TW201437315A - Adhesive tape - Google Patents

Abstract

This invention provides an adhesive tape useful as a cutting tape, having the less standard deviation in the thickness non-uniformity and having the uniform stress from expansion or pin propping on the tape surface. The adhesive tape of this invention has an adhesive layer on at least one side of the substrate, and the standard deviation in the thickness non-uniformity of the adhesive tape is less than 2.0 micron.

Description

Adhesive tape

The present invention relates to an adhesive tape.

For semiconductor dicing, by cutting a semiconductor wafer on a dicing tape (adhesive tape), the semiconductor wafer is diced (wafered) into a wafer, and the wafer is picked up from the dicing tape, and continues in the subsequent steps. Use (for example, refer to Patent Document 1). As a method of picking up a wafer from a dicing tape, the surface of the dicing tape on which the wafer is not mounted is pushed up by a rod called a pin or a needle (so-called "pin-up"), and then the quilt is used. An adsorption jig called a nozzle picks up and picks up the wafer from the dicing tape.

Here, the interval between the wafers immediately after the cutting is a very small interval of at most several hundred μm, and therefore, if the wafer is picked up from the dicing tape just after the cutting, other wafers are encountered ( In particular, adjacent wafers, etc., and the wafer is broken.

Therefore, in the cutting of the semiconductor, it is generally performed to expand (stretch) the dicing tape to expand the interval between the wafers and then self-cut in a state where the wafer is mounted on the dicing tape before the wafer is picked up from the dicing tape after cutting. Take the pick up chip.

However, even with this method, inconvenience sometimes occurs during pickup. Therefore, further improvements in semiconductor dicing are required.

As a representative problem of such inconvenience, it is exemplified that the adsorption separation cannot be accurately performed when the wafer is adsorbed and separated from the dicing tape by the nozzle.

As a cause of the above inconvenience, it is considered that the adhesion between the dicing tape and the wafer is too strong, but the above inconvenience is not eliminated even if the adhesion of the dicing tape to the wafer is weakened.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-019607

The inventors of the present invention conducted various studies on the reasons why the adsorption separation of the wafer from the dicing tape by the nozzle can not be accurately performed. Further, focusing on the positional deviation of the adsorption surface of the nozzle from the wafer, the research was repeated. As a result, it is considered that the stress of the dicing tape which is extended or pinned is more important in the plane of the belt. Further, it is considered that in order to make the stress of the dicing tape for the expansion or the pin evenly uniform in the belt surface, it is important that the thickness of the dicing tape is not uneven in the plane, and the standard deviation of the thickness unevenness of the dicing tape is considered. The level of σ is strictly adjusted to a specific level to complete the present invention.

That is, the object of the present invention is to provide an adhesive tape which can be used as a dicing tape, and the standard deviation σ of the thickness unevenness of the adhesive tape is small, and the stress against the expansion or the pin top is uniform in the tape surface. .

The adhesive tape of the present invention is provided with an adhesive layer on at least one side of the substrate, and

The standard deviation σ of the thickness unevenness of the adhesive tape is 2.0 μm or less.

In a preferred embodiment, the adhesive tape has an average thickness of 20 μm to 120 μm.

In a preferred embodiment, the ratio of the modulus of the adhesive tape in the MD direction of 100% stretching to the modulus of the 100% stretching in the TD direction (100% modulus in the MD direction/100% modulus in the TD direction) ) is 0.5~1.9.

In a preferred embodiment, the standard deviation σ of the thickness unevenness of the substrate is 2.0 μm or less.

In a preferred embodiment, the substrate has an average thickness of from 20 μm to 120 μm.

In a preferred embodiment, the substrate has a maximum elongation of 100% or more as measured according to JIS-K-7127 (1999).

In a preferred embodiment, the substrate is a plastic film.

In a preferred embodiment, the plastic film comprises at least one selected from the group consisting of polyvinyl chloride, polyolefin, and ethylene-vinyl acetate copolymer.

In a preferred embodiment, the adhesive layer is provided on one surface of the substrate, and a non-adhesive layer is provided on a surface of the substrate opposite to the adhesive layer.

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

In a preferred embodiment, the mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the non-adhesive layer is 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 thickness of 0.01 μm to 10 μm.

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

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, it is possible to provide an adhesive tape which can be used as a dicing tape, and the standard deviation σ of the thickness unevenness of the adhesive tape is small, and the stress against the expansion or the pin top is uniform in the tape surface.

100‧‧‧ wafer

200‧‧‧ cutting tape

Fig. 1 is a schematic view showing an arrangement state of wafers expanded in the case where the thickness accuracy is good.

Fig. 2 is a schematic view showing an arrangement state of wafers expanded in the case where the thickness accuracy is poor.

Fig. 3 is a SEM photograph showing the state of the surface side of the non-adhesive layer of the adhesive tape of the present invention.

Fig. 4 is a SEM photograph showing the state of the cross-sectional side of the non-adhesive layer of the adhesive tape of the present invention.

Fig. 5 is a SEM photograph showing the state of the cross-sectional side of the non-adhesive layer of the adhesive tape of the present invention.

The adhesive tape of the present invention is provided with an adhesive layer on at least one side of the substrate. The adhesive tape of the present invention may have an adhesive layer on both sides of the substrate, or may have an adhesive layer on one side of the substrate.

The standard deviation σ of the thickness unevenness of the adhesive tape system of the present invention is 2.0 μm or less, preferably 1.9 μm or less, more preferably 1.7 μm or less, further preferably 1.5 μm or less, and particularly preferably 1.2 μm or less. By adjusting the standard deviation σ of the thickness unevenness of the adhesive tape of the present invention to the above range, the stress of the adhesive tape of the present invention for the expansion or the pin can be made uniform in the tape surface. Regarding the adhesive tape of the present invention, since the thickness is uneven and the thickness precision is good, as shown in FIG. 1, when the adhesive tape of the present invention is used as a dicing tape, in the cutting of the semiconductor, after cutting, the self-cut tape Before the wafer is mounted on the dicing tape, when the dicing tape 200 is expanded (stretched) and the interval between the wafers 100 is widened, the wafers which are well aligned without the positional deviation of the wafer 100 can be obtained. On the other hand, if the thickness of the adhesive tape is not uniform, the thickness accuracy is deteriorated. Therefore, when the adhesive tape of the present invention is used as a dicing tape as shown in FIG. 2, in the cutting of the semiconductor, the self-cutting after cutting Before the wafer is mounted on the dicing tape, when the dicing tape 200 is expanded (stretched) to widen the interval between the wafers 100, the positional deviation of the wafer 100 may occur, and, for example, pickup failure may occur. . In particular, the LED chip is small, so the position of the wafer is prone to occur. shift. In addition, the method of measuring the standard deviation σ of the thickness unevenness will be described later.

