CN108977099A - Adhesive tape - Google Patents

Adhesive tape Download PDF

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Publication number
CN108977099A
CN108977099A CN201810806474.3A CN201810806474A CN108977099A CN 108977099 A CN108977099 A CN 108977099A CN 201810806474 A CN201810806474 A CN 201810806474A CN 108977099 A CN108977099 A CN 108977099A
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CN
China
Prior art keywords
adhesive
methyl
adhesive tape
weight
tape according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810806474.3A
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Chinese (zh)
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CN108977099B (en
Inventor
由藤拓三
矢田贝隆浩
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN108977099A publication Critical patent/CN108977099A/en
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Publication of CN108977099B publication Critical patent/CN108977099B/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/24Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245Vinyl resins, e.g. polyvinyl chloride [PVC]
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of (meth)acrylic polymer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00Presence of polysiloxane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dicing (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a kind of adhesive tape, and the rising of bonding force is able to suppress being heated because of laser cutting etc., and the taking-up of the semiconductor element of panelization is easy to the processing of the transfer of other adhesive tapes etc., and is able to suppress the residue glue to adherend.Adhesive tape of the invention is the adhesive tape for having adhesive phase at least one face of substrate, and the identation hardness at 100 DEG C obtained using nano-hardness tester on the surface of the adhesive phase is 20.0MPa or more.

Description

Adhesive tape
The application be the applying date be on April 4th, 2014, application No. is 201410137377.1, entitled " bonding The divisional application of the application of band ".
Technical field
The present invention relates to adhesive tapes.
Background technique
Semiconductor chip (chip) is will to be formed with the semiconductor crystal wafer cutting (cutting) of circuit and make.For example, logical It crosses in the cutting cutting for carrying out semiconductor crystal wafer on adhesive tape, which becomes core by panelization (chip) Piece continues to use (referring for example to patent document 1) in a subsequent process step from cutting with the chip is picked up on adhesive tape.At this In cutting off processing, adhesive tape is used for the purpose for fixing semiconductor crystal wafer.
In previous cutting off processing, the cutting edges such as rotating sword are used.But in the cutting off processing for having used cutting edge In, exist and generates cutting swarf such problems.Therefore, the laser cutting cut off with laser is carried out in recent years.
However, being led to the problem of following: after laser cutting when using previous cutting adhesive tape in laser cutting The bonding force of cutting adhesive tape is substantially increased, processing thereafter (for example, by the semiconductor element of panelization take out or to The operation etc. of other adhesive tapes transfer) it becomes difficult to carry out such problems, be generated as residue glue on the adherend of taking-up Problem.
Thought originally, this phenomenon is that the strand of the adhesive in cutting adhesive tape is cut off because of laser, bonding Agent occurs low molecule quantization and causes the result of bonding force rising.It is thus regarded that, if it can be by being added into adhesive phase Light absorber is coped with.But by this reply, to the above-mentioned phenomenon of elimination still completely without effect.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2005-019607 bulletin
Summary of the invention
Problems to be solved by the invention
The present inventor's use can not also cut off long wavelength laser as strand from the aspect of quantum chemistry and test It is found when card, when using the laser of this long wavelength, also as in the past, the bonding of cutting adhesive tape after laser cutting Power is substantially increased.Therefore, what happens the present inventor is in order to investigate when irradiating laser to semiconductor crystal wafer, selects silicon mirror Face wafer attaches adhesive tape as semiconductor crystal wafer on it, and is radiated at when being cut by laser to semiconductor crystal wafer and is made Laser observes its situation.
Finally, it is found that temperature is anxious in the tiny area that the illumination is mapped to when irradiating laser to silicon mirror wafer Play rises, although the time is very short, wafer is heated to 100 DEG C or so when being cut off.Thought by the result, is cut after laser cutting The chemometamorphism that the reason of being substantially increased with the bonding force of adhesive tape is not the adhesive as caused by laser is cut, the reason is that physics becomes Matter, that is, adhesive softens due to heating, and the area for being sealed at adherend (semiconductor crystal wafer) increases.
That is, can press down being heated because of laser cutting etc. the issue of the present invention is to provide a kind of adhesive tape The rising of bonding force processed, the taking-up of the semiconductor element of panelization are easy to the processing of the transfer of other adhesive tapes etc., and can Inhibit the residue glue to adherend.
The solution to the problem
Using the adhesive with various hardness at 100 DEG C, the cutting after confirmation is cut by laser bonds the present inventor It is found when the degree that the bonding force of band rises, if the impression at 100 DEG C obtained using nano-hardness tester of adhesive surface Hardness is defined size or more, then will not cause on bonding force as causing adverse effect in the processing after laser cutting It rises.
Adhesive tape of the invention is the adhesive tape for having adhesive phase at least one face of substrate,
Identation hardness at 100 DEG C obtained using nano-hardness tester on the surface of the adhesive phase is 20.0MPa or more.
In a preferred embodiment, the pressure at 23 DEG C obtained using nano-hardness tester on the surface of above-mentioned adhesive phase Trace hardness is 0.5MPa~10.0MPa.
In a preferred embodiment, the attaching preservation bonding force of above-mentioned adhesive phase is after 23 DEG C × 30 minutes 0.15N/20mm or more.
In a preferred embodiment, above-mentioned adhesive phase includes epoxy crosslinking agent.
In a preferred embodiment, above-mentioned adhesive phase includes (methyl) acrylic polymer.
In a preferred embodiment, the maximum elongation rate according to measurement in JIS-K-7127 (1999) of above-mentioned substrate is 100% or more.
In a preferred embodiment, above-mentioned substrate is plastic film.
In a preferred embodiment, above-mentioned plastic film includes to be selected from polyvinyl chloride, polyolefin, ethene-vinyl acetate Ester copolymer it is at least one kind of.
In a preferred embodiment, has above-mentioned adhesive phase in the single side of above-mentioned substrate, in the viscous with this of the substrate The opposite face of mixture layer has non-adhesive.
In a preferred embodiment, above-mentioned non-adhesive is the mixing of polysiloxanes and (methyl) acrylic polymer Layer.
In a preferred embodiment, the polysiloxanes in above-mentioned non-adhesive and (methyl) acrylic polymer is mixed Composition and division in a proportion is using weight ratio meter as polysiloxanes: (methyl) acrylic polymer=1:50~50:1.
In a preferred embodiment, above-mentioned non-adhesive has phase separation structure.
In a preferred embodiment, above-mentioned non-adhesive with a thickness of 0.01 μm~10 μm.
In a preferred embodiment, has release liner on the surface of above-mentioned adhesive phase.
In a preferred embodiment, adhesive tape of the invention is used for semiconductor machining.
In a preferred embodiment, adhesive tape of the invention cuts purposes for LED.
The effect of invention
In accordance with the invention it is possible to provide a kind of adhesive tape, it is able to suppress being heated because of laser cutting etc. viscous The rising of resultant force, the taking-up of the semiconductor element of panelization are easy to the processing of the transfer of other adhesive tapes etc., and are able to suppress To the residue glue of adherend.
Detailed description of the invention
Fig. 1 is the schematic cross-section of the preferred embodiment of adhesive tape of the invention.
Fig. 2 is the SEM photograph for showing the surface side state of the non-adhesive in adhesive tape of the invention.
Fig. 3 is the SEM photograph for showing the sectional side state of the non-adhesive in adhesive tape of the invention.
Fig. 4 is the SEM photograph for the sectional side state that band explanatorily shows the non-adhesive in adhesive tape of the invention.
Description of symbols
10 substrates
20 adhesive phases
30 non-adhesive
100 adhesive tapes
Specific embodiment
Adhesive tape of the invention has adhesive phase at least one face of substrate.Adhesive tape of the invention can be in base The two-sided of material has adhesive phase, can also have adhesive phase in the single side of substrate.
Fig. 1 is the schematic cross-section of the preferred embodiment of adhesive tape of the invention.In Fig. 1, adhesive tape of the invention 100 have adhesive phase 20 on a face of substrate 10.In Fig. 1, in the mask opposite with adhesive phase 20 of substrate 10 Standby non-adhesive 30.Can also have release liner (not shown) on the surface of adhesive phase 20.In Fig. 1, bonding of the invention It is non-adhesive 30 with 100, the laminated body of substrate 10 and adhesive phase 20.
The thickness of adhesive tape of the invention is preferably 20 μm~120 μm, and more preferably 30 μm~120 μm, further preferably It is 40 μm~120 μm.By adjusting the thickness of adhesive tape of the invention into above range, effect of the invention can become It is more easier to show.If the thickness of adhesive tape of the invention is too small, the worry for having treatability to be deteriorated especially has fitting operation to become Difficult worry.If the thickness of adhesive tape of the invention is excessive, there is the worry being deteriorated to the tracing ability of the deformations such as stretching.
<substrate>
The thickness of substrate is preferably 20 μm~120 μm, more preferably 30 μm~120 μm, further preferably 40 μm~120 μm.By adjusting the thickness of substrate of the invention into above range, effect of the invention can become to be more easier to show. If the thickness of substrate is too small, the worry for having treatability to be deteriorated especially has fitting operation to become difficult worry when constituting adhesive tape. If the thickness of substrate is excessive, there is the worry being deteriorated to the tracing ability of the deformations such as stretching.
