JP5946289B2 - Adhesive tape film and adhesive tape - Google Patents

Description

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

  In order to fix the wafer during dicing, the adhesive tape used for semiconductor dicing needs to fix the surface opposite to the wafer contact surface to the pedestal. In general, such fixation is performed by a negative pressure such as vacuum suction.

  When fixing with such a negative pressure, the pressure-sensitive adhesive tape may be in close contact with the pedestal due to a state in which a negative pressure is excessively applied or due to melting of the pressure-sensitive adhesive tape due to heat generated during dicing. When such over-adhesion occurs, the handling property when releasing the fixing to the pedestal is deteriorated, and for example, there is a problem that the semiconductor manufacturing process including dicing does not flow smoothly.

  In order to eliminate such a problem of over-adhesion, in the wafer surface protective tape comprising two layers of the base film and the pressure-sensitive adhesive layer, the center line surface roughness Ra of the surface opposite to the pressure-sensitive adhesive layer of the base film is set to A technique for controlling to a predetermined size has been reported (Patent Document 1).

  However, the base film of the pressure-sensitive adhesive tape used for semiconductor dicing is required to have an expanding (stretching) characteristic and a step following characteristic peculiar to the semiconductor manufacturing process. That is, the base film of the pressure-sensitive adhesive tape used for semiconductor dicing needs to be able to be satisfactorily stretched in the expanding process, and needs to follow the steps of the semiconductor well. A base film made of a material having a high elongation rate is selected as the base film that can meet such requirements. However, the surface condition of such a base film is easily affected by temperature. For this reason, even if the centerline surface roughness Ra of the surface of the base film is controlled to a predetermined size as reported in Patent Document 1, it becomes a predetermined size depending on the temperature and the temperature change of the process equipment. There is a problem that the controlled centerline surface roughness Ra is greatly changed, and the effect of the invention described in Patent Document 1 cannot be exhibited.

  For example, at the time of dicing, especially at the time of laser dicing, the wafer generates heat due to energy by laser processing. When the wafer generates heat as described above, even if the center line surface roughness Ra of the surface of the base film is controlled to a predetermined size as reported in Patent Document 1, the above problem of over-adhesion is caused. There is a problem that over-adhesion is promoted rather than being able to be solved.

  In recent years, since the size of a wafer used for semiconductor dicing has increased, the time for dicing becomes longer, resulting in increased heat generation of the wafer, and the above problem becomes more prominent.

  Among semiconductor dicing, especially in LED dicing, the semiconductor wafer used is made of a very fragile material such as gallium nitride, gallium arsenide, silicon carbide, etc., so as to prevent damage to the semiconductor wafer. The base film of the pressure-sensitive adhesive tape is required to have a single expanded (stretching) characteristic and a step following characteristic. For this reason, in the adhesive tape used for LED dicing, the said problem becomes still more remarkable.

  On the other hand, generally, the film surface is smooth, and when such a film is processed into a roll shape, a phenomenon in which the films come into contact with each other, that is, blocking occurs. A roll that has been blocked may cause problems such as difficulty in rewinding the film. In particular, a plasticizer is generally added to a film having a high elongation rate. In such a film, the plasticizer is deposited on the film surface to fill a slight gap between the films, so that the adverse effect due to blocking becomes significant. When the film surface is subjected to pressure-sensitive adhesive treatment, the pressure-sensitive adhesive itself has adhesiveness, so that the adverse effect of blocking becomes even greater.

  When the blocked roll-shaped film is rewound, an extra force for releasing the adhesion between the films is required. When such extra force is applied, the film stretches and deforms, or even if the film does not deform, it is accumulated as stress strain. When a film deformed for the above reasons is applied to an adhesive tape, it becomes difficult to follow and adhere to the adherend. In addition, when a film in which stress strain is accumulated due to the above-described causes is applied to an adhesive tape, the adherend may be damaged due to natural release of the stress strain after being bonded to the adherend. .

  When an adhesive tape is used in semiconductor processing, a semiconductor wafer as an adherend is made of a fragile material and thus is fragile or easily chipped. For this reason, when the film deform | transformed by the above causes is applied to an adhesive tape, it will become difficult to stick together following the fine circuit pattern of a semiconductor wafer. Further, when a film in which stress strain is accumulated due to the above causes is applied to an adhesive tape, the semiconductor wafer is easily damaged by spontaneous release of the stress strain after being bonded to the semiconductor wafer.

  In particular, a wafer used for an LED is made of a very fragile material such as gallium nitride, gallium arsenide, or silicon carbide. For this reason, the blocking prevention in the adhesive tape used for LED dicing etc. becomes especially important.

  There are two major techniques for preventing blocking.

  One conventional technique is to perform physical processing such as embossing on the back surface of the film (Patent Document 2). However, in this technique, since the unevenness formed on the back surface of the film has a stress concentration structure, when the film is rewound from the roll shape, the film is torn or torn starting from the unevenness due to the unwinding force. There is a problem.

  Another conventional technique is to apply a silicone release agent on the back surface of the film (Patent Document 3). However, in this technique, there is a problem that the silicone release agent has a low chemical affinity with the back surface of the film due to its surface tension, and it is difficult to be familiar with the back surface of the film. In addition, when a film having a silicone release agent applied to the back surface is applied to an adhesive tape, if the adhesive tape is stretched such as an expand, the treatment layer with the silicone release agent may not be able to follow the elongation. The problem of being crushed and causing contamination can arise. In addition, in order to increase the chemical affinity of the silicone release agent with the back of the film, there is a technology to apply a cross-linked silicone release agent, but since the cross-linked silicone generally has a very low elongation rate, When a film coated with a silicone release agent is applied to an adhesive tape, if the adhesive tape is stretched such as expand, the treatment layer with the cross-linked silicone mold release agent cannot follow the stretching, and the anchoring property cannot be maintained There is.

JP 2009-239124 A International Publication No. 2009/028069 Pamphlet JP 2010-201836 A

  An object of the present invention is a film for an adhesive tape in which a non-adhesive layer is provided on a base film, and when performing dicing or the like by adsorbing and fixing to a fixing base by negative pressure, due to heat generation of the base or the like It is possible to effectively suppress the occurrence of over-adhesion, and blocking in the roll form is effectively suppressed by providing a non-adhesive layer on the base film, and tearing when rewinding from the roll form An object of the present invention is to provide a film for pressure-sensitive adhesive tapes that is not torn, has a good familiarity with the non-adhesive layer and the base film, and has good followability to deformation such as stretching. Moreover, it is providing the adhesive tape containing such a film for adhesive tapes.

The adhesive tape film of the present invention is
A film for an adhesive tape comprising a non-adhesive layer on one side of a plastic film,
The surface of the non-adhesive layer has an uneven structure,
The indentation hardness at 80 ° C. by the nanoindenter at the convex portion on the surface of the non-adhesive layer is 6.0 MPa or more.

  In preferable embodiment, arithmetic-mean surface roughness Ra of the said non-adhesion layer is 0.1 micrometer or more.

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

  In preferable embodiment, calculation Tg of the said (meth) acrylic-type polymer is 10 degreeC or more.

In a preferred embodiment, the SP value of the (meth) acrylic polymer is 9.0 (cal / cm ³ ) ^{0.5 to} 12.0 (cal / cm ³ ) ^0.5 .

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

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

  In preferable embodiment, the non-adhesion test peeling force of the said non-adhesion layer is less than 1.0 N / 20mm.

  In preferable embodiment, the thickness of the said non-adhesion layer is 0.01 micrometer-10 micrometers.

  In preferable embodiment, the maximum elongation measured according to JIS-K-7127 of the said plastic film is 100% or more.