Further, as a method of measuring the thickness unevenness, any appropriate method such as measuring the thickness of any complex number in the plane of the measurement target and performing statistical processing can be employed. Examples of the method for measuring the thickness include a micrometer, a micro-vernier caliper, a dial gauge, and the like, and a physical contact method; and measuring the transmittance of the measurement target such as α-ray, X-ray, infrared, or electromagnetic wave or A non-contact method of reflectance; a method of cutting a measurement object at any measurement site and observing it with an optical microscope or an electron microscope; or a combination of these may be employed.

The average thickness of the adhesive tape of the present invention is preferably from 20 μm to 120 μm, more preferably from 30 μm to 120 μm, still more preferably from 40 μm to 120 μm. By adjusting the average thickness of the adhesive tape of the present invention to the above range, the stress of the adhesive tape of the present invention for expansion or pinping can be made more uniform within the tape surface. Further, if the average thickness of the adhesive tape of the present invention is too small, the handleability is deteriorated, and in particular, the bonding operation becomes difficult. If the average thickness of the adhesive tape of the present invention is too large, the followability to deformation such as elongation is deteriorated.

The ratio of the modulus at 100% stretching in the MD direction of the adhesive tape of the present invention to the modulus at 100% stretching in the TD direction (100% modulus in the MD direction/100% modulus in the TD direction) is preferably 0.5. ~1.9, more preferably 0.5 to 1.8, further preferably 0.8 to 1.6, and particularly preferably 1.0 to 1.5. By adjusting the above ratio (100% modulus in the MD direction/100% modulus in the TD direction) to the above range, the stress on the expansion or pin of the adhesive tape of the present invention can be more uniform in the belt surface. .

<Substrate>

As a factor causing uneven thickness of the adhesive tape of the present invention, it is considered that the thickness of the substrate is not uniform, the thickness of the adhesive layer is not uniform, and the thickness of the non-adhesive layer which may be provided on the opposite side of the substrate from the adhesive layer is not Equal factors.

Among the above factors, the factor that causes the greatest influence on the thickness unevenness of the adhesive tape is the uneven thickness of the substrate. The reason is that in the components of the adhesive tape, the extension or pin top The stress applied the strongest is the substrate, so if the thickness of the substrate is not uniform, the stress on the expansion or pin of the adhesive tape of the present invention becomes uneven in the surface of the tape. . Further, the adhesive layer or the non-adhesive layer is provided on the surface of the substrate for coating or the like. If the thickness of the substrate is not uniform, the coating accuracy of the adhesive layer or the non-adhesive layer may be improved anyway. The thickness of the adhesive layer or the non-adhesive layer is also uneven due to the influence of the uneven thickness of the substrate.

For the reason described above, the standard deviation σ of the thickness unevenness of the substrate is preferably 2.0 μm or less, more preferably 1.8 μm or less, still more preferably 1.6 μm or less. By adjusting the standard deviation σ of the thickness unevenness of the substrate to the above range, the stress of the adhesive tape of the present invention for expansion or pinning can be made more uniform in the tape surface. The method for measuring the standard deviation σ of the thickness unevenness will be described later.

The average thickness of the substrate is preferably from 20 μm to 120 μm, more preferably from 30 μm to 120 μm, still more preferably from 40 μm to 120 μm. By adjusting the average thickness of the substrate of the present invention to the above range, the stress on the expansion or pin of the adhesive tape of the present invention can be made more uniform in the belt surface. Moreover, when the average thickness of the base material is too small, the handleability is deteriorated, and in particular, it is difficult to perform the bonding operation when the adhesive tape is formed. If the average thickness of the substrate is too large, there is a problem that the followability to deformation such as elongation is deteriorated.

The maximum elongation of the substrate measured according to JIS-K-7127 (1999) is preferably 100% or more, more preferably 200% to 1000%. By using a substrate exhibiting the above-described maximum elongation, the stress of the adhesive tape of the present invention for expansion or pinping can be made more uniform within the tape surface. Further, by using a substrate exhibiting the above maximum elongation, it is possible to impart appropriate elongation to the adhesive tape of the present invention, for example, to improve the followability to the adherend.

As the substrate, any suitable material can be selected as long as the above characteristics are not impaired. As the substrate, a plastic film is preferred.

The plastic film may comprise any suitable resin material. As the resin material as described above, preferred examples thereof include polyvinyl chloride, polyolefin, and ethylene-vinyl acetate copolymerization. Examples of the material, the polyester, the polyimide, the polyamine, and the like include polyvinyl chloride, a polyolefin, and an ethylene-vinyl acetate copolymer. More preferably, polyvinyl chloride is used. Polyvinyl chloride is excellent in stress relaxation property, and therefore it is particularly preferably used for an adhesive tape used in semiconductor processing such as LED cutting.

As the content ratio of the above-mentioned resin material in the plastic film, any appropriate content ratio can be set 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 to 100% by weight.

A plasticizer may also be included in the plastic film. The content ratio of the plasticizer in the plastic film is preferably from 0.5% by weight to 50% by weight, more preferably from 1.0% by weight to 40% by weight, based on the above-mentioned resin material in the plastic film. By including the plasticizer in the above-mentioned content ratio in the plastic film, the stress of the adhesive tape of the present invention for the expansion or the pin can be made more uniform in the belt surface. Moreover, by including the plasticizer in the above-described content ratio in the plastic film, the adhesive tape of the present invention is more excellent in followability to deformation such as stretching.

Examples of the plasticizer include a phthalate type, a trimellitic acid ester type (manufactured by DAINIPPON INK CORPORATION, W-700, trioctyl trimellitate, etc.), and an adipate type ( J-PLUS Co., Ltd., D620, dioctyl adipate, diisononyl adipate, etc.), phosphate ester (tricresyl phosphate, etc.), adipic acid ester, citric acid ester (B) Mercapto tributyl citrate, etc., sebacate, sebacate, maleate, benzoate, polyether polyester, epoxy polyester (epoxidized soybean oil, epoxidized linen) Kernel oil, etc., polyester (low molecular weight polyester formed from 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.

Any suitable other components may be included in the plastic film to the extent that the effects of the present invention are not impaired.

The present inventors have found that a substrate having a small standard deviation σ of thickness unevenness and a high thickness precision can be obtained by careful design of a substrate.

The substrate can be produced by any appropriate manufacturing method within the range in which the effects of the present invention can be exhibited. Examples of such a production method include injection molding, extrusion molding, inflation molding, calender molding, and blow molding. Among these, in order to obtain a substrate having a small standard deviation σ of thickness unevenness and high thickness precision, calender molding is preferred.

As the calender molding, any appropriate molding machine can be employed depending on the number or arrangement of the calender rolls. As such a molding machine, for example, four L-types, four inverted L-types, four Z-types, an inclined type in which these are deformed, and six types in which rolls are added for stabilization are exemplified. .

In order to obtain a substrate having a particularly small standard deviation σ of thickness unevenness and a particularly high thickness precision, it is important to strictly control the conditions of the calendering.