The maximum elongation rate according to measurement in JIS-K-7127 (1999) of substrate is preferably 100% or more, more preferably 200%~1000%.By using the substrate for showing such maximum elongation rate, effect of the invention can become to be more easier Show.In addition, adhesive tape of the invention can be assigned by using the substrate for showing such maximum elongation rate with appropriateness Extensibility, such as the tracing ability of adherend can be improved.
As substrate, as long as meeting above-mentioned characteristic, may be selected within the scope of the effect of the invention any suitable When material.As such substrate, preferably plastic film.
Plastic film may include any suitable resin material.As such resin material, example is preferably enumerated Such as polyvinyl chloride, polyolefin, ethylene-vinyl acetate copolymer, polyester, polyimides, polyamide, it may be more preferable to enumerate Polyvinyl chloride, polyolefin, ethylene-vinyl acetate copolymer can further preferably enumerate polyvinyl chloride.Polyvinyl chloride is answered Power slackness is excellent, therefore can be particularly suitablely for the adhesive tape used in the semiconductor machinings such as LED cutting.
It, can be any suitable according to purpose/purposes setting as the containing ratio of the above-mentioned resin material in plastic film Containing ratio.As this containing ratio, such as the preferably 50 weight % of weight %~100, more preferably 60 weight %~100 Weight %, further preferably 70 weight of weight %~100 %.
Also it may include plasticizer in plastic film.The containing ratio of plasticizer in plastic film is thin relative to the plastics Above-mentioned resin material in film is preferably the 0.5 weight % of weight %~50, more preferably 1.0 weight of weight %~40 %.Pass through Plasticizer is included with above-mentioned containing ratio in plastic film, adhesive tape of the invention becomes more the tracing ability of the deformations such as stretching Add good.
It as above-mentioned plasticizer, such as can enumerate: phthalic acid ester system, trimellitate system (DIC CORPORATION System, W-700, trioctyl trimellitate (TOTM) etc.), adipate ester system (J-PLUS Co., Ltd system, D620, dioctyl adipate, oneself two Sour dinonyl etc.), phosphate system (tricresyl phosphate etc.), adipic acid system ester, citrate (citroflex A-4 Deng), sebacate, azelate, maleate, benzoic ether, polyether system polyester, epoxy polyester (epoxidised soybean oil, ring Aoxidize linseed oil etc.), polyester (low molecule polyester formed by carboxylic acid and glycol etc.) etc..In the present invention, it is preferred to use ester It is plasticizer.Plasticizer can be only a kind, or two or more.
Within the scope of the effect of the invention, any suitable other compositions also be may include in plastic film.
In the range of can show effect of the invention, substrate can be manufactured using any suitable manufacturing method.Make It for this manufacturing method, such as can enumerate: injection molding, extrusion molding, inflation molding, calendering formation, blow molding etc..
<adhesive phase>
The thickness of adhesive phase is preferably 1.0 μm~30 μm, more preferably 1.0 μm~20 μm, further preferably 3.0 μm ~15 μm.When the thickness of adhesive phase is less than 1.0 μm, whether there is or not the worries that method shows sufficient bonding force.The thickness of adhesive phase When greater than 30 μm, depending on the application, have bonding force it is excessive and remove etc. whens adherend rupture worry.
As the material of above-mentioned adhesive phase, can be used within the scope of the effect of the invention any suitable viscous Mixture.
It as the material of adhesive phase, such as can enumerate: (methyl) acrylic polymer;Natural rubber;It is grafted with The special natural rubber of the monomers such as methyl methacrylate;SBS, SBR, SEPS, SIS, SEBS, polybutene, polyisobutene (polyisobutene), the synthetic rubber such as polyisobutene (polyisobutylene), butyl rubber;Deng.In these, from stripping From it is rear it is few to the residue glue of adherend, set out with high cohesion, the excellent aspect of the transparency, preferred (methyl) acrylic Object.The material of adhesive phase can be only a kind, or two or more.For example, when selection (methyl) acrylic polymer, The polymer can be only a kind, or two or more.
It should be noted that " (methyl) acrylic acid " refers to acrylic acid and/or (methyl) acrylic acid in this specification, " (methyl) acrylate " refers to acrylate and/or (methyl) acrylate.
When adhesive phase includes (methyl) acrylic polymer, (methyl) acrylic polymer in adhesive phase Containing ratio can be suitably set according to purpose.
Above-mentioned (methyl) acrylic polymer is by the monomer comprising (methyl) acrylic monomer as principal monomer The resin that ingredient is constituted.Constitute (methyl) acrylic monomer in the monomer component of above-mentioned (methyl) acrylic polymer Containing ratio is preferably 50 weight % or more, more preferably the 70 weight % of weight %~100, and further preferably 90 weight %~ 100 weight %, particularly preferably 95 weight of weight %~100 %.Monomer in above-mentioned monomer component can be only a kind, can also Think two or more.
As (methyl) acrylic monomer, (methyl) acrylate, (methyl) acrylic acid are preferably enumerated.
It as (methyl) acrylate, such as can enumerate: (the first for the alkyl (also including naphthenic base) that carbon number is 1~30 Base) alkyl acrylate, hydroxyl (methyl) acrylate etc..(methyl) acrylate can be only a kind, or 2 kinds More than.
As (methyl) alkyl acrylate for the alkyl (also including naphthenic base) that carbon number is 1~30, such as can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) Butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) third Olefin(e) acid pentyl ester ((meth) acrylic acid pentyl), (methyl) amyl acrylate ((meth) acrylic acid Amyl), (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) heptylacrylate, (methyl) acrylic acid -2- second The own ester of base, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) nonyl acrylate, the different nonyl of (methyl) acrylic acid Ester, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) acrylic acid ten Dialkyl ester, (methyl) tridecyl acrylate, (methyl) acrylic acid tetradecane base ester, (methyl) acrylic acid pentadecyl Ester, (methyl) octadecyl acrylate, (methyl) acrylic acid nonadecane base ester, (methyl) acrylic acid eicosane base ester, (first Base) carbon numbers such as lauryl acrylate be 1~30 alkyl (also including naphthenic base) (methyl) alkyl acrylate etc..These In (methyl) acrylate, preferably carbon number be 2~20 alkyl (also include naphthenic base) (methyl) alkyl acrylate, More preferably carbon number be 4~18 alkyl (also include naphthenic base) (methyl) alkyl acrylate.
It as hydroxyl (methyl) acrylate, such as can enumerate: (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -4- hydroxybutyl etc..
In order to sufficiently show the effect as adhesive, the monomer component for constituting above-mentioned (methyl) acrylic polymer is excellent It selects comprising being selected from at least one kind of of hydroxyl monomer, carboxyl group-containing monomer.More preferably carboxyl group-containing monomer.
In addition, constituting the monomer of above-mentioned (methyl) acrylic polymer to sufficiently show the effect as adhesive Ingredient can contain acrylonitrile.
It as hydroxyl monomer, such as can enumerate: (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid -2- hydroxyl Base propyl ester, (methyl) acrylic acid -4- hydroxybutyl, allyl alcohol etc..Hydroxyl monomer can be only a kind, or 2 kinds with On.
It as carboxyl group-containing monomer, such as can enumerate: (methyl) acrylic acid, (methyl) carboxy ethyl acrylate, (methyl) third Olefin(e) acid carboxylic pentyl ester, crotonic acid, maleic acid, fumaric acid, itaconic acid etc..Carboxyl group-containing monomer can be only a kind, or 2 kinds with On.
When constituting the monomer component of above-mentioned (methyl) acrylic polymer and containing hydroxyl monomer, constitute above-mentioned (methyl) The containing ratio of hydroxyl monomer in the monomer component of acrylic polymer is preferably the 0.1 weight % of weight %~20, more Preferably 0.1 weight of weight %~10 %.The monomer component for constituting above-mentioned (methyl) acrylic polymer contains list containing carboxyl When body, the containing ratio for constituting the carboxyl group-containing monomer in the monomer component of above-mentioned (methyl) acrylic polymer is preferably 0.1 The weight % of weight %~20, more preferably 0.1 weight of weight %~10 %.In this way, by making to constitute above-mentioned (methyl) acrylic acid The monomer component of quasi polymer contain selected from hydroxyl monomer, carboxyl group-containing monomer it is at least one kind of, using crosslinking agent the case where Under, the cross-linking reaction with the crosslinking agent can more effectively occur, can sufficiently show the effect as adhesive.In turn, lead to Containing ratio, the composition for overregulating the hydroxyl monomer in the monomer component for constituting above-mentioned (methyl) acrylic polymer are above-mentioned The containing ratio of carboxyl group-containing monomer in the monomer component of (methyl) acrylic polymer and be in above range, energy The rupture of adherend when being enough effectively prevented strip operation.In the monomer component for constituting above-mentioned (methyl) acrylic polymer The containing ratio of hydroxyl monomer constitutes containing for carboxyl group-containing monomer in the monomer component of above-mentioned (methyl) acrylic polymer Have ratio compared to above range it is excessive when, bonding force becomes excessive, has the worry for being easy to produce adhesion, in addition, when strip operation There is the worry for the rupture for being easy to produce adherend.
