CN104137231B - Adhesive tape thin film and adhesive tape - Google Patents

Adhesive tape thin film and adhesive tape Download PDF

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Publication number
CN104137231B
CN104137231B CN201380011399.7A CN201380011399A CN104137231B CN 104137231 B CN104137231 B CN 104137231B CN 201380011399 A CN201380011399 A CN 201380011399A CN 104137231 B CN104137231 B CN 104137231B
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China
Prior art keywords
adhesive
methyl
adhesive tape
thin film
acrylic acid
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CN201380011399.7A
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CN104137231A (en
Inventor
由藤拓三
铃木俊隆
白井稚人
安藤雅彦
关口裕香
浅井量子
远藤明日香
林内梨惠
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/203—Adhesives in the form of films or foils characterised by their carriers characterised by the structure of the release feature on the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/006—Presence of halogenated polymer in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C09J2433/005—Presence of (meth)acrylic polymer in the release coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0095—Post-treatment of devices, e.g. annealing, recrystallisation or short-circuit elimination

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Dicing (AREA)

Abstract

A kind of adhesive tape thin film is provided, it is the adhesive tape thin film being provided with non-adhesive on base film, its can effectively suppress using negative-pressure adsorption be fixed on fixing with occur when carrying out on base cutting etc. because base heating etc. cause excessively closely sealed, in addition, by non-adhesive is arranged on base film, the adhesion under web-like form can effectively be suppressed, fracture or damaged will not occur when from the form debatching of web-like, this non-adhesive is good with the amalgamation of this base film, good to the tracing ability of the deformation such as stretching.Additionally, also providing a kind of adhesive tape comprising such adhesive tape thin film.The adhesive tape thin film of the present invention possesses non-adhesive in the one side of plastic sheeting, and the surface of this non-adhesive has concaveconvex structure, and the elastic modelling quantity at 80 DEG C obtained by atomic force microscope of the male portion on the surface of this non-adhesive is more than 0.2GPa.

Description

Adhesive tape thin film and adhesive tape
Technical field
The present invention relates to adhesive tape thin film and adhesive tape.
Background technology
Adhesive tape used in cutting for quasiconductor, in cutting in order to fix wafer, needs will be closely sealed with wafer The contrary face in face is fixed on base.This fixation is generally carried out by the negative pressure of vac sorb etc..
Carry out this utilization negative pressure fixing when, due to be excessively applied with negative pressure state, because cutting when heating lead The melting of the adhesive tape causing, adhesive tape is excessively closely sealed with base sometimes.If occurring this excessively closely sealed, releasing and the consolidating of base The treatability of timing is deteriorated, and produces the such as semiconductor fabrication sequence including cutting and can not be smoothed out down such asking Topic.
In order to eliminate this excessively closely sealed problem, report has following technology：By base film and adhesive phase this In the crystal column surface protection band that two-layer is formed, by the centrage surface roughness on surface contrary with adhesive phase for base film Ra is controlled to the size (patent documentation 1) of regulation.
But, it is desirable to semiconductor manufacturing work for the base film of adhesive tape used in the cutting of quasiconductor Skill distinctive extension (stretching) characteristic and difference in height follow characteristic.That is, the base material of adhesive tape used in the cutting of quasiconductor Thin film needs can stretch well in extension operation, in addition, it is necessary to follow the difference in height of quasiconductor well.As meeting The base film of such requirement, selects the base film being formed by the big material of percentage elongation.But, the table of this base film Surface state is easily affected by temperature.Therefore, though as patent documentation 1 reported as by the surface of base film Heart line surface roughness Ra is controlled to the size of regulation, there is also following problem：Temperature due to temperature, process unit becomes Change, the centrage surface roughness Ra being controlled as the size of regulation significantly changes it is impossible to show described in patent documentation 1 The effect of invention.
For example, in cutting, especially in cut, due to laser machining the energy that brings and wafer heating.If picture So wafer heating, even if then also exist the centrage surface on the surface of base film as patent documentation 1 is reported Roughness Ra is controlled to the size of regulation, and excessively closely sealed problem as described above also cannot eliminate, or even can promote excessively close Close such problem.
In addition, in recent years, used in the cutting of quasiconductor, the size of wafer is maximizing, and the time of therefore cutting is elongated, As a result, the heating of wafer becomes big, the problems referred to above become more to project.
In the cutting of quasiconductor, especially in LED cutting, the semiconductor crystal wafer of use is by gallium nitride, GaAs, carbonization The highly brittle material such as silicon is constituted, therefore in order to prevent the breakage of this semiconductor crystal wafer it is desirable to the base film of adhesive tape has Further extension (stretching) characteristic and difference in height follow characteristic.Therefore, in the adhesive tape for LED cutting, the problems referred to above become Obtain more prominent.
In addition, usual film surface smooths, if such processing film is become web-like, thin film is occurred to contact with each other and close The phenomenon closed, i.e. adhesion.In the volume creating adhesion, the operation that thin film is carried out debatching is sometimes occurred to become the inconvenience such as difficulty. Especially, in the big thin film of percentage elongation, generally it is added with plasticizer.In such thin film, plasticizer separates out in film surface, Thus the slight void between thin film is landfilled, therefore, the harmful effect that adhesion leads to becomes apparent.Film surface is implemented using viscous During the bonding processing of mixture, because this binding agent has adaptation in itself, therefore, the harmful effect of adhesion becomes much larger.
When the thin film of the web-like of adhesion is carried out debatching, it is unnecessary, for releasing thin film closely sealed power each other to need.By In apply this unnecessary power, film elongation and deform, even if or thin film indeformable also in the form of ess-strain accumulate.If By because as described above the reason and the thin film that deforms is applied to adhesive tape, then be difficult to fit with following adherend.If in addition, by because As mentioned above the reason and the thin film that have accumulated ess-strain is applied to adhesive tape, then because produce after fitting in adherend should The Spontaneous release of ess-strain, has the damaged worry of adherend.
When in semiconductor machining using adhesive tape, the semiconductor crystal wafer as adherend is made up of the material of fragility, because This understands embrittlement or easily has defect.Therefore, if by because as described above the reason and the thin film that deforms is applied to adhesive tape, difficult Fitted with following the fine exquisite circuit pattern of semiconductor crystal wafer.If in addition, will because as described above the reason and have accumulated The thin film of ess-strain is applied to adhesive tape, then produce the Spontaneous release of this ess-strain after fitting in semiconductor crystal wafer, and half Semiconductor wafer is easily damaged.
Especially, the wafer for LED is to be made up of the highly brittle material such as gallium nitride, GaAs, carborundum.Therefore, Become particular importance for the anti in the adhesive tape of LED cutting etc..
As the prior art of anti, can substantially include two kinds of technology.
A kind of prior art can include the technology (patent documentation implementing the physical treatments such as embossing processing at the back side of thin film 2).But, in the art, concavo-convex in the formation of the back side of thin film becomes stress concentration structure, therefore in the form from web-like During debatching, there is because of debatching power thin film and fracture or damaged such problem concavo-convex are occurred for starting point with this.
Another kind of prior art can include the technology (patent documentation of the backsize polyorganosiloxane release agent in thin film 3).But, in the art, polyorganosiloxane release agent is low with the chemical affinity at the thin film back side because of its surface tension, exists It is difficult to be blended in the such problem in the thin film back side.In addition, the thin film being overleaf coated with polyorganosiloxane release agent is applied to glue During crossed belt, if being extended waiting adhesive tape stretching, the process layer processing sometimes with polyorganosiloxane release agent cannot be followed and be drawn Stretch, it is possible to create this process layer ruptures and leads to pollute such problem.It should be noted that in order to improve the polysiloxanes demoulding The chemical affinity at agent and the thin film back side is although also there is the technology of coating cross-linking type polyorganosiloxane release agent, but the poly- silicon of cross-linking type The usual percentage elongation of oxygen alkane is very little, and the thin film being therefore overleaf coated with cross-linking type polyorganosiloxane release agent is applied to adhesive tape When, if being extended waiting adhesive tape stretching, there is the process layer processing using cross-linking type polyorganosiloxane release agent cannot follow and drawing Stretch, be unable to maintain that the such problem of anchoring.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2009-239124 publication
Patent documentation 2：No. 2009/028069 pamphlet of International Publication No.
Patent documentation 3：Japanese Unexamined Patent Publication 2010-201836 publication
Content of the invention
Problems to be solved by the invention
The problem of the present invention is to provide a kind of adhesive tape thin film, and it is to be provided with non-adhesive on base film Adhesive tape thin film, it can suppress be fixed on fixing appearance when carrying out on base cutting etc. using negative-pressure adsorption effectively Because base heating etc. cause excessively closely sealed, in addition, by base film arrange non-adhesive, can effectively suppress web-like Adhesion under form, will not rupture or damaged when from web-like form debatching, the amalgamation of this non-adhesive and this base film Well, good to the tracing ability of the deformation such as stretching.In addition, the problem of the present invention also resides in offer comprises this adhesive tape thin film Adhesive tape.