As a preferable means for obtaining a substrate having a particularly small standard deviation σ of thickness unevenness and particularly high thickness precision, it is exemplified that the unevenness of the temperature of the mixture of the final product is controlled within ±5% in the calendering. By controlling the temperature unevenness of the final product in the calendering to within ±5%, a substrate having a particularly small standard deviation σ of thickness unevenness and particularly high thickness precision can be obtained, and the adhesive tape of the present invention The stress against the expansion or pin can become more uniform within the belt surface.

Another preferred means for obtaining a substrate having a particularly small standard deviation σ of thickness unevenness and particularly high thickness precision is exemplified by the last three rolls in the calendering process (including the last three of the last half of the roll). The temperature difference of the root roller is controlled within ±20%, preferably within ±18%, more preferably within ±16%, and even more preferably within ±15%. By controlling the temperature difference of the last three rolls (including the three consecutive rolls of the last half of the last roll) within the above range in the calendering, the standard deviation σ of the thickness unevenness is particularly small, and the thickness precision is particularly high. The substrate, and the stress of the adhesive tape of the present invention for expansion or pinning can become more uniform within the tape surface.

In the present invention, in order to obtain a substrate having a particularly small standard deviation σ of thickness unevenness and particularly high thickness precision, the above two means are particularly preferably exemplified.

In order to obtain a substrate having a particularly small standard deviation σ of thickness unevenness and a particularly high thickness precision, it is also effective to control the temperature of the mixture in the range of 140 to 220 ° C in the calendering.

In order to obtain a substrate having a particularly small standard deviation σ of thickness unevenness and a particularly high thickness precision, it is also effective to control the unevenness of the rotational speed of each roller within ±5% in the calender molding.

<Adhesive layer>

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

As the material of the above adhesive layer, any appropriate 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 grafted with a monomer such as methyl methacrylate; SBS, SBR, SEPS, SIS, SEBS, and poly Synthetic rubber such as butene, polyisobutene, polyisobutylene, butyl rubber; Among these, it is preferable that at least one type of (meth)acrylic polymer is used in the case where the paste adhered to the adherend is small, has high cohesiveness, and is excellent in transparency.

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

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

Preferred examples of the (meth)acrylic monomer include (meth)acrylate and (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 hydroxyl group-containing (meth) acrylate, 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 , (meth)acrylic acid pentyl, (meth)acrylic acid amyl, (meth) hexyl acrylate, cyclohexyl (meth) acrylate, Heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, (methyl) Isodecyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylate Trialkyl ester, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, pentadecyl (meth) acrylate, ( Ethyl (meth) acrylate, (meth) propyl An alkyl (meth)acrylate having an alkyl group having 1 to 30 carbon atoms (including a cycloalkyl group) such as lauryl olefin. Among the (meth) acrylates, an alkyl (meth) acrylate having an alkyl group having 2 to 20 carbon atoms (including a cycloalkyl group) is preferred, and an alkane having a carbon number of 4 to 18 is more preferred. An alkyl (meth)acrylate of a base (also including 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 carboxyl group-containing monomer. Moreover, in order to fully exhibit the effect as an adhesive, the above is constituted. The monomer component of the (meth)acrylic polymer may contain acrylonitrile.

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

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

When the monomer component constituting the (meth)acrylic polymer contains a hydroxyl group-containing monomer, the content of the hydroxyl group-containing monomer in the monomer component constituting the (meth)acrylic polymer is preferably 0.1% by weight. ~20% by weight, more preferably 0.1% by weight to 10% by weight. When the monomer component constituting the (meth)acrylic polymer contains a carboxyl group-containing monomer, the content ratio of the carboxyl group-containing monomer in the monomer component constituting the (meth)acrylic polymer is preferably 0.1% by weight. ~20% by weight, more preferably 0.1% by weight to 10% by weight. In this way, the monomer component constituting the (meth)acrylic polymer contains 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 may be effectively caused to occur. The cross-linking reaction of the cross-linking agent can sufficiently exhibit the effect as an adhesive. Further, the content ratio of the hydroxyl group-containing monomer in the monomer component constituting the (meth)acrylic polymer or the carboxyl group-containing monomer in the monomer component constituting the (meth)acrylic polymer When the content ratio is adjusted to be within the above range, the breakage 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 When the range is too large, the adhesive force becomes too large, and there is a tendency that adhesion tends to occur, and when the peeling operation is performed, it is likely to cause breakage of the adherend.

The adhesive layer preferably contains a crosslinking agent. When the adhesive layer contains a crosslinking agent, the content ratio of the crosslinking agent in the adhesive layer can be appropriately set according to the purpose, preferably 100 weights relative to the main resin component (preferably (meth)acrylic polymer). Parts are 0.1 parts by weight to 20 weights Quantities. By setting the content ratio of the crosslinking agent in the adhesive layer to the above range, a moderate crosslinking reaction can be produced, and the breakage of the adherend at the time of the peeling operation can be effectively prevented.

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

The adhesive layer may also contain a plasticizer. When the adhesive layer contains a plasticizer, the content ratio of the plasticizer in the adhesive layer can be appropriately set according to the purpose, and is 100 parts by weight based on 100 parts by weight of the main resin component (preferably (meth)acrylic polymer). 0.1 parts by weight to 70 parts by weight. The effect of the present invention can be more effectively exhibited by setting the content ratio of the plasticizer in the adhesive layer to the above range. When the content ratio of the plasticizer in the adhesive layer is more than 70 parts by weight based on 100 parts by weight of the main resin component (preferably (meth)acrylic polymer), the adhesive layer becomes too soft and easy. Produces a residue of the paste or is contaminated by the adherent.

Examples of the plasticizer include a phthalate type, a trimellitic acid ester type (manufactured by DAINIPPON INK CORPORATION, W-700, trioctyl trimellitate, etc.), and an adipate type ( J-PLUS Co., Ltd., D620, dioctyl adipate, diisononyl adipate, etc.), phosphate ester (tricresyl phosphate, etc.), adipic acid ester, citric acid ester (B) Mercapto tributyl citrate, etc., sebacate, sebacate, maleate, benzoate, polyether polyester, epoxy polyester (epoxidized soybean oil, epoxidized linen) Kernel oil, etc., polyester (low molecular weight polyester formed from 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.

In order to promote a crosslinking reaction or the like, the adhesive layer may contain any appropriate catalyst. Adhesive When the agent layer contains a catalyst, the content ratio of the catalyst in the adhesive layer can be appropriately set according to the purpose, and is 0.01 part by weight based on 100 parts by weight of the main resin component (preferably (meth)acrylic polymer). ~10 parts by weight. The effect of the present invention can be more effectively exhibited by making the content ratio of the catalyst in the adhesive layer within the above range.

