TWI576405B - Adhesive tape and 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.

In order to fix the wafer during dicing, the adhesive tape used for the dicing of the semiconductor must be fixed to the susceptor on the opposite side of the wafer adhesion surface. Usually, such fixing is carried out by a vacuum such as vacuum adsorption.

When such a fixing using a negative pressure is performed, there is a case where the adhesive tape is excessively adhered to the susceptor due to a state in which a negative pressure is excessively applied or a melting of the adhesive tape due to heat generation during dicing. If such excessive adhesion occurs, there is a problem in that the operability at the time of releasing the fixing to the susceptor is deteriorated, and the semiconductor manufacturing step including the dicing cannot be smoothly performed.

In order to eliminate the problem of such excessive adhesion, the following technique has been reported: in the wafer surface protection tape comprising two layers of the substrate film and the adhesive layer, the center line of the surface of the substrate film opposite to the adhesive layer The surface roughness Ra is controlled to a specific size (Patent Document 1).

However, for the base film of the adhesive tape used for the dicing of semiconductors, the expansion characteristics and the step following characteristics unique to the semiconductor manufacturing process are required. That is, the base film of the adhesive tape used for the dicing of the semiconductor must be well extended in the extending step, and the step of the semiconductor must be satisfactorily followed. As a base film which responds to such a request, a base material film containing a material having a large elongation coefficient can be selected. However, with regard to such a substrate film, the surface state thereof is easily affected by temperature. Therefore, as reported in Patent Document 1, there is a problem that even if the center line surface roughness Ra of the surface of the base film is controlled to a specific size, The temperature of the temperature or the temperature of the process device is changed, and the surface roughness Ra of the center line controlled to a specific size is largely changed, and the effect of the invention described in Patent Document 1 cannot be exhibited.

For example, the energy of laser processing can cause the wafer to heat up during cutting, especially during laser cutting. When the wafer is heated, as reported in Patent Document 1, there is a problem that even if the center line surface roughness Ra of the surface of the base film is controlled to a specific size, the excessive adhesion as described above cannot be eliminated. The problem, on the contrary, promotes excessive closeness.

Further, in recent years, since the size of wafers used for dicing semiconductors has increased in size, the time for dicing has become longer, and as a result, heat generation of wafers has increased, and the above problems have become more apparent.

In semiconductor dicing, especially in LED dicing, the semiconductor wafer used is composed of a very fragile material such as gallium nitride, gallium arsenide or tantalum carbide. Therefore, in order to prevent breakage of the semiconductor wafer, adhesion is performed. The substrate film of the tape requires further expansion characteristics and step following characteristics. Therefore, the above problems become more apparent for the adhesive tape used for LED cutting.

On the other hand, in general, the surface of the film is smooth, and when the film is processed into a roll shape, the film is brought into contact with each other and adhered to each other, that is, adhered. Regarding the roll in which the adhesion has occurred, there are cases where it is difficult to perform the work of rewinding the film. In particular, a plasticizer is usually added to a film having a large elongation coefficient. In such a film, since a plasticizer is deposited on the surface of the film to cause a small gap between the films to be filled, the adverse effect caused by the adhesion becomes conspicuous. When the adhesive film is adhered to the surface of the film, since the adhesive itself has adhesiveness, the adverse effect of the adhesion increases.

When rewinding the adhered roll film, an extra force for releasing the adhesion of the films to each other is required. By applying such excess force, the film is stretched and deformed, or even when the film is not deformed, it is accumulated in the form of stress strain. When a film deformed as described above is applied to an adhesive tape, it is difficult to adhere to the adherend. Again, if When the film in which the stress strain is accumulated as described above is applied to the adhesive tape, there is a concern that the stress and strain are naturally released after being bonded to the adherend, and the adherend is broken.

In the case where an adhesive tape is used in semiconductor processing, since the semiconductor wafer as the adherend is composed of a fragile material, it is weak or easily damaged. Therefore, when a film deformed as described above is applied to an adhesive tape, it is difficult to adhere to the fine and delicate circuit pattern of the semiconductor wafer. Further, when a film in which stress and strain is accumulated as described above is applied to an adhesive tape, the stress and strain are naturally released after bonding to the semiconductor wafer, and the semiconductor wafer is easily broken.

In particular, the wafers used in LEDs are made of very fragile materials such as gallium nitride, gallium arsenide and tantalum carbide. Therefore, the anti-adhesion of the adhesive tape used for LED cutting or the like is particularly important.

As a prior art of anti-adhesion, two techniques can be roughly cited.

In the first prior art, physical processing such as embossing is performed on the back surface of the film (Patent Document 2). However, in this technique, since the concavities and convexities formed on the back surface of the film are stress-concentrating structures, there is a problem in that, when rewinding from the form of a roll, the film is broken due to the force of the rewinding, starting from the unevenness or damaged.

Another prior art is exemplified by coating a polyfluorene release agent on the back side of the film (Patent Document 3). However, this technique has a problem in that the polyoxoxime release agent has a low chemical affinity with the back surface of the film due to its surface tension, and it is difficult to adapt to 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 an adhesive tape is stretched or the like is extended, there is a problem in that a treatment layer using a polyfluorene release agent is present. Unable to follow the extension, the treatment layer is broken and becomes a cause of contamination. Furthermore, in order to improve the chemical affinity of the polyfluorene oxygen release agent to the back side of the film, there is also a technique of coating a crosslinked polyoxylizer release agent, but since the crosslinked polyoxylized oxygen generally has a very small elongation coefficient. Therefore, when a film having a cross-linked polyfluorinated release agent coated on the back side is applied to an adhesive tape, if an adhesive tape is stretched or the like In the case of elongation, there is a problem that the treatment layer using the cross-linked polyoxyl release agent cannot follow the extension and cannot maintain the grip.

[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 is adsorbed and fixed to a fixing base by a negative pressure and is cut or the like. It is possible to effectively suppress excessive adhesion due to heat generation of the susceptor, and it is also possible to effectively prevent adhesion in a roll form by providing a non-adhesive layer on the base film. When the form is rewinded, it is not broken or broken, and the non-adhesive layer has good compatibility with the base film, and has good followability for deformation such as elongation. Further, the present invention provides an adhesive tape comprising such a film for an adhesive tape.

Adhesive tape film of the present invention

The non-adhesive layer is provided on one side of the plastic film, and the surface of the non-adhesive layer has a concave-convex structure, and the convex portion of the surface of the non-adhesive layer has an elastic modulus at 80 ° C measured by an atomic force microscope of 0.2 GPa or more.

In a preferred embodiment, the non-adhesive layer has an arithmetic mean surface roughness Ra of 0.1 μm or more.

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 (meth)acrylic polymer has a calculated Tg of 10 ° C or higher.

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

In a preferred embodiment, the non-adhesive layer has a phase separation structure.

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 has a thickness of 0.01 μm to 10 μm.

In a preferred embodiment, the plastic film has a maximum elongation of 100% or more as measured according to JIS-K-7127.