Adhesive phase preferably comprises crosslinking agent.When adhesive phase includes crosslinking agent, crosslinking agent in adhesive phase contains Ratio can be suitably set according to purpose, relative to principal resinous ingredients (preferably (methyl) acrylic polymer) 100 weights Measure part, preferably 0.1 parts by weight~30 parts by weight, more preferably 1.0 parts by weight~27 parts by weight, further preferably 3.0 weights Measure part~25 parts by weight, particularly preferably 5.0 parts by weight~23 parts by weight.By make the crosslinking agent in adhesive phase containing than Rate is within the above range, it is possible to provide following adhesive tape: being able to suppress bonding force being heated because of laser cutting etc. Rising, the taking-up of the semiconductor element of panelization is easy to the processing of the transfer of other adhesive tapes etc., and is able to suppress to quilt The residue glue of viscous object.In addition, the containing ratio by making the crosslinking agent in adhesive phase is within the above range, appropriateness can be generated Cross-linking reaction, the rupture of adherend when can be effectively prevented strip operation.
It as crosslinking agent, such as can enumerate: epoxy crosslinking agent, isocyanates system crosslinking agent, melamine series crosslinking Agent, peroxide system crosslinking agent, metal alkoxide system crosslinking agent, metallo-chelate system crosslinking agent, metal salt system crosslinking agent, carbon two are sub- Amine system crosslinking agent, oxazoline system crosslinking agent, aziridine system crosslinking agent, amine system crosslinking agent etc..Crosslinking agent can be only a kind, can also Think two or more.
Crosslinking agent preferably comprises epoxy crosslinking agent.By that must include epoxy crosslinking agent as crosslinking agent, it is possible to provide Following adhesive tape: the rising of bonding force, the semiconductor element of panelization are able to suppress being heated because of laser cutting etc. The taking-up of part is easy to the processing of the transfer of other adhesive tapes etc., and is able to suppress the residue glue to adherend.
Must comprising epoxy crosslinking agent as crosslinking agent when, the containing ratio of the epoxy crosslinking agent in adhesive phase can It is suitably set according to purpose, it is excellent relative to principal resinous ingredients (preferably (methyl) acrylic polymer) 100 parts by weight It is selected as 0.1 parts by weight~30 parts by weight, more preferably 0.2 parts by weight~25 parts by weight, further preferably 0.5 parts by weight~20 Parts by weight, particularly preferably 0.7 parts by weight~15 parts by weight.By the containing ratio for making the epoxy crosslinking agent in adhesive phase Within the above range, it is possible to provide following adhesive tape: being able to suppress bonding force being heated because of laser cutting etc. Rise, the taking-up of the semiconductor element of panelization is easy to the processing of the transfer of other adhesive tapes etc., and is able to suppress to being glued The residue glue of object.
As epoxy crosslinking agent, any suitable epoxy crosslinking agent can be used.As commercially available product, such as can enumerate Out: " the ADEKA RESIN that " TETRAD C ", the ADEKA CORPORATION of Mitsubishi Gas Chemical Co., Ltd's manufacture are manufactured EPU SERIES ", " ADEKA RESIN EPR SERIES ", " CELLOXIDE " of DAICEL CORPORATION manufacture etc..Especially It, the adhesive hybrid manipulation when manufacturing adhesive phase becomes readily aspect, and liquid epoxy resins as them are Preferably.
Must comprising epoxy crosslinking agent as crosslinking agent when, other crosslinking agents can also be applied in combination.As such Crosslinking agent can enumerate above-mentioned isocyanates system crosslinking agent, melamine series crosslinking agent, peroxide system crosslinking agent, metal Alkoxide system crosslinking agent, metallo-chelate system crosslinking agent, metal salt system crosslinking agent, carbodiimide system crosslinking agent, the crosslinking of oxazoline system Agent, aziridine system crosslinking agent, amine system crosslinking agent etc..In these crosslinking agents, from the side that can sufficiently show effect of the invention Face is set out, preferably melamine series crosslinking agent, isocyanates system crosslinking agent, more preferable melamine series crosslinking agent.
Adhesive phase also may include plasticizer.When adhesive phase includes plasticizer, plasticizer in adhesive phase contains There is ratio that can be suitably set according to purpose, relative to principal resinous ingredients (preferably (methyl) acrylic polymer) 100 Parts by weight are 0.1 parts by weight~70 parts by weight.By making the containing ratio of the plasticizer in adhesive phase be in above range It is interior, it can more efficiently show effect of the invention.Relative to principal resinous ingredients (preferably (methyl) acrylic Object) 100 parts by weight, if the containing ratio of the plasticizer in adhesive phase is bigger than 70 parts by weight, adhesive phase becomes excessively soft It is soft, there is the worry for being easy to produce residue glue, adherend pollution.
It as above-mentioned plasticizer, such as can enumerate: phthalic acid ester system, trimellitate system (DIC CORPORATION System, W-700, trioctyl trimellitate (TOTM) etc.), adipate ester system (J-PLUS Co., Ltd system, D620, dioctyl adipate, oneself two Sour dinonyl etc.), phosphate system (tricresyl phosphate etc.), adipic acid system ester, citrate (citroflex A-4 Deng), sebacate, azelate, maleate, benzoic ether, polyether system polyester, epoxy polyester (epoxidised soybean oil, ring Aoxidize linseed oil etc.), polyester (low molecule polyester formed by carboxylic acid and glycol etc.) etc..In the present invention, it is preferred to use ester It is plasticizer.Plasticizer can be only a kind, or two or more.
In order to promote cross-linking reaction etc., adhesive phase may include any suitable catalyst.Adhesive phase includes catalysis When agent, the containing ratio of the catalyst in adhesive phase can be suitably set according to purpose, (preferably relative to principal resinous ingredients For (methyl) acrylic polymer) 100 parts by weight are 0.01 parts by weight~20 parts by weight.By making urging in adhesive phase The containing ratio of agent within the above range, can more efficiently show effect of the invention.
As this catalyst, such as can enumerate: tetraisopropyl titanate, tetra-n-butyl titanate, tin octoate, lead octoate, Cobalt octoate, zinc octoate, calcium octoate, lead naphthenate, cobalt naphthenate, dibutyltin diacetate, two sad dibutyl tins, tin dilaurate The organo-metallic compounds such as dibutyl tin, tin dilaurate dioctyl tin, dibutyitin maleate;Butylamine, dibutyl amine, hexylamine, uncle The alkali compounds such as butylamine, ethylenediamine, isophorone diamine, imidazoles, lithium hydroxide, potassium hydroxide, sodium methoxide;To toluene sulphur Acid, trichloroacetic acid, phosphoric acid, single alkyl phosphonic acid, Acidic phosphates, senecioate-hydroxy methacrylate phosphate, monoalkyl phosphorous The acid compounds such as acid, dialkyl group phosphorous acid;Deng.Catalyst can be only a kind, or two or more.
Identation hardness at 100 DEG C obtained using nano-hardness tester on the surface of adhesive phase is 20.0MPa or more, excellent It is selected as 20.0MPa~1000MPa, more preferably 20.0MPa~100MPa.By the utilization nanometer pressure for making the surface of adhesive phase Identation hardness at trace instrument obtain 100 DEG C is within the above range, it is possible to provide following adhesive tape: even if because of laser cutting etc. And it is heated the rising for being also able to suppress bonding force, the taking-up of the semiconductor element of panelization, to transfer of other adhesive tapes etc. Processing be easy, and be able to suppress the residue glue to adherend.If 100 obtained using nano-hardness tester on the surface of adhesive phase Identation hardness at DEG C is detached from above range and too small, then has the worry for example deteriorated in laser cutting post-processing.If viscous Identation hardness at 100 DEG C obtained using nano-hardness tester on the surface of mixture layer is detached from above range and excessive, then just like Under worry: for example, because in laser cutting process workpiece (be also pasted in addition to adherend in cutting belt ring frame etc., The practical sample for laser cutting process) external force such as the vibration that generates in conveying etc. and generated between adhesive tape and adherend Float, generate positional shift, adhesive tape falls off from adherend.Wherein, about the identation hardness obtained using nano-hardness tester The details of measurement be then illustrated.
Identation hardness at 23 DEG C obtained using nano-hardness tester on the surface of adhesive phase be preferably 0.5MPa~ 10.0MPa, more preferably 0.5MPa~8.0MPa, further preferably 0.5MPa~7.0MPa, particularly preferably 1.0MPa~ 6.0MPa.By make adhesive phase surface 100 DEG C obtained using nano-hardness tester at identation hardness be in above-mentioned model In enclosing and make adhesive phase surface 23 DEG C obtained using nano-hardness tester at identation hardness within the above range, It, can will be of the invention in room temperature region due to can moderately ensure the bonding force in the room temperature region near 23 DEG C Adhesive tape is certainly attached at adherend, and can provide following adhesive tape: being heated because of laser cutting etc. Enough inhibiting the rising of bonding force, the taking-up of the semiconductor element of panelization is easy to the processing of the transfer of other adhesive tapes etc., and It is able to suppress the residue glue to adherend.Wherein, the details about the measurement of the identation hardness obtained using nano-hardness tester are subsequent It is illustrated.