Examples of the catalyst include tetraisopropyl titanate, tetra-n-butyl titanate, tin octylate, lead octoate, cobalt octoate, zinc octoate, calcium octylate, lead naphthenate, cobalt naphthenate, and diacetic acid. Organometallic compounds such as dibutyltin, dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin maleate; butylamine, dibutylamine, hexylamine, tert-butylamine, ethylenediamine , basic compounds such as isophorone diamine, imidazole, lithium hydroxide, potassium hydroxide, sodium methoxide; p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphate, dialkyl phosphate, acrylic acid - An acidic compound such as a phosphate of β-hydroxyethyl ester, a monoalkyl phosphite, or a dialkyl phosphite; The catalyst may be used alone or in combination of two or more.

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

The adhesive layer may contain any suitable additives within the scope of the effects of the present invention. Examples of the additive as described above 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 employed. Examples of such a release liner include a substrate having a release layer such as a plastic film or paper which has been subjected to surface treatment with a release agent such as polyfluorene-based, long-chain alkyl, fluorine or molybdenum sulfide; Low-adhesion group formed of fluorine-based polymer such as tetrafluoroethylene, polychlorotrifluoroethylene, polyfluorinated ethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, or chlorofluoroethylene-vinylidene fluoride copolymer A low-adhesive substrate formed of a non-polar polymer such as an olefin resin (for example, polyethylene or polypropylene);

As a method of providing an adhesive layer on a substrate, any appropriate means can be employed without departing from the effects of the present invention. As a means as described above, a method of providing an adhesive layer by applying a coating liquid for forming an adhesive layer to a substrate is preferred.

In the formation of the applied adhesive layer as described above, uneven coating at the time of coating may affect the thickness unevenness of the adhesive tape. As one of means for alleviating such effects, the winding tension of the adhesive tape obtained after coating is preferably 200 N/m or less, more preferably 30 N/m to 180 N/m, and further preferably It is preferably set to 30 N/m to 160 N/m, and more preferably set to 30 N/m to 150 N/m. The so-called take-up tension refers to the tension when the adhesive tape is wound into a roll. By adjusting the above-mentioned extraction tension to the above range, the influence of coating unevenness on the unevenness of the adhesive tape on coating can be alleviated, and the stress on the expansion or pin of the adhesive tape of the present invention is The inside of the belt can be made more uniform.

As another means for reducing the influence of uneven coating on the unevenness of the adhesive tape during coating, the drying temperature of the adhesive tape obtained after coating is preferably set to 200 ° C or less. More preferably, it is 180 ° C or less, and further preferably 160 ° C or less. By adjusting the drying temperature to the above range, the influence of coating unevenness on the unevenness of the adhesive tape on the coating can be alleviated, and the stress on the expansion or pin of the adhesive tape of the present invention is The inside of the belt can be made more uniform.

As the coating method, any appropriate coating method can be employed without departing from the effects of the present invention. Examples of the coating method as described above include a reverse mode, a direct mode, and various methods in which a metering roll is combined. In order to sufficiently exhibit the effects of the present invention, it is preferred to adjust the thickness unevenness of the coating layer in a wet state containing a solvent to within ±20% in the width direction.

<non-adhesive layer>

Preferably, the adhesive tape of the present invention has an adhesive layer on one side of the substrate, and the base is The surface opposite to the adhesive layer has a non-adhesive layer.

The composition and the like of the non-adhesive layer as described above are not particularly limited, and examples thereof include a polyfluorene oxide layer, a (meth)acrylic polymer layer, a polyfluorene oxide layer, and a (meth)acrylic polymerization. The mixed layer of the layer is graft-polymerized with a polyoxynitride layer of a (meth)acrylic polymer. Among these, a mixed layer of a polyfluorene oxide and a (meth)acrylic polymer is preferable. By making the non-adhesive layer a mixed layer of polyoxymethylene and (meth)acrylic polymer, the adaptability of the non-adhesive layer to the substrate (especially the plastic film) becomes good, and the adhesive tape pair of the present invention The follow-up of the deformation such as extension is good.

The surface of the non-adhesive layer preferably has a textured structure. By providing the surface of the non-adhesive layer with a concave-convex structure, excessive adhesion to the base can be effectively suppressed. 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 to 2.0 μm. By setting the arithmetic mean surface roughness Ra of the non-adhesive layer within the above range, excessive adhesion can be suppressed when the adsorption by the negative pressure is performed. Further, the method of measuring the arithmetic mean surface roughness Ra of the non-adhesive layer will be described later.

The glass transition temperature Tg obtained by differential scanning calorimetry (DSC measurement) of the non-adhesive layer is preferably 20 ° C or higher, more preferably 30 ° C or higher, further preferably 50 ° C or higher, and particularly preferably 55 ° C or higher. The upper limit of the glass transition temperature Tg of the non-adhesive layer by the differential scanning calorimetry is not particularly limited, and is preferably 200 ° C or less, more preferably 170 ° C or less, and further preferably 150 ° C or less from the viewpoint of handleability and the like. It is preferably 130 ° C or less, preferably 100 ° C or less. When the glass transition temperature Tg obtained by the differential scanning calorimetry of the non-adhesive layer is within the above range, the hardness of the surface of the non-adhesive layer is moderately high even at a high temperature, so that the heat resistance is high, and the negative pressure is used. In the case where the adhesive tape of the invention is adsorbed and fixed to the fixing base and cut or the like, excessive adhesion due to heat generation of the base or the like can be effectively suppressed. Furthermore, the use of differential scanning calorimetry (DSC) for non-adhesive layers The measurement method of the glass transition temperature Tg obtained by the measurement) is demonstrated later.

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, it is 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 according to the Small formula. The calculation of the SP value can be carried out by a method described in a well-known literature (for example, Journal of Applied Chemistry, 3, 71, 1953, etc.).

The non-adhesive layer preferably has a phase separation structure. By having a phase-separated structure in the non-adhesive layer, a minute uneven structure can be effectively formed on the surface of the non-adhesive layer. For example, the case where the non-adhesive layer is a mixed layer of a polyoxymethylene and a (meth)acrylic polymer is exemplified, or it may be presumed that poly(oxy)oxy or (meth)acrylic polymerization is generated due to the phase separation structure. Concavities and convexities are generated by differences in the mobility of substances. In the adhesive tape of the present invention, excessive adhesion can be suppressed in the adhesive tape by the negative pressure, and the adhesion in the form of the roll can be effectively suppressed, and the form of the self-rolling can be suppressed. Broken or broken when unwinding.