  In preferable embodiment, the thickness of the said plastic film is 20 micrometers-200 micrometers.

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

  In another embodiment of the present invention, an adhesive tape is provided. The pressure-sensitive adhesive tape of the present invention includes a pressure-sensitive adhesive layer on the surface of the plastic film of the present invention opposite to the non-stick layer of the plastic film.

  In a preferred embodiment, the pressure-sensitive adhesive layer contains at least one (meth) acrylic polymer.

In a preferred embodiment, SP value of the adhesive layer is ^{9.0 (cal} / cm 3) is ^{0.5 ~12.0 (cal / cm 3)} 0.5.

  In a preferred embodiment, a release liner is provided on the surface of the pressure-sensitive adhesive layer.

  In a preferred embodiment, the pressure-sensitive adhesive tape of the present invention is used for semiconductor processing.

  In preferable embodiment, the adhesive tape of this invention is used for LED dicing use.

  According to the present invention, a non-adhesive layer is a film for an adhesive tape provided on a base film, and when performing dicing or the like by adsorbing and fixing to a fixing base by negative pressure, due to heat generation of the base or the like It is possible to effectively suppress the occurrence of over-adhesion, and blocking in the roll form is effectively suppressed by providing a non-adhesive layer on the base film, and tearing when rewinding from the roll form It is possible to provide a film for an adhesive tape that is not torn, has a good familiarity with the non-adhesive layer and the substrate film, and has good followability to deformation such as stretching. Moreover, the adhesive tape containing such a film for adhesive tapes can be provided.

It is a photograph figure of SEM which shows the state of the surface side of the non-adhesion layer in the film for adhesive tapes of this invention. It is a photograph figure of SEM which shows the state of the cross section side of the non-adhesion layer in the film for adhesive tapes of this invention. It is a photograph figure of SEM which shows the state of the cross section side of the non-adhesion layer in the film for adhesive tapes of this invention with description.

<< 1. Film for adhesive tape >>
The film for pressure-sensitive adhesive tapes of the present invention includes a non-adhesive layer on one surface of a plastic film.

<1-1. Plastic film>
The plastic film is not particularly limited, and may include any appropriate resin material. As such a resin material, preferably, for example, polyvinyl chloride, polyolefin, polyester, polyimide, polyamide and the like are mentioned, more preferably, polyvinyl chloride and polyolefin are mentioned, and still more preferably, polyvinyl chloride is used. Can be mentioned. Since polyvinyl chloride is excellent in stress relaxation properties, it can be suitably used particularly for an adhesive tape film that can be used for an adhesive tape used for semiconductor processing such as LED dicing.

  As the content ratio of the resin material in the plastic film, any appropriate content ratio can be set according to the purpose and application. As such a content rate, it becomes like this. Preferably it is 50 to 100 weight%, More preferably, it is 60 to 100 weight%, More preferably, it is 70 to 100 weight%.

  The plastic film may contain a plasticizer. The content of the plasticizer in the plastic film is preferably 0.5% by weight to 50% by weight, more preferably 1.0% by weight to 40% by weight with respect to the resin material in the plastic film. is there. By including the plasticizer in the above-mentioned content ratio in the plastic film, the followability to deformation such as stretching becomes even better.

  Examples of the plasticizer include phthalate ester-based, trimellitic ester-based (Dainippon Ink Co., Ltd., W-700, trimellitic trioctyl, etc.), adipate ester-based (manufactured by J-Plus, D620, dioctyl adipate, diisononyl adipate, etc.), phosphate esters (such as tricresyl phosphate), adipic acid esters, citrate esters (such as acetyl citrate tributyl), sebacic acid esters, aceleic acid esters, maleic acid esters Benzoic acid ester, polyether polyester, epoxy polyester (epoxidized soybean oil, epoxidized linseed oil, etc.), polyester (low molecular polyester comprising carboxylic acid and glycol, etc.) and the like. In the present invention, it is preferable to use an ester plasticizer. Only one type of plasticizer may be used, or two or more types may be used.

  The plastic film may contain any appropriate other component as long as the effects of the present invention are not impaired.

  The maximum elongation of the plastic film measured according to JIS-K-7127 is preferably 100% or more, more preferably 200% to 1000%. By using a plastic film exhibiting such maximum elongation, it is possible to impart appropriate stretchability to the adhesive tape film of the present invention. For example, when the adhesive tape film of the present invention is used for an adhesive tape In addition, the followability to the adherend can be improved.

  The thickness of the plastic film is preferably 20 μm to 200 μm, more preferably 40 μm to 150 μm, and still more preferably 50 μm to 100 μm. When the thickness of the plastic film is less than 20 μm, the handleability may be deteriorated. In particular, when the pressure-sensitive adhesive tape is formed, the bonding operation may be difficult. If the thickness of the plastic film is larger than 200 μm, the followability to deformation such as stretching may be deteriorated.

<1-2. Non-adhesive layer>
The non-adhesive layer is not particularly limited in composition as long as the surface has an uneven structure defined below, and an example thereof is a mixed layer of silicone and (meth) acrylic polymer. is there. By making the non-adhesive layer a mixed layer of silicone and (meth) acrylic polymer, the familiarity between the non-adhesive layer and the plastic film is improved, and the film for the adhesive tape of the present invention and the adhesive tape including the same are stretched, etc. The followability with respect to the deformation is good.

  The surface of the non-adhesive layer has an uneven structure. Specifically, the concavo-convex structure has an arithmetic average surface roughness Ra of the non-adhesive layer of preferably 0.1 μm or more, more preferably 0.1 μm to 3.0 μm, and still more preferably 0.2 μm. ˜2.0 μm, particularly preferably 0.3 μm to 2.0 μm, and most preferably 0.5 μm to 2.0 μm. When the arithmetic average surface roughness Ra of the non-adhesive layer falls within the above range, it is possible to suppress the occurrence of over-adhesion when performing adsorption fixation by negative pressure.

  The non-adhesive layer has an indentation hardness at 80 ° C. by a nanoindenter on the convex portion of the surface of 6.0 MPa or more, preferably 10 MPa or more, more preferably 15 MPa or more, and further preferably 18 MPa or more. It is. The upper limit of the indentation hardness at 80 ° C. by the nanoindenter in the convex part of the surface of the non-adhesive layer is not particularly limited, but is preferably 100 MPa or less, more preferably 70 MPa or less, and further preferably 50 MPa or less. Yes, particularly preferably 40 MPa or less. If the indentation hardness at 80 ° C. by the nanoindenter in the convex part of the surface of the non-adhesive layer falls within the above range, the hardness of the convex part in the surface of the non-adhesive layer, particularly at high temperatures, When the dicing or the like is performed by adhering and fixing the adhesive tape film of the present invention to the fixing base by negative pressure, excessive adhesion due to heat generation of the base may occur. Can be effectively suppressed. In addition, the measuring method of the indentation hardness at 80 degreeC by the nanoindenter in the convex part of the surface of a non-adhesion layer is mentioned later.

  When the non-adhesive layer is a mixed layer of silicone and (meth) acrylic polymer, the (meth) acrylic polymer in the non-adhesive layer has a calculated Tg of 10 ° C or higher, preferably 20 ° C or higher, More preferably, it is 30 degreeC or more, More preferably, it is 45 degreeC or more. The upper limit of the calculated Tg of the (meth) acrylic polymer in the non-adhesive layer is not particularly limited, but is preferably 200 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 100 ° C. or lower. When the calculated Tg of the (meth) acrylic polymer in the non-adhesive layer is within the above range, the heat resistance in the fine uneven structure on the surface of the non-adhesive layer is increased, and the pressure-sensitive adhesive film of the present invention is negative pressure. Accordingly, when dicing or the like is performed by adsorbing and fixing to the fixing base, it is possible to effectively suppress the occurrence of over-adhesion due to heat generation of the base.

