TWI567154B - Film for pressure-sensitive adhesive tape and pressure-sensitive adhesive tape - Google Patents

Description

Adhesive tape and adhesive tape

The present invention relates to a film for an adhesive tape and an adhesive tape.

The adhesive tape used in semiconductor dicing fixes the wafer during dicing, so it is necessary to fix the surface opposite to the wafer adhesion surface to the susceptor. Usually, such fixing is carried out by a vacuum such as vacuum adsorption.

When such a fixing by the negative pressure is performed, the adhesive tape may be excessively adhered to the base due to the melting of the adhesive tape due to the excessive application of the negative pressure or the heat generated during the cutting. When such excessive adhesion occurs, the operability when the susceptor is unsecured is deteriorated, and for example, there is a problem that the semiconductor manufacturing step including dicing cannot be smoothly performed.

In order to solve the above problem of excessive adhesion, the following technique is reported: the surface line surface roughness of the surface of the substrate film opposite to the adhesive layer in the wafer surface protection tape including the base film and the adhesive layer 2 layers The Ra control is a specific small size (Patent Document 1).

However, for the base film of the adhesive tape used in semiconductor dicing, it is required to have the extension (extension) characteristic and the step follow characteristic unique to the semiconductor manufacturing process. That is, the base film of the adhesive tape used in semiconductor dicing must be well extended in the expanding step, and it is necessary to follow the step of the semiconductor well. As the substrate film that satisfies such requirements, a substrate film containing a material having a large elongation can be selected. However, the surface state of such a substrate film is susceptible to temperature. Therefore, there is a problem that the center line surface roughness Ra of the surface of the substrate film is controlled to be special as reported in Patent Document 1. When the temperature is changed by the temperature or the temperature of the process unit, the surface roughness Ra of the center line controlled to a specific size is significantly changed, and the effects of the invention described in Patent Document 1 cannot be expressed.

In semiconductor dicing, especially in LED dicing, the semiconductor wafer used is composed of a very brittle material such as gallium nitride, gallium arsenide or tantalum carbide. Therefore, in order to prevent breakage of the semiconductor wafer, an adhesive tape is required. The base film further has expansion (extension) characteristics and step following characteristics. Therefore, the above problems become apparent in the adhesive tape used for LED cutting.

Usually, the film has a smooth surface, and when such a film is processed into a roll shape, the film comes into contact with each other and adheres to each other, that is, adheres. In the roll in which the adhesion occurs, there is a problem that the work of unwinding the film becomes difficult. In particular, a plasticizer is usually added to a film having a large elongation. In such a film, since a small space between the films is filled due to precipitation of a plasticizer on the surface of the film, the adverse effect of adhesion becomes conspicuous.

In the case where the surface of the film is adhered by an adhesive, since the adhesive itself has adhesiveness, the adverse effect of the adhesion becomes more and more obvious. In the case where the roll film to which the adhesion occurs is unwound, extra force is required to release the adhesion of the films to each other. By applying such additional force, the film is elongated and deformed, or the additional force accumulates as stress strain even when the film is not deformed. When the film deformed by the above reason is applied to the adhesive tape, it is difficult to follow the adherend. Further, when the film in which the stress strain is accumulated due to the above-described causes is applied to the adhesive tape, the adherend is bonded to the adherend, and the stress and strain are naturally released to cause the adherend to be damaged. For the use of adhesive tape for semiconductor processing In the case of a shape, since the semiconductor wafer as the adherend is made of a brittle material, it is easily embrittled or defective.

Therefore, when a film deformed by the above reason is applied to an adhesive tape, it is difficult to follow the fine and delicate circuit pattern of the semiconductor wafer. Further, when a film in which stress strain is accumulated due to the above-described causes is applied to an adhesive tape, the semiconductor wafer is easily bonded to the semiconductor wafer, and the semiconductor wafer is easily damaged.

In particular, wafers for LEDs are composed of very brittle materials such as gallium nitride, gallium arsenide, and tantalum carbide. Therefore, it is extremely important to prevent adhesion in an adhesive tape for LED cutting or the like.

As a prior art for preventing adhesion, two kinds of techniques can be roughly cited.

As a prior art, physical processing such as embossing is performed on the back surface of the film (Patent Document 2). However, this technique has a problem in that the unevenness formed on the back surface of the film serves as a stress concentration structure. Therefore, when unwinding from the roll form, the film starts to be torn or broken by the unevenness as a starting point due to the unwinding force.

As another prior art, a polyfluorene oxygen release agent is applied to the back surface of the film (Patent Document 3). However, the problem with this technique is that the polyoxymethylene release agent has a low chemical affinity with the back surface of the film due to its surface tension, and is difficult to be compatible with the back surface of the film. Further, when a film having a polyfluorinated release agent coated on the back surface is applied to an adhesive tape, if the adhesive tape is stretched or the like, the following problems may occur: sometimes treatment with a polyfluorene release agent The layer cannot follow the extension, and the treatment layer is broken to cause contamination. Furthermore, there is also a technique for coating a cross-linked polyfluorinated mold release agent for improving the chemical affinity of the polyfluorene oxygen release agent to the back side of the film, but the crosslinked polyoxymethylene usually has a very high elongation. When the film having the back-coated polyfluorinated release agent coated on the back side is applied to the adhesive tape, if the adhesive tape is extended or the like, there is a problem in that the cross-linked polyfluorene is used. The treatment layer of the molding agent cannot follow the extension, so that the fixing property cannot be maintained.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-239124

[Patent Document 2] International Publication No. 2009/028069

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-201836

An object of the present invention is to provide a film for an adhesive tape which is provided with a non-adhesive layer on a base film, and which can suppress excessive adhesion when performing adsorption and fixation by a negative pressure, and The non-adhesive layer is disposed on the material film, which can effectively inhibit the adhesion of the roll form, and does not tear or break when unrolling from the roll form, and the non-adhesive layer has better compatibility with the base film, The follow-up of the deformation such as extension is good. Further, an object of the present invention is to provide an adhesive tape comprising such a film for an adhesive tape.

The film for an adhesive tape of the present invention comprises a non-adhesive layer on one side of a plastic film having a maximum elongation of 100% or more as measured according to JIS-K-7127, and the arithmetic mean surface roughness Ra of the non-adhesive layer is 0.1. More than μm.

In a preferred embodiment, the non-adhesive layer has a non-adhesive test peel force of less than 1.0 N/20 mm.

In a preferred embodiment, the non-adhesive layer is a mixed layer of a polyoxymethylene and a (meth)acrylic polymer.

In a preferred embodiment, the mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the non-adhesive layer is polyoxyn:poly(meth)acrylic polymer=1:50 by weight ratio. ~50:1.

In a preferred embodiment, the non-adhesive layer comprises a polyfluorene-rich phase containing more poly(oxy)oxygen than a (meth)acrylic polymer, and a richer (meth)acrylic polymer than polyoxynium. (Meth)acrylic polymer phase.

In a preferred embodiment, the plastic film has a thickness of 20 μm to 200 μm.

In a preferred embodiment, the non-adhesive layer has a thickness of 0.01 μm to 10 μm.