The non-adhesive layer preferably comprises a polyfluorene-rich phase containing more poly(oxy)oxygen than a (meth)acrylic polymer and a rich (meth)acrylic polymer containing more (poly)oxygen. Polymer phase. More specifically, the non-adhesive layer is preferably a mutually separate phase-separated structure comprising the above-mentioned rich polyoxygen phase and the above-mentioned rich (meth)acrylic polymer phase, and more preferably the above-mentioned rich polyoxygen phase exists in the air. On the interface side (the opposite side of the substrate (especially the plastic film)), the above-mentioned rich (meth)acrylic polymer phase is present on the substrate (especially the plastic film) side. By having the phase separation structure as described above, the adhesion is effectively suppressed by the enriched xenon phase present on the air interface side, and the adaptability of the non-adhesive layer to the substrate (especially the plastic film) is present in the substrate. The (meth)acrylic polymer phase on the side (especially on the plastic film) becomes good, and the deformation followability becomes good. The phase separation structure as described above can be formed by adjusting the mixing of the polyfluorene oxide and the (meth)acrylic polymer in the non-adhesive layer as described below.

The non-adhesive layer has a phase-separated structure, or contains a polyfluorene-rich phase containing more poly(oxy)oxygen than the (meth)acrylic polymer as described above and more than poly(an) comprising a (meth)acrylic polymer. The oxygen-rich (meth)acrylic polymer phase can be observed by any suitable method. As the observation method as described above, for example, a non-adhesive layer profile is performed 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). Method of morphological observation. The 2-layer separation structure can be identified by the depth of the morphological observation image. Further, a method of observing the change in the content of germanium or carbon contained in the composition while changing the depth of the probe light from the side of the non-adhesive layer air interface by infrared absorption spectrometry based on the total reflection method may be mentioned. This is observed. Further, a method of observation using an X-ray microanalyzer or X-ray photoelectron spectroscopy may be mentioned. Further, these methods can be combined as appropriate to observe.

The non-adhesive layer has a rich enriched oxygen phase present on the air interface side (the opposite side of the substrate (especially the plastic film)) and a rich (meth)acrylic polymer present on the substrate (especially the plastic film) side. In the case of a phase-separated structure, when the non-adhesive layer is adsorbed and fixed to the fixing base by a negative pressure for cutting or the like, if the fixing base generates heat, the phase-separated structure is caused by the heat load due to the heat generation. The surface structure is broken, in particular, the surface structure of the phase separation structure having a convex portion in contact with the fixing base which is heated is broken, and a rich (meth)acrylic polymer phase at the air interface may be present at the convex portion. The side is exposed. However, in the adhesive tape of the present invention, the glass transition temperature Tg obtained by the differential scanning calorimetry of the non-adhesive layer is preferably within the above range, so that the hardness of the convex portion subjected to the heat load is moderately high, whereby the heat resistance is changed. high. Therefore, when the adhesive tape of the present invention is adsorbed and fixed to the fixing base by a negative pressure for cutting or the like, excessive adhesion due to heat generation of the chassis or the like can be effectively suppressed.

When 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 a weight ratio. Polyoxymethylene: (meth)acrylic polymer = 1:50 to 50:1, more preferably polyoxyn: (meth)acrylic polymer = 1:30 to 30:1, and further preferably poly Oxygen: (meth)acrylic polymer = 1:10~10:1, especially preferably polyoxyl: (meth)acrylic polymer = 1:5~5:1, optimally polyoxyl : (Meth)acrylic polymer = 1:3 to 5:1. If the content ratio of the polyoxygen in the non-adhesive layer is too large, the chemical affinity with the back surface of the substrate (especially the plastic film) becomes low, and it is difficult to adapt to the flaw of the back surface of the substrate (especially the plastic film). Further, if the content ratio of the polyfluorene oxide in the non-adhesive layer is too large, the followability to deformation such as elongation is deteriorated when the adhesive tape is formed, and the non-adhesive layer is broken to cause contamination. 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 adhesion tends to occur easily.

As the polyoxygen oxide, any suitable polyoxane can be used. As the polyfluorene oxide as described above, for example, a platinum-based compound is used as a catalyst, and an alkenyl group-containing polydialkyloxirane and a polydialkylhydrogenpolysiloxane are formed by an addition reaction. a condensed polyoxyl obtained by reacting a hydroxymethylpolydialkyl siloxane with a polydialkylhydrogenpolysiloxane using a tin-based catalyst . Examples of the addition polyoxyl oxide include "KS-776A" and "KS-839L" manufactured by Shin-Etsu Silicone. Examples of the condensation type polyfluorene oxide include "KS723A/B" manufactured by Shin-Etsu Silicone. 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 polyoxymethylene are classified into an emulsion type which is dissolved in an organic solvent such as toluene, an emulsion type obtained by emulsifying it, and a solventless type composed of polyfluorene oxide. Further, in addition to the addition of polyfluorene oxide or condensed polyfluorene oxide, a polyfluorene/acrylic graft polymer, a polyfluorene/acrylic block polymer or the like can be used. Examples of the polyoxymethylene/acrylic 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 polyoxyn/acrylic block polymer include MODIPER FS700, FS710, FS720, FS730, and FS770 (the above is Japanese) Oil Co., Ltd.) and so on.

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

The (meth)acrylic polymer is a polymer composed of 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% to 100% by weight, particularly preferably 95% by weight to 100% by weight. The monomer in the monomer component may be one type or two or more types.

Preferred examples of the (meth)acrylic monomer include (meth)acrylate and (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 hydroxyl group-containing (meth) acrylate, 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 , (meth)acrylic acid pentyl, (meth)acrylic acid amyl, (meth) hexyl acrylate, cyclohexyl (meth) acrylate, Heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, (methyl) Isodecyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylate Trialkyl ester, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, octadecyl (meth) acrylate, pentadecyl (meth) acrylate, ( Ethyl (meth) acrylate, (meth) propyl Carbon number such as lauryl enoate It is an alkyl (meth)acrylate of 1 to 30 alkyl groups (including a cycloalkyl group). Among the (meth) acrylates, an alkyl (meth) acrylate having an alkyl group having 2 to 20 carbon atoms (including a cycloalkyl group) is preferred, and an alkane having a carbon number of 4 to 18 is more preferred. An alkyl (meth)acrylate of a base (also including 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 effects of the present invention, 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.

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

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

When the non-adhesive layer contains a (meth)acrylic polymer, the (meth)acrylic polymer in the non-adhesive layer preferably has a content ratio of a hydroxyl group-containing (meth) acrylate in the monomer component constituting the non-adhesive layer. The total amount of the monomer components other than the hydroxyl group-containing (meth) acrylate is preferably 2% by weight to 30% by weight, more preferably 3% by weight to 25% by weight, even more preferably 5% by weight to 20% by weight. %. When the non-adhesive layer contains a (meth)acrylic polymer, it constitutes a single (meth)acrylic polymer in the non-adhesive layer with respect to the total amount of the monomer components other than the hydroxyl group-containing (meth)acrylate. When the content ratio of the hydroxyl group-containing (meth) acrylate in the body component is within the above range, a minute uneven structure is more effectively formed on the surface of the non-adhesive layer, and the adhesive structure of the present invention is formed by the formation of the uneven structure. In the belt, when the adsorption by the negative pressure is performed, the excessive adhesion can be further suppressed, and the adhesion in the form of the roll can be more effectively suppressed, and the occurrence of breakage or breakage during unwinding in the form of the self-rolling 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 a hydroxyl group-containing (meth)acrylic acid in the monomer component constituting the same. (meth)acrylic acid and/or (meth)acrylic acid ester may be contained in the monomer component other than an ester. In this case, the content ratio of (meth)acrylic acid to (meth)acrylic acid ester is preferably 0:100 to 20:80, more preferably 0, by weight ratio of (meth)acrylic acid:(meth)acrylic acid ester. : 100~10:90, and further preferably 0:100~5:95.