For solution to problem
The adhesive tape thin film of the present invention is to possess the adhesive tape thin film of non-adhesive in the one side of plastic sheeting,
The surface of this non-adhesive has concaveconvex structure,
Elastic modelling quantity at 80 DEG C obtained by atomic force microscope of the male portion on the surface of this non-adhesive is More than 0.2GPa.
In a preferred embodiment, arithmetic mean surface roughness Ra of above-mentioned non-adhesive is more than 0.1 μm.
In a preferred embodiment, above-mentioned non-adhesive is the mixing of polysiloxanes and (methyl) acrylic acid series polymeric compounds Layer.
In a preferred embodiment, the calculating Tg of above-mentioned (methyl) acrylic acid series polymeric compounds is more than 10 DEG C.
In a preferred embodiment, the SP value of above-mentioned (methyl) acrylic acid series polymeric compounds is 9.0 (cal/cm3)0.5~ 12.0(cal/cm3)0.5.
In a preferred embodiment, the polysiloxanes in above-mentioned non-adhesive and (methyl) acrylic acid series polymeric compounds is mixed Composition and division in a proportion is with weight ratio meter as polysiloxanes：(methyl) acrylic acid series polymeric compounds=1：50～50：1.
In a preferred embodiment, above-mentioned non-adhesive has phase separation structure.
In a preferred embodiment, the non-adhering test peeling force of above-mentioned non-adhesive is less than 1.0N/20mm.
In a preferred embodiment, the thickness of above-mentioned non-adhesive is 0.01 μm～10 μm.
In a preferred embodiment, above-mentioned plastic sheeting according to the maximum elongation rate that JIS-K-7127 measures is More than 100%.
In a preferred embodiment, the thickness of above-mentioned plastic sheeting is 20 μm～200 μm.
In a preferred embodiment, above-mentioned plastic sheeting comprises polrvinyl chloride.
Other embodiments of the present invention provide adhesive tape.The adhesive tape of the present invention is in the adhesive tape thin film of the present invention The face contrary with above-mentioned non-adhesive of above-mentioned plastic sheeting possess adhesive phase.
In a preferred embodiment, above-mentioned adhesive phase comprises at least one (methyl) acrylic acid series polymeric compounds.
In a preferred embodiment, the SP value of above-mentioned adhesive phase is 9.0 (cal/cm3)0.5～12.0 (cal/cm3 )0.5.
In a preferred embodiment, possesses release liner on the surface of above-mentioned adhesive phase.
In a preferred embodiment, the adhesive tape of the present invention is used for semiconductor machining.
In a preferred embodiment, the adhesive tape of the present invention is used for LED cutting purposes.
The effect of invention
In accordance with the invention it is possible to provide a kind of adhesive tape thin film, it is to be provided with non-adhesive on base film Adhesive tape thin film, it can suppress be fixed on fixing appearance when carrying out on base cutting etc. using negative-pressure adsorption effectively Because base heating etc. cause excessively closely sealed, in addition, by base film arrange non-adhesive, can effectively suppress web-like Adhesion under form, will not rupture or damaged when from web-like form debatching, the amalgamation of this non-adhesive and this base film Well, good to the tracing ability of the deformation such as stretching.In addition, the present invention can also provide the bonding comprising this adhesive tape thin film Band.
Brief description
Fig. 1 is the SEM photograph of the face side state of the non-adhesive in the adhesive tape thin film illustrate the present invention.
Fig. 2 is the SEM photograph of the sectional side state of the non-adhesive in the adhesive tape thin film illustrate the present invention.
Fig. 3 is that the SEM of the sectional side state of the non-adhesive that band explanatorily illustrates in the adhesive tape thin film of the present invention shines Piece.
Specific embodiment
<<1. adhesive tape thin film>>
The adhesive tape thin film of the present invention possesses non-adhesive in the one side of plastic sheeting.
<1-1. plastic sheeting>
To plastic sheeting, there is no particular limitation, can comprise arbitrarily suitable resin material.As such resinous wood Material, preferably includes such as polrvinyl chloride, polyolefin, polyester, polyimides, polyamide etc. it may be more preferable to include polychlorostyrene Ethylene, polyolefin, can further preferably include polrvinyl chloride.The stress relaxation of polrvinyl chloride is excellent, therefore, it is possible to special It is suitably used for adhesive tape thin film, described adhesive tape thin film can be used in used in the semiconductor machining such as LED cutting Adhesive tape.
As the containing ratio of the above-mentioned resin material in plastic sheeting, it is arbitrarily suitable to be set according to purpose/purposes Containing ratio.As this containing ratio, such as preferably 50 weight %～100 weight %, more preferably 60 weight %～100 Weight %, more preferably 70 weight %～100 weight %.
Plasticizer can also be comprised in plastic sheeting.The containing ratio of the plasticizer in plastic sheeting is thin with respect to this plastics Above-mentioned resin material in film is preferably 0.5 weight %～50 weight %, more preferably 1.0 weight %～40 weight %.Pass through In plastic sheeting, plasticizer is comprised with above-mentioned containing ratio, more preferable is become to the tracing ability of the deformation such as stretching.
As above-mentioned plasticizer, for example, can include：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 ester system (tricresyl phosphate etc.), adipic acid system ester, citrate (citroflex A-4 Deng), sebacate, azelate, maleate, benzoate, polyethers system polyester, epoxy polyester (epoxidised soybean oil, ring Oxidation Semen Lini oil etc.), polyester (low molecule polyester being formed by carboxylic acid and glycol etc.) etc..In the present invention, it is preferred to use ester It is plasticizer.Plasticizer can for only a kind or two or more.
In the range of the effect not damaging the present invention, arbitrarily suitable other compositions in plastic sheeting, can also be comprised.
The maximum elongation rate preferably more than 100% measuring according to JIS-K-7127 of plastic sheeting, more preferably 200% ～1000%.By using showing the plastic sheeting of such maximum elongation rate, the adhesive tape of the present invention can be given with thin Film with appropriate extensibility, such as when the adhesive tape thin film by the present invention is used for adhesive tape, it is possible to increase to adherend Tracing ability.
The thickness of plastic sheeting is preferably 20 μm～200 μm, more preferably 40 μm～150 μm, more preferably 50 μm ～100 μm.When the thickness of plastic sheeting is less than 20 μm, there is the worry of treatability variation, especially have the patch when constituting adhesive tape Closing operation becomes difficult worry.If the thickness of plastic sheeting is more than 200 μm, there is the load that the tracing ability to deformation such as stretchings is deteriorated The heart.
＜ 1-2. non-adhesive ＞
As long as its surface of non-adhesive has the concaveconvex structure of following provisions, its composition etc. is just not particularly limited, as Wherein one, be the mixed layer of polysiloxanes and (methyl) acrylic acid series polymeric compounds.By make non-adhesive be polysiloxanes and The mixed layer of (methyl) acrylic acid series polymeric compounds, the amalgamation of non-adhesive and plastic sheeting improves, and the adhesive tape of the present invention is used Thin film and the adhesive tape comprising it improve to the tracing ability of the deformation such as stretching.
The surface of non-adhesive has concaveconvex structure.For this concaveconvex structure, specifically, the arithmetic average of non-adhesive Surface roughness Ra is preferably more than 0.1 μm, more preferably 0.1 μm～3.0 μm, more preferably 0.2 μm～2.0 μm, special Not You Xuanwei 0.3 μm～2.0 μm, most preferably 0.5 μm～2.0 μm.By making the arithmetic mean surface roughness of non-adhesive Within the above range, when can suppress to carry out to fix using the absorption of negative pressure, appearance is excessively closely sealed for Ra.
Elastic modelling quantity at 80 DEG C obtained by atomic force microscope (AFM) of the male portion on the surface of non-adhesive is More than 0.2GPa, more preferably more than 0.4GPa, more preferably more than 0.8GPa, particularly preferably more than 1.0GPa.Non- The upper limit of the elastic modelling quantity at 80 DEG C obtained by atomic force microscope of the male portion on the surface of adhesive layer is not particularly limited, It is preferably below 5.0GPa, more preferably below 4.0GPa, more preferably below 3.0GPa.The surface of non-adhesive convex Elastic modelling quantity at partial 80 DEG C being obtained by atomic force microscope within the above range when, the surface of non-adhesive small Concaveconvex structure in, especially male portion hardness at high temperature also appropriateness uprise, therefore, thermostability uprises, and can effectively press down The adhesive tape of the present invention is being absorbed and fixed at fixing appearance when carrying out on base cutting etc. the bottom of because of using negative pressure by system with thin film Seat heating etc. and cause excessively closely sealed.It should be noted that the male portion on the surface of non-adhesive by atomic force microscope The assay method of the elastic modelling quantity at 80 DEG C obtaining will be described later.