In the present invention, the “calculated Tg” of a copolymer (such as a (meth) acrylic polymer in the non-adhesive layer) is a formula for calculating Fox with respect to Tg of a structural unit derived from a monomer constituting the copolymer. Is the calculated glass transition temperature obtained by The Fox equation means the glass transition temperature Tg (° C.) of a copolymer as shown below, and the glass transition temperature Tg _i (° C.) of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer. ). In the following Fox equation, Tg (° C.) is the glass transition temperature of the copolymer, W _i is the weight fraction of monomer i, and T g _i (° C.) is the glass transition of the homopolymer of monomer i. Indicates temperature.
1 / (273 + Tg) = Σ (W _i / (273 + Tg _i ))

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

When 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 , and even 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 by the Small formula. The SP value can be calculated by a method described in a known document (for example, Journal of Applied Chemistry, 3, 71, 1953., etc.).

  The non-adhesive layer preferably has a phase separation structure. When the non-adhesive layer has a phase separation structure, a fine uneven structure can be efficiently formed on the surface of the non-adhesive layer. This is probably because, for example, when the non-adhesive layer is a mixed layer of silicone and (meth) acrylic polymer, the mass transfer of silicone and (meth) acrylic polymer during phase separation structure formation It is estimated that unevenness is generated due to the difference. By forming this concavo-convex structure, in the film for the pressure-sensitive adhesive tape of the present invention, it is possible to suppress over-adhesion when performing suction fixation by negative pressure, and it is possible to effectively suppress blocking in a roll form, It is possible to suppress tearing or tearing when rewinding from the shape.

  The non-adhesive layer preferably includes a silicone-rich phase containing more silicone than the (meth) acrylic polymer and a (meth) acrylic polymer-rich phase containing more (meth) acrylic polymer than silicone. More specifically, the non-adhesive layer preferably includes a phase-separated structure in which the silicone-rich phase and the (meth) acrylic polymer-rich phase are independent from each other, and more preferably, the silicone-rich phase is an air interface. It exists on the side (opposite side of the plastic film), and the (meth) acrylic polymer rich phase is present on the plastic film side. By having such a phase separation structure, blocking is effectively suppressed by the silicone-rich phase present on the air interface side, and the non-adhesive layer and the plastic film are represented by the (meth) acrylic polymer-rich phase present on the plastic film side. The familiarity with and the deformation followability become good. Such a phase separation structure can be formed by adjusting the mixing ratio of the silicone 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, a silicone-rich phase containing more silicone than (meth) acrylic polymer and a more (meth) acrylic polymer than silicone (meta) The inclusion of an acrylic polymer rich phase can be observed by any suitable method. As such an observation method, for example, the cross-section of the non-adhesive layer is measured using an electron microscope such as a transmission electron microscope (TEM), a scanning electron microscope (SEM), or a field emission scanning electron microscope (FE-SEM). There is a method of morphological observation. The two-layer separation structure can be read by the density of the morphological observation image. Observation is also made by observing changes in the content of silicon and carbon contained in the composition while changing the probe light depth from the non-adhesive layer air interface side to the inside by infrared absorption spectroscopy using the total reflection method. A method is also mentioned. In addition, a method of observing with an X-ray microanalyzer or X-ray photoelectron spectroscopy is also included. Moreover, you may observe combining these methods suitably.

  When the non-adhesive layer has a phase separation structure of the silicone-rich phase present on the air interface side (opposite side of the plastic film) and the (meth) acrylic polymer-rich phase present on the plastic film side, the non-adhesive layer is When the fixing pedestal generates heat when it is adsorbed and fixed to the fixing pedestal by dicing or the like, the surface structure of the phase separation structure is destroyed by the heat load caused by the heat generation, and particularly, the heated pedestal is in contact with the heated pedestal. It is possible that the surface structure of the phase separation structure in the convex portion is destroyed and the (meth) acrylic polymer rich phase is exposed on the air interface side in the convex portion. However, since the indentation hardness at 80 ° C. by the nanoindenter in the convex portion on the surface of the non-adhesive layer is within the above range, the film for the adhesive tape of the present invention has a convex portion subjected to a thermal load. Hardness is moderately high, and thus heat resistance is high. For this reason, when adhering and fixing the film for adhesive tapes of this invention to a fixing base by negative pressure and performing dicing etc., it can suppress effectively that the excessive adhesion | attachment by the heat_generation | fever etc. of a base occurs.

  When the non-adhesive layer is a mixed layer of silicone and (meth) acrylic polymer, the mixing ratio of silicone and (meth) acrylic polymer in the non-adhesive layer is weight ratio, preferably silicone: (meth) acrylic System polymer = 1: 50-50: 1, more preferably silicone: (meth) acrylic polymer = 1: 30-30: 1, and more preferably silicone: (meth) acrylic polymer = 1 : 10 to 10: 1, particularly preferably silicone: (meth) acrylic polymer = 1: 5 to 5: 1, and most preferably silicone: (meth) acrylic polymer = 1: 3 to 5 : 1. When the content ratio of silicone in the non-adhesive layer is too large, the chemical affinity with the back surface of the plastic film is lowered, and there is a possibility that it is difficult to be familiar with the back surface of the plastic film. In addition, if the silicone content in the non-adhesive layer is too large, when the film for an adhesive tape or an adhesive tape containing the same is used, followability to deformation such as stretching becomes worse, and the non-adhesive layer is crushed and contaminated. May cause this. When the content ratio of the (meth) acrylic polymer in the non-adhesive layer is too large, the non-adhesive layer may act as an acrylic adhesive, and blocking may easily occur.

  Any appropriate silicone can be adopted as the silicone. As such silicones, for example, addition type silicones obtained by curing a alkenyl group-containing polydialkylsiloxane and polydialkylhydrogenpolysiloxane by an addition reaction using a platinum compound as a catalyst to form a peelable film, tin-based Examples include a condensation type silicone obtained by reacting a methylol group-containing polydialkylsiloxane and a polydialkylhydrogenpolysiloxane using a catalyst. Examples of the addition type silicone include “KS-776A” and “KS-839L” manufactured by Shin-Etsu Silicone. Examples of the condensation type silicone include, for example, “KS723A / B” manufactured by Shin-Etsu Silicone. In addition, when manufacturing silicone, you may use other crosslinking agents, a crosslinking accelerator, etc. suitably other than a platinum-type catalyst and a tin-type catalyst. The properties of silicone are classified into a type dissolved in an organic solvent such as toluene, an emulsion type obtained by emulsifying these, and a solventless type consisting only of silicone. In addition to addition-type silicone and condensation-type silicone, silicone / acrylic graft polymer, silicone / acrylic block polymer, and the like can be used. Examples of the silicone / acrylic graft polymer include Cymac GS-30, GS101, US-270, US-350, US-380 (above, manufactured by Toagosei Co., Ltd.). Examples of the silicone / acrylic block polymer include Modiper FS700, FS710, FS720, FS730, and FS770 (manufactured by NOF Corporation).

  Any appropriate (meth) acrylic polymer can be adopted as the (meth) acrylic polymer. In the present invention, “(meth) acryl” means “acryl and / or methacryl”.

  The (meth) acrylic polymer is a polymer composed of monomer components 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, and 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 only one type or two or more types.