When the content ratio of (meth)acrylic acid to (meth)acrylic acid ester is in the above range, a minute uneven structure is more effectively formed on the surface of the non-adhesive layer, and the adhesive structure of the present invention is formed by the formation of the uneven structure. In the belt, when the adsorption by the negative pressure is performed, the excessive adhesion can be further suppressed, and the adhesion in the form of the roll can be more effectively suppressed, and the occurrence of breakage or breakage during the unwinding of the form of the self-rolling can be further suppressed.

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

The non-adhesive layer may contain any suitable additives within the scope of the effects of the present invention. Examples of the additive as described above include a catalyst, 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 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 tends to occur. When the thickness of the non-adhesive layer is more than 10 μm, the followability to deformation such as elongation is deteriorated. When the thickness of the non-adhesive layer is less than 0.01 μm, the effect of the present invention is hard to be revealed, or the production becomes difficult.

As a method of forming a non-adhesive layer on one side of a substrate (especially a plastic film), for example, a material of a non-adhesive layer is coated on one side of a substrate (especially a plastic film) and dried. Non-adhesive layer method. Examples of the coating method include a bar coater, a gravure coater, a spin coater, a roll coater, a knife coater, and an applicator.

The adhesive tape of the present invention can be used for any suitable purpose. When the adhesive tape of the present invention is fixed to the fixing base by vacuum suction for cutting or the like as described above, excessive adhesion due to heat generation of the base or the like can be effectively suppressed, and the roll shape can be effectively suppressed. The adhesion in the form does not break or break when the shape of the roll is unwound, and the non-adhesive layer has good adaptability to the plastic film, and has good followability to deformation such as elongation. Therefore, it can be suitably used for semiconductor processing using a semiconductor wafer composed of a brittle material and having a fine and delicate circuit pattern as an adherend. When the adhesive tape of the present invention is used for semiconductor processing, when it is fixed by a vacuum suction to a fixing base for cutting or the like, excessive adhesion due to heat generation of the chassis or the like can be effectively suppressed, and therefore, cutting can be included. The semiconductor manufacturing steps proceed smoothly. Moreover, when the adhesive tape of the present invention is used for semiconductor processing, film deformation or stress strain which is conventionally caused by adhesion does not occur, so that it is possible to accurately follow the fine and delicate circuit pattern of the semiconductor wafer. Moreover, the natural release of stress and strain after bonding to the semiconductor wafer does not occur, so that the semiconductor wafer can be effectively prevented from being broken. In particular, the wafer for LED is composed of a very brittle material such as gallium nitride, gallium arsenide or tantalum carbide, and therefore the adhesive tape of the present invention is particularly useful for cutting (LED cutting) of a wafer for an LED. suitable.

[Examples]

Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited by the Examples. Parts are parts by weight. Further, the amount of the reagent to be supplied in the form of a solution is expressed by the amount of the solid content (the amount of solid content converted) remaining to volatilize the solution.

<average thickness>

Using a 1/1000 dial gauge, 55 points were measured in the MD direction at intervals of 50 mm, and 55 portions were measured in the TD direction. Regarding the measurement of the TD direction, if the length is insufficient, the position is moved by 50 mm in the MD direction, and the measurement is continued and the value is calculated. Then, 5 points were removed from the maximum value of the total of 110 measurements, and 5 points were removed from the minimum value to obtain 100 points. Then use the AVERAGE function of EXCEL to calculate the average value.

<Standard deviation σ of thickness unevenness>

Using a 1/1000 dial gauge, 55 points were measured in the MD direction at intervals of 50 mm, and 55 portions were measured in the TD direction. Regarding the measurement of the TD direction, if the length is insufficient, it is on the MD side. After moving the position up by 50 mm, the measurement is continued and the value is calculated. Then, 5 points were removed from the maximum value of the total of 110 measurements, and 5 points were removed from the minimum value to obtain 100 points. Then, the standard deviation σ of the thickness unevenness is calculated using the STDEV function of EXCEL.

<Modulus of 100% extension in the MD direction and 100% extension in the TD direction>

The measurement was carried out by an INSTRON type tensile tester (manufactured by Shimadzu Corporation, AUTOGRAPH) in accordance with JIS-K-7127 (1999). Specifically, a sample having a width of 20 mm and a length of 100 mm was placed at a distance of 50 mm between the chucks, and then stretched at a stretching speed of 0.3 m/min. Then, the chart is read, and the load at 100% extension (when 50 mm is extended) is taken as the modulus.

<Cutting conditions>

Device: Product name "DFD-651" (manufactured by DISCO Corporation)

Blade: Product name "27HECC" (manufactured by DISCO)

Blade speed: 40,000 rpm

Cutting speed: 120mm/sec

Cutting depth: 25μm

Cut mode: undercut

Cutting size: 3.0mm × 3.0mm

Expansion amount: 10mm

<extensibility>

The adhesive tape obtained in the examples and the comparative examples was attached to the polished 6-inch semiconductor wafer (thickness = 30 μm) by reciprocating twice in a 23 ° C, 50% RH atmosphere. surface. Then, the wafer is cut using the above cutting conditions, and then expanded.

The offset of the continuously connected 20 wafers after the expansion was measured and evaluated based on the following criteria. Furthermore, the basis for the deviation is set to the center line of 20 wafers.

○: Among 20, the offset of 1 mm or more was 1.0 or less.

×: Among 20, the offset of 1 mm or more exceeded 1.0.

<maximum elongation>

The maximum elongation was measured by an INSTRON type tensile tester (manufactured by Shimadzu Corporation, AUTOGRAPH) in accordance with JIS-K-7127 (1999). Specifically, a sample having a width of 20 mm and a length of 100 mm was placed 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 measurement was carried out by an INSTRON type tensile tester (manufactured by Shimadzu Corporation, AUTOGRAPH) in accordance with JIS-K-7127 (1999). Specifically, a sample having a width of 20 mm and a length of 100 mm was placed at a distance of 50 mm between the chucks, and then stretched at a tensile speed of 0.3 m/min to obtain an initial elastic modulus. The initial elastic modulus is a value obtained by making a tangent in a region where the elongation at break is 0 to 2% and extending the tangent to a value of 100% elongation in a straight line, and is corrected in terms of the sectional area of the sample.

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

After observing the non-adhesive layer profile, the morphology was observed by a transmission electron microscope (SEM).