When non-adhesive is the mixed layer of polysiloxanes and (methyl) acrylic acid series polymeric compounds, (methyl) in non-adhesive The calculating Tg of acrylic acid series polymeric compounds is more than 10 DEG C, preferably more than 20 DEG C, more preferably more than 30 DEG C, more preferably More than 45 DEG C.The upper limit of the calculating Tg of (methyl) acrylic acid series polymeric compounds in non-adhesive is not particularly limited, preferably Less than 200 DEG C, more preferably less than 150 DEG C, more preferably less than 100 DEG C.Gathered by making above-mentioned (methyl) acrylic acid seriess Within the above range, the thermostability at the minute unevenness structure on the surface of non-adhesive uprises the calculating Tg of compound, Neng Gouyou The adhesive tape of the present invention is being absorbed and fixed at fixation with going out when carrying out and cutting etc. on base using negative pressure by the suppression of effect ground with thin film Now because base heating etc. cause excessively closely sealed.
In the present invention, " the calculating Tg " of copolymer ((methyl) acrylic acid series polymeric compounds in above-mentioned non-adhesive etc.) refers to The calculating glass transition temperature that the Tg of the construction unit from the monomer constituting copolymer is obtained using Fox calculating formula.Fox Formula is glass transition temperature Tg (DEG C) as follows, copolymer and constitute the equal of the respective homopolymerization of the monomer of copolymer The glass transition temperature Tg of polymersiRelational expression between (DEG C).It should be noted that in following Fox formula, Tg (DEG C) table Show glass transition temperature, the W of copolymeriRepresent weight fraction, the Tg of monomer ii(DEG C) represents the glass of the homopolymer of monomer i Change transition temperature.
1/ (273+Tg)=Σ (Wi/(273+Tgi))
Wherein, as the glass transition temperature Tg of homopolymeri(DEG C), specifically, it is possible to use " Polymer Value described in Handbook 3rd Edition " (A WILEY-INTERSCIENCE PUBLICATION, 1989).
When non-adhesive comprises (methyl) acrylic acid series polymeric compounds, (methyl) acrylic acid series polymeric compounds 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, more preferably 9.5 (cal/cm3)0.5～11.0 (cal/cm3)0.5.SP value be according to Small formula calculate molten Solution degree parameter.The calculating of SP value can using known document (such as Journal of Applied Chemistry, 3,71, 1953. etc.) method described in is carrying out.
Non-adhesive preferably has phase separation structure.Non-adhesive, can be in this non-adhering by having phase separation structure The surface of layer is effectively formed small concaveconvex structure.This is substantially speculated as：With such as non-adhesive for polysiloxanes and (first Base) acrylic acid series polymeric compounds mixed layer in case of, due to polysiloxanes when phase separation structure generates, (methyl) propylene The difference of the substance mobility of sour based polymer and generate concavo-convex.Due to the formation of this concaveconvex structure, the adhesive tape of the present invention is used Thin film can suppress the appearance when carrying out fixing using the absorption of negative pressure excessively closely sealed, and can effectively suppress under web-like form Adhesion, can suppress to occur fracture or damaged when the form debatching of web-like.
Non-adhesive preferably comprise comprise polysiloxanes be more than (methyl) acrylic acid series polymeric compounds rich polysiloxanes phase with Comprise richness (methyl) the acrylic acid series polymeric compounds phase that (methyl) acrylic acid series polymeric compounds are more than polysiloxanes.Non-adhesive is more specific For, preferably above-mentioned richness polysiloxanes phase is comprised with phase separation structure independent mutually and to gather with above-mentioned richness (methyl) acrylic acid seriess Compound phase, more preferably above-mentioned richness polysiloxanes phase is present in Air Interface side (opposition side of plastic sheeting), above-mentioned richness (first Base) acrylic acid series polymeric compounds phase is present in plastic sheeting side.By having such phase separation structure, due to being present in air circle The rich polysiloxanes phase of surface side, adhesion is inhibited effectively, by being present in richness (methyl) acrylic acid seriess of plastic sheeting side Polymer phase, non-adhesive is improved with the amalgamation of plastic sheeting, and deformation tracing ability improves.By as described below to non-adhering Polysiloxanes in layer are adjusted with the mixing ratio of (methyl) acrylic acid series polymeric compounds, can form such separated knot Structure.
Non-adhesive has a case that phase separation structure, is more than (methyl) propylene containing comprising polysiloxanes as above The rich polysiloxanes phase of sour based polymer is more than richness (methyl) propylene of polysiloxanes with comprising (methyl) acrylic acid series polymeric compounds The situation of sour based polymer phase can be observed by arbitrarily suitable method.As such observational technique, for example, can arrange Enumerate：Using transmission electron microscope (TEM), scanning electron microscope (SEM), field emission type scanning electron microscope Etc. (FE-SEM) method that ultramicroscope carries out morphologic observation to non-adhesive section.2 layers of isolating construction can pass through form The depth observing image is recognizing.In addition, following method also can be included：Using the INFRARED ABSORPTION light splitting based on total reflection method, From non-adhesive Air Interface side to inside, change probe optical depth, while observing containing of contained silicon in composition, carbon etc. Amount change, is thus observed.In addition, also can include being seen using X-ray microanalysis instrument, x-ray photoelectron power spectrum The method examined.Observed alternatively, it is also possible to be combined as these methods.
Non-adhesive has and is present in the rich polysiloxanes of Air Interface side (opposition side of plastic sheeting) and is present in In the case of the phase separation structure of richness (methyl) acrylic acid series polymeric compounds phase of plastic sheeting side, if this is non-using negative pressure Adhesive layer is absorbed and fixed at fixation, and this fixes with base heating when carrying out cutting etc. with base, then due to this, to send out heat thermogenetic negative Lotus, the surface texture of this phase separation structure is destroyed, especially more with this fixing base contacts of heating male portion The surface texture of this phase separation structure is destroyed, and may cause in this male portion rich (methyl) acrylic acid series polymeric compounds in sky Aerosphere surface side exposes.But, adhesive tape thin film being shown by atomic force due to the male portion on the surface of non-adhesive of the present invention Elastic modelling quantity at micro mirror obtain 80 DEG C is within the above range, therefore, moderately high by the hardness of the male portion of thermic load, because And thermostability uprises.Therefore, it is possible to effectively suppress be absorbed and fixed at admittedly the adhesive tape thin film of the present invention using negative pressure Fixed occur when carrying out cutting etc. with base because base heating etc. cause excessively closely sealed.
When non-adhesive is the mixed layer of polysiloxanes and (methyl) acrylic acid series polymeric compounds, the poly- silica in non-adhesive The mixing ratio of alkane and (methyl) acrylic acid series polymeric compounds is preferably polysiloxanes with weight ratio meter：(methyl) acrylic acid series polymeric compounds =1：50～50：1, more preferably polysiloxanes：(methyl) acrylic acid series polymeric compounds=1：30～30：1, more preferably poly- Siloxanes：(methyl) acrylic acid series polymeric compounds=1：10～10：1, particularly preferably polysiloxanes：(methyl) acrylic polymeric Thing=1：5～5：1, most preferably polysiloxanes：(methyl) acrylic acid series polymeric compounds=1：3～5：1.If poly- in non-adhesive The content ratio of siloxanes is excessive, then the chemical affinity step-down with the plastic sheeting back side, is difficult to melt with the plastic sheeting back side The worry closed.If in addition, the content ratio of polysiloxanes in non-adhesive is excessive, making adhesive tape thin film or bag During containing its adhesive tape, the tracing ability of the deformation such as stretching is deteriorated, has non-adhesive rupture to lead to the worry polluting.If non-stick The content ratio of (methyl) acrylic acid series polymeric compounds in conjunction layer is excessive, then have non-adhesive to play as acrylic adhesive The worry of effect, has the easy worry producing adhesion.