In a preferred embodiment, the plastic film comprises polyvinyl chloride.

In another embodiment of the invention, an adhesive tape is provided. The adhesive tape of the present invention comprises an adhesive layer on the opposite side of the non-adhesive layer of the plastic film in the film for an adhesive tape of the present invention.

In a preferred embodiment, the adhesive layer comprises a (meth)acrylic polymer.

In a preferred embodiment, the adhesive layer has an SP value of 9.0 (cal/cm ³ ) of ^0.5 to 12.0 (cal/cm ³ ) ^0.5 .

In a preferred embodiment, a release liner is included on the surface of the adhesive layer.

In a preferred embodiment, the adhesive tape of the present invention is used in semiconductor processing.

In a preferred embodiment, the semiconductor processing is LED dicing.

According to the present invention, it is possible to provide a film for an adhesive tape which is provided with a non-adhesive layer on a substrate film, and which suppresses excessive adhesion when performing adsorption fixation by a negative pressure, and The non-adhesive layer is disposed on the material film, which can effectively inhibit the adhesion of the roll form, and does not tear or break when unrolling from the roll form, and the non-adhesive layer has better compatibility with the base film, The follow-up of the deformation such as extension is good. Further, the present invention can provide an adhesive tape comprising the film for such an adhesive tape.

<<1. Adhesive tape film>>

The film for an adhesive tape of the present invention comprises a non-adhesive layer on one side of the plastic film.

<1-1. Plastic film>

The maximum elongation (MD) of the plastic film measured in accordance with JIS-K-7127 is 100% or more, preferably 200% or more, and most preferably 300% or more. The upper limit of the maximum elongation (MD) is preferably 1000% or less. Such a plastic film may contain any suitable resin material. As such a resin material, for example, polyvinyl chloride, polyolefin, polyester, polyimide, polyamine or the like is preferable, and polyvinyl chloride, polyolefin, and more preferably polyvinyl chloride are exemplified. . Polyvinyl chloride is excellent in stress relaxation property, and therefore can be preferably used for a film for an adhesive tape which can be used for an adhesive tape used for semiconductor processing such as LED cutting.

The content ratio of the above-mentioned resin material in the plastic film can be set to any suitable content ratio depending on the purpose and use. As such a content ratio For example, it is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, still more preferably 70% by weight to 100% by weight.

A plasticizer may also be contained in the plastic film. The content of the plasticizer in the plastic film is preferably from 0.5% by weight to 50% by weight, more preferably from 1.0% by weight to 40% by weight, based on the above-mentioned resin material in the plastic film. By including the plasticizer in the above-mentioned content ratio in the plastic film, the followability to deformation such as stretching can be further improved.

Examples of the plasticizer include a phthalic acid ester type, a trimellitic acid ester type (W-700 manufactured by Dainippon Ink Co., Ltd., and trioctyl trimellitate). Acid ester (D620 manufactured by J-PLUS Co., Ltd., dioctyl adipate and diisononyl adipate), phosphate ester (such as tricresyl phosphate), adipic acid ester, lemon Ester (Ethyl triethyl citrate, etc.), sebacate, sebacate, maleate, benzoate, polyether polyester, epoxy polyester (epoxidation) Soybean oil and epoxidized linseed oil, etc., and polyester (including low molecular weight polyesters of carboxylic acids and diols). In the present invention, an ester-based plasticizer is preferably used. The plasticizer may be used alone or in combination of two or more.

In the plastic film, any other suitable component may be contained within a range that does not impair the effects of the present invention.

The thickness of the plastic film is preferably from 20 μm to 200 μm, more preferably from 40 μm to 150 μm, and even more preferably from 50 μm to 100 μm. When the thickness of the plastic film is less than 20 μm, there is a problem that the workability is deteriorated, and particularly when the adhesive tape is formed, it is difficult to attach the cooperation industry. If the thickness of the plastic film is more than 200 μm, there is a problem that the followability to deformation such as elongation is deteriorated.

<1-2. Non-adhesive layer>

The arithmetic mean surface roughness Ra of the non-adhesive layer is 0.1 μm or more, preferably 0.1 μm to 3.0 μm, more preferably 0.2 μm to 2.0 μm. By controlling the arithmetic mean surface roughness Ra of the non-adhesive layer within the above range, it is possible to suppress excessive adhesion when the adsorption by the negative pressure is performed. In the present invention, the arithmetic mean surface roughness Ra of the non-adhesive layer is measured based on the following method.

The non-adhesive test peeling force of the non-adhesive layer is preferably less than 1.0 N/20 mm, more preferably less than 0.5 N/20 mm, and even more preferably less than 0.2 N/20 mm. By controlling the non-adhesive test peeling force of the non-adhesive layer to the above range, it is possible to further suppress excessive adhesion when the adsorption by the negative pressure is performed. In the present invention, the non-adhesive test peeling force of the non-adhesive layer was measured based on the following method.

The non-adhesive layer is preferably a mixed layer of a polyfluorene oxide and a (meth)acrylic polymer. By using the non-adhesive layer as a mixed layer of polyoxymethylene and (meth)acrylic polymer, the compatibility between the non-adhesive layer and the plastic film can be improved, and the adhesive tape film of the present invention and The adhesive tape including the same has a good followability to deformation such as extension.

The mixing ratio of the polyoxymethylene to the (meth)acrylic polymer in the non-adhesive layer is preferably a polyoxyn: (meth)acrylic polymer = 1:50 to 50:1 by weight ratio. Preferably, the poly(oxymethylene) polymer: (meth)acrylic polymer = 1:30 to 30:1, and more preferably polyfluorene: (meth)acrylic polymer = 1:10 to 10:1, preferably It is a polyoxymethylene: (meth)acrylic polymer = 1:5 to 5:1, and most preferably polyoxyl: (meth)acrylic polymer = 1:3 to 5:1. If When the proportion of the polyoxyl oxide in the non-adhesive layer is too large, the chemical affinity between the non-adhesive layer and the back surface of the plastic film is lowered, and it is difficult to be compatible with the back surface of the plastic film. Further, if the content ratio of the polyfluorene oxide in the non-adhesive layer is too large, when the film for an adhesive tape or the adhesive tape containing the same is formed, the followability to deformation such as elongation is deteriorated, and the non-adhesive layer is broken. The blasphemy of pollution.

If the content ratio of the (meth)acrylic polymer in the non-adhesive layer is too large, the non-adhesive layer acts as an acrylic adhesive, and adhesion tends to occur easily. The non-adhesive layer preferably comprises a polyfluorene-rich phase containing more poly(oxy)oxygen than the (meth)acrylic polymer, and a rich (meth)acrylic acid containing more (poly)oxyl (meth)acrylic polymer. It is a polymer phase. More specifically, the non-adhesive layer preferably contains the above-mentioned rich polyoxygen phase and the above-mentioned rich (meth)acrylic polymer phase in a phase separation structure independent of each other, and more preferably the above-mentioned rich polyoxygen phase exists in the air. On the interface side (the side opposite to the plastic film), the above-mentioned rich (meth)acrylic polymer phase is present on the plastic film side. By having such a phase separation structure, the enriched xenon phase existing on the air interface side can be used to effectively inhibit adhesion, and the non-adhesive layer can be made by using the rich (meth)acrylic polymer phase present on the plastic film side. The compatibility of the plastic film is improved, and the deformation followability becomes good. Such a phase separation structure can be formed by adjusting the mixing ratio of the polyfluorene oxide and the (meth)acrylic polymer in the non-adhesive layer as described above.