(Observation by infrared spectrometry based on total reflection method (ATR-IR))

The total reflectance measurement method was selected using an infrared spectroscopic spectrometer (manufactured by Perkinermer, Spectrum One), and two types of total reflection measurement ruthenium (ZnSe45°, Ge45°) were used to change the depth of analysis of the probe light, and the ATR of the non-adhesive layer was performed. IR measurement.

<Arithmetic average surface roughness Ra>

A confocal laser microscope "LEXT3000" manufactured by OLYMPUS was used to measure in a 3D mode with a 20-fold objective lens. The observation range of the 3D mode is determined by setting the positions where the CF image (confocal image) becomes all black when the lens is moved up and down, and the positions of the observation range are Top and Bottom, respectively.

The image acquisition method in the 3D mode performs image acquisition by a step method at a distance of 0.2 μm.

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 Glass Transfer Temperature Tg Using Non-Adhesive Layer by Differential Scanning Calorimetry (DSC Measurement)>

The non-adhesive layer was collected with a Feather blade, and about 3 mg was sealed in a dish for solid measurement of DSC.

The disk was put into a high-sensitivity differential scanning calorimeter Q2000 of TA INSTRUMENT, and the temperature was raised from 0 ° C to 200 ° C at a temperature increase rate of 2 ° C / min.

Further, cooling was carried out under the same conditions, and the temperature was further raised. The intersection of the straight line portion below the connection transition region of the second round and the straight line portion above the transition region is inserted at the intersection of the straight line and the measurement curve, and this is taken as the glass transition temperature Tg.

[Example 1] (substrate)

100 parts by weight of a polyvinyl chloride containing a DOP plasticizer (bis(2-ethylhexyl phthalate), J-PLUS), and 27 parts by weight of a soft polychlorinated product with respect to a polymerization degree of P = 0,050 by a calendering method. Vinyl film. Specifically, the temperature of the mixture of the final materials at the time of film formation was not more than ±3%, and the temperature difference of the last three rolls was set to within ±10%, and the film was formed by an inverted L type calender. The obtained soft polyvinyl chloride film (1A) has a thickness of 70 μm, and the modulus of elasticity (MD) measured according to JIS-K-7127 (1999) is 485 MPa, and the maximum elongation measured according to JIS-K-7127 (1999). The rate (MD) is 300%.

(non-adhesive layer)

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.), and acrylic copolymer (methyl propylene) Methyl enoate (MMA) / butyl acrylate (BA) / hydroxyethyl acrylate (HEA) = 60 / 30/10) 50 parts by weight, tin-based catalyst (Cat-PS3, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts by weight The mixture was mixed in a solution state to obtain a mixed solution. The mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the mixed solution (1B) is polyoxymethylene in a weight ratio: (meth)acrylic polymer = 2:1.

The mixed solution was applied to one side of a soft polyvinyl chloride film (1A), and dried at a drying temperature of 160 ° C or lower to form a non-adhesive layer (1B) having a thickness of 1.0 μm.

When the non-adhesive layer (1B) was observed by SEM, as shown in FIG. 3, FIG. 4, and FIG. 5, the depth of the image was observed according to the morphology, and it was confirmed that the air interface side and the plastic film side were different in composition, and the inclusion of the inclusion layer was included. The polyoxymethylene phase having more oxygen than the (meth)acrylic polymer and the (meth)acrylic polymer phase containing more (poly)oxygen of the (meth)acrylic polymer, and the polyoxygen phase A phase-separated structure independent of the (meth)acrylic polymer, it is observed that the rich polyoxygen phase exists on the air interface side (opposite side of the plastic film), and the (meth)acrylic polymer phase exists in Plastic film side.

Further, when the non-adhesive layer (1B) is subjected to infrared spectroscopy (ATR-IR) based on total reflection, the peak near 800 cm ^-1 from Si-CH _{3 is} measured relative to the phase derived from (meth)acrylic polymer. The absorbance ratio of the peak near the 1725 cm ^-1 of the carbonyl group in the middle of the carbonyl group was found to be larger than the peak of 800 cm ^-1 when Ge 45 ° was used as compared with ZnSe 45 °. Therefore, it is understood that the content ratio of ruthenium is higher on the air interface side than on the substrate side.

Further, the enriched xenon phase in the non-adhesive layer (1B) is present on the air interface side (opposite side of the plastic film) and can also be confirmed in FT-IR. The FT-IR measurement was performed using the "Spectrum One" manufactured by Perkinermer, and the air interface side was measured by the ATR method using two kinds of ruthenium (ZnSe45°, Ge45°) having different depth directions. When the resulting graph confirmed, it was confirmed: the non-adhesive layer from the vicinity of the Si-CH ₃ peak of 800cm ^-1 with respect to a home-based polymer C from the (meth) acrylate of = O 1720cm ^-1 ~ 1730cm ^-1 The absorbance of the peak becomes larger than that of Ge 45° which is shallower in the analysis depth direction. Thereby, it can be confirmed that the concentration of polyoxane at the air interface side becomes higher.

The principle of minimizing the observation results and the surface free energy is considered, and it is understood that the non-adhesive layer has a two-layer structure having a rich pseudo-oxygen phase on the air interface side.

(adhesive layer)

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

The adhesive solution is applied to the surface of the soft polyvinyl chloride film (1A) on the opposite side of the non-adhesive layer (1B), and then dried at a drying temperature of 160 ° C or lower, in a soft polyvinyl chloride film. An adhesive layer (1C) having a thickness of 10 μm was formed on the side opposite to the non-adhesive layer (1B) on (1A).

(adhesive tape)

The laminate structure of the non-adhesive layer (1B)/soft polyvinyl chloride film (1A)/adhesive layer (1C) was formed as described above, and the tape was stretched at a tensile tension of 100 N/m to produce an adhesive tape (1). ).

The results are summarized in Table 1.

[Embodiment 2]

An adhesive tape (2) was produced in the same manner as in Example 1 except that the stretching was performed at a tensile tension of 150 N/m.

The results are summarized in Table 1.

[Example 3] (substrate)

100 parts by weight of polyvinyl chloride with respect to polymerization degree P=1050 is produced by calendering method DOP plasticizer (bis(2-ethylhexyl phthalate), manufactured by J-PLUS) 27 parts by weight of a soft polyvinyl chloride film. Specifically, the temperature of the mixture of the final stock at the time of film formation was not more than ±4.5%, and the temperature difference of the last three rolls was set to within ±15%, and the film was formed by an inverted L type calender. The obtained soft polyvinyl chloride film (3A) had a thickness of 70 μm, and the modulus of elasticity (MD) measured according to JIS-K-7127 (1999) was 501 MPa, and the maximum elongation was measured in accordance with JIS-K-7127 (1999). The rate (MD) is 480%.

(non-adhesive layer)

In the same manner as in Example 1, a non-adhesive layer (3B) having a thickness of 1.0 μm was formed on one surface of the soft polyvinyl chloride film (3A).