  As a (meth) acrylic-type monomer, Preferably, (meth) acrylic acid ester and (meth) acrylic acid are mentioned.

  Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl esters having 1 to 30 carbon atoms (including cycloalkyl groups), hydroxyl group-containing (meth) acrylic acid esters, and the like. Only one (meth) acrylic acid ester may be used, or two or more may be used.

  Examples of the alkyl (meth) acrylate alkyl ester having 1 to 30 carbon atoms (including a cycloalkyl group) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic Amyl acid, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) Nonyl acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, ( T) Isodecyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, (meta And (meth) acrylic acid alkyl esters having 1 to 30 carbon atoms (including cycloalkyl groups) such as nonadecyl acrylate, eicosyl (meth) acrylate, and lauryl (meth) acrylate. Among these (meth) acrylic acid esters, a (meth) acrylic acid alkyl ester of an alkyl group having 2 to 20 carbon atoms (including a cycloalkyl group) is preferable, and 4 to 18 carbon atoms are more preferable. (Meth) acrylic acid alkyl ester of an alkyl group (including a cycloalkyl group).

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

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

  Examples of the hydroxyl group-containing monomer include allyl alcohol. Only one type of hydroxyl group-containing monomer may be used, or two or more types may be used.

  Examples of the carboxyl group-containing monomer include carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, and the like. Only one type of carboxyl group-containing monomer may be used, or two or more types may be used.

  When the non-adhesive layer contains a (meth) acrylic polymer, the (meth) acrylic polymer in the non-adhesive layer is preferably such that the content ratio of the hydroxyl group-containing (meth) acrylic ester in the monomer component constituting it is The total amount of monomer components other than the hydroxyl group-containing (meth) acrylic acid ester is preferably 2% by weight to 30% by weight, more preferably 3% by weight to 25% by weight, and particularly preferably 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) acrylic acid ester in the monomer component constituting the (meth) acrylic polymer in the non-adhesive layer is ) If the total amount of monomer components other than the acrylate ester is within the above range, a fine uneven structure is more efficiently formed on the surface of the non-adhesive layer. By forming this uneven structure, the adhesive of the present invention is formed. In the film for tape, it is possible to further suppress the occurrence of over-adhesion when performing adsorption fixation with negative pressure, and it is possible to more effectively suppress blocking in the roll form, and tear when rewinding from the roll form. Can be further suppressed.

  When the non-adhesive layer contains a (meth) acrylic polymer, the (meth) acrylic polymer in the non-adhesive layer is preferably in a monomer component other than the hydroxyl group-containing (meth) acrylic acid ester in the monomer component constituting it. (Meth) acrylic acid and / or (meth) acrylic acid ester may be included. In this case, the content ratio of (meth) acrylic acid and (meth) acrylic acid ester is (meth) acrylic acid: (meth) acrylic acid ester by weight ratio, preferably 0: 100 to 20:80. More preferably, it is 0: 100-10: 90, More preferably, it is 0: 100-5: 95.

  If the content ratio of (meth) acrylic acid and (meth) acrylic acid ester is within the above range, a fine uneven structure is more efficiently formed on the surface of the non-adhesive layer. In the film for pressure-sensitive adhesive tapes of the invention, it is possible to further suppress the occurrence of over-adhesion when performing adsorbing and fixing by negative pressure, and it is possible to more effectively suppress blocking in the roll-like form, and to rewind from the roll-like form. It is possible to further suppress tearing or tearing.

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

  The non-adhesive layer may contain any appropriate additive as long as the effects of the present invention are not impaired. Examples of such additives include catalysts, ultraviolet absorbers, fillers, anti-aging agents, tackifiers, pigments, dyes, and silane coupling agents.

  The non-adhesive layer has a non-adhesive test peel force of 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. When the non-adhesive test peeling force of the non-adhesive layer is within the above range, it is possible to further suppress the occurrence of over-adhesion when performing adsorption fixation by negative pressure. In the present invention, the non-adhesive test peel force of the non-adhesive layer is measured based on the method described below.

  The thickness of the non-adhesive layer is preferably 0.01 μm to 10 μm, more preferably 0.1 μm to 5 μm, and still more preferably 0.1 μm to 2 μm. When the thickness of the non-adhesive layer is less than 0.01 μm, blocking tends to occur. When the thickness of the non-adhesive layer is larger than 10 μm, the followability to deformation such as stretching may be deteriorated. If the thickness of the non-adhesive layer is less than 0.01 μm, the effects of the present invention may be difficult to be exhibited or the manufacture may be difficult.

  Examples of the method for forming the non-adhesive layer on one side of the plastic film include a method of forming the non-adhesive layer by applying the material of the non-adhesive layer on one side of the plastic film and drying. Examples of the coating method include a method using a bar coater, a gravure coater, a spin coater, a roll coater, a knife coater, an applicator and the like.

≪2. Adhesive tape >>
The pressure-sensitive adhesive tape of the present invention includes a pressure-sensitive adhesive layer on the surface of the plastic film of the present invention opposite to the non-stick layer of the plastic film.

  The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is preferably 1.0 μm to 30 μm, more preferably 1.0 μm to 20 μm, and further preferably 3.0 μm to 15 μm. When the thickness of the pressure-sensitive adhesive layer is less than 1.0 μm, there is a possibility that sufficient adhesive force cannot be expressed. When the thickness of the pressure-sensitive adhesive layer is larger than 30 μm, the adhesive force becomes too large depending on the use, and the adherend may be crushed during peeling or the like.

  As the material for the pressure-sensitive adhesive layer, any appropriate pressure-sensitive adhesive can be adopted as long as the effects of the present invention are not impaired.

  Examples of the material for the pressure-sensitive adhesive layer include (meth) acrylic polymer; natural rubber; special natural rubber grafted with monomers such as methyl methacrylate; SBS, SBR, SEPS, SIS, SEBS, polybutene, polyisobutene, polyisobutylene, And synthetic rubbers such as butyl rubber. Among these, at least one (meth) acrylic polymer is preferable from the viewpoint that there is little adhesive residue on the adherend after peeling, high cohesiveness, and excellent transparency.

  When the pressure-sensitive adhesive layer contains a (meth) acrylic polymer, the content ratio of the (meth) acrylic polymer in the pressure-sensitive adhesive layer can be appropriately set according to the purpose.

  The said (meth) acrylic-type polymer is resin comprised from the monomer component which contains a (meth) acrylic-type 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, and still more preferably 90% by weight to It is 100% by weight, particularly preferably 95% by weight to 100% by weight. The monomer in the monomer component may be only one type or two or more types.

  As a (meth) acrylic-type monomer, Preferably, (meth) acrylic acid ester and (meth) acrylic acid are mentioned.

  Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl esters having 1 to 30 carbon atoms (including cycloalkyl groups), hydroxyl group-containing (meth) acrylic acid esters, and the like. Only one (meth) acrylic acid ester may be used, or two or more may be used.

  Examples of the alkyl (meth) acrylate alkyl ester having 1 to 30 carbon atoms (including a cycloalkyl group) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic Amyl acid, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) Nonyl acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, ( T) Isodecyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, (meta And (meth) acrylic acid alkyl esters having 1 to 30 carbon atoms (including cycloalkyl groups) such as nonadecyl acrylate, eicosyl (meth) acrylate, and lauryl (meth) acrylate. Among these (meth) acrylic acid esters, a (meth) acrylic acid alkyl ester of an alkyl group having 2 to 20 carbon atoms (including a cycloalkyl group) is preferable, and 4 to 18 carbon atoms are more preferable. (Meth) acrylic acid alkyl ester of an alkyl group (including a cycloalkyl group).