By providing the non-adhesive layer with the phase separation structure as described above, it is preferable that the surface of the non-adhesive layer is formed with a minute uneven structure having an arithmetic mean surface roughness Ra of 0.1 μm or more. It is speculated that the unevenness may be the difference in the mobility of the poly(oxy)oxygen and the (meth)acrylic polymer when the phase separation structure is formed. Generated separately. By forming the structure of the concavities and convexities, the film for an adhesive tape of the present invention can be prevented from being excessively adhered when the film is adsorbed and fixed by a negative pressure, and the adhesion of the roll-like form can be effectively suppressed, and the self-rolling can be suppressed. Tearing or breakage occurs when the shape is unwound.

The non-adhesive layer comprises a polyfluorene-rich phase containing more poly(oxy)oxygen than the (meth)acrylic polymer as described above, and a rich (meth)acrylic polymer containing more polyoxymethylene (methyl) The acrylic polymer phase can be observed by any suitable method. As such a method, for example, an electron microscope such as a transmission electron microscope (TEM), a scanning electron microscope (SEM), or a field emission scanning electron microscope (FE-SEM) can be used to observe the morphology of the non-adhesive layer profile. method. The two-layer separation structure can be identified based on the faintness of the observed image. Further, a method of observing by observing the depth of the probe light from the side of the non-adhesive layer air to the inside while observing the depth of the probe light by the infrared absorption spectroscopy of the total reflection method while observing the ruthenium or carbon contained in the composition Such as the content changes. In addition to this, a method of observation by an X-ray microanalyzer or X-ray photoelectron spectroscopy may be mentioned.

Further, these methods can be combined as appropriate for observation. As the polyoxygen oxide, any suitable polyoxane can be used. Examples of such a polyfluorene oxide include, for example, addition of polyfluorene oxide, which is a platinum-based compound as a catalyst, and an alkenyl group-containing polydialkyloxirane and a polydialkylhydrogenpolyoxyl An alkane is subjected to an addition reaction to thereby form a release film by hardening; and a condensation type polyoxane is a tin-based catalyst, and a hydroxymethyl group-containing polydialkyloxirane and a polydialkyl group are used. Hydrogen polyoxyalkylene is obtained by carrying out a reaction. As an example of the addition of polyfluorene oxide, for example, it can be produced by Shin-Etsu Silicones. "KS-776A" and "KS-839L", etc. Examples of the condensed polyfluorene oxide include "KS723A/B" manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Further, in the production of polyfluorene oxide, other crosslinking agents, crosslinking accelerators, and the like may be suitably used in addition to the platinum-based catalyst or the tin-based catalyst. Further, the properties of polyfluorene oxide can be classified into a type dissolved in an organic solvent such as toluene, an emulsion type obtained by emulsifying the same, a non-solvent type composed of polyfluorene oxide, and the like. Further, in addition to the addition of polyfluorene oxide or condensed polyfluorene oxide, a polyfluorene/acrylic graft polymer, a polyfluorene/acrylic block polymer or the like may be used. Examples of the polyoxyn/acrylic graft polymer include Symac GS-30, GS101, US-270, US-350, and US-380 (all of which are by TOAGOSEI CO., LTD.). ) Manufacturing) and so on. Examples of the polyoxyn/acrylic block polymer include Modiper FS700, FS710, FS720, FS730, and FS770 (all of which are manufactured by NOF CORPORATION).

As the (meth)acrylic polymer, any suitable (meth)acrylic polymer can be used. In the present invention, "(meth)acrylic" means "acrylic and/or methacrylic".

The (meth)acrylic polymer is a polymer composed of a monomer component containing a (meth)acrylic monomer as a main monomer. The content ratio of the (meth)acrylic monomer in the monomer component constituting the (meth)acrylic polymer is preferably 50% by weight or more, more preferably 70% by weight to 100% by weight, still more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight. The monomer in the monomer component may be one type or two or more types.

The (meth)acrylic monomer is preferably (meth)acrylate or (meth)acrylic acid.

Examples of the (meth) acrylate include an alkyl (meth) acrylate having an alkyl group having 1 to 30 carbon atoms (including a cycloalkyl group), and a hydroxyl group-containing (meth) acrylate. The (meth) acrylate may be used alone or in combination of two or more.

Examples of the alkyl (meth)acrylate having an alkyl group having 1 to 30 carbon atoms (including a cycloalkyl group) include methyl (meth)acrylate and ethyl (meth)acrylate. Methyl) propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third (meth) acrylate Butyl ester, pentyl (meth)acrylate, amyl(meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, Heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, (meth)acrylic acid Isodecyl ester, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, thirteen (meth)acrylate Alkyl ester, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, pentadecyl (meth) acrylate, (a) Ethyl acrylate and (meth) acrylate Lauryl acid ester having a carbon number of an alkyl group having 1 to 30 (and also including cycloalkyl) the (meth) acrylate. Among the (meth) acrylates, an alkyl (meth) acrylate having an alkyl group having 2 to 20 carbon atoms (including a cycloalkyl group) is preferred, and an alkyl group having 4 to 18 carbon atoms is more preferred. Also included are alkyl (meth)acrylates of cycloalkyl).

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. In particular, in the present invention, the (meth)acrylic polymer constituting the release layer is preferably a polymer obtained by copolymerizing a hydroxyl group-containing (meth) acrylate.

In order to sufficiently exhibit the effects of the present invention, the monomer component constituting the (meth)acrylic polymer may further contain at least one selected from the group consisting of a hydroxyl group-containing monomer and a carboxyl group-containing monomer.

Examples of the hydroxyl group-containing monomer include allyl alcohol and the like. The hydroxyl group-containing monomer may be used alone or in combination of two or more.

Examples of the carboxyl group-containing monomer include carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, crotonic acid, maleic acid, fumaric acid, and itaconic acid. The carboxyl group-containing monomer may be used alone or in combination of two or more.

The (meth)acrylic polymer can be produced by any suitable polymerization method.

In the non-adhesive layer, any suitable additive may be contained within a range that does not impair the effects of the present invention. Examples of such an additive include a catalyst, an ultraviolet absorber, a filler, an anti-aging agent, an adhesion-imparting agent, a pigment, a dye, and a decane coupling agent.

The thickness of the non-adhesive layer is preferably from 0.01 μm to 10 μm, more preferably from 0.1 μm to 5 μm, still more preferably from 0.1 μm to 2 μm. When the thickness of the non-adhesive layer is less than 0.01 μm, adhesion is likely to occur. If the thickness of the non-adhesive layer is more than 10 μm, there is a problem that the followability to deformation such as elongation is deteriorated. If When the thickness of the non-adhesive layer is less than 0.01 μm, it is difficult to express the effect of the present invention, or it is difficult to manufacture.