(adhesive layer)

In the same manner as in Example 1, an adhesive layer (3C) having a thickness of 10 μm was formed on the surface of the soft polyvinyl chloride film (3A) opposite to the non-adhesive layer (3B).

(adhesive tape)

The laminate structure of the non-adhesive layer (3B)/soft polyvinyl chloride film (3A)/adhesive layer (3C) was formed as described above, and the film was taken up by a tensile tension of 150 N/m to produce an adhesive tape (3). ).

The results are summarized in Table 1.

[Comparative Example 1] (substrate)

100 parts by weight of a polyvinyl chloride containing a DOP plasticizer (bis(2-ethylhexyl phthalate), J-PLUS), and 27 parts by weight of a soft polychlorinated product with respect to a polymerization degree of P = 0,050 by a calendering method. Vinyl film. Specifically, the temperature of the mixture of the final stock at the time of film formation was not more than ±10%, and the temperature difference of the last three rolls was set to within ±20%, and the film was formed by an inverted L type calender. The obtained soft polyvinyl chloride film (C1A) has a thickness of 80 μm, and the modulus of elasticity (MD) measured according to JIS-K-7127 (1999) is 450 MPa, and the maximum elongation measured according to JIS-K-7127 (1999). The rate (MD) is 530%.

(non-adhesive layer)

In the same manner as in Example 1, a non-adhesive layer (C1B) having a thickness of 1.0 μm was formed on one surface of a soft polyvinyl chloride film (C1A). The drying temperature at the time of formation was maintained at 170 ° C or lower.

(adhesive layer)

In the same manner as in Example 1, an adhesive layer (C1C) having a thickness of 10 μm was formed on the surface of the soft polyvinyl chloride film (C1A) on the side opposite to the non-adhesive layer (C1B). The drying temperature at the time of formation was maintained at 170 ° C or lower.

(adhesive tape)

The laminate structure of the non-adhesive layer (C1B)/soft polyvinyl chloride film (C1A)/adhesive layer (C1C) was formed as described above, and the tape was stretched at a tensile tension of 250 N/m to produce an adhesive tape (C1). ).

The results are summarized in Table 1.

[Comparative Example 2] (substrate)

100 parts by weight of a polyvinyl chloride containing a DOP plasticizer (bis(2-ethylhexyl phthalate), J-PLUS), and 27 parts by weight of a soft polychlorinated product with respect to a polymerization degree of P = 0,050 by a calendering method. Vinyl film. Specifically, the temperature of the mixture of the final stock at the time of film formation was not more than ±10%, and the temperature difference of the last three rolls was set to within ±10%, and the film was formed by an inverted L type calender. The obtained soft polyvinyl chloride film (C2A) had a thickness of 77 μm, and the modulus of elasticity (MD) measured according to JIS-K-7127 (1999) was 450 MPa, and the maximum elongation was measured in accordance with JIS-K-7127 (1999). The rate (MD) is 520%.

(non-adhesive layer)

In the same manner as in Example 1, a non-adhesive layer (C2B) having a thickness of 1.0 μm was formed on one surface of a soft polyvinyl chloride film (C2A). The drying temperature at the time of formation was maintained at 170 ° C or lower.

(adhesive layer)

In the same manner as in Example 1, the non-adhesive layer was formed on the soft polyvinyl chloride film (C2A). (C2B) The adhesive layer (C2C) having a thickness of 10 μm was formed on the opposite side. The drying temperature at the time of formation was maintained at 170 ° C or lower.

(adhesive tape)

The laminate structure of the non-adhesive layer (C2B)/soft polyvinyl chloride film (C2A)/adhesive layer (C2C) was formed as described above, and the tape was stretched at a tensile tension of 150 N/m to produce an adhesive tape (C2). ).

The results are summarized in Table 1.

[Industrial availability]

The standard deviation σ of the thickness unevenness of the adhesive tape system of the present invention is small, and the stress for the expansion or the pin top is uniform within the tape surface. Therefore, the fine and delicate circuit pattern of the semiconductor wafer can be accurately followed and adhered, and the natural release of stress and strain after bonding to the semiconductor wafer does not occur, so that the semiconductor wafer can be effectively prevented from being broken. In particular, the wafer for LED is composed of a very brittle material such as gallium nitride, gallium arsenide or tantalum carbide. Therefore, the adhesive tape of the present invention is particularly suitable for LED cutting or the like.

100‧‧‧ wafer

200‧‧‧ cutting tape

Claims (17)

An adhesive tape which is provided with an adhesive layer on at least one side of a substrate, and has a standard deviation σ of thickness unevenness of the adhesive tape of 2.0 μm or less. The adhesive tape of claim 1, wherein the adhesive tape has an average thickness of from 20 μm to 120 μm. The adhesive tape of claim 1 or 2, wherein the ratio of the modulus of the 100% stretched MD direction of the adhesive tape to the modulus of 100% of the TD direction is stretched (MD direction 100% modulus/TD direction) The 100% modulus is 0.5 to 1.9. The adhesive tape according to any one of claims 1 to 3, wherein a standard deviation σ of the thickness unevenness of the substrate is 2.0 μm or less. The adhesive tape according to any one of claims 1 to 4, wherein the substrate has an average thickness of from 20 μm to 120 μm. The adhesive tape according to any one of claims 1 to 5, wherein the substrate has a maximum elongation of 100% or more as measured according to JIS-K-7127 (1999). The adhesive tape according to any one of claims 1 to 6, wherein the substrate is a plastic film. The adhesive tape of claim 7, wherein the plastic film comprises at least one selected from the group consisting of polyvinyl chloride, polyolefin, and ethylene-vinyl acetate copolymer. The adhesive tape according to any one of claims 1 to 8, comprising the adhesive layer on one side of the substrate, and a non-adhesive layer on a surface of the substrate opposite to the adhesive layer. The adhesive tape of claim 9, wherein the non-adhesive layer is a mixed layer of a polyoxymethylene and a (meth)acrylic polymer. The adhesive tape of claim 10, wherein the mixing ratio of the polyfluorene oxide to the (meth)acrylic polymer in the non-adhesive layer is polyoxylium by weight: (meth)acrylic polymer=1: 50~50:1. The adhesive tape according to any one of claims 9 to 11, wherein the non-adhesive layer has a phase separation structure. The adhesive tape according to any one of claims 9 to 12, wherein the non-adhesive layer has a thickness of from 0.01 μm to 10 μm. The adhesive tape according to any one of claims 1 to 13, wherein the adhesive layer comprises at least one (meth)acrylic polymer. The adhesive tape according to any one of claims 1 to 14, which is provided with a release liner on the surface of the above-mentioned adhesive layer. An adhesive tape according to any one of claims 1 to 15, which is used for semiconductor processing. The adhesive tape of any one of claims 1 to 16, which is used for LED cutting purposes.