As polysiloxanes, can be using arbitrarily suitable polysiloxanes.As such polysiloxanes, for example, can enumerate Go out：Using platinum series compound as catalyst, polydialkysiloxane containing thiazolinyl is made to pass through addition with poly-diakyl hydrogen polysiloxanes Reaction solidify to form addition type polysiloxane obtained from fissility epithelium；Using stannum series catalysts, make containing methylol poly- two Alkylsiloxane and poly-diakyl hydrogen polysiloxanes react obtained from condensed type polysiloxanes etc..As addition type polysiloxane Example, for example can include：" KS-776A ", " KS-839L " that SHIN-ETSU SILICONE Co., Ltd manufacture etc..Make For the example of condensed type polysiloxanes, for example, can include：" the KS723A/ that SHIN-ETSU SILICONE Co., Ltd manufacture B " etc..Additionally, when manufacturing polysiloxanes, in addition to platinum group catalyst, stannum series catalysts, can also be suitably used other Cross-linking agent, crosslinking accelerator etc..In addition, as the character of polysiloxanes, can be categorized into：It is dissolved in the organic solvents such as toluene Type, by their lo-tionized emulsion-types, only comprise no-solvent type of polysiloxanes etc..In addition, except additive poly silicon Beyond oxygen alkane, condensed type polysiloxanes, polysiloxanes/acrylic acid graft polymer, polysiloxanes/acrylic acid block can be used Polymer etc..As polysiloxanes/acrylic acid graft polymer, for example, can include：SYMAC GS-30、GS101、US-270、 US-350, US-380 (manufacturing for Toagosei Co., Ltd above) etc..As polysiloxanes/acrylic acid block polymer, example As included：MODIPER FS700, FS710, FS720, FS730, FS770 (manufacturing for Japan Oil Co above) etc..
As (methyl) acrylic acid series polymeric compounds, can be using (methyl) acrylic acid series polymeric compounds being arbitrarily suitable for.Need Illustrate, in the present invention, " (methyl) acrylic acid " refers to " acrylic acid and/or methacrylic acid ".
(methyl) acrylic acid series polymeric compounds are by the monomer component comprising (methyl) acrylic monomer as principal monomer The polymer constituting.Constitute containing of (methyl) acrylic monomer in the monomer component of above-mentioned (methyl) acrylic acid series polymeric compounds Ratio is had to be preferably more than 50 weight %, more preferably 70 weight %～100 weight %, more preferably 90 weight～100 Weight %, particularly preferably 95 weight %～100 weight %.Monomer in above-mentioned monomer component can for only a kind or Two or more.
As (methyl) acrylic monomer, preferably include (methyl) acrylate, (methyl) acrylic acid.
As (methyl) acrylate, for example, can include：Carbon number is the (first of 1～30 alkyl (also including cycloalkyl) Base) alkyl acrylate, hydroxyl (methyl) acrylate etc..(methyl) acrylate can be only a kind or 2 kinds More than.
(methyl) alkyl acrylate of the alkyl (also including cycloalkyl) being 1～30 as carbon number, for example, can include： (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) Butyl acrylate, (methyl) Isobutyl 2-propenoate, (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) 1-Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, 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, (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 number such as lauryl acrylate is 1～30 (methyl) alkyl acrylate of alkyl (also including cycloalkyl) etc..These In the middle of (methyl) acrylate, preferably carbon number is (methyl) alkyl acrylate of 2～20 alkyl (also including cycloalkyl), more Preferably carbon number is (methyl) alkyl acrylate of 4～18 alkyl (also including cycloalkyl).
As hydroxyl (methyl) acrylate, for example, can include：(methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -4- hydroxybutyl etc..
In order to fully show the effect of the present invention, the monomer component constituting above-mentioned (methyl) acrylic acid series polymeric compounds is permissible Containing at least one selected from hydroxyl monomer, carboxyl group-containing monomer.
As hydroxyl monomer, for example, can include：1-propenol-3 etc..Hydroxyl monomer can be only a kind or 2 More than kind.
As carboxyl group-containing monomer, for example, can include：(methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, bar Bean acid, maleic acid, fumaric acid, itaconic acid etc..Carboxyl group-containing monomer can for only a kind or two or more.
In the case that non-adhesive contains (methyl) acrylic acid series polymeric compounds, (methyl) acrylic acid seriess in non-adhesive gather Preferably, the containing ratio constituting hydroxyl (methyl) acrylate in its monomer component is with respect to this hydroxyl for compound The total amount of the monomer component beyond (methyl) acrylate, preferably 2 weight %～30 weight %, more preferably 3 weight %～ 25 weight %, particularly preferably 5 weight %～20 weight %.Non-adhesive contains the situation of (methyl) acrylic acid series polymeric compounds Under, with respect to the total amount of the monomer component beyond this hydroxyl (methyl) acrylate, constitute (methyl) third in non-adhesive Hydroxyl (methyl) in the monomer component of olefin(e) acid based polymer if the containing ratio of acrylate within the above range, The surface of non-adhesive more effectively forms small concaveconvex structure, by the formation of this concaveconvex structure, the adhesive tape of the present invention Occur excessively closely sealed when can be suppressed further with thin film to carry out fixing using the absorption of negative pressure, and can more effectively suppress Adhesion under web-like form, can suppress fracture or breakage when the form debatching of web-like further.
In the case that non-adhesive contains (methyl) acrylic acid series polymeric compounds, (methyl) acrylic acid seriess in non-adhesive gather Compound preferably, can wrap in the monomer component beyond hydroxyl (methyl) acrylate in constituting its monomer component Contain (methyl) acrylic acid and/or (methyl) acrylate.Now, the content ratio of (methyl) acrylic acid and (methyl) acrylate With weight ratio meter, (methyl) acrylic acid：(methyl) acrylate is preferably 0：100～20：80, more preferably 0：100～10： 90, more 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 this concaveconvex structure, can suppress gluing of the present invention further Crossed belt thin film occurs excessively closely sealed when carrying out fixing using the absorption of negative pressure, and can more effectively suppress the shape of web-like Adhesion under state, can suppress fracture or breakage when the form debatching of web-like further.
(methyl) acrylic acid series polymeric compounds can be manufactured by arbitrarily suitable polymerization.
In the range of the effect not damaging the present invention, non-adhesive can comprise arbitrarily suitable additive.As this The additive of sample, for example, can include：Catalyst, UV absorbent, filler, age resistor, viscosifier, pigment, dyestuff, silicon Alkane coupling agent etc..
The non-adhering test peeling force of non-adhesive is preferably shorter than 1.0N/20mm, more preferably less than 0.5N/20mm, enters one Step is preferably shorter than 0.2N/20mm.Peeling force is tested within the above range by the non-adhering making non-adhesive, can be further When suppression carries out fixing using the absorption of negative pressure, appearance is excessively closely sealed.In the present invention, the non-adhering test of non-adhesive is peeled off Power measures according to method described later.
The thickness of non-adhesive is preferably 0.01 μm～10 μm, more preferably 0.1 μm～5 μm, more preferably 0.1 μm ～2 μm.When the thickness of non-adhesive is less than 0.01 μm, become easily to produce adhesion.If the thickness of non-adhesive is more than 10 μm, There is the worry that the tracing ability to deformation such as stretchings is deteriorated.If the thickness of non-adhesive is less than 0.01 μm, there is the effect of the present invention It is difficult to the worry showing, the worry manufacturing change difficulty.
The method forming non-adhesive as the one side in plastic sheeting, for example, can include：By in plastic sheeting The material of coated on one side non-adhesive is simultaneously dried the method to form non-adhesive.As the method for above-mentioned coating, for example Can include：Method using bar coater, gravure coater, spin coater, roll coater, knife type coater, applicator etc..
<<2. adhesive tape>>
Above-mentioned plastic sheeting in the adhesive tape thin film of the present invention for the adhesive tape of the present invention with above-mentioned non-adhesive Contrary face possesses adhesive phase.
To the thickness of adhesive phase, there is no particular limitation, preferably 1.0 μm～30 μm, more preferably 1.0 μm～20 μm, More preferably 3.0 μm～15 μm.When the thickness of adhesive phase is less than 1.0 μm, has and cannot show sufficient bonding force Worry.When the thickness of adhesive phase is more than 30 μm, according to purposes, there is bonding force excessive and so that adherend is ruptured in stripping etc. Worry.
As the material of above-mentioned adhesive phase, can be glued using arbitrarily suitable in the range of the effect not damaging the present invention Mixture.
As the material of adhesive phase, for example, can include：(methyl) acrylic acid series polymeric compounds；Natural rubber；It is grafted with The special natural rubber of the monomers such as methyl methacrylate；SBS, SBR, SEPS, SIS, SEBS, polybutene, polyisobutylene (polyisobutene), the synthetic rubber such as polyisobutylene (polyisobutylene), butyl rubber；Deng.In the middle of these, from stripping From the rear cull to adherend few, there is high cohesion, the excellent aspect of the transparency is set out, preferably at least a kind of (methyl) propylene Sour based polymer.
When adhesive phase comprises (methyl) acrylic acid series polymeric compounds, (methyl) acrylic acid series polymeric compounds in adhesive phase Containing ratio suitably can set according to purpose.