In a preferred embodiment, the plastic film has a thickness of 20 μm to 200 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 has an adhesive layer on the surface of the plastic film of the adhesive tape of the present invention opposite to the non-adhesive layer.

In a preferred embodiment, the adhesive layer comprises at least one (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 provided 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 adhesive tape of the present invention is used for LED cutting applications.

According to the present invention, there is provided a film for an adhesive tape which is provided on a substrate film and which is provided with a non-adhesive layer, and which is adsorbed and fixed to a fixing base by a negative pressure and is cut or the like. It is possible to effectively suppress excessive adhesion due to heat generation of the susceptor, and it is also possible to effectively prevent adhesion in a roll form by providing a non-adhesive layer on the base film. When the form is rewinded, it is not broken or broken, and the non-adhesive layer has good compatibility with the base film, and has good followability for deformation such as elongation. Further, an adhesive tape comprising such a film for an adhesive tape can be provided.

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

Fig. 2 is a SEM photograph showing a state of a cross-sectional side of a non-adhesive layer in the film for an adhesive tape of the present invention.

Fig. 3 is a SEM photograph showing the state of the cross-sectional side of the non-adhesive layer in the film for an adhesive tape of the present invention.

≪1. Adhesive tape for film ≫

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

<1-1. Plastic film>

The plastic film is not particularly limited and may include any suitable resin material. The resin material is preferably, for example, polyvinyl chloride, polyolefin, polyester, polyimine or polyamine. More preferably, it is polyvinyl chloride or polyolefin, and more preferably List polyvinyl chloride. Polyvinyl chloride is particularly suitable for use in an adhesive tape which can be used in an adhesive tape used for semiconductor processing such as LED dicing because it is excellent in stress relaxation property.

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

A plasticizer may also be included 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. Since the plastic film contains the plasticizer in the above-described content ratio, the followability to deformation such as elongation becomes better.

Examples of the plasticizer include a phthalic acid ester type, a trimellitic acid ester type (W-700 manufactured by Dainippon Ink Co., Ltd., trioctyl trimellitate, etc.), and Diacid ester system (D620 manufactured by J-PLUS Co., Ltd., dioctyl adipate, diisononyl adipate, etc.), phosphate ester (such as tricresyl phosphate), adipic acid ester , citrate (acetyl tributyl citrate, etc.), sebacate, sebacate, maleate, benzoate, polyether polyester, epoxy polyester (ring Oxidized soybean oil, epoxidized linseed oil, etc.), polyester (low molecular weight polyester containing carboxylic acid and diol, etc.). In the present invention, an ester-based plasticizer is preferably used. The plasticizer may be used alone or in combination of two or more.

The plastic film may contain any suitable other components insofar as it does not impair the effects of the present invention.

The maximum elongation of the plastic film measured according to JIS-K-7127 is preferably 100% or more, more preferably 200% to 1000%. The film for an adhesive tape of the present invention can be imparted with a moderate elongation by using a plastic film exhibiting such a maximum elongation, for example, when the film for an adhesive tape of the present invention is used for an adhesive tape, the pair can be improved. Followed by the adhesive.

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 operability is deteriorated, and it is particularly difficult to carry out the bonding work when the adhesive tape is formed. 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 non-adhesive layer is composed as long as it has a concave-convex structure as defined below. It is not particularly limited, and as an example thereof, it is a mixed layer of a polyfluorene oxide and a (meth)acrylic polymer. By making the non-adhesive layer a mixed layer of polyoxymethylene and a (meth)acrylic polymer, the adaptability of the non-adhesive layer and the plastic film becomes good, and the film for an adhesive tape of the present invention and the adhesive tape containing the same It is a good follower for deformation such as extension.

The surface of the non-adhesive layer has a concave-convex structure. With respect to the uneven structure, specifically, the arithmetic mean surface roughness Ra of the non-adhesive layer is preferably 0.1 μm or more, more preferably 0.1 μm to 3.0 μm, still more preferably 0.2 μm to 2.0 μm, and particularly preferably 0.3 μm. ~2.0 μm, preferably 0.5 μm~2.0 μm. When the arithmetic mean surface roughness Ra of the non-adhesive layer converges within the above range, when the adsorption is fixed by the negative pressure, excessive adhesion is suppressed.

In the non-adhesive layer, the elastic modulus at 80 ° C measured by an atomic force microscope (AFM) of the non-adhesive layer is 0.2 GPa or more, more preferably 0.4 GPa or more, and further preferably 0.8 GPa or more. , especially good for 1.0 GPa or more. The upper limit of the elastic modulus at 80 ° C measured by atomic force microscopy of the convex portion of the surface of the non-adhesive layer is not particularly limited, but is preferably 5.0 GPa or less, more preferably 4.0 GPa or less, still more preferably 3.0 GPa or less. If the elastic modulus at 80 ° C measured by atomic force microscopy of the surface of the non-adhesive layer converges within the above range, the hardness of the uneven structure on the surface of the non-adhesive layer, especially the convex portion, even at high temperatures In the film for an adhesive tape of the present invention, when it is adsorbed and fixed to a fixing base by a negative pressure and is cut or the like, it can be effectively suppressed. Excessive adhesion due to heat generation of the susceptor. Further, the method of measuring the elastic modulus at 80 ° C measured by an atomic force microscope on the convex portion of the surface of the non-adhesive layer is explained below.

In the case where the non-adhesive layer is a mixed layer of a polyoxymethylene and a (meth)acrylic polymer, the (meth)acrylic polymer in the non-adhesive layer has a calculated Tg of 10 ° C or more, preferably 20 ° C or more, more preferably 30 ° C or more, further preferably 45 ° C or more. The upper limit of the calculated Tg of the (meth)acrylic polymer in the non-adhesive layer is not particularly limited, and is preferably 200 ° C or less, more preferably 150 ° C or less, further preferably 100 ° C or less. When the calculated Tg of the (meth)acrylic polymer converges within the above range, the heat resistance in the minute uneven structure on the surface of the non-adhesive layer becomes high, and in the film for an adhesive tape of the present invention, When it is adsorbed and fixed to the fixing base by a negative pressure and cut or the like, it is possible to effectively suppress excessive adhesion due to heat generation of the susceptor or the like.

In the present invention, the "calculated Tg" of the copolymer (the (meth)acrylic polymer in the non-adhesive layer, etc.) means the Tg derived from the structural unit of the monomer constituting the copolymer, by Fox Calculate the glass transition temperature calculated by the calculation formula. The formula of Fox refers to the relationship between the glass transition temperature Tg (° C.) of the copolymer shown below and the glass transition temperature Tg _i (° C.) of the homopolymer obtained by separately polymerizing each of the monomers constituting the copolymer. . Further, in the following Fox formula, Tg (°C) represents the glass transition temperature of the copolymer, W _i represents the weight fraction of the monomer i, and Tg _i (° C) represents the glass transition temperature of the homopolymer of the monomer i. .