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

  The monomer component constituting the (meth) acrylic polymer preferably contains at least one selected from a hydroxyl group-containing monomer and a carboxyl group-containing monomer in order to sufficiently develop the effect as an adhesive. More preferably, it is a carboxyl group-containing monomer. Moreover, the monomer component which comprises the said (meth) acrylic-type polymer may contain acrylonitrile in order to fully express 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. Only one type of hydroxyl group-containing monomer may be used, or two or more types may be used.

  Examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid, maleic acid, fumaric acid, and itaconic acid. Only one type of carboxyl group-containing monomer may be used, or two or more types may be used.

  When the monomer component constituting the (meth) acrylic polymer includes a hydroxyl group-containing monomer, the content ratio of the hydroxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer is preferably 0.1% by weight to It is 20% by weight, more preferably 0.1% by weight to 10% by weight. When the monomer component constituting the (meth) acrylic polymer includes a carboxyl group-containing monomer, the content ratio of the carboxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer is preferably 0.1 wt. % To 20% by weight, more preferably 0.1% to 10% by weight. Thus, when the monomer component constituting the (meth) acrylic polymer contains at least one selected from a hydroxyl group-containing monomer and a carboxyl group-containing monomer, when a crosslinking agent is used, A cross-linking reaction can be efficiently generated, and the effect as an adhesive can be sufficiently exhibited. Furthermore, the content ratio of the hydroxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer and the content ratio of the carboxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer are within the above range. By adjusting so that it may be settled in the inside, crushing of the adherend during the peeling operation can be effectively prevented. The content ratio of the hydroxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer and the content ratio of the carboxyl group-containing monomer in the monomer component constituting the (meth) acrylic polymer are more than the above range. When the amount is too large, the adhesive force becomes too large, and blocking may occur easily. Further, the adherend may be easily crushed during the peeling operation.

  The pressure-sensitive adhesive layer preferably contains a cross-linking agent. When the pressure-sensitive adhesive layer contains a cross-linking agent, the content of the cross-linking agent in the pressure-sensitive adhesive layer can be appropriately set according to the purpose, but preferably the main resin component (preferably a (meth) acrylic polymer). On the other hand, it is 0.1 to 20% by weight. By keeping the content of the crosslinking agent in the pressure-sensitive adhesive layer within the above range, an appropriate crosslinking reaction can be caused, and the adherend can be effectively prevented from being broken during the peeling operation.

  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, a metal chelate crosslinking agent, a metal salt crosslinking agent, and a carbodiimide crosslinking. Agents, oxazoline crosslinking agents, aziridine crosslinking agents, amine crosslinking agents and the like. Among these crosslinking agents, melamine-based crosslinking agents, epoxy-based crosslinking agents, and isocyanate-based crosslinking agents are preferable because the effects of the present invention can be sufficiently expressed. Moreover, a crosslinking agent can be suitably selected as needed and may be only 1 type, and 2 or more types of mixed systems may be sufficient as it.

  The pressure-sensitive adhesive layer may contain a plasticizer. When the pressure-sensitive adhesive layer contains a plasticizer, the content of the plasticizer in the pressure-sensitive adhesive layer can be appropriately set according to the purpose, but is preferably 0.1% by weight to 50% by weight. By keeping the content of the plasticizer in the pressure-sensitive adhesive layer within the above range, the effect of the present invention can be expressed more effectively. When the content ratio of the plasticizer in the pressure-sensitive adhesive layer is larger than 50% by weight, the pressure-sensitive adhesive layer becomes too flexible, and there is a possibility that adhesive residue and adherend contamination are likely to occur.

  Examples of the plasticizer include phthalate ester-based, trimellitic ester-based (Dainippon Ink Co., Ltd., W-700, trimellitic trioctyl, etc.), adipate ester-based (manufactured by J-Plus, D620, dioctyl adipate, diisononyl adipate, etc.), phosphate esters (such as tricresyl phosphate), adipic acid esters, citrate esters (such as acetyl citrate tributyl), sebacic acid esters, aceleic acid esters, maleic acid esters Benzoic acid ester, polyether polyester, epoxy polyester (epoxidized soybean oil, epoxidized linseed oil, etc.), polyester (low molecular polyester comprising carboxylic acid and glycol, etc.) and the like. In the present invention, it is preferable to use an ester plasticizer. Only one type of plasticizer may be used, or two or more types may be used.

  The pressure-sensitive adhesive layer may contain any appropriate catalyst in order to promote a crosslinking reaction or the like. When the pressure-sensitive adhesive layer contains a catalyst, the content ratio of the catalyst in the pressure-sensitive adhesive layer can be appropriately set according to the purpose, but is preferably 0.01% by weight to 10% by weight. By keeping the content ratio of the catalyst in the pressure-sensitive adhesive layer within the above range, the effect of the present invention can be expressed more effectively.

  Examples of such catalysts include tetraisopropyl titanate, tetra-n-butyl titanate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, and dibutyltindi Organometallic compounds such as acetate, dibutyltin dioctate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin maleate; butylamine, dibutylamine, hexylamine, t-butylamine, ethylenediamine, isophoronediamine, imidazole, lithium hydroxide, potassium hydroxide, Basic compounds such as sodium methylate; p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, phosphoric acid of β-hydroxyethyl acrylate Ester, monoalkyl phosphite, acidic compounds such as dialkyl phosphite; and the like. Only one type of catalyst may be used, or two or more types of catalysts may be used.

The pressure-sensitive adhesive layer preferably has an SP value of 9.0 (cal / cm ³ ) ^{0.5 to} 12.0 (cal / cm ³ ) ^{0.5 in} order to further manifest the effects of the present invention. And 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 by the Small formula. The SP value can be calculated by a method described in a known document (for example, Journal of Applied Chemistry, 3, 71, 1953., etc.).

  The pressure-sensitive adhesive layer may contain any appropriate additive as long as the effects of the present invention are not impaired. Examples of such additives include ultraviolet absorbers, fillers, anti-aging agents, tackifiers, pigments, dyes, and silane coupling agents.

  The pressure-sensitive adhesive tape of the present invention may have a release liner on the surface of the pressure-sensitive adhesive layer.

  Any appropriate separator can be adopted as the release liner. As such a release liner, for example, a base material having a release layer such as a plastic film or paper surface-treated with a release agent such as silicone-based, long-chain alkyl-based, fluorine-based, molybdenum sulfide; polytetrafluoroethylene, Low-adhesive substrate made of a fluoropolymer such as polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, chlorofluoroethylene / vinylidene fluoride copolymer; And a low-adhesive substrate made of a nonpolar polymer such as a resin (for example, polyethylene, polypropylene, etc.).

  The pressure-sensitive adhesive tape of the present invention can be used for any appropriate application. Since the pressure-sensitive adhesive tape of the present invention has the film for pressure-sensitive adhesive tapes of the present invention, as described above, overadhesion due to heat generation of the pedestal occurs when dicing or the like is performed by adsorbing and fixing to the fixing pedestal by negative pressure. Can be effectively suppressed, and blocking in the roll-shaped form is effectively suppressed, and when unrolling from the roll-shaped form, it does not tear or tear, and the non-adhesive layer and the plastic film Familiarity is good and followability to deformation such as stretching is good. Therefore, it can be suitably used for semiconductor processing using a semiconductor wafer made of a fragile material and having a fine and fine circuit pattern as an adherend. When the adhesive tape of the present invention is used for semiconductor processing, it is possible to effectively suppress the occurrence of over-adhesion due to heat generation or the like of the pedestal when performing dicing or the like by adsorbing and fixing to the pedestal for fixing by negative pressure, and therefore The semiconductor manufacturing process including dicing can proceed smoothly. In addition, when the adhesive tape of the present invention is used for semiconductor processing, film deformation and stress strain accumulation caused by blocking in the past do not occur. In addition, since the stress strain is not released spontaneously after being bonded to the semiconductor wafer, the semiconductor wafer can be effectively prevented from being crushed. In particular, since the wafer used for the LED is made of a very fragile material such as gallium nitride, gallium arsenide, or silicon carbide, the pressure-sensitive adhesive tape of the present invention is very suitable for LED dicing.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all. Parts mean parts by weight. The amount of the reagent supplied in the solution is represented by the amount of solid content remaining after the solution is volatilized (solid content conversion amount).