Above-mentioned (methyl) acrylic acid series polymeric compounds are by the monomer comprising (methyl) acrylic monomer as principal monomer The resin that composition is constituted.(methyl) acrylic monomer in the monomer component of composition above-mentioned (methyl) acrylic acid series polymeric compounds More than containing ratio preferably 50 weight %, more preferably 70 weight %～100 weight %, more preferably 90 weight %～ 100 weight %, particularly preferably 95 weight %～100 weight %.Monomer in above-mentioned monomer component can be only a kind, also may be used Think two or more.
As (methyl) acrylic monomer, preferably include (methyl) acrylate, (methyl) acrylic acid.
As (methyl) acrylate, for example, can include：Carbon number is the (first of 1～30 alkyl (also including cycloalkyl) Base) alkyl acrylate, hydroxyl (methyl) acrylate etc..(methyl) acrylate can be only a kind or 2 kinds More than.
(methyl) alkyl acrylate of the alkyl (also including cycloalkyl) being 1～30 as carbon number, for example, can include： (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) Butyl acrylate, (methyl) Isobutyl 2-propenoate, (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) 1-Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, 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, (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 number such as lauryl acrylate is 1～30 (methyl) alkyl acrylate of alkyl (also including cycloalkyl) etc..These In the middle of (methyl) acrylate, preferably carbon number is (methyl) alkyl acrylate of 2～20 alkyl (also including cycloalkyl), more Preferably carbon number is (methyl) alkyl acrylate of 4～18 alkyl (also including cycloalkyl).
As hydroxyl (methyl) acrylate, for example, can include：(methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -4- hydroxybutyl etc..
In order to fully show the effect as binding agent, constitute the monomer component of above-mentioned (methyl) acrylic acid series polymeric compounds Preferably comprise at least one selected from hydroxyl monomer, carboxyl group-containing monomer.More preferably carboxyl group-containing monomer.In addition, for abundant table Reveal the effect as binding agent, the monomer component constituting above-mentioned (methyl) acrylic acid series polymeric compounds can contain acrylonitrile.
As hydroxyl monomer, for example, can include：(methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid -2- hydroxyl Base propyl ester, (methyl) acrylic acid -4- hydroxybutyl, 1-propenol-3 etc..Hydroxyl monomer can for only a kind or 2 kinds with On.
As carboxyl group-containing monomer, for example, can include：(methyl) acrylic acid, (methyl) carboxy ethyl acrylate, (methyl) third Olefin(e) acid carboxylic pentyl ester .beta.-methylacrylic acid, maleic acid, fumaric acid, itaconic acid etc..Carboxyl group-containing monomer can for only a kind or 2 kinds with On.
When the monomer component of composition above-mentioned (methyl) acrylic acid series polymeric compounds contains hydroxyl monomer, constitute above-mentioned (methyl) The containing ratio of the hydroxyl monomer in the monomer component of acrylic acid series polymeric compounds is preferably 0.1 weight %～20 weight %, more It is preferably 0.1 weight %～10 weight %.The monomer component constituting above-mentioned (methyl) acrylic acid series polymeric compounds contains list containing carboxyl During body, the containing ratio constituting the carboxyl group-containing monomer in the monomer component of above-mentioned (methyl) acrylic acid series polymeric compounds is preferably 0.1 Weight %～20 weight %, more preferably 0.1 weight %～10 weight %.So, by making composition above-mentioned (methyl) acrylic acid The monomer component of based polymer contains at least one selected from hydroxyl monomer, carboxyl group-containing monomer, in the situation using cross-linking agent Under, the cross-linking reaction with this cross-linking agent can more effectively occur, can fully show the effect as binding agent.And then, By in the containing ratio of the hydroxyl monomer in the monomer component of regulation composition above-mentioned (methyl) acrylic acid series polymeric compounds, composition State the containing ratio of the carboxyl group-containing monomer in the monomer component of (methyl) acrylic acid series polymeric compounds and be in above range, The rupture of adherend when can be effectively prevented strip operation.Constitute in the monomer component of above-mentioned (methyl) acrylic acid series polymeric compounds The containing ratio of hydroxyl monomer, the carboxyl group-containing monomer constituting in the monomer component of above-mentioned (methyl) acrylic acid series polymeric compounds Containing ratio compare above range excessive when, bonding force becomes too much, has the easy worry producing adhesion, in addition, have peeling off The worry of the rupture of adherend is easily produced during operation.
Adhesive phase preferably comprises cross-linking agent.When adhesive phase comprises cross-linking agent, the containing of cross-linking agent in adhesive phase Ratio suitably can set according to purpose, with respect to principal resinous ingredients (preferably (methyl) acrylic acid series polymeric compounds), preferably For 0.1 weight %～20 weight %.By the containing ratio that makes the cross-linking agent in adhesive phase within the above range, can produce The cross-linking reaction of raw appropriateness, can be effectively prevented the rupture of adherend during strip operation.
As cross-linking agent, for example, can include：Epoxy cross-linking agent, isocyanates system cross-linking agent, melamine series are crosslinked Agent, peroxide system cross-linking agent, metal alkoxide system cross-linking agent, metallo-chelate system cross-linking agent, slaine system cross-linking agent, carbon two are sub- Amine system cross-linking agent, oxazoline system cross-linking agent, aziridine system cross-linking agent, amine system cross-linking agent etc..In the middle of these cross-linking agent, from can fill The aspect dividing the effect showing the present invention is set out, and preferably melamine series cross-linking agent, epoxy cross-linking agent, isocyanates system hand over Connection agent.In addition, cross-linking agent can suitably select as desired, can be only a kind or mixed system of more than two kinds.
Adhesive phase can also comprise plasticizer.When adhesive phase comprises plasticizer, the containing of plasticizer in adhesive phase There is ratio suitably can be set according to purpose, preferably 0.1 weight %～50 weight %.By making the plasticizer in adhesive phase Containing ratio within the above range, can more efficiently show the effect of the present invention.Plasticizer in adhesive phase If containing ratio be more than 50 weight %, adhesive phase becomes excessively soft, has and easy produces cull, the load of adherend pollution The heart.
As above-mentioned plasticizer, for example, can include：Phthalic acid ester system, trimellitate system (DIC Corporation system, W-700, trioctyl trimellitate (TOTM) etc.), adipate ester system (J-PLUS Co., Ltd system, D620, adipic acid Dioctyl ester, diisononyl adipate etc.), phosphate ester system (tricresyl phosphate etc.), adipic acid system ester, citrate (acetyl group Tributyl citrate etc.), sebacate, azelate, maleate, benzoate, polyethers system polyester, epoxy polyester (ring Oxidation soybean oil, epoxidation Semen Lini oil etc.), polyester (low molecule polyester being formed by carboxylic acid and glycol etc.) etc..In the present invention In, preferably use ester system plasticizer.Plasticizer can for only a kind or two or more.
In order to promote cross-linking reaction etc., adhesive phase can comprise arbitrarily suitable catalyst.Adhesive phase comprises to be catalyzed During agent, the containing ratio of the catalyst in adhesive phase suitably can set according to purpose, preferably 0.01 weight %～10 weight Amount %.By the containing ratio that makes the catalyst in adhesive phase within the above range, can more efficiently be shown this The effect of invention.
As this catalyst, for example, can include：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 compoundss such as butylamine, ethylenediamine, isophorone diamine, imidazoles, Lithium hydrate, potassium hydroxide, Feldalat NM；To toluene sulphur Acid, trichloroacetic acid, phosphoric acid, single alkyl phosphonic acid, Acidic phosphates, the phosphate ester of senecioate-hydroxy methacrylate, monoalkyl phosphorous The acid compounds such as acid, dialkyl group phosphorous acid；Deng.Catalyst can for only a kind or two or more.
In order to show the effect of the present invention further, the SP value of adhesive phase is preferably 9.0 (cal/cm3)0.5～12.0 (cal/cm3)0.5, more preferably 9.5 (cal/cm3)0.5～11.0 (cal/cm3)0.5.SP value calculates according to Small formula Solubility parameter.The calculating of SP value can using known document (for example, Journal of Applied Chemistry, 3, 71,1953. etc.) method described in is carried out.
In the range of the effect not damaging the present invention, adhesive phase can comprise arbitrarily suitable additive.As this The additive of sample, for example, can include：UV absorbent, filler, age resistor, viscosifier, pigment, dyestuff, silane coupled Agent etc..
The adhesive tape of the present invention can also possess release liner on the surface of adhesive phase.
As release liner, can be using arbitrarily suitable slider.As this release liner, for example, can include： There is plastic sheeting, the paper carrying out surface treatment using removers such as polysiloxane series, chain alkyl system, fluorine system, molybdenum sulfides Base material Deng peel ply；By politef, polychlorotrifluoroethylene, poly- ethylene fluoride, Kynoar, tetrafluoroethene hexafluoro The low cementability base material that the fluorine system polymer such as propylene copolymer, chlorine fluorothene vinylidene fluoride copolymers are formed；By olefin-based tree The low cementability base material that the polar polymeric such as fat (for example, polyethylene, polypropylene etc.) are formed；Deng.