It is preferably 0.15N/20mm or more after 23 DEG C × 30 minutes that the attaching of adhesive phase, which saves bonding force, more preferably 0.15N/20mm~2.00N/20mm, further preferably 0.15N/20mm~1.00N/20mm, particularly preferably 0.20N/ 20mm~1.00N/20mm.Attaching by making adhesive phase saves bonding force after 23 DEG C × 30 minutes in above range It is interior, adhesive tape of the invention can be certainly attached at adherend in room temperature region.Wherein, bonding force is saved about attaching The details of measurement be then illustrated.
Adhesive phase attaching save bonding force heat 30 minutes at 100 DEG C after in turn after 23 DEG C × 30 minutes, it is excellent 2.00N/20mm is selected as hereinafter, more preferably 0.15N/20mm~1.50N/20mm, further preferably 0.15/20mm~ 1.00N/20mm particularly preferably 0.15N/20mm~0.50N/20mm.Attaching by making adhesive phase saves bonding force and exists After being heated 30 minutes at 100 DEG C so that after 23 DEG C × 30 minutes within the above range, it is possible to provide following adhesive tape: even if The rising for being also able to suppress bonding force is heated because of laser cutting etc., the taking-up of the semiconductor element of panelization is glued to other The processing of the transfer of crossed belt etc. is easy, and is able to suppress the residue glue to adherend.Wherein, about the measurement for attaching preservation bonding force Details be then illustrated.
Within the scope of the effect of the invention, adhesive phase may include any suitable additive.As this The additive of sample, such as can enumerate: ultraviolet absorbing agent, filler, anti-aging agent, tackifier, pigment, dyestuff, silane coupled Agent etc..
Adhesive tape of the invention can also have release liner on the surface of adhesive phase.
As release liner, any suitable slider can be used.As this release liner, such as can enumerate: With plastic film, the paper for carrying out surface treatment using removers such as polysiloxane series, chain alkyl system, fluorine system, molybdenum sulfides The substrate of equal peeling layers;By polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene, poly- ethylene fluoride, Kynoar, tetrafluoroethene hexafluoro The low cementability substrate that the fluorine system polymers such as propylene copolymer, chlorine vinyl fluoride vinylidene fluoride copolymers are formed;By olefin-based tree The low cementability substrate that the polar polymerics such as rouge (for example, polyethylene, polypropylene etc.) are formed;Deng.
As the method that adhesive phase is arranged on substrate, it can use appoint within the scope of the effect of the invention It anticipates means appropriate.As such means, set preferably by the coating liquid for forming adhesive phase to be coated on substrate The method for setting adhesive phase.
As coating method, any suitable coating method can be used within the scope of the effect of the invention. As such coating method, such as can enumerate: reverse mode, direct mode, combination have metering roll (metering roll) Various modes etc..
<non-adhesive>
Adhesive tape of the invention is preferably, have adhesive phase in the single side of substrate, in the substrate and the adhesive The opposite face of layer has non-adhesive.
The composition etc. of such non-adhesive is not particularly limited, as its an example, can be enumerated: silicone layer, (methyl) acrylic polymer layer, silicone layer and the mixed layer of (methyl) acrylic polymer layer, graft polymerization have The silicone layer etc. of (methyl) acrylic polymer.In these, preferably polysiloxanes and (methyl) acrylic The mixed layer of object.By making the mixed layer of non-adhesive polysiloxanes Yu (methyl) acrylic polymer, non-adhesive with The adaptability of substrate (especially plastic film) becomes well, and adhesive tape of the invention is good to the tracing ability of the deformations such as stretching It is good.
The surface of non-adhesive preferably has concaveconvex structure.It, can by making the surface of non-adhesive that there is concaveconvex structure It effectively inhibits to the excessive closely sealed of pedestal.About the concaveconvex structure, specifically, the arithmetical average surface of non-adhesive is coarse Spending Ra is preferably 0.1 μm or more, and more preferably 0.1 μm~3.0 μm, further preferably 0.2 μm~2.0 μm, particularly preferably 0.3 μm~2.0 μm, most preferably 0.5 μm~2.0 μm.Arithmetic mean surface roughness Ra by making non-adhesive is in upper It states in range, it is excessively closely sealed to be able to suppress the appearance when carrying out fixed using the absorption of negative pressure.Wherein, the arithmetic of non-adhesive is flat The measuring method of equal surface roughness Ra is then illustrated.
Non-adhesive using Differential Scanning Calorimetry measurement (DSC measurement) glass transition temperature Tg be preferably 20 DEG C with On, more preferably 30 DEG C or more, further preferably 50 DEG C or more, particularly preferably 55 DEG C or more.Utilization to non-adhesive The upper limit of the glass transition temperature Tg of Differential Scanning Calorimetry measurement is not particularly limited, excellent from the viewpoint of treatability etc. Be selected as 200 DEG C hereinafter, more preferably 170 DEG C hereinafter, further preferably 150 DEG C hereinafter, particularly preferably 130 DEG C hereinafter, most Preferably 100 DEG C or less.If the glass transition temperature Tg using Differential Scanning Calorimetry measurement of non-adhesive is in above-mentioned model In enclosing, then the hardness on the surface of non-adhesive can moderately be got higher at high temperature, therefore heat resistance is got higher, and utilize negative pressure Adhesive tape of the invention is absorbed and fixed at it is fixed with being carried out on pedestal in the case where cutting etc., can effectively inhibit appearance because It is excessively closely sealed caused by fever of pedestal etc..Wherein, the glass using Differential Scanning Calorimetry measurement (DSC measurement) of non-adhesive The measuring method for changing transition temperature Tg is then illustrated.
When non-adhesive includes (methyl) acrylic polymer, (methyl) acrylic polymer in non-adhesive SP value is preferably 9.0 (cal/cm3)0.5~12.0 (cal/cm3)0.5, more preferably 9.5 (cal/cm3)0.5~11.5 (cal/ cm3)0.5, further preferably 9.5 (cal/cm3)0.5~11.0 (cal/cm3)0.5.SP value is calculated according to Small formula Solubility parameter.The calculating of SP value can use well known document (for example, Journal of Applied Chemistry, 3, 71,1953. etc.) method documented by carries out.
Non-adhesive preferably has phase separation structure.It, can be non-adhering at this by making non-adhesive that there is phase separation structure The surface of layer is effectively formed small concaveconvex structure.This can probably speculate are as follows: for example using non-adhesive as polysiloxanes and (first Base) acrylic polymer mixed layer in case where, due to phase separation structure generate when polysiloxanes, (methyl) propylene The difference of the substance mobility of acids polymers and generate bumps.Due to the formation of the concaveconvex structure, in adhesive tape of the invention In, it is excessively closely sealed to can inhibit the appearance when carrying out fixed using the absorption of negative pressure, and the form of web-like can be effectively inhibited In adhesion, from the form of web-like carry out debatching when can inhibit fracture or breakage.
Non-adhesive preferably comprises: comprising polysiloxanes more than (methyl) acrylic polymer rich polysiloxanes phase, With richness (methyl) the acrylic polymer phase for being more than polysiloxanes comprising (methyl) acrylic polymer.Non-adhesive has more For body, preferably with mutual independent phase separation structure including above-mentioned rich polysiloxanes phase and above-mentioned rich (methyl) acrylic compounds Polymer phase, more preferably above-mentioned rich polysiloxanes are mutually present in the Air Interface side (phase of substrate (especially plastic film) Toss about), above-mentioned richness (methyl) acrylic polymer is mutually present in substrate (especially plastic film) side.It is such by having Phase separation structure, due to being present in the rich polysiloxanes phase of Air Interface side, adhesion is effectively inhibited, by being present in base Richness (methyl) acrylic polymer phase of material (especially plastic film) side, non-adhesive and substrate (especially plastic film) Adaptability become good, deformation tracing ability becomes good.By by non-adhesive polysiloxanes and (methyl) acrylic compounds The mixing ratio of polymer is adjusted as described below, can form such phase separation structure.
Non-adhesive has the case where phase separation structure, containing as described above comprising polysiloxanes more than (methyl) propylene The rich polysiloxanes phase of acids polymers and richness (methyl) propylene for being more than polysiloxanes comprising (methyl) acrylic polymer The case where acids polymers phase, can be observed by any suitable method.As such observation method, such as can arrange It enumerates: using transmission electron microscope (TEM), scanning electron microscope (SEM), field emission type scanning electron microscope (FE-SEM) method that electron microscopes carry out morphologic observation to non-adhesive section such as.2 layers of separated structure can pass through form The depth of image is observed to recognize.In addition, also the following methods can be enumerated: it is divided using the infrared absorption based on total reflection method, From non-adhesive Air Interface side to inside, change probe optical depth on one side, observe containing for silicon, carbon contained in composition etc. on one side Amount variation, is thus observed.It is seen in addition, can also enumerate using X-ray microanalysis instrument, x-ray photoelectron spectroscopy The method examined.It is observed alternatively, it is also possible to be appropriately combined these methods.
