. 2A shows 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, it can be cited for example that: the metals such as copper and stainless steel, Yi Jiju Heat-resistant resins such as imide resin and glass epoxy resin etc..

Opening portion 21 is the hole for penetrating through the surface back side of frame component 20.For the shape of opening portion 21, as long as energy It is enough that semiconductor chip CP is accommodated in the shape in frame, it is 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 shows the schematic diagram of the process for illustrating that semiconductor chip CP is made to be pasted on adhesive phase 12.

After so that 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.

It for the manufacture of semiconductor chip CP, is manufactured by implementing for example following process: to being formed with electricity Back grinder sequence that the back side of the semiconductor wafer on road is ground and by the cutting action of semiconductor wafer singualtion.It is cutting It cuts in process, semiconductor wafer is made to be pasted on the adhesive layer of cutting sheet, use the disconnecting 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 well known cutter device can be used.In addition, the condition for cutting does not have yet It is particularly limited to.It should be noted that laser cutting method or stealthy patterning method etc. can be used also to be cut instead of using cutter The method cut.

After cutting action, it is possible to implement stretched to cutting sheet, to expand the interval between multiple semiconductor chip CP Spread sheet process.By implementing spread sheet process, the conveyers such as opening folder can be used to pick up semiconductor chip CP.In addition, By implementing spread sheet process, cutting sheet can be reduced to the bonding force of adhesive layer, semiconductor chip CP is made to become easy pickup.

In the case where cooperating energy line polymerizable compound in the adhesive composite of cutting sheet or adhesive layer, from The substrate side of cutting sheet solidifies energy line polymerizable compound adhesive layer irradiation energy line.Make energy line polymerism After closing object solidification, the cohesiveness of adhesive layer is improved, and the bonding force of adhesive layer can be made to reduce.As energy line, Ke Yiju Out such as ultraviolet light (UV) and electron beam (EB), preferred ultraviolet light.The irradiation of energy line can paste semiconductor wafer it Afterwards, any stage before the removing (pickup) of semiconductor chip carries 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 shows close for illustrating to carry out the semiconductor chip CP and frame component 20 that are pasted on bonding sheet 10 The schematic diagram of the process of envelope.

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

It is not particularly limited with the method that sealing resin 30 coats semiconductor chip CP and frame component 20.

In the present embodiment, it enumerates for the mode for having used the sealing resin 30 of sheet and is illustrated.Place piece The sealing resin 30 of shape simultaneously makes it cover semiconductor chip CP and frame component 20, and sealing resin 30 is made to be heating and curing and form sealing Resin layer 30A.So, semiconductor chip CP and frame component 20 are embedded in sealing resin layer 30A.Use the close of sheet In the case where sealing resin 30, preferably it is 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 can prevent from generating gap between semiconductor chip CP and frame component 20.Using the heating temperature of vacuum layer platen press Spending condition and range is, for example, 80 DEG C or more and 120 DEG C or less.

In sealing process, resin sheet branch of the sealing resin 30 by polyethylene terephthalate etc. of sheet can be used Laminated sheet made of support.In this case, will be set after placing laminated sheet in the way of covering semiconductor chip CP and frame component 20 Rouge piece is removed from sealing resin 30, and sealing resin 30 is made to be heating and curing.As such laminated sheet, it can be cited for example that: ABF Film (manufacture of Ajinomoto Fine-Techno company).

As the method being 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 storing the semiconductor core being pasted on bonding sheet 10 in the mould inside of sealing device Piece CP and frame component 20.To the resin material of the inside of mold injection mobility, solidify resin material.The case where shifting formwork method Under, the condition of heating and pressure is not particularly limited.It is by 150 DEG C or more as an example of the usual conditions in shifting formwork method Temperature, 4MPa or more and 15MPa pressure holding 30 seconds below or more and 300 seconds or less.Then, pressurization is released, from sealing Solidfied material is taken out in device, is stood in an oven, and temperature 2 hours or more and 15 hours or less of 150 DEG C or more are kept.Such one Come, semiconductor chip CP and frame component 20 are sealed.

In the case where using sealing resin 30 of sheet in above-mentioned sealing process, 30 thermosetting of sealing resin 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 It is suppressed under conditions of degree, time and pressure.By implementing the first heating suppression process, sealing resin 30 is easy to be filled into In the gap of semiconductor chip CP and frame component 20.In addition, by implementing heating suppression process, it can also be to by sealing resin 30 The bumps of the sealing resin layer 30A of composition are planarized.

If bonding sheet 10 is removed after heat curing processes, can be obtained 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 is shown for illustrating the schematic diagram for making stiffener 40 be pasted on the process on seal 50.