<Maximum elongation>
The maximum elongation was measured by an Instron type tensile tester (manufactured by Shimadzu Corporation, Autograph) according to JIS-K-7127. Specifically, after a sample having a width of 20 mm and a length of 100 mm was set at a distance between chucks of 50 mm, the sample was pulled at a pulling speed of 0.3 m / min, and the value at the time of breaking was measured.

<Elastic modulus>
The elastic modulus was measured according to JIS-K-7127.

<Observation of non-adhesive layer>
(SEM observation)
After processing so that the cross section of the non-adhesive layer could be observed, the morphology was observed with a transmission electron microscope (SEM).
(Observation by infrared spectroscopic measurement by total reflection method (ATR-IR))
Two types of total reflection measurement prisms (ZnSe45 °, Ge45 °) are used to select the total reflection measurement method and change the analysis depth of the probe light using an infrared spectrophotometer (Perkinermer, Spectrum One). Then, ATR-IR measurement of the non-adhesive layer was performed.

<Arithmetic mean surface roughness Ra>
Using a confocal laser microscope “LEXT3000” manufactured by OLYMPUS, measurement was performed in 3D mode with an objective lens of 20 times. The observation range in the 3D mode was determined by setting the positions where the CF image (confocal image) becomes dark when the lens is moved up and down as the observation range Top and Bottom, respectively.
As the image capturing method in the 3D mode, image capturing was performed at a pitch of 0.2 μm by the Step method.
Arithmetic mean surface roughness Ra was measured by measuring Ra at an arbitrary place by analysis mode roughness analysis. In addition, the value was calculated | required by the average value of n = 5.

<Measurement of indentation hardness at 80 ° C. with a nanoindenter on the convex portion of the non-adhesive layer surface>
The indentation layer was subjected to an indentation test under the following conditions, and the indentation hardness was determined from the results. In addition, in the adhesive tape which is not provided with a non-adhesion layer like the comparative example 1, it measured about the outermost layer surface on the opposite side to an adhesive layer.
(Measurement equipment and measurement conditions)
Apparatus: Tribo Indenter (manufactured by Hystron Inc.)
Working indenter: Berkovich (triangular pyramid type)
Measurement method: Single indentation measurement Measurement temperature: 80 ° C
Indentation depth setting: about 100nm
Indentation speed: about 10nm / sec
Measurement atmosphere: In air (measurement method)
Using the above apparatus, the temperature was raised from room temperature to 80 ° C. and held for 1 hour, and then a shape image was measured using a Barkovic diamond indenter. Next, the portion observed as a convex portion was pushed vertically from the surface to a depth of 100 nm with the above-described indenter. Using the analysis software “Triboscan Ver. 9.2.12.0”, the indentation hardness of the surface was determined from the displacement and load obtained when the indenter was indented and the indentation area calculated theoretically. The elastic modulus was obtained from the displacement and load obtained after removing the indenter and the indentation area calculated theoretically.

<Adsorption test at high temperature>
20mm (vertical) x 50mm (horizontal) slide glass with adhesive tape film or adhesive tape on the back (in the case of adhesive tape film, non-adhesive layer side surface, in the case of adhesive tape) It was stuck so that the surface on the opposite side of the pressure-sensitive adhesive layer) would be the front. Next, under the 80 ° C. environment, the tape-attached slide glass and the slide glass (blue plate edge polished product, size: 65 mm × 165 mm × 1.35 mmt) to be adhered are placed on the back surface of the tape-attached slide glass. The side and the non-tin surface side of the slide glass were brought into contact with each other and allowed to stand for 15 minutes. Then, the slide glass was reciprocated once with a 2 kg roller, and the slide glass and the back surface of the tape-attached slide glass were bonded together. Left for a minute. After being left to cool to room temperature, it was peeled at 0 ° with an Instron type tensile tester (manufactured by Shimadzu Corporation, Autograph) at a tensile speed of 0.3 m / min. The peel force (maximum value) at that time was measured and evaluated according to the following criteria.
○: Peeling force less than 5.0N.
(Triangle | delta): Peeling force 5.0N or more and less than 15.0N.
X: Peeling force 15.0N or more.

<Non-stick test peel strength>
Referring to JIS-Z-0237, the film for adhesive tape or the adhesive tape containing the adherend and the non-adhesive layer is retained for 1 hour or more under storage at 23 ° C., and then the non-adhesive surface is applied to SUS430BA with a linear pressure of 8 kg / m, crimping at a crimping speed of 0.3 m / min, and the peeling force after 30 minutes was measured at a tensile speed of 0.3 m / min and 180 ° peel.
A: Less than 0.5 N / 20 mm.
○: 0.5 N / 20 mm or more and less than 1.0 N / 20 mm.
X: 1.0 N / 20 mm or more.

<Blocking test>
The pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive tape is pressure-bonded to the outermost surface (back layer) opposite to the pressure-sensitive adhesive layer of the same pressure-sensitive adhesive tape at a linear pressure of 8 kg / m and a pressure bonding speed of 0.3 m / min. Stored for 48 hr. After storage, peeling was performed by a 180 ° peel test at a tensile rate of 0.3 m / min (based on JIS-Z-0237), and blocking (peeling force) between the pressure-sensitive adhesive layer surface and the back layer was measured.
The evaluation was made as a comprehensive evaluation by measuring the peeling force, and confirming that the back layer dropped off and the pressure-sensitive adhesive layer was destroyed (cohesive failure, glue residue due to throwing failure).
Evaluation was according to the following criteria.
○: Peeling force less than 3.0 N / 20 mm, no visual drop-out, no destruction of the adhesive layer.
X: Peeling force is 3.0 N / 20 mm or more, or there is a dropout by visual observation and destruction of the pressure-sensitive adhesive layer.

<Throwing property confirmation test>
(Throwing property confirmation test A)
The film for adhesive tape or the adhesive tape is stretched to 200% at a tensile speed of 0.3 m / min to 3 m / min, and the outermost side opposite to the adhesive layer of the film for adhesive tape or the adhesive tape at the time of stretching and after stretching. The detachability of the outer surface (back layer) was visually evaluated.
(Throwing property confirmation test B)
After stretching in the same manner as the anchoring property confirmation test A, a NO. 31B manufactured by Nitto Denko Corporation was used as the back treatment layer, and the crimping speed was 0.3 m / min with a 2 kg roller (25 mm width). And then stored at 23 ° C. × 50% RH for 1 minute, peeled 90 ° at a peeling speed of 0.3 m / min to 3 m / min, and visually evaluated the back-off property.
(Evaluation)
The above evaluation was comprehensively judged and the anchoring performance was evaluated according to the following criteria.
A: There was no dropout of the back surface that could be visually confirmed in both the anchoring property confirmation test A and the anchoring property confirmation test B.
○: The back-side dropout that can be visually confirmed was not confirmed in the anchoring property confirmation test A, but was slightly confirmed in the anchoring property confirmation test B (confirmed in the form of dots).
X: Dropping of the back surface was confirmed in the anchoring property confirmation test A, or separation of the back surface was confirmed in the anchoring property confirmation test B.