1/(273+Tg)=Σ(W _i /(273+Tg _i ))

Further, as the glass transition temperature Tg _i (°C) of the homopolymer, specifically, the values described in "Polymer Handbook 3rd Edition" (A WILEY-INTERSCIENCE PUBLICATION, 1989) can be used.

In the case where the non-adhesive layer contains a (meth)acrylic polymer, the SP value of the (meth)acrylic polymer in the non-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 11.5 (cal/cm ³ ) ^0.5 , further preferably 9.5 (cal/cm ³ ) ^0.5 to 11.0 (cal/cm ³ ) ^0.5 . The SP value is a solubility parameter calculated by the formula of Small. 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., etc.).

The non-adhesive layer preferably has a phase separation structure. The minute uneven structure can be efficiently formed on the surface of the non-adhesive layer by providing the non-adhesive layer with a phase-separated structure. It is presumed that, for example, in the case where the non-adhesive layer is a mixed layer of polyoxymethylene and a (meth)acrylic polymer, the poly(oxy)oxy (meth)acrylic acid is formed by the phase separation structure. Concavities and convexities are generated by the difference in the mobility of the substances of the polymer. By the formation of the uneven structure, in the case of the film for an adhesive tape of the present invention, when the film is adsorbed and fixed by a negative pressure, excessive adhesion can be suppressed, and the form of the roll can be effectively suppressed. Adhesion can inhibit cracking or breakage when rewinding from a roll shape.

The non-adhesive layer preferably comprises: a polyfluorene-rich polyphase containing more polyoxymethylene than the (meth)acrylic polymer, and more (meth)acrylic polymerization than polyfluorene. The (meth)acrylic polymer is enriched in the phase. More specifically, the non-adhesive layer is preferably contained in a phase-separated structure in which the polyfluorene-rich phase and the (meth)acryl-based polymer-rich phase are independent of each other, more preferably the above-mentioned polyfluorene-enriched The phase exists on the air interface side (opposite side of the plastic film), and the above (meth)acrylic polymer-rich phase exists on the plastic film side. By having such a phase separation structure, adhesion can be effectively suppressed by the polyfluorene-rich phase existing on the air interface side, and the (meth)acrylic polymer-rich phase existing on the plastic film side can be obtained. The non-adhesive layer has good adaptability to the plastic film, and the deformation followability is 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 follows.

The non-adhesive layer has a phase-separated structure, and as described above, contains a polyfluorene-rich polyphase containing more polyoxymethylene than the (meth)acrylic polymer, and contains more than polyfluorene. The case of enriching the phase of the (meth)acrylic polymer of the poly(meth)acrylic polymer can be observed by any appropriate method. Examples of such an observation method include a transmission electron microscope (TEM), a scanning electron microscope (SEM), and an electron emission scanning electron microscope (FE-SEM). Electron microscope) A method of morphological observation of a non-adhesive layer profile by an electron microscope. The two-layer separation structure can be interpreted by observing the faintness of the morphological image. Further, a method of observing the flaw contained in the composition while changing the depth of the probe light from the side of the non-adhesive layer air to the inside by using the infrared absorption spectrum of the total reflection method may be mentioned. The change in the content of carbon or the like is observed by this. Further, a method of observation by an X-ray microanalyzer or X-ray photoelectron spectroscopy may be cited. Further, these methods can be combined as appropriate to observe.

When the non-adhesive layer has a phase separation structure of a polyfluorene-rich phase existing on the air interface side (opposite side of the plastic film) and a (meth)acrylic polymer-rich phase existing on the plastic film side, When the non-adhesive layer is adsorbed and fixed to the fixing base by a negative pressure to perform cutting or the like, the fixing base generates heat, and the surface structure of the phase-separated structure is caused by the heat load caused by the heat generation. The surface structure of the phase separation structure in the convex portion of the fixing base which is broken, especially in contact with heat, is broken, causing a situation in which the air interface side (meth) is in the convex portion The acrylic polymer enriched phase is exposed. However, in the film for an adhesive tape of the present invention, since the elastic modulus at 80 ° C measured by an atomic force microscope of the surface of the non-adhesive layer converges within the above range, the hardness of the convex portion subjected to the heat load is moderately It is higher, so the heat resistance becomes higher. Therefore, in the film for an adhesive tape of the present invention, when it is adsorbed and fixed to the fixing base by a negative pressure and is cut or the like, it is possible to effectively suppress excessive adhesion due to heat generation of the susceptor or the like. .

In the case where the non-adhesive layer is a mixed layer of a polyoxymethylene and a (meth)acrylic polymer, the mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the non-adhesive layer is Preferably, it is a polyoxymethylene: (meth)acrylic polymer = 1:50 to 50:1, more preferably polyoxyn: (meth)acrylic polymer = 1:30 to 30:1, and further preferably Polyoxyl: (meth)acrylic polymer = 1:10~10:1, especially polyoxyl: (meth)acrylic polymer = 1:5~5:1, the best is poly Oxygen: (meth)acrylic polymer = 1:3 to 5:1. If the proportion of the polyoxyl oxide in the non-adhesive layer is too large, the chemical affinity with the back surface of the plastic film is lowered, and it is difficult to adapt to the back of the plastic film. Further, when the content ratio of the polyfluorene oxide in the non-adhesive layer is too large, when it is used as a film for an adhesive tape or an adhesive tape including the same, the followability to deformation such as elongation is deteriorated, and the non-adhesive layer is broken. Original pollution Because of it. If the content ratio of the (meth)acrylic polymer in the non-adhesive layer is too large, the non-adhesive layer functions as an acrylic adhesive, and there is a possibility that adhesion tends to occur.

As the polyoxane, any suitable polyoxane can be used. Examples of such a polyfluorene oxide include addition-formed polyfluorene oxide which uses a platinum-based compound as a catalyst, and an alkenyl group-containing polydialkyloxirane and polydioxane by an addition reaction. The hydrogen hydride is cured to form a detachable film; the condensed polyoxyxene is a polydialkyl oxirane containing a hydroxymethyl group and a polydialkyl hydrogen condensed by a tin-based catalyst. The oxirane is reacted to obtain an equivalent. Examples of the addition polyoxyl oxide include "KS-776A" and "KS-839L" manufactured by Shin-Etsu Silicones. Examples of the condensed polyfluorene oxide include "KS723A/B" manufactured by Shin-Etsu Silicones. 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 the polyoxane can be classified into a type in which an organic solvent such as toluene is dissolved, an emulsion type obtained by emulsifying it, and the like, and a solvent-free type including only polyfluorene. Further, in addition to the addition of polyfluorene oxide and condensed polyfluorene oxide, a polyfluorene/acrylic graft polymer, a polyoxyn/acrylic block polymer or the like can be used. Examples of the polyoxymethylene/acrylic acid graft polymer include Symac GS-30, GS101, US-270, US-350, and US-380 (the above is manufactured by Toagosei Co., Ltd.). Examples of the polyoxymethylene/acrylic acid block polymer include MODIPER FS700, FS710, FS720, FS730, and FS770 (above, manufactured by Nippon Oil Co., Ltd.).