As a method of forming a non-adhesive layer on one surface of a plastic film, for example, a method of forming a non-adhesive layer by applying a material for a non-adhesive layer on one surface of a plastic film and drying it is exemplified. Examples of the coating method include a bar coater, a gravure coater, a spin coater, a roll coater, a knife coater, and an applicator.

<<2. Adhesive tape>>

The adhesive tape of the present invention comprises an adhesive layer on the opposite side of the non-adhesive layer of the plastic film in the film for an adhesive tape of the present invention.

The thickness of the adhesive layer is preferably from 1.0 μm to 30 μm, more preferably from 1.0 μm to 20 μm, still more preferably from 3.0 μm to 15 μm. When the thickness of the adhesive layer is less than 1.0 μm, there is a possibility that sufficient adhesion cannot be exhibited. When the thickness of the adhesive layer is more than 30 μm, the adhesive force becomes excessive depending on the application, and the adhesive body is broken when peeled off or the like.

As the material of the above adhesive layer, any suitable adhesive can be employed within a range that does not impair the effects of the present invention.

Examples of the material of the adhesive layer include a (meth)acrylic polymer; a natural rubber; a special natural rubber grafted with a monomer such as methyl methacrylate; and SBS, SBR, SEPS, SIS, SEBS, Synthetic rubber such as polybutene, polyisobutene, polyisobutylene butyl rubber, and the like. Among these, a (meth)acrylic polymer is preferred because it has less residual residue on the adherend after peeling, has high cohesiveness, and is excellent in transparency.

When the (meth)acrylic polymer is contained in the adhesive layer, the content ratio of the (meth)acrylic polymer in the adhesive layer can be appropriately set depending on the purpose.

The (meth)acrylic polymer is a resin composed of a monomer component containing a (meth)acrylic monomer as a main monomer. The content ratio of the (meth)acrylic monomer in the monomer component constituting the (meth)acrylic polymer is preferably 50% by weight or more, more preferably 70% by weight to 100% by weight, still more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight. The monomer in the monomer component may be one type or two or more types.

The (meth)acrylic monomer is preferably (meth)acrylate or (meth)acrylic acid.

Examples of the (meth) acrylate include an alkyl (meth) acrylate having an alkyl group having 1 to 30 carbon atoms (including a cycloalkyl group), and a hydroxyl group-containing (meth) acrylate. The (meth) acrylate may be used alone or in combination of two or more.

Examples of the alkyl (meth)acrylate having an alkyl group having 1 to 30 carbon atoms (including a cycloalkyl group) include methyl (meth)acrylate and ethyl (meth)acrylate. Methyl) propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third (meth) acrylate Butyl ester, pentyl (meth)acrylate, amyl(meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, Heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, Isodecyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, (A) Tridecyl acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, hexadecane (meth) acrylate A (meth)acrylic acid alkyl ester having a carbon number of 1 to 30 (including a cycloalkyl group) having a carbon number of 1 to 30, such as an alkyl ester of (meth)acrylate and a lauryl (meth)acrylate. Among the (meth) acrylates, an alkyl (meth) acrylate having an alkyl group having 2 to 20 carbon atoms (including a cycloalkyl group) is preferred, and an alkyl group having 4 to 18 carbon atoms is more preferred. (Alkylalkyl) (alkyl) alkyl (meth)acrylate.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

In order to sufficiently exhibit the effect as an adhesive, the monomer component constituting the (meth)acrylic polymer preferably contains at least one selected from the group consisting of a hydroxyl group-containing monomer and a carboxyl group-containing monomer. More preferably, it is a monomer having a carboxyl group. Further, in order to sufficiently exhibit the effect as an adhesive, the monomer component constituting the (meth)acrylic polymer may contain acrylonitrile.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and allyl alcohol. The hydroxyl group-containing monomer may be used alone or in combination of two or more.

Examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, crotonic acid, maleic acid, and fumaric acid. Ikonic acid and so on. The carboxyl group-containing monomer can only One type may be used in two or more types.

When the monomer component constituting the (meth)acrylic polymer contains a hydroxyl group-containing monomer, the content ratio of the hydroxyl group-containing monomer constituting the monomer component of the (meth)acrylic polymer is higher. It is preferably from 0.1% by weight to 20% by weight, more preferably from 0.1% by weight to 10% by weight. When the monomer component constituting the (meth)acrylic polymer contains a carboxyl group-containing monomer, the content ratio of the carboxyl group-containing monomer in the monomer component constituting the (meth)acrylic polymer is higher. It is preferably from 0.1% by weight to 20% by weight, more preferably from 0.1% by weight to 10% by weight. The monomer component constituting the (meth)acrylic polymer described above contains at least one selected from the group consisting of a hydroxyl group-containing monomer and a carboxyl group-containing monomer, and is effective when a crosslinking agent is used. The crosslinking reaction with the crosslinking agent occurs to sufficiently exhibit the effect as an adhesive. Further, the content ratio of the hydroxyl group-containing monomer in the monomer component constituting the (meth)acrylic polymer and the carboxyl group-containing content in the monomer component constituting the (meth)acrylic polymer The content ratio of the monomer is adjusted within the above range, and it is possible to effectively prevent the adhering body from being broken at the time of the peeling operation. The content ratio of the hydroxyl group-containing monomer in the monomer component constituting the (meth)acrylic polymer or the content of the carboxyl group-containing monomer in the monomer component constituting the (meth)acrylic polymer When the ratio is too large relative to the above range, the adhesive force becomes too large, and the adhesion tends to occur, and the peeling operation is likely to occur when the adhesive body is broken.

The adhesive layer preferably contains a crosslinking agent. In the case where the adhesive layer contains a crosslinking agent, the content ratio of the crosslinking agent in the adhesive layer can be appropriately set depending on the purpose, preferably relative to the main resin component (preferably (meth)acrylic acid). The polymer) is from 0.1% by weight to 20% by weight. By controlling the content ratio of the crosslinking agent in the adhesive layer within the above range, a moderate crosslinking reaction can be produced, and the fracture of the adhering body during the peeling operation can be effectively prevented.

Examples of the crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a metal alkoxide crosslinking agent, and a metal chelate compound. A crosslinking agent, a metal salt crosslinking agent, a carbodiimide crosslinking agent, An oxazoline crosslinking agent, an aziridine crosslinking agent, and an amine crosslinking agent. Among these crosslinking agents, a melamine-based crosslinking agent, an epoxy-based crosslinking agent, and an isocyanate-based crosslinking agent are preferable in terms of sufficiently exhibiting the effects of the present invention. Further, the crosslinking agent may be appropriately selected as needed, and may be one type or a mixture of two or more types.

The adhesive layer may also contain a plasticizer. In the case where the adhesive layer contains a plasticizer, the content ratio of the plasticizer in the adhesive layer can be appropriately set according to the purpose, and is preferably from 0.1% by weight to 50% by weight. The effect of the present invention can be further effectively exhibited by controlling the content ratio of the plasticizer in the adhesive layer to the above range. If the content of the plasticizer in the adhesive layer is more than 50% by weight, the adhesive layer becomes too soft, and it is liable to cause residue of the paste or contamination by the adherend.