After bonding sheet 10 is removed, implement to be formed again the cloth again of wiring layer to the circuit face of the semiconductor chip CP of exposing The process of line procedures and setting protrusion (バ Application プ pays け).In order to improve such cabling processes again and be arranged in the process of protrusion Seal 50 operability, can according to need implement be pasted on stiffener 40 on seal 50 process (reinforce structure Part adhering processes).In the case where implementing stiffener adhering processes, preferably implement before removing bonding sheet 10.Such as Fig. 2 D institute Show, seal 50 is supported with the state clamped by bonding sheet 10 and stiffener 40.

In the present embodiment, stiffener 40 has the stiffening plate 41 of heat resistance and the adhesive layer 42 of heat resistance.As Stiffening plate 41, it can be cited for example that the tabular component comprising heat-resistant resins such as glass epoxy resins.Adhesive layer 42 makes stiffening plate 41 is Nian Jie with seal 50.It can be suitable for selection according to stiffening plate 41 and the material of sealing resin layer 30A as adhesive layer 42.

In stiffener adhering processes, the second heating suppression process below is preferably implemented: in the sealing of seal 50 Adhesive layer 42 is sandwiched between resin layer 30A and stiffening plate 41, then uses tabular component respectively from 41 side of stiffening plate and 10 side of bonding sheet Clamping is suppressed under conditions of given temperature, time and pressure.By the second heating suppression process, by seal 50 It is pre-fixed with stiffener 40.It, preferably will be close after fixation in order to solidify adhesive layer 42 after the second heating suppression process 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 being suitable for setting, for example, 185 DEG C, 80 minutes and 2.4MPa of condition.In the second heating suppression process, make For tabular component, the metal plate of stainless steel etc. can be used for example.

Stripping process

Fig. 2 E shows the schematic diagram of the process for illustrating to remove bonding sheet 10.

In the present embodiment, in the flexible situation of substrate 11 of bonding sheet 10, can make bonding sheet 10 be bent and Easily removed from frame component 20, semiconductor chip CP and sealing resin layer 30A.Peel angle θ is not particularly limited, preferably Bonding sheet 10 is removed with 90 degree or more of peel angle θ.If peel angle θ is 90 degree or more, will can easily glue Piece 10 is closed to remove from frame component 20, semiconductor chip CP and sealing resin layer 30A.Peel angle θ be preferably 90 degree or more and Below 180 degree, it is more preferably 135 degree or more and 180 degree or less.It is shelled while being bent bonding sheet 10 in this way From, it can reduce and frame component 20, semiconductor chip CP and sealing resin layer the 30A load applied are removed, so as to To inhibit the damage of the semiconductor chip CP and sealing resin layer 30A that generate by the removing of bonding sheet 10.Bonding sheet 10 is shelled From rear, implement above-mentioned cabling processes again and the process etc. of protrusion is set.After the removing of bonding sheet 10, implements cabling processes again and set Before process for setting protrusion etc., it also can according to need and implement above-mentioned stiffener adhering processes.

In the case where pasting stiffener 40, after process for implementing cabling processes again and protrusion being arranged etc., not The stage of the support of stiffener 40 is needed to remove stiffener 40 from seal 50.

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

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

As the adherend that adhesive phase 12 is contacted, 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 substrate Therefore even if bonding sheet 10 is exposed under hot conditions, it can also prevent between 11 and adhesive phase 12 comprising oligomer sealant 13 Only immersion of the oligomer in substrate 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)

Second embodiment and first embodiment the difference lies in that having oligomer close on the substrate two sides of bonding sheet Sealing.Second embodiment is identical with first embodiment in other aspects, therefore its explanation is omitted or simplified.

Fig. 3 shows the constructed profile of the bonding sheet 10A of second embodiment.

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

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

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

Oligomer sealant 14 (the second oligomer sealant) is to be precipitated second in substrate 11 for preventing from being heated The oligomer of substrate surface 11b 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 oligomer illustrated by first embodiment The thickness of the same range of sealing 13.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, oligomer sealant 13 and oligomer sealant 14 with a thickness of 100nm or more and 200nm or less can be 150nm or so.

The manufacturing method of bonding sheet 10A is also not particularly limited.

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

Bonding sheet 10A can also apply application method same as the bonding sheet 10 of first embodiment, can be with bonding Piece 10 similarly uses in the manufacturing 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, It can prevent from being precipitated and pollute the component other than adherend and device in the oligomer attachment on the second substrate surface 11b.For example, In the manufacturing method of semiconductor device, can prevent heating suppression process in the bonding sheet 10A tabular component contacted Pollution.

(deformation of embodiment)

The present invention is not limited to above embodiment, deformation and improvement in the range of can be realized 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 with component illustrated by above embodiment Etc. identical, identical symbol is just assigned, and its explanation is omitted or simplified.

In addition, bonding sheet can be provided with the state of monolithic or be provided with the state of multiple bonding sheet laminations.The feelings Under condition, for example, adhesive phase can also be covered by the substrate of other bonding sheets to lamination.