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

The (meth)acrylic polymer is a polymer containing 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, and more preferably 70%. The weight % to 100% by weight, more preferably 90% to 100% by weight, particularly preferably 95% by weight to 100% by weight. The monomer in the above 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 a carbon number of 1 to 30 (including a cycloalkyl group), a (meth)acrylate containing a hydroxyl group, and the like. The (meth) acrylate may be used alone or in combination of two or more.

Examples of the (meth)acrylic acid alkyl ester having an alkyl group having 1 to 30 carbon atoms (including a cycloalkyl group) include methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl). ) propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate , amyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, (methyl) Isodecyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, ( Pentadecyl methyl methacrylate, octadecyl (meth) acrylate, hexadecyl (meth) acrylate, eicosyl (meth) acrylate, lauryl (meth) acrylate An alkyl group having a carbon number of 1 to 30 (also including a ring) An alkyl (meth) acrylate or the like. 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 a carbon number of 4 to 18 is more preferred. An alkyl (meth)acrylate of an alkyl group (also containing a cycloalkyl group).

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

The monomer component constituting the above (meth)acrylic polymer is sufficient to present the hair The effect of the invention may also be at least one selected from the group consisting of a monomer having a hydroxyl group and a monomer having a carboxyl group.

Examples of the hydroxyl group-containing monomer include allyl alcohol and the like. The monomer having a hydroxyl group may be one type or two or more types.

Examples of the carboxyl group-containing monomer include carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, crotonic acid, maleic acid, fumaric acid, and methylene butadiene. Acid, etc. The monomer having a carboxyl group may be one type or two or more types.

When the non-adhesive layer contains a (meth)acrylic polymer, the (meth)acrylic polymer in the non-adhesive layer is preferably a hydroxyl group-containing (meth) acrylate in the monomer component constituting the non-adhesive layer. The content ratio is preferably 2% by weight to 30% by weight, more preferably 3% by weight to 25% by weight, based on the total amount of the monomer components other than the hydroxyl group-containing (meth) acrylate. It is 5% by weight to 20% by weight. When the non-adhesive layer contains a (meth)acrylic polymer, the content ratio of the hydroxyl group-containing (meth) acrylate in the monomer component of the (meth)acrylic polymer in the non-adhesive layer, When the total amount of the monomer components other than the hydroxyl group-containing (meth) acrylate is condensed within the above range, a minute uneven structure can be further efficiently formed on the surface of the non-adhesive layer. In the film for an adhesive tape of the present invention, in the case of adsorption and fixation by a negative pressure, excessive adhesion can be further suppressed, and adhesion in a roll form can be further effectively suppressed. It can further suppress cracking or breakage when rewinding from the roll form.

When the non-adhesive layer contains a (meth)acrylic polymer, the (meth)acrylic polymer in the non-adhesive layer is preferably one of the monomer components constituting the hydroxyl group (methyl group). The monomer component other than the acrylate contains (meth)acrylic acid and/or (meth)acrylic acid ester. In this case, the ratio of (meth)acrylic acid to (meth) acrylate is in a weight ratio, and (meth)acrylic acid: (meth) acrylate is preferably 0:100 to 20:80, more preferably It is 0:100~10:90, and further preferably 0:100~5:95.

When the content ratio of the (meth)acrylic acid to the (meth)acrylic acid ester converges within the above range, a fine uneven structure is further efficiently formed on the surface of the non-adhesive layer, and the uneven structure is formed by the uneven structure. In the film for an adhesive tape of the invention, when the film is adsorbed and fixed by a negative pressure, the excessive adhesion can be further suppressed, and the adhesion in the form of a roll can be further effectively suppressed, and the form is returned from the roll shape. Cracking or breakage can be further suppressed when rolling.

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

In the non-adhesive layer, any suitable additive may be included in the range which 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.

Regarding the non-adhesive layer, the non-adhesive test peeling force is preferably less than 1.0 N/20 mm, more preferably less than 0.5 N/20 mm, and further preferably less than 0.2 N/20 mm. The peeling force by the non-adhesive layer of the non-adhesive layer converges within the above range, and when the adsorption is fixed by the negative pressure, the excessive adhesion is further suppressed. In the present invention, the non-adhesive test peeling force of the non-adhesive layer was measured according to the following method.

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 the thickness of the non-adhesive layer is less than 0.01 μm, there is a possibility that the effect of the present invention is hard to be exhibited, or there is a flaw in that it is difficult to manufacture.

As a method of forming a non-adhesive layer on one side of a plastic film, for example, a method in which a non-adhesive layer is formed by coating a material of a non-adhesive layer on one side 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 is applied to the above-mentioned plastic film in the film for an adhesive tape of the present invention. The opposite side of the non-adhesive layer is provided with an adhesive layer.

The thickness of the adhesive layer is not particularly limited, but is preferably 1.0 μm to 30 μm, more preferably 1.0 μm to 20 μm, still more preferably 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, there is a tendency that the adhesive force is excessively increased according to the use, and the adherend is broken at the time of peeling or the like.

As the material of the above adhesive layer, any suitable adhesive can be employed without departing from 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 obtained by grafting a monomer such as methyl methacrylate; SBS, SBR, SEPS, SIS, SEBS. , synthetic rubber such as polybutene, polyisobutylene, polyisobutylene, butyl rubber, etc. Among these, at least one (meth)acrylic polymer is preferred in that the adherend after the peeling has a small amount of residual residue, high cohesiveness, and excellent transparency.

In the case where the adhesive layer contains a (meth)acrylic polymer, 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 containing a monomer component containing a (meth)acrylic monomer as a main monomer. The content 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 above 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 a carbon number of 1 to 30 (including a cycloalkyl group), a (meth)acrylate containing a hydroxyl group, and the like. (methyl) The acrylate may be used alone or in combination of two or more.

Examples of the (meth)acrylic acid alkyl ester having an alkyl group having 1 to 30 carbon atoms (including a cycloalkyl group) include methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl). ) propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate , amyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, (methyl) Isodecyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, ( Pentadecyl methyl methacrylate, octadecyl (meth) acrylate, hexadecyl (meth) acrylate, eicosyl (meth) acrylate, lauryl (meth) acrylate An alkyl group having a carbon number of 1 to 30 (also including a ring) An alkyl (meth) acrylate or the like. 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 a carbon number of 4 to 18 is more preferred. An alkyl (meth)acrylate of an alkyl group (also containing a cycloalkyl group).

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, the monomer component constituting the (meth)acrylic polymer may contain acrylonitrile in order to sufficiently exhibit the effect as an adhesive.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and allyl alcohol. The monomer having a hydroxyl group may be one type or two or more types.