Examples of the plasticizer include a phthalic acid ester type, a trimellitic acid ester type (W-700 manufactured by Dainippon Ink Co., Ltd., and trioctyl trimellitate). Acid ester (D620 manufactured by J-PLUS Co., Ltd., dioctyl adipate and diisononyl adipate), phosphate ester (such as tricresyl phosphate), adipic acid ester, lemon Acid esters (tributyl citrate, etc.), sebacate, sebacate, maleate, Benzoic acid ester, polyether polyester, epoxy polyester (such as epoxidized soybean oil and epoxidized linseed oil), and polyester (such as low molecular weight polyester containing carboxylic acid and diol). In the present invention, an ester-based plasticizer is preferably used. The plasticizer may be used alone or in combination of two or more. In order to promote the crosslinking reaction and the like, the adhesive layer may also contain any suitable catalyst.

In the case where the adhesive layer contains a catalyst, the content ratio of the catalyst in the adhesive layer can be appropriately set according to the purpose, and is preferably 0.01% by weight to 10% by weight. The effect of the present invention can be further effectively exhibited by controlling the content ratio of the catalyst in the adhesive layer within the above range.

Examples of such a catalyst include tetraisopropyl titanate, tetra-n-butyl titanate, tin octylate, lead octoate, cobalt octoate, zinc octoate, calcium octylate, lead naphthenate, cobalt naphthenate, and the like. Organometallic compounds such as dibutyltin acetate, dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dilaurate and dibutyltin maleate; butylamine, dibutylamine, hexylamine, tert-butylamine, Basic compounds such as ethylenediamine, isophoronediamine, imidazole, lithium hydroxide, potassium hydroxide and sodium methoxide; and p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkylphosphoric acid, dialkylphosphoric acid, An acidic compound such as a phosphate of β-hydroxyethyl acrylate, a monoalkylphosphite, or a dialkylphosphoric acid. The catalyst may be used alone or in combination of two or more.

In order to further exhibit the effects of the present invention, the SP value of the adhesive layer is preferably 9.0 (cal/cm ³ ) ^0.5 to 12.0 (cal/cm ³ ) ^0.5 , more preferably 9.5 (cal/cm ³ ) ^0.5 to 11.0 (cal /cm ³ ) ^0.5 . The SP value is a solubility parameter calculated based on the Small formula. The calculation of the SP value can be carried out by a method described in a well-known literature (for example, Journal of Applied Chemistry, 3, 71, 1953).

In the adhesive layer, any suitable additive may be contained within a range that does not impair the effects of the present invention. Examples of such an additive include an ultraviolet absorber, a filler, an anti-aging agent, an adhesion-imparting agent, a pigment, a dye, and a decane coupling agent.

The adhesive tape of the present invention may also comprise a release liner on the surface of the adhesive layer.

As the release liner, any suitable separator can be employed. Examples of such a release liner include a substrate comprising a release layer such as a plastic film or a paper surface-treated with a release agent such as a polyoxymethylene system, a long-chain alkyl group, a fluorine-based or a molybdenum sulfide; Low adhesion of fluorine-based polymers such as tetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, and chlorofluoroethylene-vinylidene fluoride copolymer a substrate; and a low-adhesive substrate comprising a non-polar polymer such as an olefin resin (for example, polyethylene or polypropylene). The adhesive tape of the present invention can be used for any suitable purpose.

Since the adhesive tape of the present invention comprises the film for an adhesive tape of the present invention, as described above, when the adsorption by the negative pressure is performed, excessive adhesion can be suppressed, and the adhesion of the roll form can be effectively suppressed. The non-adhesive layer has good compatibility with the plastic film and has good followability to deformation such as elongation when it is unwound from the roll form. Therefore, it can be preferably used for processing a semiconductor wafer composed of a brittle material and having a fine and delicate circuit pattern as a semiconductor to be bonded. When the adhesive tape of the present invention is used for semiconductor processing, excessive adhesion can be suppressed when the adsorption by the negative pressure is performed, so that the semiconductor manufacturing step including the dicing can be smoothly performed. Moreover, if the adhesive tape of the present invention is used for semiconductor addition The work does not involve the accumulation of film deformation or stress strain caused by adhesion, so it can accurately follow the fine and delicate circuit pattern of the semiconductor wafer for bonding, and does not occur after bonding to the semiconductor wafer. The natural release of stress and strain can effectively prevent semiconductor wafer breakage. In particular, the wafer for LED is composed of a very brittle material such as gallium nitride, gallium arsenide or tantalum carbide. Therefore, the adhesive tape of the present invention is very suitable for LED cutting and the like.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples. However, the invention is not limited by the examples. “Parts” means “parts by weight”. Further, the amount of the reagent supplied as a solution is represented by the amount of the solid content (the amount of the solid content converted) remaining in the volatilization of the solution.

<maximum elongation>

The maximum elongation was measured by an Instron type tensile tester (manufactured by Shimadzu Corporation, Autograph) in accordance with JIS-K-7127. Specifically, a sample having a width of 20 mm and a length of 100 mm was set at a distance of a clamp of 50 mm, and then stretched at a tensile speed of 0.3 m/min, and the value at the time of fracture was measured.

<Elastic Modulus>

The modulus of elasticity was measured in accordance with JIS-K-7127.

<Observation of non-adhesive layer> (using TEM observation)

Morphological observation was performed by a transmission electron microscope (TEM) after processing in a manner in which the non-adhesive layer profile was observed.

(observed by infrared spectrometry (ATR-IR) using total reflection method)

Using an infrared spectrometer (manufactured by PerkinElmer, Spectrum One), the total reflection measurement method was selected. Since the analysis depth of the probe light was changed, two types of total reflection measurement were used (ZnSe45°, Ge45). °) ATR-IR measurement was performed on the non-adhesive layer.

<Arithmetic average surface roughness Ra>

The arithmetic mean surface roughness Ra was measured in a 3D mode using a conjugated focal laser microscope "LEXT3000" manufactured by Olympus Corporation (OLYMPUS) using a 20-fold objective lens. The observation range of the 3D mode is determined by setting the positions where the CF image (confocal image) is blacked when the lens is moved up and down, respectively, to the top (Top) and bottom (Bottom) of the observation range.

The image scanning method of the 3D mode performs image scanning at intervals of 0.2 μm in a stepwise manner.

The measurement of the arithmetic mean surface roughness Ra is performed by measuring the Ra of an arbitrary part by the roughness analysis of an analysis mode. Further, the value of the roughness is obtained by an average value of n=5.

<Adsorption test>

Attach the adhesive tape to the glass slide of 20 mm (vertical) × 50 mm (horizontal) with the back side as the outer side, and attach the slide glass with the adhesive tape to the slide glass to be the adhesive body ( Blue plate edging, size: 65 mm × 165 mm × 1.35 mmt) placed in an environment of 50 ° C for 10 minutes, then the slide is attached to the back of the adhesive tape by a reciprocating motion of 2 Kg roller. Leave in a °C environment for 30 minutes. After standing, it was peeled off by 0° at a tensile speed of 0.3 m/min using an Instron type tensile tester (manufactured by Shimadzu Corporation, Autograph). The peeling force at this time was measured and evaluated according to the following criteria. price.