In addition, bonding sheet can be provided in the form of the piece of strip or be provided with the state being rolled into a roll.It is rolled up The rear use such as desired size is cut into after can extracting out from volume at the bonding sheet of web-like.

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 is coated with remover in peeling base and the stripping that is formed From oxidant layer.In addition, stripping film only can have peeling agent layer in the one side of peeling base, it can also be in two masks of peeling base There is peeling agent layer.As peeling base, it can be cited for example that: paper base material, the thermoplasticities such as laminated polyethylene on the paper base material Laminated paper and plastic foil made of resin 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 the polyester films such as polyethylene naphthalate and the polyolefin films such as polypropylene and polyethylene etc..As remover, Ke Yiju Out for example: olefine kind resin, heat-resistant powder filler (such as butadiene type resin, isoprene resin 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 20 μm or more and 200 μm hereinafter, preferably 25 μm or more and 150 μm or less.

The thickness of peeling agent layer is not particularly limited, the case where coating includes the solution of remover and forms peeling agent layer Under, the thickness of peeling agent layer is preferably 0.01 μm or more and 2.0 μm hereinafter, more preferably 0.03 μm or more and 1.0 μm or less.

Use plastic foil as in the case where peeling base, the thickness of the plastic foil be preferably 3 μm or more and 50 μm hereinafter, More preferably 5 μm or more and 40 μm or less.

Bonding sheet with stripping film is for example manufactured by following process.Firstly, the coating adhesive group on stripping film Object is closed, film is formed, then, makes dried coating film, forms adhesive phase 12.In addition, as illustrated by above embodiment, Oligomer sealant 13 is formd on the first base material face 11a of substrate 11.Make the adhesive phase 12 and substrate 11 on stripping film On oligomer sealant 13 be bonded.In the case where mode with oligomer sealant 14, formd on the two sides of substrate 11 After oligomer sealant 13,14, adhesive phase 12 is bonded with oligomer sealant 13.

For the above embodiment, list sealing resin 30 material be heat-curing resin in case where into Explanation is gone, but the present invention is not limited to such modes.For example, sealing resin 30 is also possible to utilize the energy such as ultraviolet light The cured energy ray-curable resin of line.

For the above embodiment, in the explanation of the manufacturing method of semiconductor device, enumerating keeps frame component 20 viscous It is affixed on for the mode of bonding sheet 10 and is illustrated, but the present invention is not limited to such modes.Bonding sheet 10 can also be with It is used in the manufacturing method for the semiconductor device being sealed without using frame component to semiconductor element.

Embodiment

Hereinafter, enumerating 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.It, will after heating Bonding sheet removing.Utilize digit microscope (manufacture of KEYENCE company, digit microscope；VHX-1000) to partly leading after removing It is observed in the face that is attached of body chip, it is thus identified that whether there is or not residues, observe multiplying power and are set as 500 times.Residue will not confirmed The case where situation is determined as " A ", will confirm that residue is determined as " B ".

It should be noted that residue whether be oligomer from substrate confirmation according to method as shown below into Row.Using the spectrum of Raman spectrum analysis method measurement residue, being consistent by spectrum with the feature of the substrate of bonding sheet, it is residual to confirmed Slag object is derived from the oligomer of substrate.

(production of bonding sheet)

(embodiment 1)

(1) the coating preparation of oligomer sealant solution

Cooperate 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), solid component concentration of DIC company manufacture: 40 mass %, Weight-average molecular Amount: 25000

(B) petchem

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

(C) multifunctional amino-compound

" the CYMEL 303 " (quotient that hexamethoxymethyl melamine, NIHON CYTEC INDUSTRIES INC. are manufactured 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 above-mentioned 100 mass parts of (A) bisphenol A type epoxy compound Benzene dilute solution (solid component concentration: 30%) 14.29 mass parts and above-mentioned 11.4 matter of (C) hexamethoxymethyl melamine Part is measured, again with toluene/methyl ethyl ketone=50 mass of mass %/50 % mixed solvent is diluted, so that solid component 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 100 mass parts of (A) bisphenol A type epoxy compound), it is close to have obtained coating oligomer Seal agent solution.

(2) production of oligomer sealant

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

(3) production of adhesive composition

Cooperate material below (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 component)

By 92.8 mass % of 2-EHA, 7.0 mass % of acrylic acid 2- hydroxy methacrylate and 0.2 matter of acrylic acid 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 component)

Crosslinking agent: the 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 ingredient)

Retarder thinner: methyl ethyl ketone is used, coating is adjusted to 30 mass % with the solid component concentration of adhesive liquid.