The adhesive tape of the present invention can be used for arbitrarily suitable purposes.The adhesive tape of the present invention has the adhesive tape of the present invention With thin film, therefore as described above, can effectively suppress be fixed on fixation with cutting etc. on base using negative-pressure adsorption When occur because base heating etc. cause excessively closely sealed, in addition, the adhesion under can effectively suppressing the form of web-like, from web-like Form debatching when fracture or damaged will not occur, this non-adhesive is good with the amalgamation of this plastic sheeting, and stretching etc. is become The tracing ability of shape is good.Therefore, it can be suitably used for be made up of and can have the circuit diagram of fine exquisiteness the material of fragility The semiconductor crystal wafer of case is the semiconductor machining of adherend.If the adhesive tape of the present invention is used for semiconductor machining, can have The suppression of effect ground is being fixed on the fixing mistake being caused with appearance when carrying out on base cutting etc. because of base heating etc. using negative-pressure adsorption Degree is closely sealed, therefore, it is possible to make the semiconductor fabrication sequence including cutting successfully carry out.If in addition, the present invention is viscous Crossed belt is used for semiconductor machining, then will not produce the deformation of thin membrane in the past producing, the accumulation of ess-strain due to adhesion, therefore Fitted, in addition, fitting in semiconductor crystal wafer while the fine exquisite circuit pattern of semiconductor crystal wafer can be followed exactly Be not in the Spontaneous release of ess-strain afterwards, therefore, it is possible to be effectively prevented semiconductor crystal wafer rupture.Especially, due to being used for The wafer of LED is to be made up of the highly brittle material such as gallium nitride, GaAs, carborundum, and the adhesive tape of the therefore present invention is special It is suitable for LED cutting etc..
Embodiment
Hereinafter, illustrate the present invention by embodiment, but the present invention is not subject to any restriction of these embodiments.Part it is Refer to weight portion.In addition, amount (the solid of solid constituent that the amount of the reagent supplying as a solution is remained with making solution evaporation Composition conversion amount) representing.
<Maximum elongation rate>
For maximum elongation rate, according to JIS-K-7127, using INSTRON type cupping machine (Shimadzu Seisakusho Ltd. manufactures, Autograph) it is measured.Specifically, after the sample of width 20mm × length 100mm is set apart from 50mm between with chuck, Stretched with the draw speed of 0.3m/ minute, measured value during fracture.
<Elastic modelling quantity>
Elastic modelling quantity is measured according to JIS-K-7127.
<The observation of non-adhesive>
(using the observation of SEM)
It is processed into after can observing non-adhesive section, carry out morphologic observation with transmission electron microscope (SEM).
(measuring the observation of (ATR-IR) using the infrared spectroscopy based on total reflection method)
Using infrared spectroscopy spectrogrph (Perkinermer manufacture, Spectrum One), select total reflection algoscopy, be Change the analysis depth of probe light, using 2 kinds of total reflection mensure with prism (ZnSe45 °, Ge45 °), carry out non-adhesive ATR-IR measures.
<Arithmetic mean surface roughness Ra>
The confocal laser microscope " LEXT3000 " being manufactured using OLYMPUS, is measured with 3D pattern with 20 times of object lens. The determination of the range of observation of 3D pattern is carried out as follows：When lens will be made to move up and down, CF image (confocal images) is changed into completely black position Put Top and Bottom being respectively set as range of observation.
Image acquiring method under 3D pattern 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 optional position by the Roughness analysis of analytical model. Wherein, value is obtained by the meansigma methodss of n=5.
The survey of the elastic modelling quantity at 80 DEG C obtained by atomic force microscope (AFM) of the male portion on ＜ non-adhesive surface Determine ＞
For the adhesive tape not possessing non-adhesive as comparative example 1, to the outermost being in opposition side with adhesive phase Layer surface is measured.
By sample at 120 DEG C heat treated more than 37 hours.Then, it is fixed on atomic force microscope (AFM) special Sample fixed station, is arranged on the special cooler heater adnexa of AFM, keeps more than 30 minutes, then, use at 80 DEG C AFM " MFP-3D-SA-J " and the cantilever " R150- of NANOSENSORS manufacture that Asylum Technology Co., Ltd. manufacture NCL-10 (material Si, spring constant 48N/m, radius of curvature 150nm of front end) ", measures the shape graph of AC pattern at 80 DEG C Picture.For the part now observed as protuberance, under Contact pattern measure force curve (at 80 DEG C, the mobile speed of cantilever 2 μm/s of degree, maximum indentation load 2 μ N).
By the Force-Ind curve obtaining from force curve, carry out the subsidiary software " IgorPro6.22A of AFM device The subsidiary parsing theoretical based on Hertz in MFP3D101010+1313 ", thus obtain elastic modelling quantity.It should be noted that with Tip Geometry=Sphere, Radius=150nm, Select=Fused Silica, νTip=0.17, ETip= 74.9GPa、νSample=0.33, the High=90% of Low=10%, Force label of Force label is calculated, with n=5 Meansigma methodss obtain.
<Adsorption test under the condition of high temperature>
By adhesive tape thin film or adhesive tape with the back side (in embodiment and comparative example, in the case of adhesive tape thin film For being the face being in opposition side with adhesive phase in the case of the face of non-adhesive side, adhesive tape) mode that becomes surface attaches On the microscope slide of 20mm (indulging) × 50mm (horizontal).Then, under 80 DEG C of environment, for the above-mentioned microscope slide being pasted with band and work Microscope slide (flat board edging product, size for adherend：65mm × 165mm × 1.35mm), make the above-mentioned microscope slide being pasted with band Rear side contact with the non-stannum surface side of above-mentioned microscope slide, place 15 minutes after, made a round trip with 2kg roller thus by microscope slide with The back side laminating of the above-mentioned microscope slide being pasted with band, places 30 minutes under 80 DEG C of environment.After placement, it is cooled to room temperature, then Using INSTRON type cupping machine (Shimadzu Seisakusho Ltd.'s manufacture, Autograph), under draw speed 0.3m/ minute, carry out 0 ° Peel off.Measure peeling force (maximum) now, evaluated according to following benchmark.
○：Peeling force is less than 5.0N.
△：Peeling force is 5.0N less than 15.0N.
×：Peeling force is more than 15.0N.
<Non-adhering tests peeling force>
With reference to JIS-Z-0237, under preserving at 23 DEG C, by adherend and the adhesive tape thin film comprising non-adhesive or viscous Crossed belt keeps more than 1 hour, then, non-adhering face is crimped on line pressure 8kg/m, crimping speed 0.3m/ minute Peeling force on SUS430BA, after measuring 30 minutes under the draw speed of 0.3m/ minute, 180 ° of strippings.
◎：Less than 0.5N/20mm.
○：0.5N/20mm is less than 1.0N/20mm.
×：1.0N/20mm more than.
<Adhesion test>
The binding agent aspect of adhesive tape is crimped on same adhesive tape with line pressure 8Kg/m, crimping speed 0.3m/ minute It is in the outmost surface (back layer) of opposition side with adhesive phase, after crimping, preserved with 50 DEG C × 48hr.After preservation, with Draw speed 0.3m/ minute, the disbonded test according to 180 ° of strippings is peeled off (according to JIS-Z-0237), measures adhesive phase Face and the adhesion (peeling force) of back layer.
Be evaluated as confirming while measuring peeling force the coming off of back layer when peeling off, adhesive phase destruction (cohesion Destroy, fastening destruction leads to cull) etc., carry out overall merit.
Evaluate according to following benchmark.
○：Peeling force is less than 3.0N/20mm, does not visually come off, the destruction of adhesive phase.
×：Peeling force comes off for more than 3.0N/20mm or visual presence, the destruction of adhesive phase.
<Anchoring validation test>
(anchoring validation test A)
By draw speed 0.3m/ minute～3m/ minute, adhesive tape thin film or adhesive tape are stretched to 200%, pass through During visual valuation stretching and after the stretching, outmost surface being in opposition side with adhesive phase of adhesive tape thin film or adhesive tape The deciduous of (back layer).
(anchoring validation test B)
After carrying out the stretching same with anchoring validation test A, " NO.31B " that Nitto Denko Corp is manufactured makees For back side process layer, made a round trip with the crimping speed of 0.3m/ minute with 2Kg roller (25mm width), then 23 DEG C × 50% Keeping 1 minute under RH, carries out 90 ° of strippings under the peeling rate of 0.3m/ minute～3m/ minute, evaluates the back side by visual observation Deciduous.
(evaluation)
More than comprehensive descision evaluate, according to following benchmark evaluation anchorings.