○: The peeling force was less than 5 N.

×: The peeling force was 5 N or more.

<non-adhesive test peeling force>

Referring to JIS-Z-0237, the adhesive tape and the adhesive tape containing the non-adhesive layer are kept at 23 ° C for 1 hour, and the non-adhesive surface is pressed at a pressure of 8 kg/m and 0.3. The crimping speed of m/min was pressure-bonded to SUS430BA, and the peeling force after 30 minutes was measured at a tensile speed of 0.3 m/min and a peeling of 180°.

◎: Not up to 0.5 N/20 mm.

○: 0.5 N/20 mm or more and less than 1.0 N/20 mm.

×: 1.0 N/20 mm or more.

<Adhesion test>

Adhesive layer of the adhesive tape is crimped at a pressure of 8 Kg/m and a crimping speed of 0.3 m/min to the outermost side (back layer) of the same adhesive tape opposite to the adhesive layer, after crimping Store at 50 ° C × 48 hr. After the storage, the adhesion was carried out at a tensile speed of 0.3 m/min by a peeling test at 180° (in accordance with JIS-Z-0237), and the adhesion (peeling force) between the adhesive layer and the back layer was measured.

In the evaluation, the peeling force was measured, and the peeling of the back layer and the destruction of the adhesive layer (residue of the paste due to aggregation failure or fixation failure) at the time of peeling were confirmed. The evaluation was carried out based on the following criteria.

◎: The peeling force was 1.0 N/20 mm or less, and was not observed under visual observation. Shedding, destruction of the adhesive layer.

○: The peeling force was less than 3.0 N/20 mm, and no peeling or damage of the adhesive layer was observed under visual observation.

×: The peeling force was 3.0 N/20 mm or more, or the peeling and the destruction of the adhesive layer were observed under visual observation.

<fixation confirmation test> (fixation confirmation test A)

The film or adhesive tape for the adhesive tape was extended to 200% at a stretching speed of 0.3 m/min to 3 m/min to visually evaluate the opposite side of the film or adhesive tape for the adhesive tape and the adhesive tape at the time of extension and extension. The outermost (back layer) is detachable.

(fixation confirmation test B)

After performing the same extension as the fixing confirmation test A, "NO. 31B" manufactured by NITTO DENKO CORPORATION was used as the back surface treatment layer by a 2 Kg roll (width 25 mm) at 0.3 m. The pressure-receiving speed of /min was reciprocated once, and then stored under conditions of 23 ° C × 50% RH for 1 minute, and 90 ° peeling was performed at a peeling speed of 0.3 m / min to 3 m / min to visually evaluate the peeling of the back surface. Sex.

(Evaluation)

The above evaluation was comprehensively judged, and the fixing property was evaluated based on the following criteria.

◎: There was no peeling of the back surface which can be visually confirmed in the fixation confirmation test A and the fixation confirmation test B.

○: In the fixation test A, there was no peeling of the back surface which was visually confirmed, and a slight degree of back peeling was confirmed in the fixation test B. Fall (confirmed as a dot).

X: The peeling of the back surface was confirmed in the fixing property confirmation test A, or the peeling of the back surface was confirmed in the fixing property confirmation test B.

[Manufacturing Example 1]: Manufacturing of plastic film

By the calendering method, the DOP plasticizer (bis(2-ethylhexyl) phthalate, manufactured by J-PLUS) is contained in an amount of 27 parts by weight based on 100 parts by weight of the polyvinyl chloride having a polymerization degree of P=1050. Soft polyvinyl chloride film. The thickness of the soft polyvinyl chloride film was 70 μm, the modulus of elasticity (MD) measured according to JIS-K-7127 was 250 MPa, and the maximum elongation (MD) measured according to JIS-K-7127 was 400%. Further, the surface roughness (arithmetic mean surface roughness Ra) immediately after the production was 0.1 μm.

[Example 1]

60 parts by weight of polyoxyxylene resin (KS-723A, manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxynoxy resin (KS-723B, manufactured by Shin-Etsu Chemical Co., Ltd.), 40 parts by weight, acrylic copolymer (methyl methacrylate ( MMA)/butyl acrylate (BA)/hydroxyethyl acrylate (HEA)=70/30/10) 100 parts by weight, tin-based catalyst (Cat-PS3, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts by weight, and methyl group 1.0 parts by weight of a hydroquinone-based hardening accelerator X92-122 (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed in a solution state to obtain a mixed solution (1). The mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the mixed solution (1) is polyoxymethylene in a weight ratio: (meth)acrylic polymer = 1:1.

The mixed solution (1) was applied onto one surface of a soft polyvinyl chloride film produced in Production Example 1 and dried to form a non-adhesive layer having a thickness of 1.0 μm and an arithmetic mean surface roughness Ra of 0.3 μm.

Thus, a film (1) for an adhesive tape was obtained.

Various evaluation results are shown in Table 1.

Further, when the non-adhesive layer was observed by TEM, as shown in Fig. 1, the shading of the image was observed according to the morphology, and it was confirmed that the composition of the air interface side and the plastic film side were different, and it was observed that the non-adhesive layer contained polyfluorene. More oxygen than the (meth)acrylic polymer-rich polyoxo phase, and the (meth)acrylic polymer containing more polyoxymethylene rich (meth)acrylic polymer phase, and form an enriched fluorene The phase separation structure of the oxygen phase and the rich (meth)acrylic polymer are independent of each other, the rich polyoxygen phase exists on the air interface side (the side opposite to the plastic film), and the rich (meth)acrylic polymer phase exists. On the side of the plastic film.

Further, the non-adhesive layer was subjected to infrared spectrometry (ATR-IR) using a total reflection method, and the peak near 800 cm ^-1 derived from Si-CH _{3 in} the (meth)acrylic polymer phase was measured. The absorbance ratio of the peak near the carbonyl group at 1725 cm ^-1 was found to be larger at around 800 cm ^-1 when Ge 45 ° 稜鏡 was used than in the case of using ZnSe 45 ° 。.

Therefore, it is understood that the enthalpy content of the air interface side is higher than that of the substrate side. Considering these observations and the principle of minimizing the surface free energy, it is understood that a two-layer structure having a rich pseudo-oxygen phase on the air interface side is formed in the non-adhesive layer.

[Embodiment 2]

Preparation of a toluene solution containing an adhesive of the following materials: 100 parts by weight of an acrylic copolymer composed of butyl acrylate (BA) / acrylonitrile (AN) / acrylic acid (AA) = 85 / 15 / 2.5 (weight ratio), melamine Crosslinking agent (butanol modified melamine-formaldehyde resin, "SUPER BECKAMINE J-820-60N", 1 part by weight of a polyester (Nippon Polyurethane) and 60 parts by weight of a DOP plasticizer (bis(2-ethylhexyl) phthalate, manufactured by J-PLUS).

The adhesive solution was applied to the surface of the film for adhesive tape (1) obtained in Example 1 on the opposite side to the non-adhesive layer, and then dried at 130 ° C × 90 seconds for soft polymerization. A pressure-sensitive adhesive layer having a thickness of 10 μm was formed on the opposite side of the vinyl chloride film from the non-adhesive layer. The pressure-sensitive adhesive layer formed had an SP value of 10.5.