(4) production of adhesive phase

Prepared coating is coated on binder solution equipped with organic using comma coater (registered trademark) Transparent polyethylene terephthalate film stripping film (Lindeke Co., Ltd's manufacture of 38 μm of silicon class peeling layer；SP- PET382150) removing level side, and make it is dry after film thickness be 50 μm, heating in 90 seconds is carried out at 90 DEG C, is connect Heating in 90 seconds is carried out at 115 DEG C, make dried coating film.

(5) production of bonding sheet

The adhesive phase for removing made in film surface is bonded with oligomer sealant made on substrate surface, is obtained The bonding sheet of embodiment 1 is arrived.

(embodiment 2)

For the bonding sheet of embodiment 2, other than polymer and 1 difference of embodiment contained by the adhesive phase, with Embodiment 1 has been carried out similarly production.

Polymer used in embodiment 2 is by 80.8 mass % of 2-EHA, acrylic acid 2- hydroxy methacrylate 7 12 mass % of quality %, 4- acryloyl morpholine and 0.2 mass % of acrylic acid copolymerization and prepare.

(comparative example 1)

For the bonding sheet of comparative example 1, in addition to bonding agent contained in adhesive phase is different from embodiment 1, base Material is different from embodiment 1 and does not have other than oligomer sealant, is made similarly to Example 1.

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.

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

(comparative example 2)

For the bonding sheet of comparative example 2, in addition to bonding agent contained in adhesive phase it is different from comparative example 1 with Outside, production has been carried out similarly with comparative example 1.

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, in addition to adhesive contained in adhesive phase is different from embodiment 1, bonding The thickness of oxidant layer is different from embodiment 1, substrate and embodiment 1 are different and do not have other than oligomer sealant, with embodiment 1 has been carried out similarly production.

Silicone adhesive category has been used in comparative example 3.

In comparative example 3, cooperate following component:

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

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

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

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

5 mass parts (solid component) of bottom coating (BY24-712), 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 removing level side of stripping film with adhesive liquid and is dried, so that dry After dry with a thickness of 30 μm, made adhesive phase.Drying condition is 130 DEG C and 2 minutes.Substrate used in comparative example 3 makes It is polyethylene terephthalate film (Mitsubishi Plastics Inc's manufacture；DIAFOIL PET50T-100,50 μ of thickness M, the storage modulus at 100 DEG C is 3.2 × 10⁹Pa〕.The adhesive phase made in film surface will be removed to be bonded with substrate, 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

Think the bonding sheet due to comparative example 1~3 due to not having oligomer sealant between adhesive phase and substrate, Therefore residue has been precipitated on adherend (semiconductor chip) surface in the case where being exposed to 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 substrate Object sealant, thus it is residual if exposed to not also being precipitated under 190 DEG C of hot conditions on adherend (semiconductor chip) surface Slag object.

Claims (10)

1. a kind of bonding sheet is used when being sealed to the semiconductor element on bonding sheet, which is included

Substrate,

Adhesive phase comprising adhesive and

The oligomer sealant being set between the substrate and described adhesive layer,

The oligomer sealant is to solidify envelope made of solidifying oligomer sealant composition,

The oligomer sealant includes with composition: epoxide, petchem and multifunctional amino-compound,

The oligomer sealant with a thickness of 50nm or more and 500nm hereinafter,

The use when bonding sheet is sealed semiconductor element under the conditions of 180 DEG C or more and 200 DEG C of temperature below.

2. bonding sheet according to claim 1, wherein the oligomer sealant includes with composition:

(A) 50 mass % or more and 80 mass % bisphenol A type epoxy compound below,

(B) 5 mass % or more and 30 mass % petchem below and

(C) 10 mass % or more and 40 mass % multifunctional amino-compound below.

3. bonding sheet according to claim 1 or 2, wherein storage modulus of the substrate at 100 DEG C is 1 × 10⁷Pa More than.

4. bonding sheet according to claim 1 or 2, wherein described adhesive layer contains acrylic pressure-sensitive adhesive compositions Or silicone adhesive category composition.

5. bonding sheet according to claim 4, wherein described adhesive layer contains the acrylic adhesives combination Object, the acrylic pressure-sensitive adhesive compositions include the acrylic copolymer using 2-EHA as principal monomer Object.

6. bonding sheet according to claim 4, wherein described adhesive layer contains the silicone adhesive category combination Object, the silicone adhesive category composition include polyaddition type organic siliconresin.

7. bonding sheet according to claim 1 or 2, wherein there is the oligomer sealant on the two sides of the substrate.

8. bonding sheet according to claim 1 or 2, wherein the substrate includes polyester resin.

9. bonding sheet according to claim 8, wherein the quality of polyester resin is constituting the total of the material of the substrate Shared ratio is 50 mass % or more in quality.

10. bonding sheet according to claim 1 or 2, wherein the oligomer sealant with a thickness of 80nm or more and 300nm or less.