[Production Example 1]: Production of plastic film Soft poly (polyethylene chloride) containing 27 parts by weight of DOP plasticizer (bis (2-ethylhexyl phthalate), manufactured by J-Plass) with respect to 100 parts by weight of polyvinyl chloride having a polymerization degree P = 1050 A vinyl chloride film was produced by the calendar method. This soft polyvinyl chloride film had a thickness of 70 μm, an elastic modulus (MD) measured according to JIS-K-7127 of 250 MPa, and a maximum elongation (MD) measured according to JIS-K-7127 of 400%. . Moreover, the surface roughness (arithmetic average surface roughness Ra) immediately after manufacture was 0.1 μm.

[Example 1]
60 parts by weight of silicone resin (KS-723A, manufactured by Shin-Etsu Chemical Co., Ltd.), 40 parts by weight of silicone resin (KS-723B, manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic copolymer (methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxy 50 parts by weight of ethyl acrylate (HEA) = 90/10/10) and 10 parts by weight of a tin-based catalyst (Cat-PS3, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed in a solution state to obtain a mixed solution (1). The mixing ratio of the silicone and the (meth) acrylic polymer in the mixed solution (1) was silicone: (meth) acrylic polymer = 2: 1 by weight. The calculated Tg of the acrylic copolymer was 67.8 ° C., and the SP value was 10.7 (cal / cm ³ ) ^0.5 .
The mixed solution (1) is applied to one side of the 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 average surface roughness Ra = 0.5 μm. I let you.
In this way, a film for adhesive tape (1) was obtained.
Various evaluation results are shown in Table 1.
Moreover, when the non-adhesive layer is observed by SEM, as shown in FIGS. 1, 2, and 3, it can be confirmed that the composition is different between the air interface side and the plastic film side due to the density of the morphology observation image, Silicone rich phase containing more silicone than (meth) acrylic polymer and (meth) acrylic polymer rich phase containing more than (meth) acrylic polymer than silicone, silicone rich phase and (meth) The acrylic polymer-rich phase has a phase separation structure independent of each other, the silicone-rich phase exists on the air interface side (opposite side of the plastic film), and the (meth) acrylic polymer-rich phase is on the plastic film side It was observed that
Moreover, non-adhesive layer on was subjected to infrared spectroscopy by total reflection method (ATR-IR), (meth) from Si-CH ₃ to a peak around 1725 cm ^-1 derived from carbonyl group of the acrylic polymer phase As a result of measuring the absorbance ratio of the peak in the vicinity of 800 cm ^−1, it was found that the peak in the vicinity of 800 cm ⁻¹ becomes larger when a Ge45 ° prism is used than in ZnSe45 °. Therefore, it was found that the silicon content was higher on the air interface side than on the base material side.
It was also confirmed by FT-IR that the silicone-rich phase was present on the air interface side (opposite side of the plastic film) in the non-adhesive layer. For measurement by FT-IR, “Spectrum One” manufactured by Perkinermer was used, and the air interface side was measured by the ATR method using two types of prisms (ZnSe 45 °, Ge45 °) having different analysis depth directions. The resulting chart was confirmed, the non-stick layer (meth) to the peak of ^{1720cm -1 -1730cm} -1 attributable to C = O derived from an acrylic polymer, Si-CH ₃ peak around 800 cm ^-1 from It was confirmed that the absorbance ratio was increased when a shallow Ge45 ° prism in the analysis depth direction was used. This proved that the concentration of silicone was higher on the air interface side.
Considering these observation results and the principle of minimizing the surface free energy, it was found that a two-layer structure having a silicone-rich phase on the air interface side was formed in the non-adhesive layer.

[Example 2]
In Example 1, the mixed solution (1) was applied to one surface of the soft polyvinyl chloride film produced in Production Example 1, and the same procedure as in Example 1 was carried out. The thickness was 0.7 μm and the arithmetic average surface roughness was obtained. A non-adhesive layer with Ra = 0.1 μm was formed.
In this way, a film for adhesive tape (2) was obtained.
Various evaluation results are shown in Table 1.

Example 3
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-based crosslinking agent (butanol-modified melamine formaldehyde resin) , "Super Becamine J-820-60N", manufactured by Nippon Polyurethane), 10 parts by weight of DOP plasticizer (bis (2-ethylhexyl phthalate), manufactured by J-Plass), 60 parts by weight of a pressure-sensitive adhesive toluene solution was prepared. .
After applying this adhesive solution to the surface opposite to the non-adhesive layer of the film for adhesive tape (1) obtained in Example 1, it was dried at 130 ° C. for 90 seconds to form an adhesive layer having a thickness of 10 μm. It formed in the surface on the opposite side to the non-adhesion layer of a soft polyvinyl chloride film. The SP value of the formed pressure-sensitive adhesive layer was 10.5.
In this way, an adhesive tape (3) was obtained.
Various evaluation results are shown in Table 1.

Example 4
Implemented except that 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / ethyl acrylate (EA) / hydroxyethyl acrylate (HEA) = 90/10/10 was used as the acrylic copolymer for forming the non-adhesive layer It carried out like Example 1 and obtained the film (4) for adhesive tapes. An adhesive tape (4) was obtained in the same manner as in Example 3 except that this adhesive tape film (4) was used in place of the adhesive tape film (1).
The calculated Tg of the acrylic copolymer was 74.3 ° C., and the SP value was 10.3 (cal / cm ³ ) ^0.5 .
The non-adhesive layer had a thickness of 1.0 μm and an arithmetic average surface roughness Ra = 0.5 μm.
Various evaluation results are shown in Table 1.

Example 5
Implemented except that 50 parts by weight of acrylic copolymer of methyl methacrylate (MMA) / cyclohexyl acrylate (CHA) / hydroxyethyl acrylate (HEA) = 90/10/10 was used as the acrylic copolymer for forming the non-adhesive layer It carried out like Example 1 and obtained the film (5) for adhesive tapes. Except having used this film for adhesive tapes (5) instead of the film for adhesive tapes (1), it carried out similarly to Example 3 and obtained the adhesive tape (5).
The calculated Tg of the acrylic copolymer was 80.0 ° C., and the SP value was 10.4 (cal / cm ³ ) ^0.5 .
The non-adhesive layer had a thickness of 1.0 μm and an arithmetic average surface roughness Ra = 0.5 μm.
Various evaluation results are shown in Table 1.

Example 6
Implemented except that 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 95/5/15 was used as the acrylic copolymer for forming the non-adhesive layer. It carried out like Example 1 and obtained the film (6) for adhesive tapes. Except having used this film for adhesive tapes (6) instead of the film for adhesive tapes (1), it carried out similarly to Example 3, and obtained the adhesive tape (6).
The calculated Tg of the acrylic copolymer was 73.0 ° C., and the SP value was 10.5 (cal / cm ³ ) ^0.5 .
The non-adhesive layer had a thickness of 1.0 μm and an arithmetic average surface roughness Ra = 1.0 μm.
Various evaluation results are shown in Table 1.

Example 7
Implemented except that 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 80/20/10 was used as the acrylic copolymer for forming the non-adhesive layer It carried out like Example 1 and obtained the film (7) for adhesive tapes. Except having used this film for adhesive tapes (7) instead of the film for adhesive tapes (1), it carried out similarly to Example 3 and obtained the adhesive tape (7).
The calculated Tg of the acrylic copolymer was 48.5 ° C., and the SP value was 10.1 (cal / cm ³ ) ^0.5 .
The non-adhesive layer had a thickness of 1.0 μm and an arithmetic average surface roughness Ra = 0.2 μm.
Various evaluation results are shown in Table 1.