Non-adhesive has the poly- silicon oxygen of richness for being present in Air Interface side (opposite side of substrate (especially plastic film)) The feelings of alkane phase and the phase separation structure of richness (methyl) the acrylic polymer phase for being present in substrate (especially plastic film) side Under condition, when the non-adhesive is absorbed and fixed at fixation with cut etc. on pedestal using negative pressure, if the fixation pedestal Fever, then since because of thermic load caused by the fever, the surface texture of the phase separation structure is destroyed, especially with fever should Fixed pedestal has the surface texture of the phase separation structure in the convex portion of contact to be destroyed more, may go out in the convex portion Existing richness (methyl) acrylic polymer mutually exposes in Air Interface side.But the benefit of the non-adhesive of adhesive tape of the invention It is preferably in above range with the glass transition temperature Tg that Differential Scanning Calorimetry measures, therefore the convex portion by thermic load Hardness moderately get higher, so that heat resistance is got higher.Therefore, adhesive tape of the invention is being absorbed and fixed at fixation using negative pressure When with cut etc. on pedestal, it can effectively inhibit excessively closely sealed caused by occurring because of fever of pedestal etc..
Poly- silicon oxygen when non-adhesive is the mixed layer of polysiloxanes and (methyl) acrylic polymer, in non-adhesive The mixing ratio of alkane and (methyl) acrylic polymer is with weight ratio meter, preferably polysiloxanes: (methyl) acrylic Object=1:50~50:1, more preferably polysiloxanes: (methyl) acrylic polymer=1:30~30:1, further preferably Polysiloxanes: (methyl) acrylic polymer=1:10~10:1, particularly preferably polysiloxanes: (methyl) acrylic polymer Close object=1:5~5:1, most preferably polysiloxanes: (methyl) acrylic polymer=1:3~5:1.If in non-adhesive The content ratio of polysiloxanes is excessive, then the chemical affinity with substrate (especially plastic film) back side is lower, and is difficult to fit Answer the worry at substrate (especially plastic film) back side.In addition, if the containing ratio of the polysiloxanes in non-adhesive is excessive, When adhesive tape is made, it is deteriorated to the tracing ability of the deformations such as stretching, there is the worry for the reason of non-adhesive ruptures and becomes pollution. If the containing ratio of (methyl) acrylic polymer in non-adhesive is excessive, there is non-adhesive as acrylic adhesive The worry that agent plays a role has the worry for being easy to produce adhesion.
As polysiloxanes, any suitable polysiloxanes can be used.As such polysiloxanes, such as can enumerate Out: using platinum series compound as catalyst, polydialkysiloxane containing alkenyl and poly-diakyl hydrogen polysiloxanes being made to pass through addition Reaction is formed by curing addition type polysiloxane obtained from fissility epithelium;Using tin series catalysts, make containing methylol poly- two Condensed type polysiloxanes etc. obtained from alkylsiloxane is reacted with poly-diakyl hydrogen polysiloxanes.As addition type polysiloxane Example, such as can enumerate: " KS-776A " of Shin-Etsu Silicone Co., Ltd manufacture, " KS-839L " etc..Make It for the example of condensed type polysiloxanes, such as can enumerate: " the KS723A/ of Shin-Etsu Silicone Co., Ltd manufacture B".In addition, other than platinum group catalyst, tin series catalysts, other friendships can also be suitably used when manufacturing polysiloxanes Join agent, crosslinking accelerator etc..In addition, the character as polysiloxanes, can be categorized into: the class being dissolved in the organic solvents such as toluene Type, by their emulsion-types made of lo-tionized, only comprising no-solvent type etc. of polysiloxanes.In addition, in addition to additive poly silicon oxygen Other than alkane, condensed type polysiloxanes, polysiloxanes/acrylic acid graft polymer, polysiloxanes/acrylic acid block can also be used Polymer etc..As polysiloxanes/acrylic acid graft polymer, such as can enumerate: SYMAC GS-30, GS101, US-270, US-350, US-380 (the above are Toagosei Co., Ltd's manufactures) etc..As polysiloxanes/acrylic acid block polymer, example It can such as enumerate: MODIPER FS700, FS710, FS720, FS730, FS770 (the above are Japan Oil Co's manufactures).
As (methyl) acrylic polymer, any suitable (methyl) acrylic polymer can be used.This hair In bright, " (methyl) acrylic acid " refers to " acrylic acid and/or methacrylic acid ".
(methyl) acrylic polymer is by the monomer component comprising (methyl) acrylic monomer as principal monomer The polymer of composition.Constitute containing for (methyl) acrylic monomer in the monomer component of above-mentioned (methyl) acrylic polymer Having ratio is preferably 50 weight % or more, more preferably the 70 weight % of weight %~100, and further preferably 90 weight %~ 100 weight %, particularly preferably 95 weight of weight %~100 %.Monomer in above-mentioned monomer component can be only a kind, can also Think two or more.
As (methyl) acrylic monomer, (methyl) acrylate, (methyl) acrylic acid are preferably enumerated.
It as (methyl) acrylate, such as can enumerate: (the first for the alkyl (also including naphthenic base) that carbon number is 1~30 Base) alkyl acrylate, hydroxyl (methyl) acrylate etc..(methyl) acrylate can be only a kind, or 2 kinds More than.
As (methyl) alkyl acrylate for the alkyl (also including naphthenic base) that carbon number is 1~30, such as can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) Butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) third Olefin(e) acid pentyl ester ((meth) acrylic acid pentyl), (methyl) amyl acrylate ((meth) acrylic acid Amyl), (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) heptylacrylate, (methyl) acrylic acid -2- second The own ester of base, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) nonyl acrylate, the different nonyl of (methyl) acrylic acid Ester, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) acrylic acid ten Dialkyl ester, (methyl) tridecyl acrylate, (methyl) acrylic acid tetradecane base ester, (methyl) acrylic acid pentadecyl Ester, (methyl) octadecyl acrylate, (methyl) acrylic acid nonadecane base ester, (methyl) acrylic acid eicosane base ester, (first Base) carbon numbers such as lauryl acrylate be 1~30 alkyl (also including naphthenic base) (methyl) alkyl acrylate etc..These In (methyl) acrylate, preferably carbon number be 2~20 alkyl (also include naphthenic base) (methyl) alkyl acrylate, more It is preferred that (methyl) alkyl acrylate for the alkyl (also including naphthenic base) that carbon number is 4~18.
It as hydroxyl (methyl) acrylate, such as can enumerate: (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -4- hydroxybutyl etc..
In order to sufficiently show effect of the invention, the monomer component for constituting above-mentioned (methyl) acrylic polymer can contain Have selected from hydroxyl monomer, carboxyl group-containing monomer it is at least one kind of.
It as hydroxyl monomer, such as can enumerate: allyl alcohol etc..Hydroxyl monomer can be only a kind, or 2 Kind or more.
As carboxyl group-containing monomer, such as can enumerate: (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, bar Beans acid, maleic acid, fumaric acid, itaconic acid etc..Carboxyl group-containing monomer can be only a kind, or two or more.
When non-adhesive includes (methyl) acrylic polymer, (methyl) acrylic polymer in non-adhesive is excellent Choosing, constitutes the containing ratio of hydroxyl (methyl) acrylate in its monomer component relative to the hydroxyl (methyl) The total amount of monomer component other than acrylate, the preferably 2 weight % of weight %~30, more preferably 3 weights of weight %~25 Measure %, particularly preferably 5 weight of weight %~20 %.When non-adhesive includes (methyl) acrylic polymer, relative to this The total amount of monomer component other than hydroxyl (methyl) acrylate constitutes (methyl) acrylic polymer in non-adhesive Monomer component in hydroxyl (methyl) if the containing ratio of acrylate within the above range, in the table of non-adhesive Face more effectively forms small concaveconvex structure, is utilized in adhesive tape of the invention by the formation of the concaveconvex structure The absorption of negative pressure can further suppress appearance when fixed excessively closely sealed, and can more effectively inhibit in the form of web-like Adhesion can further suppress fracture or breakage when carrying out debatching from the form of web-like.
When non-adhesive includes (methyl) acrylic polymer, (methyl) acrylic polymer in non-adhesive is excellent Choosing can include (first in the monomer component other than hydroxyl (methyl) acrylate in the monomer component for constituting it Base) acrylic acid and/or (methyl) acrylate.At this point, the content ratio of (methyl) acrylic acid and (methyl) acrylate is with weight Amount is than meter, and (methyl) acrylic acid: (methyl) acrylate is preferably 0:100~20:80, more preferably 0:100~10:90, into One step is preferably 0:100~5:95.
(methyl) acrylic acid and (methyl) if the content ratio of acrylate within the above range, in non-adhesive Surface more effectively forms small concaveconvex structure, by the formation of the concaveconvex structure, in adhesive tape of the invention, carries out benefit It is excessively closely sealed that appearance can be further suppressed when being fixed with the absorption of negative pressure, and can more effectively be inhibited in the form of web-like Adhesion, from the form of web-like carry out debatching when can further suppress fracture or breakage.
(methyl) acrylic polymer can be manufactured by any suitable polymerization.
Within the scope of the effect of the invention, non-adhesive may include any suitable additive.As this The additive of sample, such as can enumerate: catalyst, ultraviolet absorbing agent, filler, anti-aging agent, tackifier, pigment, dyestuff, silicon Alkane coupling agent etc..
The thickness of non-adhesive is preferably 0.01 μm~10 μm, more preferably 0.1 μm~5 μm, further preferably 0.1 μm ~2 μm.When the thickness of non-adhesive is lower than 0.01 μm, generation adhesion is become easy.The thickness of non-adhesive is if more than 10 μm, then There is the worry being deteriorated to the tracing ability of the deformations such as stretching.If the thickness of non-adhesive has effect of the invention less than 0.01 μm It is difficult to the worry shown, the worry that manufacture becomes difficult.