◎：Being capable of coming off in anchoring validation test A and anchoring validation test B all with the back side that visually confirms Do not occur.
○：Can with the back side that visually confirms come off unconfirmed in anchoring validation test A arrive, true in anchoring Recognize come off (the confirming as point-like) confirming pettiness in test B.
×：Confirm coming off of the back side in anchoring validation test A, or confirm the back of the body in anchoring validation test B The coming off of face.
(Production Example 1)：The manufacture of plastic sheeting
Comprise DOP plasticizer using rolling process manufacture with respect to polrvinyl chloride 100 weight portion of degree of polymerization P=1050 (adjacent Phthalic acid double (2- Octyl Nitrite), J-PLUS Co., Ltd manufactures) the soft PVC thin film of 27 weight portions.This is soft poly- The thickness of vinyl chloride film is 70 μm, is 250MPa according to the elastic modelling quantity (MD) that JIS-K-7127 measures, according to JIS-K- The maximum elongation rate (MD) of 7127 mensure is 400%.In addition, surface roughness (the arithmetic mean surface roughness after firm manufacture Ra) it is 0.1 μm.
(embodiment 1)
By polyorganosiloxane resin (KS-723A, SHIN-ETSU HANTOTAI's chemical industry manufacture) 60 weight portions, polyorganosiloxane resin (KS- 723B, SHIN-ETSU HANTOTAI chemical industry manufacture) 40 weight portions, acrylic copolymer polymer (methyl methacrylate (MMA)/acrylic acid Butyl ester (BA)/2-(Acryloyloxy)ethanol (HEA)=90/10/10) 50 weight portions, stannum series catalysts (Cat-PS3, SHIN-ETSU HANTOTAI's chemical industry Manufacturing) 10 weight portions are mixed with solution state, obtain mixed solution (1).Polysiloxanes in mixed solution (1) and (first Base) acrylic acid series polymeric compounds mixing ratio with weight ratio meter as polysiloxanes：(methyl) acrylic acid series polymeric compounds=2：1.In addition, The calculating Tg of acrylic copolymer polymer is 67.8 DEG C, and SP value is 10.7 (cal/cm3)0.5.
The above-mentioned mixed solution of the coated on one side (1) of the soft PVC thin film manufacturing in Production Example 1, forms thickness 1.0 μm, the non-adhesive of arithmetic mean surface roughness Ra=0.5 μm.
So operate, obtain adhesive tape thin film (1).
Various evaluation results are shown in table 1.
In addition, when observing non-adhesive using SEM, as shown in Figure 1, Figure 2, Figure 3 shows, according to the depth of morphologic observation image, Be able to confirm that different from the composition of plastic sheeting side in Air Interface side, define containing comprise polysiloxanes be more than (methyl) third The rich polysiloxanes phase of olefin(e) acid based polymer is more than the richness (methyl) third of polysiloxanes with comprising (methyl) acrylic acid series polymeric compounds Olefin(e) acid based polymer phase and the rich polysiloxanes phase phase separation structure mutually independent mutually with rich (methyl) acrylic acid series polymeric compounds, Observe that rich polysiloxanes phase is present in Air Interface side (opposition side of plastic sheeting), rich (methyl) acrylic acid series polymeric compounds phase It is present in plastic sheeting side.
And then, when non-adhesive is carried out with infrared spectroscopy mensure (ATR-IR) based on total reflection method, measure and be derived from Si- CH3800cm-1Neighbouring peak is with respect to the 1725cm in the carbonyl source in (methyl) acrylic acid series polymeric compounds phase-1Neighbouring peak Dulling luminosity ratio as a result, understanding compared with ZnSe45 °, during using Ge45 ° of prism, 800cm-1Neighbouring peak becomes big.Therefore, Understand that the containing ratio of silicon is higher in Air Interface side compared with substrate side.
In addition, in non-adhesive rich polysiloxanes phase be present in Air Interface side (opposition side of plastic sheeting) also can be Confirm in FT-IR.Mensure based on FT-IR uses " the Spectrum One " that Perkinermer manufactures, by analysis depth side ATR method is used to measure Air Interface side to (ZnSe45 °, Ge45 °) different of 2 kinds of prisms.During the chart of confirmation gained, it is able to confirm that Arrive：In Ge45 ° shallow using analysis depth direction of prism, relatively belong to (methyl) acrylic acid seriess from non-adhesive The 1720cm of the C=O of polymer-1～1730cm-1Peak, be derived from Si-CH3800cm-1The dulling luminosity ratio at neighbouring peak becomes Greatly.Thus, the concentration of provable polysiloxanes becomes higher in Air Interface side.
The principle that these observed results and surface free energy are minimized take into account it is known that in non-adhesive shape 2 Rotating fields of rich polysiloxanes phase are become to have in Air Interface side.
(embodiment 2)
In embodiment 1, the above-mentioned mixed solution of coated on one side of the soft PVC thin film manufacturing in Production Example 1 (1), carry out similarly to Example 1, form 0.7 μm of thickness, the non-adhesive of arithmetic mean surface roughness Ra=0.1 μm.
So operate, obtain adhesive tape thin film (2).
Various evaluation results are shown in table 1.
(embodiment 3)
Preparation comprises to be made up of butyl acrylate (BA)/acrylonitrile (AN)/acrylic acid (AA)=85/15/2.5 (weight ratio) Acrylic copolymer polymer 100 weight portion, melamine series cross-linking agent (butylated melamine-formaldehvde resin, " SUPER BECKAMINE J-820-60N ", Japanese polyurethane manufacture) 10 weight portions, the DOP plasticizer (double (2- of phthalic acid Octyl Nitrite), J-PLUS Co., Ltd system) 60 weight portions binding agent toluene solution.
By this binder solution coating obtain in embodiment 1 adhesive tape thin film (1) be in phase with non-adhesive On the face tossed about, then it was dried with 130 DEG C × 90 seconds, is in opposition side in soft PVC thin film and non-adhesive Face on formed 10 μm of thickness adhesive phase.The SP value of the adhesive phase being formed is 10.5.
So operate, obtain adhesive tape (3).
Various evaluation results are shown in table 1.
(embodiment 4)
The acrylic copolymer polymer being formed as non-adhesive, using methyl methacrylate (MMA)/acrylic acid Acrylic copolymer polymer 50 weight portion of ethyl ester (EA)/2-(Acryloyloxy)ethanol (HEA)=90/10/10, in addition with reality Apply example 1 similarly to carry out, obtain adhesive tape thin film (4).Replace adhesive tape thin film (1) using this adhesive tape with thin film (4), Carry out similarly to Example 3 in addition, obtain adhesive tape (4).
The calculating Tg of acrylic copolymer polymer is 74.3 DEG C, SP value is 10.3 (cal/cm3)0.5.
The thickness of non-adhesive is 1.0 μm, arithmetic mean surface roughness Ra=0.5 μm.
Various evaluation results are shown in table 1.
(embodiment 5)
The acrylic copolymer polymer being formed as non-adhesive, using methyl methacrylate (MMA)/acrylic acid Acrylic copolymer polymer 50 weight portion of cyclohexyl (CHA)/2-(Acryloyloxy)ethanol (HEA)=90/10/10, in addition Carry out similarly to Example 1, obtain adhesive tape thin film (5).Replace adhesive tape thin film using this adhesive tape with thin film (5) (1), carry out similarly to Example 3 in addition, obtain adhesive tape (5).
The calculating Tg of acrylic copolymer polymer is 80.0 DEG C, SP value is 10.4 (cal/cm3)0.5.
The thickness of non-adhesive is 1.0 μm, arithmetic mean surface roughness Ra=0.5 μm.
Various evaluation results are shown in table 1.
(embodiment 6)
The acrylic copolymer polymer being formed as non-adhesive, using methyl methacrylate (MMA)/acrylic acid Acrylic copolymer polymer 50 weight portion of butyl ester (BA)/2-(Acryloyloxy)ethanol (HEA)=95/5/15, in addition with reality Apply example 1 similarly to carry out, obtain adhesive tape thin film (6).Replace adhesive tape thin film (1) using this adhesive tape with thin film (6), Carry out similarly to Example 3 in addition, obtain adhesive tape (6).
The calculating Tg of acrylic copolymer polymer is 73.0 DEG C, SP value is 10.5 (cal/cm3)0.5.
The thickness of non-adhesive is 1.0 μm, arithmetic mean surface roughness Ra=1.0 μm.
Various evaluation results are shown in table 1.
(embodiment 7)
The acrylic copolymer polymer being formed as non-adhesive, using methyl methacrylate (MMA)/acrylic acid Acrylic copolymer polymer 50 weight portion of butyl ester (BA)/2-(Acryloyloxy)ethanol (HEA)=80/20/10, in addition with reality Apply example 1 similarly to carry out, obtain adhesive tape thin film (7).Replace adhesive tape thin film (1) using this adhesive tape with thin film (7), Carry out similarly to Example 3 in addition, obtain adhesive tape (7).