Example 8
Implemented except that 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 99/1/5 was used as the acrylic copolymer for forming the non-adhesive layer It carried out like Example 1 and obtained the film for adhesive tapes (8). Except having used this film for adhesive tapes (8) instead of the film for adhesive tapes (1), it carried out similarly to Example 3 and obtained the adhesive tape (8).
The calculated Tg of the acrylic copolymer was 94.3 ° C., and the SP value was 10.1 (cal / cm ³ ) ^0.5 .
The non-adhesive layer had a thickness of 1.0 μm and an arithmetic average surface roughness Ra = 0.5 μm.
Various evaluation results are shown in Table 1.

Example 9
As a release liner, a 38 μm thick PET liner subjected to Si treatment was attached to the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive tape (5) obtained in Example 5 to obtain a pressure-sensitive adhesive tape (9).
The non-adhesive layer had a thickness of 1.0 μm and an arithmetic average surface roughness Ra = 0.5 μm.
Various evaluation results are shown in Table 1.

Example 10
Implemented except that 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 95/5/10 was used as the acrylic copolymer for forming the non-adhesive layer It carried out similarly to Example 1 and obtained the film (10) for adhesive tapes. Except having used this film for adhesive tapes (10) instead of the film for adhesive tapes (1), it carried out similarly to Example 3 and obtained the adhesive tape (10).
The calculated Tg of the acrylic copolymer was 77.2 ° C., and the SP value was 10.3 (cal / cm ³ ) ^0.5 .
The non-adhesive layer had a thickness of 1.0 μm and an arithmetic average surface roughness Ra = 0.7 μm.
Various evaluation results are shown in Table 1.

Example 11
Implemented except that 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 70/30/10 was used as the acrylic copolymer for forming the non-adhesive layer It carried out like Example 1 and obtained the film (11) for adhesive tapes. Except having used this film for adhesive tapes (11) instead of the film for adhesive tapes (1), it carried out similarly to Example 3 and obtained the adhesive tape (11).
The calculated Tg of the acrylic copolymer was 31.2 ° C., and the SP value was 10.4 (cal / cm ³ ) ^0.5 .
The non-adhesive layer had a thickness of 1.0 μm and an arithmetic average surface roughness Ra = 0.3 μm.
Various evaluation results are shown in Table 1.

[Comparative Example 1]
In Example 3, except having not formed the non-adhesion layer, it carried out similarly to Example 3 and obtained the adhesive tape (C1).
Various evaluation results are shown in Table 1.

[Comparative Example 2]
Implemented except that 50 parts by weight of an acrylic copolymer of methyl methacrylate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 55/45/10 was used as the acrylic copolymer for forming the non-adhesive layer In the same manner as in Example 1, a film for adhesive tape (C2) was obtained. An adhesive tape (C2) was obtained in the same manner as in Example 3 except that this adhesive tape film (C2) was used instead of the adhesive tape film (1).
The calculated Tg of the acrylic copolymer was 8.6 ° C., and the SP value was 10.4 (cal / cm ³ ) ^0.5 .
The non-adhesive layer had a thickness of 1.0 μm and an arithmetic average surface roughness Ra = 0.08 μm.
Various evaluation results are shown in Table 1.

  Since the pressure-sensitive adhesive tape of the present invention has the film for pressure-sensitive adhesive tapes of the present invention, as described above, overadhesion due to heat generation of the pedestal occurs when dicing or the like is performed by adsorbing and fixing to the fixing pedestal by negative pressure. Can be effectively suppressed, and blocking in the roll-shaped form is effectively suppressed, and when unrolling from the roll-shaped form, it does not tear or tear, and the non-adhesive layer and the plastic film Familiarity is good and followability to deformation such as stretching is good. Therefore, it can be suitably used for semiconductor processing using a semiconductor wafer made of a fragile material and having a fine and fine circuit pattern as an adherend. When the pressure-sensitive adhesive tape of the present invention is used for semiconductor processing, it is possible to suppress the occurrence of over-adhesion when performing suction fixation by negative pressure, and therefore, the semiconductor manufacturing process including dicing can be smoothly advanced. In addition, when the adhesive tape of the present invention is used for semiconductor processing, film deformation and stress strain accumulation caused by blocking in the past do not occur. In addition, since the stress strain is not released spontaneously after being bonded to the semiconductor wafer, the semiconductor wafer can be effectively prevented from being crushed. In particular, since the wafer used for the LED is made of a very fragile material such as gallium nitride, gallium arsenide, or silicon carbide, the pressure-sensitive adhesive tape of the present invention is very suitable for LED dicing.

Claims (17)

A film for an adhesive tape comprising a non-adhesive layer on one side of a plastic film,
The non-adhesive layer is a mixed layer of silicone and (meth) acrylic polymer,
The surface of the non-adhesive layer has an uneven structure,
The indentation hardness at 80 ° C. by the nanoindenter in the convex part of the surface of the non-adhesive layer is 6.0 MPa or more.
Film for adhesive tape.   The film for adhesive tapes of Claim 1 whose arithmetic mean surface roughness Ra of the said non-adhesion layer is 0.1 micrometer or more. The film for adhesive tapes of Claim 1 or 2 whose calculation Tg of the said (meth) acrylic-type polymer is 10 degreeC or more. The (meth) SP value of the acrylic polymer is ^{9.0 (cal / cm 3) 0.5} ~12.0 (cal / cm 3) 0.5, according to any one of claims 1 to 3 Film for adhesive tape. The mixing ratio of silicone and (meth) acrylic polymer of the non-adhesive layer is, in weight ratio, the silicone :( meth) acrylic polymer = 1: 50 to 50: 1, any of claims 1 to 4 The film for adhesive tapes of crab. The film for adhesive tapes in any one of Claim 1 to 5 in which the said non-adhesion layer has a phase-separation structure. The film for adhesive tapes in any one of Claim 1-6 whose non-adhesion test peeling force of the said non-adhesion layer is less than 1.0 N / 20mm. The thickness of the non-adhesive layer is 0.01 to 10 m, the pressure-sensitive adhesive tape film according to any one of claims 1 to 7. The film for adhesive tapes in any one of Claim 1-8 whose maximum elongation measured according to JIS-K-7127 of the said plastic film is 100% or more. The thickness of the plastic film is 20Myuemu～200myuemu, adhesive tape film according to any one of claims 1 to 9. It said plastic film comprises a polyvinyl chloride adhesive tape film according to any one of claims 1 to 10. The opposite surface and the non-adhesive layer of the plastic film in the pressure-sensitive adhesive tape film according to any one of claims 1 to 11 provided with a pressure-sensitive adhesive layer, pressure-sensitive adhesive tape. The pressure-sensitive adhesive tape according to claim 12 , wherein the pressure-sensitive adhesive layer contains at least one (meth) acrylic polymer. The pressure-sensitive adhesive tape according to claim 12 or 13 , wherein the pressure-sensitive adhesive layer has an SP value of 9.0 (cal / cm ³ ) ^{0.5 to} 12.0 (cal / cm ³ ) ^0.5 . Comprising a release liner on the surface of the pressure-sensitive adhesive layer, pressure-sensitive adhesive tape according to any one of claims 12 to 14. The pressure-sensitive adhesive tape according to any one of claims 12 to 15 , which is used for semiconductor processing. Used in LED dicing applications, the pressure-sensitive adhesive tape according to any one of claims 12 to 16.