Thereby, the adhesive tape (2) is obtained.

Various evaluation results are shown in Table 1.

[Example 3]

In Example 2, 100 parts by weight of an acrylic copolymer of ethyl acrylate (EA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 80 / 10/10 was used as the acrylic for non-adhesive layer formation. An adhesive tape (3) was obtained in the same manner as in Example 2 except for the copolymer.

The non-adhesive layer has a thickness of 1.0 μm and an arithmetic mean surface roughness Ra of 0.2 μm.

Various evaluation results are shown in Table 1.

[Example 4]

In Example 2, 60 parts by weight of polyfluorene oxide resin (KS-723A, manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxynoxy resin (KS-723B, manufactured by Shin-Etsu Chemical Co., Ltd.), 40 parts by weight, acrylic copolymer were used. (Methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 70 / 30/10) 50 parts by weight, tin-based catalyst (Cat-PS3, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 weight A mixed solution (4) obtained by mixing 1.0 part by weight of a methylhydroquinoxane-based hardening accelerator X92-122 (manufactured by Shin-Etsu Chemical Co., Ltd.) (mixed solution (4) The mixing ratio of oxygen to the (meth)acrylic polymer is polyoxyxylene: (meth)acrylic polymer = 2:1) in place of the mixed solution (1), and the examples are the same as the examples. 2 Obtain the adhesive tape (4) in the same way.

The non-adhesive layer has a thickness of 1.0 μm and an arithmetic mean surface roughness Ra of 0.5 μm.

Various evaluation results are shown in Table 1.

[Example 5]

In the same manner as in Example 4, the adhesive tape (5) was obtained in the same manner as in Example 4 except that the thickness of the non-adhesive layer was changed to 0.5 μm.

The non-adhesive layer has a thickness of 0.5 μm and an arithmetic mean surface roughness Ra of 0.3 μm.

Various evaluation results are shown in Table 1.

[Embodiment 6]

On the side of the pressure-sensitive adhesive layer of the adhesive tape (2) obtained in Example 2, a PET liner having a thickness of 38 μm which was subjected to Si treatment was attached as a release liner to obtain an adhesive tape (6).

The non-adhesive layer has a thickness of 1.0 μm and an arithmetic mean surface roughness Ra of 0.3 μm.

Various evaluation results are shown in Table 1.

[Embodiment 7]

In Example 2, a polyfluorene oxide resin (KS-723A, by Shinhman) was used. Industrial Manufacturing) 1.2 parts by weight, polyoxynoxy resin (KS-723B, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.8 parts by weight, acrylic copolymer (methyl methacrylate (MMA) / butyl acrylate (BA) / acrylic acid hydroxy group Ethyl acetate (HEA) = 70/30/10) 100 parts by weight, tin-based catalyst (Cat-PS3, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.2 parts by weight, and methylhydroquinone-based hardening accelerator X92-122 ( 0.02 parts by weight of a mixed solution obtained by mixing in a solution state (manufactured by Shin-Etsu Chemical Co., Ltd.) (mixing ratio of polyfluorene oxide to (meth)acrylic polymer in the mixed solution (7) is by weight ratio The adhesive tape (7) was obtained in the same manner as in Example 2 except that the polyoxymethylene (meth)acrylic polymer = 1 : 50) was used instead of the mixed solution (1).

The non-adhesive layer has a thickness of 0.5 μm and an arithmetic mean surface roughness Ra of 0.1 μm.

Various evaluation results are shown in Table 1.

[Embodiment 8]

In Example 2, 60 parts by weight of polyfluorene oxide resin (KS-723A, manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxynoxy resin (KS-723B, manufactured by Shin-Etsu Chemical Co., Ltd.), 40 parts by weight, acrylic copolymer were used. (Methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 70 / 30/10) 2 parts by weight, tin-based catalyst (Cat-PS3, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts by weight, and a methylhydroquinone-based hardening accelerator X92-122 (manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0 part by weight of a mixed solution (8) obtained by mixing in a solution state (polymerization in a mixed solution (8) The mixing ratio of the argon and the (meth)acrylic polymer is polyoxyxylene: (meth)acrylic polymer = 50:1) instead of the mixed solution (1), and Example 2 is the same Way to get the adhesive tape (8).

The non-adhesive layer has a thickness of 0.5 μm and an arithmetic mean surface roughness Ra of 0.1 μm.

Various evaluation results are shown in Table 1.

[Embodiment 9]

Preparation of a toluene solution containing an adhesive of the following materials: 100 parts by weight of an acrylic copolymer composed of butyl acrylate (BA) / acrylonitrile (AN) / acrylic acid (AA) = 85 / 15 / 2.5 (weight ratio), melamine Crosslinking agent (butanol modified melamine-formaldehyde resin, "SUPER BECKAMINE J-820-60N", made of Japanese polyurethane) 10 parts by weight, and DOP plasticizer (bis(2-ethyl) phthalate Hexyl) ester, manufactured by J-PLUS, 60 parts by weight.

The adhesive solution was applied to the surface of the film for adhesive tape (1) obtained in Example 1 on the opposite side to the non-adhesive layer, and then dried at 130 ° C × 90 seconds for soft polymerization. A pressure-sensitive adhesive layer having a thickness of 10 μm was formed on the opposite side of the vinyl chloride film from the non-adhesive layer. The pressure-sensitive adhesive layer formed had an SP value of 10.5.

Thereby, an adhesive tape (9) is obtained.

Various evaluation results are shown in Table 2.

[Embodiment 10]

In Example 9, 100 parts by weight of an acrylic copolymer of ethyl acrylate (EA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 80 / 10/10 was used as the acrylic for non-adhesive layer formation. An adhesive tape (10) was obtained in the same manner as in Example 9 except that the copolymer was a copolymer.

The thickness of the non-adhesive layer is 1.0 μm, and the arithmetic mean surface roughness Ra is 0.2 μm.

Various evaluation results are shown in Table 2.

[Example 11]

In Example 9, 60 parts by weight of polyfluorene oxide resin (KS-723A, manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxynoxy resin (KS-723B, manufactured by Shin-Etsu Chemical Co., Ltd.), 40 parts by weight, acrylic copolymer were used. (Methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 70 / 30/10) 50 parts by weight, tin-based catalyst (Cat-PS3, manufactured by Shin-Etsu Chemical Co., Ltd. 10 parts by weight, and a methylhydroquinone-based hardening accelerator X92-122 (manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0 part by weight of a mixed solution (4) obtained by mixing in a solution state (mixed solution (4) The mixing ratio of the polyoxymethylene to the (meth)acrylic polymer is polyoxyxylene: (meth)acrylic polymer = 2:1) instead of the mixed solution (1), in addition to An adhesive tape (11) was obtained in the same manner as in Example 9.

The non-adhesive layer has a thickness of 1.0 μm and an arithmetic mean surface roughness Ra of 0.5 μm.

Various evaluation results are shown in Table 2.