It as the method that the single side in substrate (especially plastic film) forms non-adhesive, such as can enumerate: pass through The one side coating non-adhesive of substrate (especially plastic film) material and method to form non-adhesive is dried. It as the method for above-mentioned coating, such as can enumerate: use bar coater, gravure coater, spin coater, roll coater, blade coating The method of machine, applicator etc..
<purposes>
Adhesive tape of the invention can be used for any suitable purposes.Adhesive tape of the invention is as described above, even if because swashing Light cutting etc. and be heated the rising for being also able to suppress bonding force, the taking-up of the semiconductor element of panelization, to other adhesive tapes The processing of transfer etc. be easy, and be able to suppress the residue glue to adherend.In addition, thus it will be appreciated that utilizing negative-pressure adsorption When being fixed on fixation with cut etc. on pedestal, it can effectively inhibit excessively close caused by occurring because of fever of pedestal etc. It closes, in addition, the adhesion in the form of web-like can be effectively inhibited, will not be broken or break when carrying out debatching from the form of web-like Damage, the non-adhesive and the adaptability of the plastic film are good, good to the tracing ability of the deformations such as stretching.Therefore, can be suitable for Ground is for semiconductor crystal wafer partly the leading as adherend the circuit pattern of fine exquisiteness is made of and can had brittle material Body processing.If adhesive tape of the invention is used for semiconductor machining, it is able to suppress being heated because of laser cutting etc. The rising of bonding force, the taking-up of the semiconductor element of panelization are easy to the processing of the transfer of other adhesive tapes etc., and can press down Make the residue glue to adherend.In addition, thus it will be appreciated that cut etc. being fixed on to fix using negative-pressure adsorption on pedestal When, appearance can be effectively inhibited because excessively closely sealed caused by fever of pedestal etc., therefore, can make include cutting including partly Conductor manufacturing process smoothly carries out.In addition, if adhesive tape of the invention is used for semiconductor machining, even if because of laser cutting Deng and be heated the rising for being also able to suppress bonding force, the taking-up of the semiconductor element of panelization, the transfer to other adhesive tapes Deng processing be easy, and be able to suppress the residue glue to adherend, thus it will be appreciated that will not generate and generate in the past due to adhesion Deformation of thin membrane, ess-strain accumulation, therefore with can accurately following the circuit pattern of the fine exquisiteness of semiconductor crystal wafer It is bonded, in addition, being not in the Spontaneous release of the ess-strain after fitting in semiconductor crystal wafer, therefore can be effectively Prevent semiconductor crystal wafer from rupturing.In particular, since the wafer for LED is the material highly brittle by gallium nitride, GaAs, silicon carbide etc. What material was constituted, therefore adhesive tape of the invention is particularly suitable for for cutting of the wafer of LED (LED cutting) etc. 's.
Embodiment
Hereinafter, illustrating the present invention by embodiment, but the present invention is not by any restrictions of these embodiments.Do not having In the case where having special instruction, part refers to parts by weight, and % refers to weight %.In addition, the amount of the reagent supplied as a solution It is indicated with the amount (solid component conversion amount) of solution evaporation and remaining solid component is made.
<indentation test>
Indentation test is carried out with surface of the following conditions to adhesive phase, identation hardness and impression elasticity are found out by its result Modulus.
(measurement device and determination condition)
Device: the Tribo Indenter of Hysitron Inc. manufacture
Use pressure head: Berkovich (triangular pyramid type)
Measuring method: single indentation assaying
Measuring temperature: 25 DEG C, 100 DEG C
Depth of cup setting: about 300nm
Press-in speed: about 10nm/sec
Measure atmosphere: in air
Specimen size: about 1cm × about 1cm
(measuring method)
Using above-mentioned apparatus, after being kept for 1 hour under room temperature (23 DEG C) or 100 DEG C are risen to from room temperature and is kept for 1 hour Afterwards, until Berkovich type Buddha's warrior attendant pressure head made of stones being vertically pressed into depth 300nm from the surface of adhesive phase.Use analysis Software " Triboscan Ver.9.2.12.0 ", resulting displacement, load and the pressure theoretically calculated when by pressure head being pressed into Trace area acquires the identation hardness on surface.In addition, using above-mentioned software, by displacement resulting after removal pressure head, load and reason The elasticity modulus on surface is acquired by the area of indentation of upper calculating.
<residue glue>
It will be as the PVC film of adherend (arithmetic average table in the case where 23 DEG C save referring to JIS-Z-0237 (2000) Ra=0.5 μm of surface roughness) and adhesive tape holding 1 hour or more, then, the adhesive level of adhesive tape is pressed into 8kg/ with line M, it crimps speed 0.3m/ minutes and is crimped in PVC film, after carrying out heating in 100 DEG C × 30 minutes, 30 points are stood at 23 DEG C Clock is removed adhesive tape with 0.01m/ minutes tensile speeds, 180 ° of removings, the residue glue on visual confirmation adherend surface.It will not The case where confirming residue glue, which be evaluated as zero, will confirm that the case where residue glue is evaluated as ×.
<attach and save bonding force>
It will be as the SUS430BA plate of adherend and bonding in the case where 23 DEG C save referring to JIS-Z-0237 (2000) Band holding 1 hour or more, then, the adhesive level of adhesive tape is crimped on for speed 0.3m/ minutes with line pressure 8kg/m, crimping On SUS430BA, removed with 0.3m/ minutes tensile speeds, 180 °, the peeling force after measuring 23 DEG C × 30 minutes respectively, and Peeling force after being heated 30 minutes at 100 DEG C and then after standing 23 DEG C × 30 minutes.
<transferability test>
Attaching back side grinding in the mirror surface of 4 inches of Si mirror surface wafers, (Nitto Denko Corp manufactures, commodity with adhesive tape Name;ELEP HOLDER), it carries out the back side and is ground to wafer to be 0.1mm thick.It, will be as cutting after removing back side grinding adhesive tape The embodiment of band or the adhesive tape in comparative example are attached to mirrored sides, with the reciprocal 1 application load of hand roller, thus make band with The closely sealed abundant progress of wafer.
Above-mentioned sample is fixed on cut ring, after standing 30 minutes in the environment of 23 DEG C of temperature, humidity 50%, below The condition stated is cut.Sample is taken care of 30 minutes at 100 DEG C after cutting, and then in the environment of 23 DEG C of temperature, humidity 50% It is lower to stand 30 minutes.
After aforesaid operations, fitting and the band identical type used as cutting belt on the face for carrying out grinding of wafer Adhesive tape, with the reciprocal 1 application load of hand roller, to make closely sealed abundant progress of the band with wafer.
Said sample is stood 30 minutes under 23 DEG C of temperature, humidity 50%, then in 23 DEG C of temperature, 50% environment of humidity Under, the adhesive tape for being attached to mirrored sides is removed from wafer with the speed of tensile speed 10m/min.
The chip number of the adhesive tape on the face for carrying out grinding for being fitted in wafer will be transferred to due to strip operation Ratio the case where being lower than 95.0% be evaluated as ×, by 95.0% more than or lower than 99.0% the case where be evaluated as zero, will 99.0% or more situation is evaluated as ◎.
(cutting condition)
Cutting equipment: DFD-6450 (DISCO CORPORATION manufacture)
Chip size: 0.5mm × 0.5mm
Blade type: NBC-ZH205O-SE-27HECC (DISCO CORPORATION manufacture)
Rotating speed of flail: 30000rpm
Cutting speed: 80mm/sec
Blade height: 45 μm
<maximum elongation rate>
INSTRON type cupping machine (Shimadzu system is utilized according to JIS-K-7127 (1999) for maximum elongation rate Make manufactured, AUTOGRAPH) it is measured.Specifically, width 20mm × length 100mm is arranged with distance 50mm between chuck Sample after, stretched with 0.3m/ minutes tensile speeds, measurement fracture when value.
<elasticity modulus>
According to JIS-K-7127 (1999), using INSTRON type cupping machine (Shimadzu Seisakusho Ltd.'s manufacture, AUTOGRAPH it) is measured.Specifically, after with distance 50mm between chuck, width 20mm × length 100mm sample is set, It is stretched with 0.3m/ minutes tensile speeds, finds out initial elastic modulus.Initial elastic modulus is set as following value: making Tangent line is extended to value obtained from the value of 100% elongation with straight line by the tangent line in the region of elongation at break 0~2%, and It is modified by the sectional area conversion of sample.
<observation of non-adhesive>
(utilizing the observation of SEM)
It is processed into non-adhesive section to be able to carry out after observation, carries out Appearance View with transmission electron microscope (SEM) It examines.
(utilizing the observation of the infrared spectroscopy measurement (ATR-IR) based on total reflection method)
Using infrared spectroscopy spectrometer (Perkinermer manufacture, Spectrum One), selection total reflection measuring method is The analysis depth for changing probe light carries out non-adhesive using 2 kinds of total reflection measurements with prism (ZnSe45 °, Ge45 °) ATR-IR measurement.