Examples of the carboxyl group-containing monomer include (meth)acrylic acid and (meth)acrylic acid. Carboxylic acid ethyl ester, carboxy amyl (meth)acrylate, crotonic acid, maleic acid, fumaric acid, methylene succinic acid, and the like. The monomer having a carboxyl group may be one type or two or more types.

When the monomer component constituting the (meth)acrylic polymer contains a monomer having a hydroxyl group, the content ratio of the monomer having a hydroxyl group 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. When the monomer component constituting the (meth)acrylic polymer contains a monomer having a carboxyl group, the content ratio of the monomer having a carboxyl group 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. In this way, the monomer component constituting the (meth)acrylic polymer may contain at least one selected from the group consisting of a hydroxyl group-containing monomer and a carboxyl group-containing monomer, and when a crosslinking agent is used, it is highly efficient. A crosslinking reaction with the crosslinking agent is generated to sufficiently exhibit the effect as an adhesive. Further, the content ratio of the monomer having a hydroxyl group in the monomer component constituting the (meth)acrylic polymer and the single crystal constituting the (meth)acrylic polymer are adjusted so as to converge within the above range. The content ratio of the carboxyl group-containing monomer in the body component can effectively prevent the adhering body from being broken during the peeling operation. The content ratio of the monomer having a hydroxyl group in the monomer component constituting the (meth)acrylic polymer, and the content of the monomer having a carboxyl group in the monomer component constituting the (meth)acrylic polymer When the ratio is too large in the above range, the adhesion is excessively large, and the adhesion is liable to occur, and the crucible is likely to be broken during the peeling operation.

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, but is preferably relative to the main resin component (preferably (meth)acrylic acid) The polymer) is from 0.1% by weight to 20% by weight. By arranging the content ratio of the crosslinking agent in the adhesive layer to the above range, a moderate crosslinking reaction can be produced, thereby effectively preventing the peeling operation from being The broken body of the adhesive.

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 crosslinking. A crosslinking agent, a metal salt crosslinking agent, a carbodiimide crosslinking agent, An oxazoline crosslinking agent, an aziridine crosslinking agent, an amine crosslinking agent, and the like. Among these crosslinking agents, a melamine-based crosslinking agent, an epoxy-based crosslinking agent, and an isocyanate-based crosslinking agent are preferred in that the effects of the present invention are sufficiently exhibited. 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 depending on the purpose, but is preferably from 0.1% by weight to 50% by weight. The effect of the present invention can be further effectively exhibited by converging 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 is excessively 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., trioctyl trimellitate, etc.), and Diacid ester system (D620 manufactured by J-PLUS Co., Ltd., dioctyl adipate, diisononyl adipate, etc.), phosphate ester (such as tricresyl phosphate), adipic acid ester , citrate (acetyl tributyl citrate, etc.), sebacate, sebacate, maleate, benzoate, polyether polyester, epoxy polyester (ring Oxidized soybean oil, epoxidized linseed oil, etc.), polyester (low molecular weight polyester containing carboxylic acid and diol, etc.). In the present invention, an ester-based plasticizer is preferably used. The plasticizer may be used alone or in combination of two or more.

The adhesive layer may contain any appropriate catalyst in order to promote a crosslinking reaction or the like. In the case where the adhesive layer contains a catalyst, the content ratio of the catalyst in the adhesive layer can be appropriately set depending on the purpose, but is preferably 0.01% by weight to 10% by weight. The present invention can be further effectively rendered by converging the content ratio of the catalyst in the adhesive layer to the above range. The effect of the invention.

Examples of such a catalyst include tetraisopropyl titanate, tetra-n-butyl titanate, stannous octoate, lead octoate, cobalt octoate, zinc octoate, calcium octylate, lead naphthenate, and cobalt naphthenate. Organometallic compounds such as dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin maleate; butylamine, dibutylamine, hexylamine, third Basic compounds such as butylamine, ethylenediamine, isophorone diamine, imidazole, lithium hydroxide, potassium hydroxide, sodium methoxide; p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphate, phosphoric acid An acidic compound such as an alkyl ester, a phosphate of β-hydroxyethyl acrylate, a monoalkyl phosphite, or a dialkyl phosphite. The catalyst may be one type or two or more types.

In order to further exhibit the effects of the present invention, the adhesive layer preferably has an SP value of 9.0 (cal/cm ³ ) of ^0.5 to 12.0 (cal/cm ³ ) ^0.5 , more preferably 9.5 (cal/cm ³ ) of ^0.5 to 11.0 ( Cal/cm ³ ) ^0.5 . The SP value is a solubility parameter calculated by the formula of Small. 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., etc.).

Any suitable additive may be contained in the adhesive layer insofar as it 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, a decane coupling agent, and the like.

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

As the release liner, any suitable separator can be used. Examples of such a release liner include a substrate having 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 groups of fluorine-based polymers such as tetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, and chlorofluoroethylene-vinylidene fluoride copolymer A low-adhesive substrate containing a nonpolar 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 has the film for an adhesive tape of the present invention, as described above, when it is adsorbed and fixed to the fixing base by a negative pressure and is cut or the like, the susceptor can be effectively suppressed. When the heat is generated and the like is excessively adhered, the adhesion in the form of a roll can be effectively suppressed, and the film is not broken or broken when rewinding from the roll form, so that the non-adhesive layer and the plastic film are adapted. Good, so that the followability to deformation such as extension is good. Therefore, it can be suitably used for processing a semiconductor wafer which is composed of a fragile material and has 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 it is adsorbed and fixed to a fixing base by a negative pressure and cut or the like, it is possible to effectively suppress excessive adhesion due to heat generation of the susceptor or the like. In this case, therefore, the semiconductor manufacturing steps including the 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 can accurately follow the fine and delicate circuit pattern of the semiconductor wafer. Moreover, the natural stress relief of the semiconductor wafer is not caused to be released, so that the semiconductor wafer can be effectively prevented from being broken. In particular, the wafer used in the LED is composed of a very fragile 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 based on examples, but the present invention is not limited to the examples. Parts are parts by weight. Moreover, the amount of the reagent supplied in the solution is represented by the amount of the solid content (the amount of solid content converted) remaining to volatilize the solution.

<maximum elongation>

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

<Elastic Modulus>

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

<Observation of non-adhesive layer>

(using SEM observation)

Morphological observation was carried out by a transmission electron microscope (SEM) after processing the non-adhesive layer profile.

(Ob-IR observation by total reflection method)

An infrared spectroscopic spectrometer (Perkinermer, Spectrum One) was used, and a total reflection measurement method was selected. In order to change the depth of analysis of the probe light, two kinds of total reflection measurement flaws (ZnSe45°, Ge45°) were used to perform a non-adhesive layer. ATR-IR measurement.

<Arithmetic average surface roughness Ra>

A conjugated focal laser micromirror "LEXT3000" manufactured by OLYMPUS was used and measured with an objective lens 20 times in 3D mode. The determination of the observation range of the 3D mode is performed by setting the position where the CF image (conjugated focus image) is dark and the top of the observation range to Bottom when the lens is moved up and down.