[Embodiment 12]

In the same manner as in Example 11, except that the thickness of the non-adhesive layer was changed to 0.5 μm, the adhesive tape (12) was obtained.

The non-adhesive layer has a thickness of 0.5 μm and an arithmetic mean surface roughness Ra of 0.3 μm.

Various evaluation results are shown in Table 2.

[Example 13]

On the pressure-sensitive adhesive layer side of the adhesive tape (9) obtained in Example 9, a PET liner having a thickness of 38 μm which was subjected to Si treatment was attached as a release liner to obtain an adhesive tape (13).

The non-adhesive layer has a thickness of 1.0 μm and an arithmetic mean surface roughness Ra of 0.3 μm.

Various evaluation results are shown in Table 2.

[Embodiment 14]

In Example 9, 1.2 parts by weight of polyfluorene oxide resin (KS-723A, manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxynoxy resin (KS-723B, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.8 parts by weight, acrylic copolymer were used. (Methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 70 / 30/10) 100 parts by weight, tin-based catalyst (Cat-PS3, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.2 parts by weight, and a methylhydroquinone-based hardening accelerator X92-122 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.02 parts by weight of a mixed solution (7) obtained by mixing in a solution state (polymerization in a mixed solution (7) The mixing ratio of the argon and the (meth)acrylic polymer is polyoxyxylene: (meth)acrylic polymer = 1:50 by weight ratio instead of the mixed solution (1), and Example 9 obtained the adhesive tape (14) in the same manner.

The non-adhesive layer has a thickness of 0.5 μm and an arithmetic mean surface roughness Ra of 0.1 μm.

Various evaluation results are shown in Table 2.

[Example 15]

In Example 9, 60 parts by weight of polyfluorene oxide resin (KS-723A, manufactured by Shin-Etsu Chemical Co., Ltd.) and polyoxynoxy resin (KS-723B, by Shin-Etsu Chemical Co., Ltd.) were used. Industrial manufacturing) 40 parts by weight, acrylic copolymer (methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 70 / 30/10) 2 parts by weight, tin-based 10 parts by weight of a medium (Cat-PS3, manufactured by Shin-Etsu Chemical Co., Ltd.) and a methylhydroquinone-based hardening accelerator X92-122 (manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0 part by weight of a mixed solution obtained by mixing in a solution state (8) (The mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the mixed solution (8) is polyoxylium by weight: (meth)acrylic polymer = 50:1) instead of mixing An adhesive tape (15) was obtained in the same manner as in Example 9 except for the solution (1).

The non-adhesive layer has a thickness of 0.5 μm and an arithmetic mean surface roughness Ra of 0.1 μm.

Various evaluation results are shown in Table 2.

[Comparative Example 1]

In Example 2, an adhesive tape (C1) was obtained in the same manner as in Example 2 except that the non-adhesive layer was not formed.

Various evaluation results are shown in Table 3.

[Comparative Example 2]

In Example 2, 60 parts by weight of polyfluorene oxide resin (KS-723A, manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxynoxy resin (KS-723B, manufactured by Shin-Etsu Chemical Co., Ltd.), 40 parts by weight, tin-based catalyst were used. (Cat-PS3, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts by weight, and a methylhydroquinone-based hardening accelerator X92-122 (manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0 part by weight of a mixed solution obtained by mixing in a solution state ( C2) An adhesive tape (C2) was obtained in the same manner as in Example 2 except for the mixed solution (1).

The non-adhesive layer has a thickness of 0.5 μm and an arithmetic mean surface roughness Ra of 0.08 μm.

Various evaluation results are shown in Table 3.

[Comparative Example 3]

In Example 2, the non-adhesive layer is an acrylic copolymer (methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 70 / 30/10), in addition to An adhesive tape (C3) was obtained in the same manner as in Example 2. The non-adhesive layer has a thickness of 0.5 μm and an arithmetic mean surface roughness Ra of 0.05 μm. Various evaluation results are shown in Table 3.

[Industrial availability]

Since the adhesive tape of the present invention comprises the film for an adhesive tape of the present invention, as described above, when the adsorption by the negative pressure is performed, excessive adhesion can be suppressed, and the adhesion of the roll form can be effectively suppressed. The non-adhesive layer has good compatibility with the plastic film and has good followability to deformation such as elongation when it is unwound from the roll form. Therefore, it can be preferably used for processing a semiconductor wafer composed of a brittle material and having a fine and delicate circuit pattern as a semiconductor to be bonded. When the adhesive tape of the present invention is used for semiconductor processing, when the adsorption is fixed by a negative pressure, It is possible to suppress excessive adhesion, so that the semiconductor manufacturing steps including dicing can be performed smoothly. Moreover, when the adhesive tape of the present invention is used for semiconductor processing, film deformation or stress strain which was previously caused by adhesion does not occur, so that it is possible to accurately follow the fine and delicate circuit pattern of the semiconductor wafer. Moreover, since the natural release of stress and strain does not occur after bonding to the semiconductor wafer, the semiconductor wafer can be effectively prevented from being broken. In particular, the wafer for LED is composed of a very brittle material such as gallium nitride, gallium arsenide or tantalum carbide. Therefore, the adhesive tape of the present invention is very suitable for LED cutting and the like.

Fig. 1 is a TEM photograph showing the state of a non-adhesive layer in the film for an adhesive tape of the present invention.

Claims (12)

A film for an adhesive tape comprising a non-adhesive layer on one side of a plastic film having a maximum elongation of 100% or more as measured according to JIS-K-7127, and an arithmetic mean surface roughness Ra of the non-adhesive layer is 0.1 μm or more, the non-adhesive layer is a mixed layer of polyoxymethylene and a (meth)acrylic polymer, and the mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the non-adhesive layer is a weight ratio It is considered to be polyoxyl: (meth)acrylic polymer = 1:50 to 50:1. The adhesive tape film of claim 1, wherein the non-adhesive layer has a non-adhesive test peeling force of less than 1.0 N/20 mm. The film for an adhesive tape according to claim 1, wherein the non-adhesive layer comprises a polyfluorene-rich phase containing more poly(oxy)oxygen (meth)acrylic polymer, and more than a poly(meth)acrylic polymer An oxygen-rich (meth)acrylic polymer phase. The film for an adhesive tape according to claim 1, wherein the plastic film has a thickness of 20 μm to 200 μm. The film for an adhesive tape according to claim 1, wherein the non-adhesive layer has a thickness of 0.01 μm to 10 μm. The film for an adhesive tape according to claim 1, wherein the plastic film comprises polyvinyl chloride. An adhesive tape comprising the adhesive film on the surface of the adhesive film according to any one of claims 1 to 6 on the opposite side of the non-adhesive layer Agent layer. The adhesive tape of claim 7, wherein the adhesive layer comprises a (meth)acrylic polymer. The adhesive tape of claim 7, wherein the adhesive layer has an SP value of 9.0 (cal/cm ³ ) of ^0.5 to 12.0 (cal/cm ³ ) ^0.5 . The adhesive tape of claim 7, which comprises a release liner on the surface of the above adhesive layer. The adhesive tape of claim 7, which is used in semiconductor processing. The adhesive tape of claim 11, wherein the semiconductor processing is LED cutting.