<arithmetic mean surface roughness Ra>
The confocal laser microscope " LEXT3000 " manufactured using OLYMPUS, is measured with 20 times of object lens with 3D mode. The determination of the range of observation of 3D mode carries out as follows: CF image (confocal images) when moving up and down lens is become completely black position Set the Top and Bottom for being respectively set as range of observation.
Image acquiring method under 3D mode carries out image acquisition by Step mode with 0.2 μm of spacing.
The measurement of arithmetic mean surface roughness Ra measures the Ra of any position by the Roughness analysis of analytical model. Wherein, value is found out by the average value of n=5.
(Production Example 1): the manufacture of substrate
It is (adjacent comprising DOP plasticizer relative to 100 parts by weight of polyvinyl chloride of degree of polymerization P=1050 using rolling process manufacture Phthalic acid bis- (2- ethylhexyls), J-PLUS Co., Ltd manufacture) 27 parts by weight soft PVC film.It is resulting soft Matter polyvinyl chloride film with a thickness of 70 μm, according to JIS-K-7127 (1999) measurement elasticity modulus (MD) be 250MPa, Maximum elongation rate (MD) according to measurement in JIS-K-7127 (1999) is 400%.In addition, the arithmetical average surface after just manufacturing Roughness Ra is 0.1 μm.
(embodiment 1)
(non-adhesive)
By polyorganosiloxane resin (KS-723A, the manufacture of SHIN-ETSU HANTOTAI's chemical industry) 60 parts by weight, polyorganosiloxane resin (KS- 723B, the manufacture of SHIN-ETSU HANTOTAI's chemical industry) 40 parts by weight, acrylic copolymer (methyl methacrylate (MMA)/butyl acrylate (BA)/hydroxy-ethyl acrylate (HEA)=70/30/10) 50 parts by weight, tin series catalysts (Cat-PS3, SHIN-ETSU HANTOTAI's chemical industry system Make) 10 parts by weight are mixed with solution state, obtain mixed solution (1).Polysiloxanes and (methyl) in mixed solution (1) The mixing ratio of acrylic polymer is using weight ratio meter as polysiloxanes: (methyl) acrylic polymer=2:1.
In the above-mentioned mixed solution of one side coating (1) of the resulting soft PVC film of Production Example 1, it is dried, shape At 1.0 μm of thickness, Ra=0.5 μm of arithmetic mean surface roughness of non-adhesive (1).
In addition, when observing non-adhesive (1) using SEM, as shown in Figure 2, Figure 3, Figure 4, according to the depth of morphologic observation image Shallowly, be able to confirm that it is different from the composition of plastic film side in Air Interface side, form containing comprising polysiloxanes more than (first Base) acrylic polymer rich polysiloxanes phase and comprising (methyl) acrylic polymer be more than polysiloxanes richness (first Base) mutually mutual independent phase separates with rich (methyl) acrylic polymer for acrylic polymer phase and rich polysiloxanes phase Structure observes that rich polysiloxanes is mutually present in Air Interface side (opposite side of plastic film), rich (methyl) acrylic polymer It closes object and is mutually present in plastic film side.
In turn, when carrying out the measurement of the infrared spectroscopy based on total reflection method (ATR-IR) to non-adhesive (1), measurement is come from Si-CH3800cm-11725cm of the neighbouring peak relative to the carbonyl in (methyl) acrylic polymer phase-1Neighbouring The dulling luminosity ratio at peak, as a result, it knows compared with ZnSe45 °, when using Ge45 ° of prism, 800cm-1Neighbouring peak becomes larger.Cause This, it is known that compared with substrate side, the containing ratio of silicon is higher in Air Interface side.
In addition, rich polysiloxanes is mutually present in Air Interface side (opposite side of plastic film) in non-adhesive (1) It can confirm in FT-IR." the Spectrum One " that measurement based on FT-IR is manufactured using Perkinermer is deep by analysis It spends direction different (ZnSe45 °, Ge45 °) of 2 kinds of prisms and measures Air Interface side with ATR method.It, can when confirming resulting chart It confirms: when using shallow Ge45 ° of the prism in analysis depth direction, relative to belonging to (methyl) third from non-adhesive The 1720cm of the C=O of olefin(e) acid quasi polymer-1~1730cm-1Peak, come from Si-CH3800cm-1The extinction at neighbouring peak Degree ratio becomes larger.The concentration of provable polysiloxanes becomes higher in Air Interface side as a result,.
The principle that these observation results and surface free energy minimize is taken into account, it is known that the shape in non-adhesive At in 2 layer structure of the Air Interface side with rich polysiloxanes phase.
(adhesive phase)
Preparation butyl acrylate (BA)/acrylonitrile (AN)/acrylic acid (AA)=85/15/2.5 (weight ratio) comprising being made of 100 parts by weight of acrylic copolymer, melamine series crosslinking agent (butylated melamine-formaldehvde resin, " SUPER BECKAMINE J-820-60N ", Japanese polyurethane manufacture) 10 parts by weight, (1,3- is bis-, and (N, N- bis- shrinks sweet epoxy crosslinking agent Oily amino methyl) hexamethylene, " TETRAD C ", Mitsubishi Gas Chemical Co., Ltd's manufacture) 1.0 parts by weight, DOP plasticizer (neighbour Phthalic acid bis- (2- ethylhexyls), J-PLUS Co., Ltd manufacture) 60 parts by weight adhesive toluene solution.
The binder solution is coated on to the face with non-adhesive (1) opposite side of above-mentioned soft PVC film, so It was dried afterwards with 130 DEG C × 90 seconds, forms thickness on the face with non-adhesive (1) opposite side of soft PVC film 10 μm of adhesive phase (1).
(adhesive tape)
It operates as described above, constitutes non-adhesive (1)/soft PVC film/adhesive phase (1) stacking knot Structure manufactures adhesive tape (1).
Result is summarized in table 1.
(embodiment 2)
(non-adhesive)
By polyorganosiloxane resin (KS-723A, the manufacture of SHIN-ETSU HANTOTAI's chemical industry) 60 parts by weight, polyorganosiloxane resin (KS- 723B, the manufacture of SHIN-ETSU HANTOTAI's chemical industry) 40 parts by weight, acrylic copolymer (methyl methacrylate (MMA)/butyl acrylate (BA)/hydroxy-ethyl acrylate (HEA)=70/30/10) 50 parts by weight, tin series catalysts (Cat-PS3, SHIN-ETSU HANTOTAI's chemical industry system Make) 10 parts by weight are mixed with solution state, obtain mixed solution (2).Polysiloxanes and (methyl) in mixed solution (2) The mixing ratio of acrylic polymer is using weight ratio meter as polysiloxanes: (methyl) acrylic polymer=2:1.
In the above-mentioned mixed solution of one side coating (2) of the resulting soft PVC film of Production Example 1, it is dried, shape At 1.0 μm of thickness, Ra=0.5 μm of arithmetic mean surface roughness of non-adhesive (2).
(adhesive phase)
Preparation butyl acrylate (BA)/acrylonitrile (AN)/acrylic acid (AA)=85/15/2.5 (weight ratio) comprising being made of 100 parts by weight of acrylic copolymer, melamine series crosslinking agent (butylated melamine-formaldehvde resin, " SUPER BECKAMINE J-820-60N ", Japanese polyurethane manufacture) 10 parts by weight, (1,3- is bis-, and (N, N- bis- shrinks sweet epoxy crosslinking agent Oily amino methyl) hexamethylene, " TETRAD C ", Mitsubishi Gas Chemical Co., Ltd's manufacture) 10 parts by weight, DOP plasticizer (adjacent benzene Dioctyl phthalate bis- (2- ethylhexyls), J-PLUS Co., Ltd manufacture) 60 parts by weight adhesive toluene solution.
The binder solution is coated on to the face with non-adhesive (2) opposite side of above-mentioned soft PVC film, so It was dried afterwards with 130 DEG C × 90 seconds, forms thickness on the face with non-adhesive (2) opposite side of soft PVC film 10 μm of adhesive phase (2).
(adhesive tape)
It operates as described above, constitutes non-adhesive (2)/soft PVC film/adhesive phase (2) stacking knot Structure manufactures adhesive tape (2).
Result is summarized in table 1.
(embodiment 3)
(non-adhesive)
By polyorganosiloxane resin (KS-723A, the manufacture of SHIN-ETSU HANTOTAI's chemical industry) 60 parts by weight, polyorganosiloxane resin (KS- 723B, the manufacture of SHIN-ETSU HANTOTAI's chemical industry) 40 parts by weight, acrylic copolymer (methyl methacrylate (MMA)/butyl acrylate (BA)/hydroxy-ethyl acrylate (HEA)=70/30/10) 50 parts by weight, tin series catalysts (Cat-PS3, SHIN-ETSU HANTOTAI's chemical industry system Make) 10 parts by weight are mixed with solution state, obtain mixed solution (3).Polysiloxanes and (methyl) in mixed solution (3) The mixing ratio of acrylic polymer is using weight ratio meter as polysiloxanes: (methyl) acrylic polymer=2:1.
In the above-mentioned mixed solution of one side coating (3) of the resulting soft PVC film of Production Example 1, it is dried, shape At 1.0 μm of thickness, Ra=0.5 μm of arithmetic mean surface roughness of non-adhesive (3).