The method of acquiring an image in the 3D mode is to obtain an image at a pitch of 0.2 μm in a stepwise manner.

The measurement of the arithmetic mean surface roughness Ra measures Ra at an arbitrary position by the roughness analysis of the analytical mode. Furthermore, the value is obtained by the average of n=5.

<Measurement of the elastic modulus at 80 ° C measured by atomic force microscopy (AFM) on the convex portion of the surface of the non-adhesive layer>

The outermost surface of the side opposite to the adhesive layer was measured in the adhesive tape which does not have a non-adhesive layer as in the comparative example 1.

The sample was heat treated at 120 ° C for more than 37 hours. Thereafter, it was fixed on an atomic force microscope (AFM)-specific sample holder and placed on an AFM-specific cooler heater accessory. After holding at 80 ° C for 30 minutes or more, it was manufactured using Asylum Technology. AFM "MFP-3D-SA-J" and NANOSENSORS cantilever "R150-NCL-10 (material Si, spring constant 48 N / m, radius of curvature of the front end 150 nm)", measured at 80 ° C Shaped in AC mode. At this time, the force curve was measured in the Contact mode for the portion observed as the convex portion (the moving speed of the cantilever was 2 μm/s at 80 ° C, and the maximum indentation load was 2 μN).

Based on the Force-Ind curve obtained from the force curve, the theory of Hertz attached to the software "IgorPro 6.22A MFP3D101010+1313" attached to the AFM device is analyzed to obtain the elastic modulus. Furthermore, with Tip Geometry=Sphere, Radius=150 nm, Select=Fused Silica, ν _Tip =0.17, E _Tip =74.9 GPa, ν _Sample =0.33, Low=10% in the Force list, High=90% in the Force list The calculation was performed and found by the average value of n=5.

<Adsorption test under high temperature conditions>

On the glass slide of 20 mm (vertical) × 50 mm (horizontal), the back side (in the case of the film for the adhesive tape in the embodiment and the comparative example, the surface on the side of the non-adhesive layer, in the case of the adhesive tape) The film on the opposite side of the adhesive layer is a front side, and a film or an adhesive tape for the adhesive tape is attached. Then, in the environment of 80 ° C, the above-mentioned tape-attached slide glass was brought into contact with a slide glass (green plate edge grinding product, size: 65 mm × 165 mm × 1.35 mmt) as an adherend, and the above tape was attached to the glass. The back side of the sheet was in contact with the non-tin side of the slide, and after being left for 15 minutes, it was made to go back and forth by a 2 kg roller, and the slide was attached to the back side of the tape attached to the slide. And placed at 80 ° C for 30 minutes. After standing, the mixture was cooled at room temperature, and subjected to 0° peeling at an elongation speed of 0.3 m/min by an Instron tensile tester (manufactured by Shimadzu Corporation, an autostereograph). The peeling force (maximum value) at this time was measured, and it evaluated based on the following criteria.

○: The peeling force was less than 5.0 N.

△: The peeling force was 5.0 N or more and less than 15.0 N.

×: The peeling force was 15.0 N or more.

<non-adhesive test peeling force>

According to JIS-Z-0237, the adhesive tape and the adhesive tape including the non-adhesive layer are kept for 1 hour or more at 23 ° C, and then the linear pressure is 8 kg/m, and the crimping speed is 0.3 m. /min The non-adhesive surface 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>

The adhesive layer of the adhesive tape was crimped to the outermost surface (back layer) on the opposite side of the adhesive layer of the same adhesive tape at a line pressure of 8 Kg/m and a crimping speed of 0.3 m/min. Store at °C × 48 hr. After the storage, the adhesion (peeling force) of the adhesive layer and the back layer was measured by peeling at a tensile speed of 0.3 m/min by a peeling test of 180° peeling (according to JIS-Z-0237).

In the evaluation, the peeling force was measured, the peeling of the back layer at the time of peeling, the destruction of the adhesive layer (residue of the paste due to the cohesive failure, the damage of the grip), and the like were evaluated as a comprehensive evaluation.

The evaluation is based on the following criteria.

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

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

<Cure Checking Test>

(Currentity confirmation test A)

Extending the film or adhesive tape of the adhesive tape to 200% by a stretching speed of 0.3 m/min to 3 m/min, and by visually observing the adhesive film or adhesive tape for the adhesive tape The peeling property of the outermost surface (back surface layer) on the opposite side of the adhesive layer was evaluated.

(Currentity confirmation test B)

After performing the same extension as the gripping confirmation test A, "NO.31B" manufactured by Nitto Denko Corporation was used as the back treatment layer by a 2 Kg roll (width 25 mm) at 0.3 m/min. Pressing the speed to make a round trip, and then storing it at 23 ° C × 50% RH for 1 minute, and peeling at 90 ° at a peeling speed of 0.3 m / min to 3 m / min, and visually The peeling property of the back surface was evaluated.

(Evaluation)

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

◎: There was no peeling of the back surface which was confirmed by visual observation in both the gripping property confirmation test A and the gripping property confirmation test B.

○: The peeling of the back surface which was confirmed by the visual observation was not observed in the gripping property confirmation test A, and was slightly confirmed in the gripping property confirmation test B (checked in a dotted manner).

X: It was confirmed in the gripping property confirmation test A that the back surface was peeled off, or the back surface peeling was confirmed in the gripping property confirmation test B.

[Manufacturing Example 1]: Manufacturing of plastic film

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

[Example 1]

The mixed solution (1) was obtained by mixing the following materials in a solution state: 60 parts by weight of polyoxyxylene resin (KS-723A, manufactured by Shin-Etsu Chemical Co., Ltd.), 40 parts by weight of polyoxynoxy resin (KS-723B, manufactured by Shin-Etsu Chemical Co., Ltd.) , acrylic acid copolymer (methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 90 / 10/10) 50 parts by weight, and tin-based catalyst (Cat-PS3, 10 parts by weight manufactured by Shin-Etsu Chemical Co., Ltd.). The mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the mixed solution (1) is polyoxyn:poly(meth)acrylic polymer=2:1 by weight ratio. Further, the acrylic copolymer polymer had a calculated Tg of 67.8 ° C and an SP value of 10.7 (cal/cm ³ ) ^0.5 .

The mixed solution (1) was applied to one surface of a soft polyvinyl chloride film produced in Production Example 1 to form a non-adhesive layer having a thickness of 1.0 μm and an arithmetic mean surface roughness Ra of 0.5 μm.

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

The various evaluation results are shown in Table 1.

Further, when the non-adhesive layer was observed by SEM, as shown in Fig. 1, Fig. 2, and Fig. 3, the composition of the image was observed according to the form, and it was confirmed that the composition was different at the air interface side and the plastic film side; A (meth)acrylic polymer having a poly(xylene oxide)-rich polymer and a (meth)acrylic polymer having a more (meth)acrylic polymer than a polyfluorene-oxygen The enriched phase, the polyfluorene-rich phase and the (meth)acrylic polymer-rich phase have mutually independent phase separation structures, and the polyfluorene-rich phase exists on the air interface side (opposite side of the plastic film), The methylated acrylic polymer-rich phase is present on the plastic film side.