The calculating Tg of acrylic copolymer polymer is 48.5 DEG C, SP value is 10.1 (cal/cm3)0.5.
The thickness of non-adhesive is 1.0 μm, arithmetic mean surface roughness Ra=0.2 μm.
Various evaluation results are shown in table 1.
(embodiment 8)
The acrylic copolymer polymer being formed as non-adhesive, using methyl methacrylate (MMA)/acrylic acid Acrylic copolymer polymer 50 weight portion of butyl ester (BA)/2-(Acryloyloxy)ethanol (HEA)=99/1/5, in addition with enforcement Example 1 is similarly carried out, and obtains adhesive tape thin film (8).Replace adhesive tape thin film (1) using this adhesive tape with thin film (8), remove Carry out similarly to Example 3 beyond this, obtain adhesive tape (8).
The calculating Tg of acrylic copolymer polymer is 94.3 DEG C, SP value is 10.1 (cal/cm3)0.5.
The thickness of non-adhesive is 1.0 μm, arithmetic mean surface roughness Ra=0.5 μm.
Various evaluation results are shown in table 1.
(embodiment 9)
The adhesive phase side of the adhesive tape (5) obtaining in embodiment 5 attaches the PET of 38 μm of thickness implementing Si process Liner, as release liner, obtains adhesive tape (9).
The thickness of non-adhesive is 1.0 μm, arithmetic mean surface roughness Ra=0.5 μm.
Various evaluation results are shown in table 1.
(embodiment 10)
The acrylic copolymer polymer being formed as non-adhesive, using methyl methacrylate (MMA)/acrylic acid Acrylic copolymer polymer 50 weight portion of butyl ester (BA)/2-(Acryloyloxy)ethanol (HEA)=95/5/10, in addition with reality Apply example 1 similarly to carry out, obtain adhesive tape thin film (10).Replace adhesive tape thin film using this adhesive tape with thin film (10) (1), carry out similarly to Example 3 in addition, obtain adhesive tape (10).
The calculating Tg of acrylic copolymer polymer is 77.2 DEG C, SP value is 10.3 (cal/cm3)0.5.
The thickness of non-adhesive is 1.0 μm, arithmetic mean surface roughness Ra=0.7 μm.
Various evaluation results are shown in table 1.
(embodiment 11)
The acrylic copolymer polymer being formed as non-adhesive, using methyl methacrylate (MMA)/acrylic acid Butyl ester (BA)/2-(Acryloyloxy)ethanol (HEA)=70/30/10 acrylic copolymer polymer 50 weight portion, in addition, with reality Apply example 1 similarly to carry out, obtain adhesive tape thin film (11).Replace adhesive tape thin film using this adhesive tape with thin film (11) (1), carry out similarly to Example 3 in addition, obtain adhesive tape (11).
The calculating Tg of acrylic copolymer polymer is 31.2 DEG C, SP value is 10.4 (cal/cm3)0.5.
The thickness of non-adhesive is 1.0 μm, arithmetic mean surface roughness Ra=0.3 μm.
Various evaluation results are shown in table 1.
(comparative example 1)
In embodiment 3, do not form non-adhesive, carry out similarly to Example 3 in addition, obtain adhesive tape (C1).
Various evaluation results are shown in table 1.
(comparative example 2)
The acrylic copolymer polymer being formed as non-adhesive, using methyl methacrylate (MMA)/acrylic acid Acrylic copolymer polymer 50 weight portion of butyl ester (BA)/2-(Acryloyloxy)ethanol (HEA)=55/45/10, in addition with reality Apply example 1 similarly to carry out, obtain adhesive tape thin film (C2).Replace adhesive tape thin film using this adhesive tape with thin film (C2) (1), carry out similarly to Example 3 in addition, obtain adhesive tape (C2).
The calculating Tg of acrylic copolymer polymer is 8.6 DEG C, SP value is 10.4 (cal/cm3)0.5.
The thickness of non-adhesive is 1.0 μm, arithmetic mean surface roughness Ra=0.08 μm.
Various evaluation results are shown in table 1.
[table 1]
Industrial applicability
The adhesive tape of the present invention has the adhesive tape thin film of the present invention, therefore as described above, can effectively suppress Using negative-pressure adsorption be fixed on fixing with occur when carrying out on base cutting etc. because base heating etc. cause excessively closely sealed, separately Outward, can effectively suppress the adhesion under web-like form, fracture or damaged, this non-stick will not occur when from the form debatching of web-like Close layer good with the amalgamation of this plastic sheeting, good to the tracing ability of the deformation such as stretching.Therefore, it can be suitably used for by The semiconductor crystal wafer of the circuit pattern that the material of fragility constitutes and can have fine exquisiteness is the semiconductor machining of adherend.If will The adhesive tape of the present invention is used for semiconductor machining, then the appearance when carrying out fixing using the absorption of negative pressure can be suppressed excessively close Close, therefore, it is possible to make the semiconductor fabrication sequence including cutting successfully carry out.If in addition, the adhesive tape by the present invention For semiconductor machining, then will not produce the deformation of thin membrane in the past producing, the accumulation of ess-strain due to adhesion, therefore, it is possible to Fitted with following the fine exquisite circuit pattern of semiconductor crystal wafer exactly, in addition, after fitting in semiconductor crystal wafer Be not in the Spontaneous release of ess-strain, therefore, it is possible to be effectively prevented semiconductor crystal wafer rupture.Especially, due to for LED Wafer be to be made up of the highly brittle material such as gallium nitride, GaAs, carborundum, the adhesive tape of the therefore present invention is particularly suitable In LED cutting etc..

Claims (17)

1. a kind of adhesive tape thin film, it is to possess the adhesive tape thin film of non-adhesive in the one side of plastic sheeting,
The surface of this non-adhesive has concaveconvex structure,
Elastic modelling quantity at 80 DEG C obtained by atomic force microscope of the male portion on the surface of this non-adhesive be 0.2GPa with On,
Wherein, described non-adhesive has phase separation structure.
2. adhesive tape thin film according to claim 1, wherein, arithmetic mean surface roughness Ra of described non-adhesive For more than 0.1 μm.
3. adhesive tape thin film according to claim 1 and 2, wherein, described non-adhesive is polysiloxanes and (methyl) The mixed layer of acrylic acid series polymeric compounds.
4. adhesive tape thin film according to claim 3, wherein, the calculating Tg of described (methyl) acrylic acid series polymeric compounds is More than 10 DEG C.
5. adhesive tape thin film according to claim 3, wherein, the SP value of described (methyl) acrylic acid series polymeric compounds is 9.0(cal/cm3)0.5～12.0 (cal/cm3)0.5.
6. adhesive tape thin film according to claim 3, wherein, polysiloxanes in described non-adhesive and (methyl) third The mixing ratio of olefin(e) acid based polymer is with weight ratio meter as polysiloxanes：(methyl) acrylic acid series polymeric compounds=1：50～50：1.
7. adhesive tape thin film according to claim 1 and 2, wherein, the non-adhering test peeling force of described non-adhesive Less than 1.0N/20mm.
8. adhesive tape thin film according to claim 1 and 2, wherein, the thickness of described non-adhesive is 0.01 μm～10 μ m.
9. adhesive tape thin film according to claim 1 and 2, wherein, described plastic sheeting according to JIS-K-7127 survey Fixed maximum elongation rate is more than 100%.
10. adhesive tape thin film according to claim 1 and 2, wherein, the thickness of described plastic sheeting is 20 μm～200 μ m.
11. adhesive tape thin film according to claim 1 and 2, wherein, described plastic sheeting comprises polrvinyl chloride.
A kind of 12. adhesive tapes, the described plastic sheeting in its adhesive tape thin film any one of in claim 1～11 The face contrary with described non-adhesive possess adhesive phase.
13. adhesive tapes according to claim 12, wherein, described adhesive layer comprises at least one (methyl) acrylic acid seriess Polymer.
14. adhesive tapes according to claim 12 or 13, wherein, the SP value of described adhesive layer is 9.0 (cal/cm3)0.5 ～12.0 (cal/cm3)0.5.
15. adhesive tapes according to claim 12 or 13, it possesses release liner on the surface of described adhesive layer.
16. adhesive tapes according to claim 12 or 13, it is used for semiconductor machining.
17. adhesive tapes according to claim 12 or 13, it is used for LED cutting purposes.
CN201380011399.7A 2012-02-28 2013-02-08 Adhesive tape thin film and adhesive tape Active CN104137231B (en)

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TW201343859A (en) 2013-11-01
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JP6005952B2 (en) 2016-10-12
TWI576405B (en) 2017-04-01

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