(adhesive phase)
Preparation butyl acrylate (BA)/acrylonitrile (AN)/acrylic acid (AA)=85/15/2.5 (weight ratio) comprising being made of 100 parts by weight of acrylic copolymer, melamine series crosslinking agent (butylated melamine-formaldehvde resin, " SUPER BECKAMINE J-820-60N ", Japanese polyurethane manufacture) 1.0 parts by weight, the (bis- (shrinks of N, N- bis- of 1,3- of epoxy crosslinking agent Glycerol amino methyl) hexamethylene, " TETRAD C ", Mitsubishi Gas Chemical Co., Ltd's manufacture) 10 parts by weight, DOP plasticizer (neighbour Phthalic acid bis- (2- ethylhexyls), J-PLUS Co., Ltd manufacture) 60 parts by weight adhesive toluene solution.
The binder solution is coated on to the face with non-adhesive (3) opposite side of above-mentioned soft PVC film, so It was dried afterwards with 130 DEG C × 90 seconds, forms thickness on the face with non-adhesive (3) opposite side of soft PVC film 10 μm of adhesive phase (3).
(adhesive tape)
It operates as described above, constitutes non-adhesive (3)/soft PVC film/adhesive phase (3) stacking knot Structure manufactures adhesive tape (3).
Result is summarized in table 1.
(comparative example 1)
(non-adhesive)
By polyorganosiloxane resin (KS-723A, the manufacture of SHIN-ETSU HANTOTAI's chemical industry) 60 parts by weight, polyorganosiloxane resin (KS- 723B, the manufacture of SHIN-ETSU HANTOTAI's chemical industry) 40 parts by weight, acrylic copolymer (methyl methacrylate (MMA)/butyl acrylate (BA)/hydroxy-ethyl acrylate (HEA)=70/30/10) 50 parts by weight, tin series catalysts (Cat-PS3, SHIN-ETSU HANTOTAI's chemical industry system Make) 10 parts by weight are mixed with solution state, obtain mixed solution (C1).Polysiloxanes and (first in mixed solution (C1) Base) acrylic polymer mixing ratio using weight ratio meter as polysiloxanes: (methyl) acrylic polymer=2:1.
In the above-mentioned mixed solution of one side coating (C1) of the resulting soft PVC film of Production Example 1, it is dried, shape At 1.0 μm of thickness, Ra=0.5 μm of arithmetic mean surface roughness of non-adhesive (C1).
(adhesive phase)
Preparation butyl acrylate (BA)/acrylonitrile (AN)/acrylic acid (AA)=85/15/2.5 (weight ratio) comprising being made of 100 parts by weight of acrylic copolymer, melamine series crosslinking agent (butylated melamine-formaldehvde resin, " SUPER BECKAMINE J-820-60N ", Japanese polyurethane manufacture) 10 parts by weight, DOP plasticizer (bis- (the 2- ethyl hexyls of phthalic acid Ester), J-PLUS Co., Ltd manufacture) 60 parts by weight adhesive toluene solution.
The binder solution is coated on to the face with non-adhesive (C1) opposite side of above-mentioned soft PVC film, so It was dried, is formed on the face with non-adhesive (C1) opposite side of soft PVC film thick with 130 DEG C × 90 seconds afterwards The adhesive phase (C1) of 10 μm of degree.
(adhesive tape)
It operates as described above, constitutes non-adhesive (C1)/soft PVC film/adhesive phase (C1) stacking knot Structure manufactures adhesive tape (C1).
Result is summarized in table 1.
(comparative example 2)
(non-adhesive)
By polyorganosiloxane resin (KS-723A, the manufacture of SHIN-ETSU HANTOTAI's chemical industry) 60 parts by weight, polyorganosiloxane resin (KS- 723B, the manufacture of SHIN-ETSU HANTOTAI's chemical industry) 40 parts by weight, acrylic copolymer (methyl methacrylate (MMA)/butyl acrylate (BA)/hydroxy-ethyl acrylate (HEA)=70/30/10) 50 parts by weight, tin series catalysts (Cat-PS3, SHIN-ETSU HANTOTAI's chemical industry system Make) 10 parts by weight are mixed with solution state, obtain mixed solution (C2).Polysiloxanes and (first in mixed solution (C2) Base) acrylic polymer mixing ratio using weight ratio meter as polysiloxanes: (methyl) acrylic polymer=2:1.
In the above-mentioned mixed solution of one side coating (C2) of the resulting soft PVC film of Production Example 1, it is dried, shape At 1.0 μm of thickness, Ra=0.5 μm of arithmetic mean surface roughness of non-adhesive (C2).
(adhesive phase)
Preparation butyl acrylate (BA)/acrylonitrile (AN)/acrylic acid (AA)=85/15/2.5 (weight ratio) comprising being made of 100 parts by weight of acrylic copolymer, melamine series crosslinking agent (butylated melamine-formaldehvde resin, " SUPER BECKAMINE J-820-60N ", Japanese polyurethane manufacture) 10 parts by weight, p-methyl benzenesulfonic acid (1 grade, p- toluenesulfonic acid, KISHIDA CHEMICAL Co., Ltd. manufacture) 0.7 parts by weight, DOP plasticizer (phthalic acid bis- (2- ethylhexyls), J- PLUS Co., Ltd manufacture) 60 parts by weight adhesive toluene solution.
The binder solution is coated on to the face with non-adhesive (C2) opposite side of above-mentioned soft PVC film, so It was dried, is formed on the face with non-adhesive (C2) opposite side of soft PVC film thick with 130 DEG C × 90 seconds afterwards The adhesive phase (C2) of 10 μm of degree.
(adhesive tape)
It operates as described above, constitutes non-adhesive (C2)/soft PVC film/adhesive phase (C2) stacking knot Structure manufactures adhesive tape (C2).
Result is summarized in table 1.
[table 1]
Industrial availability
If adhesive tape of the invention is used for semiconductor machining, it is able to suppress being heated because of laser cutting etc. The rising of bonding force, the taking-up of the semiconductor element of panelization are easy to the processing of the transfer of other adhesive tapes etc., and can press down Make the residue glue to adherend.In addition, thus it will be appreciated that cut etc. being fixed on to fix using negative-pressure adsorption on pedestal When, appearance can be effectively inhibited because excessively closely sealed caused by fever of pedestal etc., therefore, can make include cutting including partly Conductor manufacturing process smoothly carries out.In addition, if adhesive tape of the invention is used for semiconductor machining, even if because of laser cutting Deng and be heated the rising for being also able to suppress bonding force, the taking-up of the semiconductor element of panelization, the transfer to other adhesive tapes Deng processing be easy, and be able to suppress the residue glue to adherend, thus it will be appreciated that will not generate and generate in the past due to adhesion Deformation of thin membrane, ess-strain accumulation, therefore with can accurately following the circuit pattern of the fine exquisiteness of semiconductor crystal wafer It is bonded, in addition, being not in the Spontaneous release of the ess-strain after fitting in semiconductor crystal wafer, therefore can be effectively Prevent semiconductor crystal wafer from rupturing.In particular, since the wafer for LED is the material highly brittle by gallium nitride, GaAs, silicon carbide etc. What material was constituted, therefore adhesive tape of the invention is particularly suitable for for cutting of the wafer of LED (LED cutting) etc. 's.

Claims (16)

1. a kind of adhesive tape is the adhesive tape for having adhesive phase at least one face of substrate,
Identation hardness at 100 DEG C obtained using nano-hardness tester on the surface of the adhesive phase is 20.0MPa or more.
2. adhesive tape according to claim 1, wherein the surface of described adhesive layer is obtained using nano-hardness tester Identation hardness at 23 DEG C is 0.5MPa~10.0MPa.
3. adhesive tape according to claim 1, wherein the attaching of described adhesive layer saves bonding force at 23 DEG C × 30 points Zhong Houwei 0.15N/20mm or more.
4. adhesive tape according to claim 1, wherein described adhesive layer includes epoxy crosslinking agent.
5. adhesive tape according to claim 1, wherein described adhesive layer includes (methyl) acrylic polymer.
6. adhesive tape according to claim 1, wherein the substrate measured most according to JIS-K-7127 (1999) Big elongation is 100% or more.
7. adhesive tape according to claim 1, wherein the substrate is plastic film.
8. adhesive tape according to claim 7, wherein the plastic film includes to be selected from polyvinyl chloride, polyolefin, second Alkene-vinyl acetate co-polymer is at least one kind of.
9. adhesive tape according to claim 1, wherein have described adhesive layer in the single side of the substrate, in the base The face opposite with the adhesive phase of material has non-adhesive.
10. adhesive tape according to claim 9, wherein the non-adhesive is polysiloxanes and (methyl) acrylic compounds The mixed layer of polymer.
11. adhesive tape according to claim 10, wherein polysiloxanes and (methyl) acrylic acid in the non-adhesive The mixing ratio of quasi polymer is using weight ratio meter as polysiloxanes: (methyl) acrylic polymer=1:50~50:1.
12. adhesive tape according to claim 9, wherein the non-adhesive has phase separation structure.
13. adhesive tape according to claim 9, wherein the non-adhesive with a thickness of 0.01 μm~10 μm.
14. adhesive tape according to claim 1, wherein have release liner on the surface of described adhesive layer.
15. adhesive tape according to claim 1, is used for semiconductor machining.
16. adhesive tape according to claim 1 is used for LED cutting purposes.
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