Further, the non-adhesive layer was subjected to the external-reflection measurement (ATR-IR) by the total reflection method, and as a result, it was found that the vicinity of 800 cm ^-1 derived from Si-CH _{3 in} the (meth)acrylic polymer phase was observed. The peak value of the peak was measured with respect to the absorbance ratio of the peak near the 1725 cm ^{-1 of the} carbonyl group, and as a result, the peak near 800 cm ^{-1 was} larger in the case of using Ge 45 ° than in the case of ZnSe 45 °. Therefore, it is understood that the content ratio of the enthalpy at the air interface side is higher than that of the substrate side.

Further, in the case where the polyfluorene-rich phase in the non-adhesive layer was present on the air interface side (the opposite side of the plastic film), it was confirmed in the FT-IR. The FT-IR measurement method uses "Spectrum One" manufactured by Perkinermer, and uses two kinds of ruthenium (ZnSe45°, Ge45°) having different depth directions to analyze by ATR method (attenuated total reflectance method). The air interface side was measured. By confirming the obtained chart, it was confirmed that the non-adhesive layer derived from the (meth)acrylic polymer originated from C=O was derived from Si when the analysis was carried out in the case where the depth of Ge4 was shallow. the phase peak of 800cm ^-1 near -CH ₃ becomes large absorbance peak 1720 cm ^-1 -1730 cm ^-1 ratio. Thereby, it can be confirmed that the concentration of polyoxane at the air interface side becomes higher.

It can be seen that considering the observation results and the principle of minimizing the surface free energy, a two-layer structure having a polyfluorene-rich phase on the air interface side is formed on the non-adhesive layer.

[Embodiment 2]

In the first embodiment, the mixed solution (1) of the soft polyvinyl chloride film produced by the production example 1 was applied in the same manner as in the first embodiment to form a thickness of 0.7 μm and an arithmetic mean. Non-adhesive layer with surface roughness Ra = 0.1 μm.

Thus, a film (2) for an adhesive tape was obtained.

The various evaluation results are shown in Table 1.

[Example 3]

Toluene solution containing an adhesive of the following materials: 100 parts by weight of an acrylic copolymer containing butyl acrylate (BA) / acrylonitrile (AN) / acrylic acid (AA) = 85 / 15 / 2.5 (weight ratio), melamine system Crosslinking agent (butanol modified melamine formaldehyde resin, "Super Beckamine J-820-60N", manufactured by Japan Polyurethane) 10 parts by weight, and DOP plasticizer (bis(2-ethylhexyl) phthalate, Made by J-PLUS) 60 parts by weight.

The adhesive solution was applied to the side opposite to the non-adhesive layer of the film for adhesive tape (1) obtained in Example 1, and then dried at 130 ° C for 90 seconds to form a soft polyvinyl chloride. An adhesive layer having a thickness of 10 μm was formed on the opposite side of the non-adhesive layer of the film. The resulting adhesive layer had an SP value of 10.5.

Thus, the adhesive tape (3) is obtained.

The various evaluation results are shown in Table 1.

[Example 4]

As the acrylic copolymer copolymer for forming a non-adhesive layer, 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / ethyl acrylate (EA) / hydroxyethyl acrylate (HEA) = 90 / 10/10 is used. Except for this, it was carried out in the same manner as in Example 1 to obtain a film (4) for an adhesive tape. An adhesive tape (4) was obtained in the same manner as in Example 3 except that the film for adhesive tape (4) was used instead of the film for adhesive tape (1).

The acrylic copolymer was calculated to have a Tg of 74.3 ° C and an SP value of 10.3 (cal/cm ³ ) ^0.5 .

Regarding the non-adhesive layer, the thickness is 1.0 μm, and the arithmetic mean surface roughness Ra = 0.5 μm.

The various evaluation results are shown in Table 1.

[Example 5]

As the acrylic copolymer for non-adhesive layer formation, 50 parts by weight of methyl methacrylate (MMA) / cyclohexyl acrylate (CHA) / hydroxyethyl acrylate (HEA) = 90 / 10/10 acrylic copolymer was used. A film (5) for an adhesive tape was obtained in the same manner as in Example 1 except for the above. An adhesive tape (5) was obtained in the same manner as in Example 3 except that the film for adhesive tape (5) was used instead of the film for adhesive tape (1).

The acrylic copolymer was calculated to have a Tg of 80.0 ° C and an SP value of 10.4 (cal/cm ³ ) ^0.5 .

Regarding the non-adhesive layer, the thickness is 1.0 μm, and the arithmetic mean surface roughness Ra = 0.5 μm.

The various evaluation results are shown in Table 1.

[Embodiment 6]

As the acrylic copolymer copolymer for forming a non-adhesive layer, 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 95/5 / 15 was used. Otherwise, it was carried out in the same manner as in Example 1 to obtain a film (6) for an adhesive tape. The film for adhesive tape (6) is used instead of the film for adhesive tape (1), and Except in the same manner as in Example 3, an adhesive tape (6) was obtained.

The acrylic copolymer was calculated to have a Tg of 73.0 ° C and an SP value of 10.5 (cal/cm ³ ) ^0.5 .

Regarding the non-adhesive layer, the thickness is 1.0 μm, and the arithmetic mean surface roughness Ra = 1.0 μm.

The various evaluation results are shown in Table 1.

[Embodiment 7]

As the acrylic copolymer copolymer for forming a non-adhesive layer, 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 80 / 20/10 was used. Except for this, it was carried out in the same manner as in Example 1 to obtain a film (7) for an adhesive tape. An adhesive tape (7) was obtained in the same manner as in Example 3 except that the film for adhesive tape (7) was used instead of the film for adhesive tape (1).

The acrylic copolymer was calculated to have a Tg of 48.5 ° C and an SP value of 10.1 (cal/cm ³ ) ^0.5 .

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

The various evaluation results are shown in Table 1.

[Embodiment 8]

As the acrylic copolymer copolymer for forming a non-adhesive layer, 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 99 / 1 / 5 is used. Except for this, it was carried out in the same manner as in Example 1 to obtain a film (8) for an adhesive tape. An adhesive tape (8) was obtained in the same manner as in Example 3 except that the film for adhesive tape (8) was used instead of the film for adhesive tape (1).

The acrylic copolymer was calculated to have a Tg of 94.3 ° C and an SP value of 10.1 (cal/cm ³ ) ^0.5 .

Regarding the non-adhesive layer, the thickness is 1.0 μm, and the arithmetic mean surface roughness Ra = 0.5 μm.

The various evaluation results are shown in Table 1.

[Embodiment 9]

On the side of the adhesive layer of the adhesive tape (5) obtained in Example 5, a PET liner having a thickness of 38 μm which had been subjected to Si treatment was attached as a release liner, thereby obtaining an adhesive tape (9).

Regarding the non-adhesive layer, the thickness is 1.0 μm, and the arithmetic mean surface roughness Ra = 0.5 μm.

The various evaluation results are shown in Table 1.

[Embodiment 10]

As the acrylic copolymer copolymer for forming a non-adhesive layer, 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 95/5/10 is used. Except for this, it was carried out in the same manner as in Example 1 to obtain a film (10) for an adhesive tape. An adhesive tape (10) was obtained in the same manner as in Example 3 except that the film for adhesive tape (10) was used instead of the film for adhesive tape (1).

The acrylic copolymer was calculated to have a Tg of 77.2 ° C and an SP value of 10.3 (cal/cm ³ ) ^0.5 .

Regarding the non-adhesive layer, the thickness is 1.0 μm, and the arithmetic mean surface roughness Ra = 0.7 μm.

The various evaluation results are shown in Table 1.

[Example 11]

As the acrylic copolymer copolymer for forming a non-adhesive layer, 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 70 / 30/10 was used. Except for this, it was carried out in the same manner as in Example 1 to obtain a film (11) for an adhesive tape. An adhesive tape (11) was obtained in the same manner as in Example 3 except that the film for adhesive tape (11) was used instead of the film for adhesive tape (1).

The acrylic copolymer was calculated to have a Tg of 31.2 ° C and an SP value of 10.4 (cal/cm ³ ) ^0.5 .

Regarding the non-adhesive layer, the thickness is 1.0 μm, and the arithmetic mean surface roughness Ra is 0.3 μm.

The various evaluation results are shown in Table 1.

[Comparative Example 1]

In the same manner as in Example 3 except that the non-adhesive layer was not formed in Example 3, an adhesive tape (C1) was obtained.

The various evaluation results are shown in Table 1.

[Comparative Example 2]

As the acrylic copolymer copolymer for forming a non-adhesive layer, 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 55 / 45/10 was used. Except for this, it was carried out in the same manner as in Example 1 to obtain a film for an adhesive tape (C2). An adhesive tape (C2) was obtained in the same manner as in Example 3 except that the film for adhesive tape (C2) was used instead of the film for adhesive tape (1).

The acrylic copolymer was calculated to have a Tg of 8.6 ° C and an SP value of 10.4 (cal/cm ³ ) ^0.5 .

Regarding the non-adhesive layer, the thickness was 1.0 μm, and the arithmetic mean surface roughness Ra was 0.08 μm.

The various evaluation results are shown in Table 1.

[Industrial availability]

Since the adhesive tape of the present invention has the film for an adhesive tape of the present invention, as described above, when it is adsorbed and fixed to the fixing base by a negative pressure and is cut or the like, the susceptor can be effectively suppressed. When the heat is generated and the like is excessively adhered, the adhesion in the form of a roll can be effectively suppressed, and the film is not broken or broken when rewinding from the roll form, and the non-adhesive layer has good compatibility with the plastic film. , good followability for deformation such as extension. Therefore, it can be suitably used for processing a semiconductor wafer which is composed of a fragile material and has 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 it is adsorbed and fixed by a negative pressure, excessive adhesion can be suppressed, and therefore, the semiconductor manufacturing step including dicing can be smoothly performed. 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 can accurately follow the fine and delicate circuit pattern of the semiconductor wafer. Moreover, the natural stress relief of the semiconductor wafer is not caused to be released, so that the semiconductor wafer can be effectively prevented from being broken. In particular, the wafer used in the LED is composed of a very fragile 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.

Claims (19)

A film for an adhesive tape which has a non-adhesive layer on one side of a plastic film, and has a concave-convex structure on a surface of the non-adhesive layer, and an elastic portion at 80° C. measured by an atomic force microscope on a convex portion of the surface of the non-adhesive layer The modulus is 0.2 GPa or more, and the non-adhesive layer is a mixed layer of polyoxymethylene and a (meth)acrylic polymer, and the non-adhesive layer has a phase separation structure comprising: (meth)acrylic polymer Compared to a poly (oxy)oxygen-rich phase containing more polyoxymethylene and a (meth)acrylic polymer-rich phase containing more (meth)acrylic polymer than polyfluorene oxide, the polyfluorene The oxygen-rich phase and the (meth)acrylic polymer-rich phase are mutually independent phase-separated structures. The film for an adhesive tape according to claim 1, wherein the non-adhesive layer has an arithmetic mean surface roughness Ra of 0.1 μm or more. The film for an adhesive tape according to claim 1, wherein the (meth)acrylic polymer has a calculated Tg of 10 ° C or more. The film for an adhesive tape according to claim 2, wherein the (meth)acrylic polymer has a calculated Tg of 10 ° C or more. The film for an adhesive tape according to claim 1, wherein the (meth)acrylic polymer has an SP value of 9.0 (cal/cm ³ ) of ^0.5 to 12.0 (cal/cm ³ ) ^0.5 . The film for an adhesive tape according to claim 2, wherein the (meth)acrylic polymer has an SP value of 9.0 (cal/cm ³ ) of ^0.5 to 12.0 (cal/cm ³ ) ^0.5 . The film for an adhesive tape according to claim 3, wherein the (meth)acrylic polymer has an SP value of 9.0 (cal/cm ³ ) of ^0.5 to 12.0 (cal/cm ³ ) ^0.5 . The film for an adhesive tape according to claim 4, wherein the (meth)acrylic polymer has an SP value of 9.0 (cal/cm ³ ) of ^0.5 to 12.0 (cal/cm ³ ) ^0.5 . The film for an adhesive tape according to any one of claims 1 to 8, wherein a mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the non-adhesive layer is polyoxylium by weight: (methyl Acrylic polymer = 1:50~50:1. The film for an adhesive tape according to any one of claims 1 to 8, 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 any one of claims 1 to 8, wherein the non-adhesive layer has a thickness of from 0.01 μm to 10 μm. The film for an adhesive tape according to any one of claims 1 to 8, wherein the plastic film has a maximum elongation of 100% or more as measured according to JIS-K-7127. The film for an adhesive tape according to any one of claims 1 to 8, wherein the plastic film has a thickness of from 20 μm to 200 μm. The film for an adhesive tape according to any one of claims 1 to 8, wherein the plastic film comprises polyvinyl chloride. An adhesive tape having an adhesive layer on a surface of the plastic film of the adhesive tape according to any one of claims 1 to 14, which is opposite to the non-adhesive layer, and an SP value of 9.0 (the adhesive layer). Cal/cm ³ ) ^0.5 ~ 12.0 (cal/cm ³ ) ^0.5 . The adhesive tape of claim 15, wherein the adhesive layer comprises at least one (meth)acrylic polymer. The adhesive tape of claim 15 or 16, wherein a release liner is provided on the surface of the adhesive layer. The adhesive tape of claim 15 or 16 is used for semiconductor processing. An adhesive tape according to claim 15 or 16, which is used for LED cutting purposes.